CA2056720C - Wet laid fiberous thermoplastic material and aqueous dispersion for producing same - Google Patents
Wet laid fiberous thermoplastic material and aqueous dispersion for producing sameInfo
- Publication number
- CA2056720C CA2056720C CA002056720A CA2056720A CA2056720C CA 2056720 C CA2056720 C CA 2056720C CA 002056720 A CA002056720 A CA 002056720A CA 2056720 A CA2056720 A CA 2056720A CA 2056720 C CA2056720 C CA 2056720C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- web
- amount
- wet
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
Abstract
A wet-laid, non-woven, glass fiber containing thermoplastic polymer web is provided that is capable of yielding improved physical properties for articles molded from the web. The web in addition to the glass fibers and thermoplastic matrix polymer contains a chemically modified thermoplastic polymer. This material is preferably present in the mat binder which is applied to the web. Generally, the amount of the chemically modified thermoplastic polymer present in the web is in the range of from about 0.1 to about 20 weight percent of the web. In addition to the chemically modified thermoplastic polymer, the mat binder also contains a film forming polymer and optionally an electron donating oregano coupling agent and a stabilizing agent such as one or more carboxylic acids and/or anhydrides which may be monocarboxylic, polycarboxylic, aliphatic or cyclic.
Description
WET LAID FIBEROUS THERMOPLASTIC ~ATT~'.RTAT.
AND AQUEOUS DISPERSION FOR PRODUCING SAME
The present invention is directed to a fiberous-containing material with thermoplastic polymer that can be molded. More particularly, the present invention is directed to a material having a thermoplastic polymer matrix and chopped chemically treated glass 10 fibers, where both the fibers and thermoplastic polymer is prepared into the moldable material by a wet-laid process.
Fiber reinforced plastics include thermoplastic moldable materials and thermosetting moldable materials. The latter includes sheet molding compounds, thick molding compounds and the like that 15 mold through curing. The fiber reinforced thermoplastics mold through flowing the material into a shape as in an in~ection, compression molding operations. In compression molding a fiber reinforced thermoplastic composite is placed in a mold and stamped to the desired shape. These materials for such an operation are produced in the form 20 of laminates cont~n~ng the fibers in various forms including chopped strand continuous strand mats and needled mats and mixtures thereof and the thermoplastic polymer matrix combined with the reinforcement through lamination, extradication processes. Also, processes have been developed recently where the reinforcement is combined with the 25 thermoplastic polymer in a wet laid process from an aqueous solution cont~n~ng the fiberous reinforcement in chopped form and the thermoplastic polymer. In this process, the composite ingredients are combined and mixed in water at low solids concentration and equipment similar to a hydropulper used in the formation of paper from paper 30 pulp. After the slurry is properly mixed, it can be pumped as a thick stock to a holding device where the slurry is further diluted and flocculated and pumped to a head box of a paper machine. Also the slurry can be pumped directed to the head box of the paper machine.
. _ - 2 - 2056720 From the head box, the composite sheet i8 formed on a continuous traveling wire mesh. The mesh takes the composite over vacuum sources to remove liquids including water and form the sheet. A mat binder usually polyvinylpyrrolidone is sprayed onto the sheet and the sheet 5 i8 dried. Representative of such processes are those described in U.S. Patentc 4,882,114; 3,716,449, 3,871,952, EPO Nos. 0 312 414 and 0 308 286 and 0 341 977.
It is an ob~ect of the present invention to provide a wet laid fiber-contain~ng thermoplastic composite or material that has 10 good tensile and flexible properties in the molded article.
SUMMARY OF THE INV~1ION
The aforementioned and other ob~ects gleaned from the disclosure herein are provided by the present invention. One aspect 15 of the present invention is the wet-laid web of the nonwoven fiberous mat and the thermoplastic polymer that can be dried into a moldable laminate or sheet, while another aspect of the invention is the dried laminate so produced, and another aspect of the invention is a foamed aqueous dispersion of the discontinuous fibers and thermoplastic 20 matrix polymer with the chemically modified thermoplastic polymer.
The wet-laid web includes: the nonwoven mat of discontinous glass fibers, thermoplastic matrix polymer, and chemically modified thermoplastic polymer having chemically reactive moieties for addition, condensation or free radical reaction to allow for coupling 25 of the glass fiber to the matrix polymer. The glass fibers have a surface treatment or "size" that allows the fibers to disperse even from the strand form in an aqueous dispersion that does or is to contain the thermoplastic matrix polymer. Dispersion of the fibers may be asslsted by surfactants in the size or in the aqueou~
30 dispersion. The aqueous dispersion of the glass fibers and thermoplastic matrix polymer may be any white water dispersion or foam dispersion for the wet-laid process of forming a web. The chemically _ ~ 3 ~ 2 0 56 7 2 0 modi~led thermoplastic polymer may be added as a powder or as pellets to the aqueous dispersion or as an emulsion or dispersion in a mat binder that is applied to the wet laid web of fibers and polymer. The foam aqueous dispersion may have sufficient surfactants to assure formation of the foam dispersion. The dried l~min~te is formed by drying the 5 web that has a reduced moisture content preferably at a te~ .dl~c elevated from ambient tempel~tul~,s. The thermoplastic l~min~te is moldable into shaped articles.
DETAILED DESCRIPTION OF TR~ INV~NTION
In the specification and in the claims, the below-defined terms have the following mean~ngs, The "white water system" is an aqueous solution in which the glass fibers are dispersed and which can contain numerous dispersants, thickeners, softening, hardening chemicals, or dispersed or emulsified thermoplastic polymers. Examples of various white water systems include aqueous solutions having polyacrylamide polymers such as the Separan polymer available from Dow Chemical Company, alone or with hydroxyethyl cellulose and the like suspending aids to provide a highly viscous aqueous solution at high material concentrations.
Also, white water systems include those having any of the numerous amine oxide surfactants as shown in U.S. Patent 4,179,331. An example 20 of the polyacrylamides are those shown in U.S. Patent 4,395,306. In addition to such chemicals as polyacrylamides or amine oxides being present in the white water system, there can also be present small amounts of surfactants such as polyethoxylated derivatives of amide condensation products of fatty acids and polyethylene polyamines as is 25 shown in U.S. Patent 4,265,704. Also numerous other chemical agents can be added to a white water system as is known by those skilled in the art.
The wet-laid process of producing a fiber-containing thermoplastic web involves forming an aqueous dispersion of ~_ _ 4 _ 2 0 5 6 7 2 0 discontinuous fibers like chopped fibers or chopped strands and the thermoplastic polymer usually with agitation in a mixing tank. The aqueous dispersion, usually referred to as slush or pulping medium, is processed into the wet-laid, sheet-like mat by such machines as 5 cylinder or Fourdrinier machines or more technologically advanced machinery, such as the Stevens Former, Roto Former, Inver Former and the VertiFormer machines. The slush is deposited from a head box onto a moving wire screen or onto the surface of a moving wire-covered cylinder. The slurry on the screen or cylinder is processed into the 10 nonwoven, sheet-like mat by the removal of water, usually by a suction and/or vacuum device, and by the application of a mat binder.
Suitable examples of mat binders for application to the web include any material that will affect a bond at a lower temperature than that which would result in consolidation of the plastics material within 15 the structure. Suitable binders include poly(vinyl alcohol), poly(vinyl acetate), carboxymethyl cellulose and starch. Water and excess binder are removed by suction and/or vacuum devices. The web of binder treated nonwoven, sheet-like glass fiber mat and thermoplastic matrix polymer is dried in one or more ovens. The 20 wet-laid process also includes the use of an aqueous foam as the aqueous dispersion to produce the slush rather than a traditional white water. The foam contains the thermoplastic polymer in addition to the glass fibers, along with one or more surfactants and water.
This process is more fully discussed in U.S. Patents 4,882,114;
25 4,690,860; and British patent documents 1,129,757 and 1,329,409.
Formation of the aqueous dispersion of the fibers and thermoplastic matrix polymer in accordance with these processes, it i~
achieved merely by placing the chopped glass fibers whether wet or dried of the desired length into a batch of water with or without the 30 addition of dispersing agents and before or after the addition of the _ - 5 -thermoplastic matrix polymer usually with agitation and/or turbulence.
Generally, the foamed aqueous dispersion is prepared with from around 20 to around 60 percent by weight of single discrete 5 fibers having a high modulus amine elasticity and from 40 to 80 percent by weight of the thermoplastic matrix polymer where the matrix polymer has a particle size of less than about 1.5mm. From this foamed aqueous dispersion in a wet-laid process, a web is formed by laying down the dispersion on a mesh to allow for removal of excess 10 water and application of any mat binder. The web is then transferred to a heating oven. The heating removes residual moisture from the web and also bonds the fiberous and plastic components together into a self-sustained permeable sheet.
In the wet-laid process, the fibers are that used are 15 generally glass fibers but can also be other fibers having a high modulus elasticity including carbon fibers, organic fibers with a high melting point such as Aramides, polyesters and others, glass wool, rock wool and cellulosic fibers. Generally, the amount of the discontinuous fibers in the aqueous dispersion can range from about 20 0.001 to about 5 and preferably about 0.01 to about 3 weight percent of the aqueous dispersion. Placement of the fibers into the dispersion occurs with or without the use of dispersing agents. When dispersing agents are not added to or are present in the aqueous solution to contain the fibers, the fibers can have a surface 25 treatment that aids in dispersing them in the aqueous dispersion.
Suitable examples of chopped glass fibers that can be used are those having a surface treatment having at least one water-soluble, film-forming polymer or copolymer that has an intrinsic viscosity of less than 500 centipoise, a matrix resin compatible organo functional 30 alkoxy silane, wherein the organic moieties is essentially devoid of primary mono-amine functionality and the alkoxy group can range from 1 to 3 and can be hydrolyzed or unhydrolyzed. Also the surface treatment in the undried aqueous form can have a water-soluble, dispersible and/or emulsifiable cationic lubricant and one or more cationic and one or more cationic epichlorohydrin polyamine adducts.
Generally, the film-forming copolymer i8 present in an effective 5 film-forming amount; there again the functional silane is present in an amount from around 0.4 to around 20, the cationic lubricant is present in an amount to around 0.1 to around 15 and the cationic amine polymer epichlorohydrin is present in an amount from around 0.4 to around an amount that is not detrimental to the dispersibility of the 10 treated fibers in water. Particularly suitable treated glass fibers are those having a surface treatment having on a weight percent solids basis around 70 to 80 weight percent of poly(vinylalcohol), around 5 to 10 weight percent cationic lubricant, around 5 to 10 weight percent ureido-modified amino silane, and around 1 to 10 weight percent 15 epichlorohydrin available from Georgia Pacific as GP2925 material.
Another suitable example are glass fibers having a surface treatment of a crosslinkable polyurethane film-forming polymer, at least one organo functional silane coupling agent, a copolymer of at least one polymerizable acrylic-type, at least one monomer that is addition 20 polymerizable and matrix-resin miscible and matrix-resin reactable.
An example of such a surface treatment is one having the poly(vinyl alcohol) polymer in an amount of around 85 to 95 weight percent of the solids, an amount of a cationic lubricant in an amount of around 0.1 to 1 weight percent of the solids and epichlorohydrin-polyamide adduct 25 like polycup 172 in an amount of around 3 to 10 weight percent and a vinyl organo functional silane like A-151 from Union Carbide Corporation in an amount from around 1 to 8 weight percent and an amount of acetic acid for hydrolyzing the silane. Typically, the amount of surface treatment present on the fibers is in the range from 30 about 0.15 to about 0.45 weight percent of the strands.
The thermoplastic matrix polymer useful in forming the aqueous dispersion and web material is in a particulate form or *Trade mark ~_ ~ 7 ~ 2 0 5 6 7 2 0 pelletized form which is then ground into a particular powder form.
Suitable materials include polyethylene, polypropylene, polystyrene, acrylonitrlle styrene butadiene, polyethylene terephthalate, poly vinyl chloride, polybutylene terephthalate and plasticized versions 5 thereof. Additional suitable examples of the thermoplastic matrix polymer include polyesters, polyamides, polyphenylene oxide, and polycarbonate. In addition, sny thermoplastic powder may be used which i~ not chemically attacked by water and which can be sufficiently softened by heat to permit fusing and/or molding wlthout 10 beinB chemically decomposed The chemically modified thermoplastic polymer which is used in con~unction with the glas~ fibers and the thermoplastic matrix polymer is added as a powder or pellet directly to the aqueous dispersion before, after or with the addition of the glass fibers and 15 the thermoplastic matrix polymer. Generally, the particle size of the chemically modified thermoplastic is similar to that of the thermoplastic matrix polymer. A nonexclusive example of a suitable particle size is that in the range of around 100 to 1100 microns. The chemically modified thermoplastic polymer is one having the chemically 20 reactive moieties which can include carboxylic acid and/or carboxylic anhydride modified polyolefins such as maleic anhydride modified polypropylene and maleic acid modified polypropylene and mixtures and blends of these. These types of materials are more fully discussed in U.S. Patent Nos. 3,416,990 (Robinson) and 3,437~550 ~Paul) and 25 3,483,276 (M~hlr~n). Generally, the acid modification involves modifying the polyolefins with carboxylic and~or polycarboxylic acids and/or anhydrides, amines or lower alkyl esters thereof. Another type of chemically modified thermoplastic polymer that can be used are the water soluble, dispersible and/or emulsifiable cationic polyamide polymers with epichlorohydrin adducts. These polyamide-20~672~
~_ - 8 -epichlorohydrin adducts generally have a polyamide backbone structure with the epichlorohydrin functionality associated with an amine group in the polymer.
These adducts can be produced by any method known to those 5 skilled in the art. One such method includes the reaction of any polycarboxylic acid, such as succinic acid, maleic acid, terephthalic acid or adipic with polyalkylene polyamine. The resultant long chain polyamide is reacted with epichlorohydrin. The amounts of these materials reacted to produced the adducts is such to yield around O.9 lO to about 1.5 moles of epichlorohydrin equivalent of the polyamide.
The adduct can have pendent functionality groups similar to the following:
CH
CH
N+
_ n In the above structure, "X" can be chloride ion or any other halogen 25 ion and "n" is an integer representing the number of repeating units in a polymer chain which is a particular value for the Mn of the polymer and the ratio of the moles of the epichlorohydrin functionality to the polyamide functionality. A nonexclusive example of a suitable epichlorohydrin polyamide resin adduct which can be used 30 is that available from Georgia Pacific Company, Resin Division, Atlanta, Georgia under the trade designation GP2925. This polyamide is an amber colored liquid having a percent solids of 20 to 20.6, a viscosity in centistokes of 140 to 200, a specific gravity of 1.04 to 1.05, a weight per gallon in pounds of 8.7, a pH at 25C of 6.9 to 35 7.3, a boiling point of 100C, a flash point of none to boiling and a storage life at 25C of six months In addition, the polyamide resin may contain a trace of free epichlorohydrin. Another such resin adduct that i8 suitable i8 the Polycup 1884, 2002, and/or 172 resin adducts. These materials have total solids by weight percent ran8ing 5 from 35 to 12.5 and specific gravities at 25C from 1.12 to 1.03.
The chemically modified thermoplastic in addition to combination with components to form the aqueous dispersion can be added to the web as the mat binder or along with traditional mat binders. In addition through use of the mat binder1 a suitable binder 10 would be that described in U.S. Patent 4,728,573 Generally, these binders have one or more amine orgaIlo coupling agents, an aqueous emulsion dispersion of carboxylic-modified polyolefin resin that has been neutralized or nearly neutralized with an organic or inorganic base with or without an aqueous soluble 15 dispersible or emulsifiable film-forming polymer and with or without a binder stabilizer. The basicity of the organic or inorganic base used to neutralize the carboxylic conta~n~ng polyolefin polymer is less than the basicity or (Kb) or any amino group of the coupling agent.
For instance, the acid modified polyolefin can be neutralized with a 20 base having a pKb or basicity similar to that of diethyl ethanolamine. Such a binder material would hsve present on a weight percent solids bas$s up to 100 percent of the solids of the chemically modified thermoplastic polymer, from 0 to about 50 percent weight solids of the organic coupling agent capable of donating electrons and 25 from 0 to 25 weight percent of the solids of the mono-, poly-, aliphatic or cyclic carboxylic acid and/or anhydride and from 0 to around 30 weight percent of a film-forming polymer. Useful film-forming polymers include epoxy polymers from epoxy emulsions, polyurethane polymers from polyurethane emulsions and epoxy 30 polyurethane copolymers from such emulsions and polyvinyl pyrrolidone and mixtures and blends of these.
*Trade mark Another suitable example of a mat binder includes flberous reinforcement selected from the group. The polymer is thermoplastic or thermosetting such as: a polyurethane, including polyester urethane and polyether urethane and polyurea-urethane, polyoxyalkylene 5 like poly(oxyethylene-oxypropylene) copolymers and thermoplastic polymers. The polymeric composition also has effective stabilizing amounts of stabilizing agents selected from: metal deactivating agents such as polydentate ligands like ethylenediaminetetraacetic acid (EDTA), low temperature anti-oxidant, and higher temperature 10 anti-oxidant. Additionally, a crosslinking agent may be present.
A suitable example is a binder having:
a. at least one matrix-compatible film-forming polymer in an effective film-forming amount, b. at least one organofunctional silane coupling agent selected from the group consisting of aminoalkyl alkoxysilanes, polyaminoalkyl alkoxysilanes in an effective coupling agent amount, c. at least two stabilizing agents selected from:
i. a metal deactivating agent selected from polydentate ligands and those having the following formula:
RH2nCn ~ CnH2nR
~ N(CH2)XN
RH2nCn ~ -- CnH2nR
ii. lower temperature anti-oxidant selected from: hydrosulfite, bisulfite, phosphorous acid, phosphite and phosphite-containing reducing agent selected from the group consisting of alkali metal hypophosphites, alkaline earth metal hypophosphites, hydrogen phosphites and ammonium hypophosphite in an effective antioxidant amount, iii. higher temperature anti-oxidant selected from alkali metal phenyl phosphinates and alkaline earth metal phenyl phosphonates, and phenyl-containing thioethers and polymers thereof, thiodlpropionate llke di(tridecyl)thiodipropionate and mixtures thereof in an effective anti-oxidant amount.
One particular formulation of such a binder is:
Solids 70 Oil-in-water emulsion of the curable 40-70 matrix-compatible polyurethane film forming polymer Water for polymer emulsion A-llOO gamma-aminopropyltriethoxy silane 62 Water for A-llOO
Hampene NA2 disodlum ethylenè diamine 100 tetraacetate Sodium Hypophosphite 100 Water for Hampene and Hypophosphite RD-1135B epoxidized polyester 20 *
Evanstab 13 (Di(Tridecyl)thiodipropionate 100 Baybond XW-116 (blocked aliphatic 70 polyisocyanate crosslinker) Hot water for Baybond Rhoplex E-693 acrylic copolymer 50 Water for Rhoplex Water for dilution to lOO gallons X Solids: 9,0 + 0,3 pH: 10 1 0.5 Viscosity: (cp)* 3 l l Temperature (F) 80 l lO
*cp = centipoise The binder can be formulated by adding the polymer latices to premix tanks with slow stirring and the addition of about 1/5 of *Trade mark the total volume of water as deionized water. In this formulation as acrylic copolymer latex is used which assists in producing improved solvent resistance for reinforcing polyamide. The Rhoplex E-693 material is available from Rohm and Haas Co., Philadelphia, 5 Pennsylvania. This material i8 a white emulsion having a solids content of 49.5 to 50.5 percent with a pH of 4.5 to 6.5 and a viscosity at LVT (1), 60 rpm 20-60. This copolymer is a self-crosslinking acrylic-type copolymer of the anionic emulsifying type with a density at 20C of 8.8 pounds per gallon and minimum 10 film-forming temperature of il2C and a temperature at which the torsional modulus of an air dried film is 300 kilograms per centimeter2 of +24C. About 2/5 of the total volume of water is added to a main mix tank and the amino organofunctional silane is added to this deionized water with slow stirring. The polymer latex premixes 15 are added to the silane mixture in the main mix and stirred for five minutes and added to the main mix tank. The polyisocyanate crosslinking agent is added to a premix tank and has added to it hot water with stirring. After the emulsion forms, it is stirred for five minutes and then added to the main mix tank. The acrylic copolymer is 20 added to a premix tank with a small amount of water, around 1/30 of the total volume of water needed for the chemical treating composition and the mixture is stirred for five minutes and added to the main mix tank. The aqueous chemical treating composition is diluted with deionized water to its final desired volume.
The aforementioned various mat binders are formulated to have a solids content in the range of around 0.1 to 32 weight percent and preferably around 5 to around 18 weight percent. The mat binders are applied to the web of nonwoven fibers and thermoplastic matrix polymer without any method known to those skilled in the art for 30 applying mat binders. This is referred to applying the binder by spraying the web after most of the water from the slush has been removed on the mesh or screen of the wet-laid process.
- 13 ~ 2 0 5 6 7 2 0 The amounts of the glass fiber thermoplastic matrlx polymer and chemically modified thermoplastic polymer present in the web produced by the wet-laid process can be in the following ranges. The nonwoven mat can range from 1 to 50 weight percent of the web; the 5 thermoplastic matrix polymer can range from around 50 to 99 weight percent of the web; and the chemically modified thermoplastic polymer can range from around 0.01 to around 20 weight percent of the web.
When the mat binder is used in con~unction with the chemically modified thermoplastic polymer, the mat binder can range from around 10 0.01 to around 20 weight percent of the web where the amount of the nonwoven fiber and thermoplastic matrix polymer both are present in a greater amount than the binder. Higher amounts of the binder are used when the chemically modified thermoplastic polymer is added with the mat binder. Generally, the amount of chemically modified 15 thermoplastic polymer present in the web varies to a degree with the amount of chemical modification of the thermoplastic polymer.
Suitable examples of materials that can be added directly to the slush include the Hercoprime material available from Himont and the Excelor material available from Exxon Chemical Company. The latter material 20 is used in an amount greater than the former since the former appears to have a greater degree of functionality. The amount for the former preferably ranges from around 0.1 to 5 weight percent of the web and the amount for the latter can range from 0.1 to 16 weight percent of the web. The amounts of the glass fiber matrix compatible 25 thermoplastic polymer and chemically modified thermoplastic polymer added to the slush or slurry or aqueous stock are those that enable production of a web with the aforementioned amounts of these materials. The amount of water in the slush is a predominant amount and ranges in the order of 80 to 99 weight percent of the slush.
With formation of the web having the chemically modified thermoplastic polymer, the web is dried to further reduce the moisture and to initiate some degree of reaction between the chemically *Trade mark ~_ - 14 - 20 5 6 7 2 0 modified thermoplastic polymer and the fibers. Typically, the drying occurs in an oven at an elevated temperature above ambient and generally in a temperature above the melting point of the thermoplastic matrix polymer. For example, when the thermoplastic 5 polymer is a polypropylene the drying temperature can be by hot air and around 100 to 240C, preferably around 120C to 180C. A suitable oven is a drying oven manufactured by Honeycomb Engineering Company.
The various aspects of the invention will be illustrated in the following examples.
ExamDle 1 In the preferred embodiment of the present invention, a wet-laid nonwoven web with thermoplastic polymer having a grammage equal to 1000 grams per meter2 and the components of Table 1 below was 15 formed. The manner of forming the web was that similar to the methods described in U.S. Patent 4,882,114.
Table 1 *
Fina 3860 Homopolymer of Polypropylene66 percent Melt Flow Index = 75 grams/10 minutes Irgafos 168 Phosphite Antioxidant 3 percent Naugard 445 Aromatic Amine Anti-oxidant1 percent 1/2 inch glass fiber strands 30 percent The weight percent of Table 1 is that of the formulation composition.
30 The glass fibers in the strands had a diameter of 16 microns and had a chemical treatment at a level of 0.30 percent by weight of the strand, where the treatment was an aqueous chemical composition composed of the following solids:
* Trade mark SIZE TR~ATMENT
* I II
Poly(vinylalcohol) Vinol 205 77.5 88.6 Cationic lubricant (Cat-X lubricant) 7.04 0.54 Ureido-modified aminosilane 8.04 --Vinylorganofunctional silane A151 -- 4.21 Epichlorohydrin-polyamide adduct (GP 2935) 7.4 6.68 (Polycup 172) The resultant nonwoven web (Grammage = 1000 g/m2) comprised of 66 percent Fina 3860, 3 percent Irgafos 168, 1 percent Naugard 445 and 30 percent glass fibers I was treated at a level 0.86 percent by welght with an aqueous chemical composition comprised of:
75% Protolube 5440 Maleic acid, Modified polypropylene emulsion from National Starch 12.8X A-llO0 gamma aminopropyltriethoxysilane from Union Carbide Corporation 5.lX Msleic acid (General Chemical Corp.) 7.2% Epirez W60-5520 epoxy polyurethane dispersion available from Rhone-Poulene O.lX Antifoam 1430 available from Dow Corning Corp.
X based on total dry solids Added to the web in con~unction with the web binder was a 30 carbon black d~spersion at a level of O.lX. The resultant treated web was dried to OX molsture at a temperature of 300F. Four dried sheets were stacked and laminated at 420F, 25 psi for 3.5 mlnutes. The resultant laminate was cooled at full pressure for 13 minutes. Said laminate was compression molded by heating it to 460F for 6 minutes 35 then shaping a flat panel at 100 tons pressure. The resultant molded panel was cut and tested in accordance with ASTM Procedures for Tensile, Flex and Izod Impact and the values are shown in the *Trade mark following table. The values stated for strength and modulus are normalized to a 30 percent glass loading by weight. This ad~ustment is accomplished by first detel ~n~ng the actual glass content via an ashing technique then determine the percentage difference between the 5 nominal and actual volume percent glass and multiplying that percentage difference by the strength or modulus value measured. This procedure is carried out for all strength and modulus values reported since webs might vary in glass content by 1 or 2 percent by weight.
EXP. Results Ten Str. Flex Str. Flex MOD Izod Imp.
(~si) (Dsi) (Dsi) (Ft-lbs/In) 15 Composition Formulation: 12,400 18,200 728,900 7.70 ExamDles 2-21 and Illustrative A and B
Twenty-one wet laid webs and two illustrative wet laid webs were prepared from components shown in Table 2. The Illustrative examples are indicated as A-B, where Illustrative Examples A and B
were made in a manner similar to Example 1, except that poly(vinylpyrrolidone) was the mat binder. Illustrative example A was 25 prepared in a manner similar to Illustrative Example B but without the presence of carbon black. Examples 2 and 3 were prepared in a manner similar to that of Example 1, but carbon black was not used. Examples 4-7 were prepared in a manner similar to that of Example 1 with one of two mat binders and without carbon black. In addition, examples 4-7 30 and 8 had an addition of the chemically modified polypropylene to the aqueous slush. Also examples 8-23 were prepared in a manner similar to Example 1 with the presence of carbon black and examples 8-12 varied the type of mat binder. Examples 13-20 were prepared in a manner similar to Example 1 but with the addition of the chemically ~ 17 - 2056720 modified polypropylene either to the slush as Hercoprime polypropylene or to the mat binder as Protolube 5440 polypropylene emulsion. In these examples the following components were used:
5 PVP K-90: Polyvinyl pyrrolidone, MW = 660,000 Hercoprime G : Maleic anhydride, Modified Polypropylene Hercoprime HG 201: Maleic anhydride, Modified Polypropylene Protolube 5440: Maleic acid, Modified Propylene 10 Profax 6201: Homopolymer of Polypropylene Melt Flow Index = 20 grams/10 minutes Weight Average MW = 210,000 Fina 3860: Homopolymer of Polypropylene Melt Flow Index = 75 grams/10 minutes Irgafos 168: Phosphite Type: Antioxidant which is Tris(2,4-Di-tert-butylphenyl) Phosphite Naugard 445: Aromatic Amine Type: Antioxidant which is 4,4'Di(2,2-dimethylbenzyl)diphenylamine Glass fiber sample A 1/2 inch length and 16 um fiber diameter Size Treatment I.
25 Glass fiber sample B 1/2 inch length 16 um fiber diameter with a surface treatment of Size Treatment II.
In examples 2-4, 6, 8, 14, 16, 18 and 20 the mat binder formulation that was used was that as used in example 1 as did examples 15, 17, 19 30 and 21 with the addition of more of the Protolube 5440 emulsion.
Examples 5, 7, 9, and 11 used the mat binder formulation indicated below as "Formulation I". Examples 10 and 12 used the mat binder formulation indicated below as "Formulation II".
35 Formulation I % bY Actual Solids Rucothane 20116 Polyurethane 56.65 A-llO0 5~34 EDTA 0.31 RD-1135b 5.34 A *Trade mark ~ - 18 - 2 0 5 6 7 2 0 Evan Stab 13 3.35 Sodium Hypophosphite 1.68 XW-116 M 8.27 Rhoplex E-693 19.06 5' - Carbon black: Black pigment.
Formulation II
In the formulation for the mat binder of Example 1 the chemically modified polypropylene was removed and replaced with 10 Rucothane 2011L polyurethane oil-in-water emulsion and it had the following formulation:
% bY Actual Solids Rucothane 2011L 51.5%
A-llO0 24.6%
Maleic acid 9.8%
Epirez W60-5520 14.0%
Anti-foam 1430 0.1%
Formulation III
% bY Actual Solids Protolube 544051.5 A-llO0 24.6 Maleic acid 9.8 Epirez W60-5520 14.0 Antifoam 1430 0.1 ~ 2056720 ~1 1 ~ ~ ~ I o ., ~ ~ o o 0 o I I I I I ! o l ~ O O
I O ~ I I I I ~
~ ~ o .~ o I I ~ ~ .~ I o I ~ I ~
o .-~ o o o ,1 I o ~ I I
~?I ~ ~ o ~
., ~1 ~D I ~ .~ 1 ~0 0 U~ ~ o o ~1 ~o ~ o o ~1 ` ~ o o ~, O ~ ~ , . t,~ ns ~] 0r~l ~ ,1 ,1~f ~ * ~ r-l k t3 ~ o ~ , t ~-~I I cq tit 0 t;'~
_t ~r t ~ r r O :> O
_t ~1 ~D O ~ ~ ' I I
~1 ` ~ O O
_I a~
~ C~
_11 ~ o ~ ,~
~o ~ o o _I ~ _I
C`J ~O
01 `D O ~ _~
~1 'D ~ O O O
_I ~
~o o O` ~D O ~ --~ I
_~ o ~ o o _I
o ,~
o~l ~ O ~ --~ I -~ D ~ O O O
¢
E~ _Io~
C~ o ~o o ~ _I I
`D ~ O O_I
~o ~Dl ~ O ~ --I I ---11 ~ ~ o o o _I ~
~ ~ o U~ ~ o ~_I . .
_~ ~o ~ o o _I
_Io~ _I
~`D O ~ --I
_I ~o ~ o o o o ~r ~O O ~ --I
_l~o ~ o o_~
H O
H H ~ O
O ,1 _I ~ 0 0 ~I) 0 1~ O ~ `
O
H ~ ~ H ~Z;C:l ~ p~
The wet laid nonwoven material with the thermoplastic polymer produced in Table 2 were molded under conditions similar to that of Example 1. The molded samples were tested in a manner similar to those of example 1 for tensile, flexural and impact properties.
5 These test results are presented in Table 3.
EXPERIMENTAL RESULTS
10 COMPOSITETEN STR. FLEX STR. FLEX MOD. IZOD IMP.
FORMULATION MD/CMD MD/CMD MD/CMD MD/CMD
(PSI) (PSI) (PSI) (FT-LBS/IN) 1 13,700 16,700 697,000 15.2 8,100 16,000 610,900 9.9 AVG lO,9OO 16,400 654,000 12.6 2 15,800 18,400 692,300 16.0 11,100 16,600 597,000 10.0 AVG 13,500 17,500 644,700 13.0 3 18,600 20,900 816,000 15.6 11,900 17,300 642,800 AVG 15,300 19,100 729,400 12.6 4 18,400 24,900 887,500 7.1 12,200 18,700 653,000 5.6 AVG 15,300 21,800 770,300 6.4 17,000 22,100 816,800 6.9 13,300 17,400 616,300 5.5 AVG 15,200 19,800 716,600 6.4 6 18,000 23,200 814,900 7.6 11,100 17,000 626,300 5.5 AVG 14,600 20,100 720,600 6.6 7 17,600 22,000 775,100 7.5 16,700 18,700 656,100 5.7 AVG 17,200 20,400 715,600 6.2 8 13,800 19,300 798,200 6.81 9,400 16,600 589,500 5.60 AVG 11,600 17,900 693,800 6.20 ~~ - 22 - 2 0 5 67 20 9 13,000 18,400 754,600 5.80 8,800 11,900 448,200 4.40 AVG 10,900 15,200 601,400 5.10 5 10 10,300 16,200 717,500 6.60 8,600 14,200 548,000 5.20 AVG 9,500 15,200 632,700 5.90 11 11,100 15,400 730,800 9.90 7,400 11,900 503,500 6.50 AVG 9,300 13,600 617,200 8.20 12 10,100 18,500 791,700 9.20 8,900 12,600 496,700 ~ Q
15 AVG 9,500 15,600 644,200 8.20 13 9,500 16,400 737,100 8.80 7,100 13,5Q0 531,800 6.80 AVG 8,300 15,000 634,500 7.80 1 13,700 16,700 697,000 15.20 8,100 16,000 610,900 9.90 AVG 10,900 16,400 654,000 12.60 Ad.iusted PhYsical Pro~erties TEN STR. FLEX STR. FLEX MOD. IZOD IMP.
TRIAL # MD/CMD MD/CMD MD/CMD MD/CMD
14 13,200 17,100 681,400 8.20 8,700 17,000 698,400 5.90 AVG 11,000 17,100 689,000 7.10 35 15 15,200 20,800 838,900 10.10 8,000 13,140 534,600 6.50 AVG 11,600 17,000 681,800 8.30 16 13,000 18,900 822,300 8.20 8,600 13,700 548,500 7.30 AVG 10,800 16,300 685,400 7.80 17 13,500 21,700 863,900 10.30 8,500 15,000 637,100 6.20 45 AVG 11,000 18,400 750,500 8.30 18 14,500 21,900 897,400 6.90 10,300 18,400 671,600 5.80 AVG 12,400 20,200 784,500 6.40 ~ - 23 - 20 56 7 2 0 19 14,100 25,800 990,100 7.40 8,200 16,100 596,800 5.50 AVG 11,200 21,000 793,500 6.50 16,700 22,000 890,300 5.30 7,400 13,300 515,200 5.10 AVG 12,100 17,700 702,800 5.20 10 21 15,600 22,700 951,400 8.80 9,100 13,600 506,300 6.50 AVG 12,400 18,200 728,900 7.70 9.751 15 22 12,600 19,800 866,700 7.709 6.808 7,300 17,100 645,900 5.909 AVG 10,000 18,500 756,300 7.60 20 23 14,400 18,200 791,900 10.02 7,900 14,900 584,800 6.20 AVG 11,200 16,600 688,400 8.10 It can be concluded from the study that composite physical properties improve as the melt flow index of the resin matrix is increased and that strength and modulus properties improve but impact performance decreases with the addition of 4 percent maleic anhydride modified polypropylene. The impact performance is reduced 30 significantly because the low molecular weight additive tends to imbrittle the resin matrix thereby reducing the composites ability to absorb energy during impact. At a 1 percent loading the maleic anhydride modified polypropylene additive offers benefits to all performance criteria. It can also be concluded from the study that 35 chemical formulation III gives the best properties of any chemical formulation studied plus the lower the level of carbon black present the better the overall physical properties performance will be.
Finally, it was determined that maleic acid and maleic anhydride modified polypropylene could be used interchangeable as part of the 40 composite formulations,
AND AQUEOUS DISPERSION FOR PRODUCING SAME
The present invention is directed to a fiberous-containing material with thermoplastic polymer that can be molded. More particularly, the present invention is directed to a material having a thermoplastic polymer matrix and chopped chemically treated glass 10 fibers, where both the fibers and thermoplastic polymer is prepared into the moldable material by a wet-laid process.
Fiber reinforced plastics include thermoplastic moldable materials and thermosetting moldable materials. The latter includes sheet molding compounds, thick molding compounds and the like that 15 mold through curing. The fiber reinforced thermoplastics mold through flowing the material into a shape as in an in~ection, compression molding operations. In compression molding a fiber reinforced thermoplastic composite is placed in a mold and stamped to the desired shape. These materials for such an operation are produced in the form 20 of laminates cont~n~ng the fibers in various forms including chopped strand continuous strand mats and needled mats and mixtures thereof and the thermoplastic polymer matrix combined with the reinforcement through lamination, extradication processes. Also, processes have been developed recently where the reinforcement is combined with the 25 thermoplastic polymer in a wet laid process from an aqueous solution cont~n~ng the fiberous reinforcement in chopped form and the thermoplastic polymer. In this process, the composite ingredients are combined and mixed in water at low solids concentration and equipment similar to a hydropulper used in the formation of paper from paper 30 pulp. After the slurry is properly mixed, it can be pumped as a thick stock to a holding device where the slurry is further diluted and flocculated and pumped to a head box of a paper machine. Also the slurry can be pumped directed to the head box of the paper machine.
. _ - 2 - 2056720 From the head box, the composite sheet i8 formed on a continuous traveling wire mesh. The mesh takes the composite over vacuum sources to remove liquids including water and form the sheet. A mat binder usually polyvinylpyrrolidone is sprayed onto the sheet and the sheet 5 i8 dried. Representative of such processes are those described in U.S. Patentc 4,882,114; 3,716,449, 3,871,952, EPO Nos. 0 312 414 and 0 308 286 and 0 341 977.
It is an ob~ect of the present invention to provide a wet laid fiber-contain~ng thermoplastic composite or material that has 10 good tensile and flexible properties in the molded article.
SUMMARY OF THE INV~1ION
The aforementioned and other ob~ects gleaned from the disclosure herein are provided by the present invention. One aspect 15 of the present invention is the wet-laid web of the nonwoven fiberous mat and the thermoplastic polymer that can be dried into a moldable laminate or sheet, while another aspect of the invention is the dried laminate so produced, and another aspect of the invention is a foamed aqueous dispersion of the discontinuous fibers and thermoplastic 20 matrix polymer with the chemically modified thermoplastic polymer.
The wet-laid web includes: the nonwoven mat of discontinous glass fibers, thermoplastic matrix polymer, and chemically modified thermoplastic polymer having chemically reactive moieties for addition, condensation or free radical reaction to allow for coupling 25 of the glass fiber to the matrix polymer. The glass fibers have a surface treatment or "size" that allows the fibers to disperse even from the strand form in an aqueous dispersion that does or is to contain the thermoplastic matrix polymer. Dispersion of the fibers may be asslsted by surfactants in the size or in the aqueou~
30 dispersion. The aqueous dispersion of the glass fibers and thermoplastic matrix polymer may be any white water dispersion or foam dispersion for the wet-laid process of forming a web. The chemically _ ~ 3 ~ 2 0 56 7 2 0 modi~led thermoplastic polymer may be added as a powder or as pellets to the aqueous dispersion or as an emulsion or dispersion in a mat binder that is applied to the wet laid web of fibers and polymer. The foam aqueous dispersion may have sufficient surfactants to assure formation of the foam dispersion. The dried l~min~te is formed by drying the 5 web that has a reduced moisture content preferably at a te~ .dl~c elevated from ambient tempel~tul~,s. The thermoplastic l~min~te is moldable into shaped articles.
DETAILED DESCRIPTION OF TR~ INV~NTION
In the specification and in the claims, the below-defined terms have the following mean~ngs, The "white water system" is an aqueous solution in which the glass fibers are dispersed and which can contain numerous dispersants, thickeners, softening, hardening chemicals, or dispersed or emulsified thermoplastic polymers. Examples of various white water systems include aqueous solutions having polyacrylamide polymers such as the Separan polymer available from Dow Chemical Company, alone or with hydroxyethyl cellulose and the like suspending aids to provide a highly viscous aqueous solution at high material concentrations.
Also, white water systems include those having any of the numerous amine oxide surfactants as shown in U.S. Patent 4,179,331. An example 20 of the polyacrylamides are those shown in U.S. Patent 4,395,306. In addition to such chemicals as polyacrylamides or amine oxides being present in the white water system, there can also be present small amounts of surfactants such as polyethoxylated derivatives of amide condensation products of fatty acids and polyethylene polyamines as is 25 shown in U.S. Patent 4,265,704. Also numerous other chemical agents can be added to a white water system as is known by those skilled in the art.
The wet-laid process of producing a fiber-containing thermoplastic web involves forming an aqueous dispersion of ~_ _ 4 _ 2 0 5 6 7 2 0 discontinuous fibers like chopped fibers or chopped strands and the thermoplastic polymer usually with agitation in a mixing tank. The aqueous dispersion, usually referred to as slush or pulping medium, is processed into the wet-laid, sheet-like mat by such machines as 5 cylinder or Fourdrinier machines or more technologically advanced machinery, such as the Stevens Former, Roto Former, Inver Former and the VertiFormer machines. The slush is deposited from a head box onto a moving wire screen or onto the surface of a moving wire-covered cylinder. The slurry on the screen or cylinder is processed into the 10 nonwoven, sheet-like mat by the removal of water, usually by a suction and/or vacuum device, and by the application of a mat binder.
Suitable examples of mat binders for application to the web include any material that will affect a bond at a lower temperature than that which would result in consolidation of the plastics material within 15 the structure. Suitable binders include poly(vinyl alcohol), poly(vinyl acetate), carboxymethyl cellulose and starch. Water and excess binder are removed by suction and/or vacuum devices. The web of binder treated nonwoven, sheet-like glass fiber mat and thermoplastic matrix polymer is dried in one or more ovens. The 20 wet-laid process also includes the use of an aqueous foam as the aqueous dispersion to produce the slush rather than a traditional white water. The foam contains the thermoplastic polymer in addition to the glass fibers, along with one or more surfactants and water.
This process is more fully discussed in U.S. Patents 4,882,114;
25 4,690,860; and British patent documents 1,129,757 and 1,329,409.
Formation of the aqueous dispersion of the fibers and thermoplastic matrix polymer in accordance with these processes, it i~
achieved merely by placing the chopped glass fibers whether wet or dried of the desired length into a batch of water with or without the 30 addition of dispersing agents and before or after the addition of the _ - 5 -thermoplastic matrix polymer usually with agitation and/or turbulence.
Generally, the foamed aqueous dispersion is prepared with from around 20 to around 60 percent by weight of single discrete 5 fibers having a high modulus amine elasticity and from 40 to 80 percent by weight of the thermoplastic matrix polymer where the matrix polymer has a particle size of less than about 1.5mm. From this foamed aqueous dispersion in a wet-laid process, a web is formed by laying down the dispersion on a mesh to allow for removal of excess 10 water and application of any mat binder. The web is then transferred to a heating oven. The heating removes residual moisture from the web and also bonds the fiberous and plastic components together into a self-sustained permeable sheet.
In the wet-laid process, the fibers are that used are 15 generally glass fibers but can also be other fibers having a high modulus elasticity including carbon fibers, organic fibers with a high melting point such as Aramides, polyesters and others, glass wool, rock wool and cellulosic fibers. Generally, the amount of the discontinuous fibers in the aqueous dispersion can range from about 20 0.001 to about 5 and preferably about 0.01 to about 3 weight percent of the aqueous dispersion. Placement of the fibers into the dispersion occurs with or without the use of dispersing agents. When dispersing agents are not added to or are present in the aqueous solution to contain the fibers, the fibers can have a surface 25 treatment that aids in dispersing them in the aqueous dispersion.
Suitable examples of chopped glass fibers that can be used are those having a surface treatment having at least one water-soluble, film-forming polymer or copolymer that has an intrinsic viscosity of less than 500 centipoise, a matrix resin compatible organo functional 30 alkoxy silane, wherein the organic moieties is essentially devoid of primary mono-amine functionality and the alkoxy group can range from 1 to 3 and can be hydrolyzed or unhydrolyzed. Also the surface treatment in the undried aqueous form can have a water-soluble, dispersible and/or emulsifiable cationic lubricant and one or more cationic and one or more cationic epichlorohydrin polyamine adducts.
Generally, the film-forming copolymer i8 present in an effective 5 film-forming amount; there again the functional silane is present in an amount from around 0.4 to around 20, the cationic lubricant is present in an amount to around 0.1 to around 15 and the cationic amine polymer epichlorohydrin is present in an amount from around 0.4 to around an amount that is not detrimental to the dispersibility of the 10 treated fibers in water. Particularly suitable treated glass fibers are those having a surface treatment having on a weight percent solids basis around 70 to 80 weight percent of poly(vinylalcohol), around 5 to 10 weight percent cationic lubricant, around 5 to 10 weight percent ureido-modified amino silane, and around 1 to 10 weight percent 15 epichlorohydrin available from Georgia Pacific as GP2925 material.
Another suitable example are glass fibers having a surface treatment of a crosslinkable polyurethane film-forming polymer, at least one organo functional silane coupling agent, a copolymer of at least one polymerizable acrylic-type, at least one monomer that is addition 20 polymerizable and matrix-resin miscible and matrix-resin reactable.
An example of such a surface treatment is one having the poly(vinyl alcohol) polymer in an amount of around 85 to 95 weight percent of the solids, an amount of a cationic lubricant in an amount of around 0.1 to 1 weight percent of the solids and epichlorohydrin-polyamide adduct 25 like polycup 172 in an amount of around 3 to 10 weight percent and a vinyl organo functional silane like A-151 from Union Carbide Corporation in an amount from around 1 to 8 weight percent and an amount of acetic acid for hydrolyzing the silane. Typically, the amount of surface treatment present on the fibers is in the range from 30 about 0.15 to about 0.45 weight percent of the strands.
The thermoplastic matrix polymer useful in forming the aqueous dispersion and web material is in a particulate form or *Trade mark ~_ ~ 7 ~ 2 0 5 6 7 2 0 pelletized form which is then ground into a particular powder form.
Suitable materials include polyethylene, polypropylene, polystyrene, acrylonitrlle styrene butadiene, polyethylene terephthalate, poly vinyl chloride, polybutylene terephthalate and plasticized versions 5 thereof. Additional suitable examples of the thermoplastic matrix polymer include polyesters, polyamides, polyphenylene oxide, and polycarbonate. In addition, sny thermoplastic powder may be used which i~ not chemically attacked by water and which can be sufficiently softened by heat to permit fusing and/or molding wlthout 10 beinB chemically decomposed The chemically modified thermoplastic polymer which is used in con~unction with the glas~ fibers and the thermoplastic matrix polymer is added as a powder or pellet directly to the aqueous dispersion before, after or with the addition of the glass fibers and 15 the thermoplastic matrix polymer. Generally, the particle size of the chemically modified thermoplastic is similar to that of the thermoplastic matrix polymer. A nonexclusive example of a suitable particle size is that in the range of around 100 to 1100 microns. The chemically modified thermoplastic polymer is one having the chemically 20 reactive moieties which can include carboxylic acid and/or carboxylic anhydride modified polyolefins such as maleic anhydride modified polypropylene and maleic acid modified polypropylene and mixtures and blends of these. These types of materials are more fully discussed in U.S. Patent Nos. 3,416,990 (Robinson) and 3,437~550 ~Paul) and 25 3,483,276 (M~hlr~n). Generally, the acid modification involves modifying the polyolefins with carboxylic and~or polycarboxylic acids and/or anhydrides, amines or lower alkyl esters thereof. Another type of chemically modified thermoplastic polymer that can be used are the water soluble, dispersible and/or emulsifiable cationic polyamide polymers with epichlorohydrin adducts. These polyamide-20~672~
~_ - 8 -epichlorohydrin adducts generally have a polyamide backbone structure with the epichlorohydrin functionality associated with an amine group in the polymer.
These adducts can be produced by any method known to those 5 skilled in the art. One such method includes the reaction of any polycarboxylic acid, such as succinic acid, maleic acid, terephthalic acid or adipic with polyalkylene polyamine. The resultant long chain polyamide is reacted with epichlorohydrin. The amounts of these materials reacted to produced the adducts is such to yield around O.9 lO to about 1.5 moles of epichlorohydrin equivalent of the polyamide.
The adduct can have pendent functionality groups similar to the following:
CH
CH
N+
_ n In the above structure, "X" can be chloride ion or any other halogen 25 ion and "n" is an integer representing the number of repeating units in a polymer chain which is a particular value for the Mn of the polymer and the ratio of the moles of the epichlorohydrin functionality to the polyamide functionality. A nonexclusive example of a suitable epichlorohydrin polyamide resin adduct which can be used 30 is that available from Georgia Pacific Company, Resin Division, Atlanta, Georgia under the trade designation GP2925. This polyamide is an amber colored liquid having a percent solids of 20 to 20.6, a viscosity in centistokes of 140 to 200, a specific gravity of 1.04 to 1.05, a weight per gallon in pounds of 8.7, a pH at 25C of 6.9 to 35 7.3, a boiling point of 100C, a flash point of none to boiling and a storage life at 25C of six months In addition, the polyamide resin may contain a trace of free epichlorohydrin. Another such resin adduct that i8 suitable i8 the Polycup 1884, 2002, and/or 172 resin adducts. These materials have total solids by weight percent ran8ing 5 from 35 to 12.5 and specific gravities at 25C from 1.12 to 1.03.
The chemically modified thermoplastic in addition to combination with components to form the aqueous dispersion can be added to the web as the mat binder or along with traditional mat binders. In addition through use of the mat binder1 a suitable binder 10 would be that described in U.S. Patent 4,728,573 Generally, these binders have one or more amine orgaIlo coupling agents, an aqueous emulsion dispersion of carboxylic-modified polyolefin resin that has been neutralized or nearly neutralized with an organic or inorganic base with or without an aqueous soluble 15 dispersible or emulsifiable film-forming polymer and with or without a binder stabilizer. The basicity of the organic or inorganic base used to neutralize the carboxylic conta~n~ng polyolefin polymer is less than the basicity or (Kb) or any amino group of the coupling agent.
For instance, the acid modified polyolefin can be neutralized with a 20 base having a pKb or basicity similar to that of diethyl ethanolamine. Such a binder material would hsve present on a weight percent solids bas$s up to 100 percent of the solids of the chemically modified thermoplastic polymer, from 0 to about 50 percent weight solids of the organic coupling agent capable of donating electrons and 25 from 0 to 25 weight percent of the solids of the mono-, poly-, aliphatic or cyclic carboxylic acid and/or anhydride and from 0 to around 30 weight percent of a film-forming polymer. Useful film-forming polymers include epoxy polymers from epoxy emulsions, polyurethane polymers from polyurethane emulsions and epoxy 30 polyurethane copolymers from such emulsions and polyvinyl pyrrolidone and mixtures and blends of these.
*Trade mark Another suitable example of a mat binder includes flberous reinforcement selected from the group. The polymer is thermoplastic or thermosetting such as: a polyurethane, including polyester urethane and polyether urethane and polyurea-urethane, polyoxyalkylene 5 like poly(oxyethylene-oxypropylene) copolymers and thermoplastic polymers. The polymeric composition also has effective stabilizing amounts of stabilizing agents selected from: metal deactivating agents such as polydentate ligands like ethylenediaminetetraacetic acid (EDTA), low temperature anti-oxidant, and higher temperature 10 anti-oxidant. Additionally, a crosslinking agent may be present.
A suitable example is a binder having:
a. at least one matrix-compatible film-forming polymer in an effective film-forming amount, b. at least one organofunctional silane coupling agent selected from the group consisting of aminoalkyl alkoxysilanes, polyaminoalkyl alkoxysilanes in an effective coupling agent amount, c. at least two stabilizing agents selected from:
i. a metal deactivating agent selected from polydentate ligands and those having the following formula:
RH2nCn ~ CnH2nR
~ N(CH2)XN
RH2nCn ~ -- CnH2nR
ii. lower temperature anti-oxidant selected from: hydrosulfite, bisulfite, phosphorous acid, phosphite and phosphite-containing reducing agent selected from the group consisting of alkali metal hypophosphites, alkaline earth metal hypophosphites, hydrogen phosphites and ammonium hypophosphite in an effective antioxidant amount, iii. higher temperature anti-oxidant selected from alkali metal phenyl phosphinates and alkaline earth metal phenyl phosphonates, and phenyl-containing thioethers and polymers thereof, thiodlpropionate llke di(tridecyl)thiodipropionate and mixtures thereof in an effective anti-oxidant amount.
One particular formulation of such a binder is:
Solids 70 Oil-in-water emulsion of the curable 40-70 matrix-compatible polyurethane film forming polymer Water for polymer emulsion A-llOO gamma-aminopropyltriethoxy silane 62 Water for A-llOO
Hampene NA2 disodlum ethylenè diamine 100 tetraacetate Sodium Hypophosphite 100 Water for Hampene and Hypophosphite RD-1135B epoxidized polyester 20 *
Evanstab 13 (Di(Tridecyl)thiodipropionate 100 Baybond XW-116 (blocked aliphatic 70 polyisocyanate crosslinker) Hot water for Baybond Rhoplex E-693 acrylic copolymer 50 Water for Rhoplex Water for dilution to lOO gallons X Solids: 9,0 + 0,3 pH: 10 1 0.5 Viscosity: (cp)* 3 l l Temperature (F) 80 l lO
*cp = centipoise The binder can be formulated by adding the polymer latices to premix tanks with slow stirring and the addition of about 1/5 of *Trade mark the total volume of water as deionized water. In this formulation as acrylic copolymer latex is used which assists in producing improved solvent resistance for reinforcing polyamide. The Rhoplex E-693 material is available from Rohm and Haas Co., Philadelphia, 5 Pennsylvania. This material i8 a white emulsion having a solids content of 49.5 to 50.5 percent with a pH of 4.5 to 6.5 and a viscosity at LVT (1), 60 rpm 20-60. This copolymer is a self-crosslinking acrylic-type copolymer of the anionic emulsifying type with a density at 20C of 8.8 pounds per gallon and minimum 10 film-forming temperature of il2C and a temperature at which the torsional modulus of an air dried film is 300 kilograms per centimeter2 of +24C. About 2/5 of the total volume of water is added to a main mix tank and the amino organofunctional silane is added to this deionized water with slow stirring. The polymer latex premixes 15 are added to the silane mixture in the main mix and stirred for five minutes and added to the main mix tank. The polyisocyanate crosslinking agent is added to a premix tank and has added to it hot water with stirring. After the emulsion forms, it is stirred for five minutes and then added to the main mix tank. The acrylic copolymer is 20 added to a premix tank with a small amount of water, around 1/30 of the total volume of water needed for the chemical treating composition and the mixture is stirred for five minutes and added to the main mix tank. The aqueous chemical treating composition is diluted with deionized water to its final desired volume.
The aforementioned various mat binders are formulated to have a solids content in the range of around 0.1 to 32 weight percent and preferably around 5 to around 18 weight percent. The mat binders are applied to the web of nonwoven fibers and thermoplastic matrix polymer without any method known to those skilled in the art for 30 applying mat binders. This is referred to applying the binder by spraying the web after most of the water from the slush has been removed on the mesh or screen of the wet-laid process.
- 13 ~ 2 0 5 6 7 2 0 The amounts of the glass fiber thermoplastic matrlx polymer and chemically modified thermoplastic polymer present in the web produced by the wet-laid process can be in the following ranges. The nonwoven mat can range from 1 to 50 weight percent of the web; the 5 thermoplastic matrix polymer can range from around 50 to 99 weight percent of the web; and the chemically modified thermoplastic polymer can range from around 0.01 to around 20 weight percent of the web.
When the mat binder is used in con~unction with the chemically modified thermoplastic polymer, the mat binder can range from around 10 0.01 to around 20 weight percent of the web where the amount of the nonwoven fiber and thermoplastic matrix polymer both are present in a greater amount than the binder. Higher amounts of the binder are used when the chemically modified thermoplastic polymer is added with the mat binder. Generally, the amount of chemically modified 15 thermoplastic polymer present in the web varies to a degree with the amount of chemical modification of the thermoplastic polymer.
Suitable examples of materials that can be added directly to the slush include the Hercoprime material available from Himont and the Excelor material available from Exxon Chemical Company. The latter material 20 is used in an amount greater than the former since the former appears to have a greater degree of functionality. The amount for the former preferably ranges from around 0.1 to 5 weight percent of the web and the amount for the latter can range from 0.1 to 16 weight percent of the web. The amounts of the glass fiber matrix compatible 25 thermoplastic polymer and chemically modified thermoplastic polymer added to the slush or slurry or aqueous stock are those that enable production of a web with the aforementioned amounts of these materials. The amount of water in the slush is a predominant amount and ranges in the order of 80 to 99 weight percent of the slush.
With formation of the web having the chemically modified thermoplastic polymer, the web is dried to further reduce the moisture and to initiate some degree of reaction between the chemically *Trade mark ~_ - 14 - 20 5 6 7 2 0 modified thermoplastic polymer and the fibers. Typically, the drying occurs in an oven at an elevated temperature above ambient and generally in a temperature above the melting point of the thermoplastic matrix polymer. For example, when the thermoplastic 5 polymer is a polypropylene the drying temperature can be by hot air and around 100 to 240C, preferably around 120C to 180C. A suitable oven is a drying oven manufactured by Honeycomb Engineering Company.
The various aspects of the invention will be illustrated in the following examples.
ExamDle 1 In the preferred embodiment of the present invention, a wet-laid nonwoven web with thermoplastic polymer having a grammage equal to 1000 grams per meter2 and the components of Table 1 below was 15 formed. The manner of forming the web was that similar to the methods described in U.S. Patent 4,882,114.
Table 1 *
Fina 3860 Homopolymer of Polypropylene66 percent Melt Flow Index = 75 grams/10 minutes Irgafos 168 Phosphite Antioxidant 3 percent Naugard 445 Aromatic Amine Anti-oxidant1 percent 1/2 inch glass fiber strands 30 percent The weight percent of Table 1 is that of the formulation composition.
30 The glass fibers in the strands had a diameter of 16 microns and had a chemical treatment at a level of 0.30 percent by weight of the strand, where the treatment was an aqueous chemical composition composed of the following solids:
* Trade mark SIZE TR~ATMENT
* I II
Poly(vinylalcohol) Vinol 205 77.5 88.6 Cationic lubricant (Cat-X lubricant) 7.04 0.54 Ureido-modified aminosilane 8.04 --Vinylorganofunctional silane A151 -- 4.21 Epichlorohydrin-polyamide adduct (GP 2935) 7.4 6.68 (Polycup 172) The resultant nonwoven web (Grammage = 1000 g/m2) comprised of 66 percent Fina 3860, 3 percent Irgafos 168, 1 percent Naugard 445 and 30 percent glass fibers I was treated at a level 0.86 percent by welght with an aqueous chemical composition comprised of:
75% Protolube 5440 Maleic acid, Modified polypropylene emulsion from National Starch 12.8X A-llO0 gamma aminopropyltriethoxysilane from Union Carbide Corporation 5.lX Msleic acid (General Chemical Corp.) 7.2% Epirez W60-5520 epoxy polyurethane dispersion available from Rhone-Poulene O.lX Antifoam 1430 available from Dow Corning Corp.
X based on total dry solids Added to the web in con~unction with the web binder was a 30 carbon black d~spersion at a level of O.lX. The resultant treated web was dried to OX molsture at a temperature of 300F. Four dried sheets were stacked and laminated at 420F, 25 psi for 3.5 mlnutes. The resultant laminate was cooled at full pressure for 13 minutes. Said laminate was compression molded by heating it to 460F for 6 minutes 35 then shaping a flat panel at 100 tons pressure. The resultant molded panel was cut and tested in accordance with ASTM Procedures for Tensile, Flex and Izod Impact and the values are shown in the *Trade mark following table. The values stated for strength and modulus are normalized to a 30 percent glass loading by weight. This ad~ustment is accomplished by first detel ~n~ng the actual glass content via an ashing technique then determine the percentage difference between the 5 nominal and actual volume percent glass and multiplying that percentage difference by the strength or modulus value measured. This procedure is carried out for all strength and modulus values reported since webs might vary in glass content by 1 or 2 percent by weight.
EXP. Results Ten Str. Flex Str. Flex MOD Izod Imp.
(~si) (Dsi) (Dsi) (Ft-lbs/In) 15 Composition Formulation: 12,400 18,200 728,900 7.70 ExamDles 2-21 and Illustrative A and B
Twenty-one wet laid webs and two illustrative wet laid webs were prepared from components shown in Table 2. The Illustrative examples are indicated as A-B, where Illustrative Examples A and B
were made in a manner similar to Example 1, except that poly(vinylpyrrolidone) was the mat binder. Illustrative example A was 25 prepared in a manner similar to Illustrative Example B but without the presence of carbon black. Examples 2 and 3 were prepared in a manner similar to that of Example 1, but carbon black was not used. Examples 4-7 were prepared in a manner similar to that of Example 1 with one of two mat binders and without carbon black. In addition, examples 4-7 30 and 8 had an addition of the chemically modified polypropylene to the aqueous slush. Also examples 8-23 were prepared in a manner similar to Example 1 with the presence of carbon black and examples 8-12 varied the type of mat binder. Examples 13-20 were prepared in a manner similar to Example 1 but with the addition of the chemically ~ 17 - 2056720 modified polypropylene either to the slush as Hercoprime polypropylene or to the mat binder as Protolube 5440 polypropylene emulsion. In these examples the following components were used:
5 PVP K-90: Polyvinyl pyrrolidone, MW = 660,000 Hercoprime G : Maleic anhydride, Modified Polypropylene Hercoprime HG 201: Maleic anhydride, Modified Polypropylene Protolube 5440: Maleic acid, Modified Propylene 10 Profax 6201: Homopolymer of Polypropylene Melt Flow Index = 20 grams/10 minutes Weight Average MW = 210,000 Fina 3860: Homopolymer of Polypropylene Melt Flow Index = 75 grams/10 minutes Irgafos 168: Phosphite Type: Antioxidant which is Tris(2,4-Di-tert-butylphenyl) Phosphite Naugard 445: Aromatic Amine Type: Antioxidant which is 4,4'Di(2,2-dimethylbenzyl)diphenylamine Glass fiber sample A 1/2 inch length and 16 um fiber diameter Size Treatment I.
25 Glass fiber sample B 1/2 inch length 16 um fiber diameter with a surface treatment of Size Treatment II.
In examples 2-4, 6, 8, 14, 16, 18 and 20 the mat binder formulation that was used was that as used in example 1 as did examples 15, 17, 19 30 and 21 with the addition of more of the Protolube 5440 emulsion.
Examples 5, 7, 9, and 11 used the mat binder formulation indicated below as "Formulation I". Examples 10 and 12 used the mat binder formulation indicated below as "Formulation II".
35 Formulation I % bY Actual Solids Rucothane 20116 Polyurethane 56.65 A-llO0 5~34 EDTA 0.31 RD-1135b 5.34 A *Trade mark ~ - 18 - 2 0 5 6 7 2 0 Evan Stab 13 3.35 Sodium Hypophosphite 1.68 XW-116 M 8.27 Rhoplex E-693 19.06 5' - Carbon black: Black pigment.
Formulation II
In the formulation for the mat binder of Example 1 the chemically modified polypropylene was removed and replaced with 10 Rucothane 2011L polyurethane oil-in-water emulsion and it had the following formulation:
% bY Actual Solids Rucothane 2011L 51.5%
A-llO0 24.6%
Maleic acid 9.8%
Epirez W60-5520 14.0%
Anti-foam 1430 0.1%
Formulation III
% bY Actual Solids Protolube 544051.5 A-llO0 24.6 Maleic acid 9.8 Epirez W60-5520 14.0 Antifoam 1430 0.1 ~ 2056720 ~1 1 ~ ~ ~ I o ., ~ ~ o o 0 o I I I I I ! o l ~ O O
I O ~ I I I I ~
~ ~ o .~ o I I ~ ~ .~ I o I ~ I ~
o .-~ o o o ,1 I o ~ I I
~?I ~ ~ o ~
., ~1 ~D I ~ .~ 1 ~0 0 U~ ~ o o ~1 ~o ~ o o ~1 ` ~ o o ~, O ~ ~ , . t,~ ns ~] 0r~l ~ ,1 ,1~f ~ * ~ r-l k t3 ~ o ~ , t ~-~I I cq tit 0 t;'~
_t ~r t ~ r r O :> O
_t ~1 ~D O ~ ~ ' I I
~1 ` ~ O O
_I a~
~ C~
_11 ~ o ~ ,~
~o ~ o o _I ~ _I
C`J ~O
01 `D O ~ _~
~1 'D ~ O O O
_I ~
~o o O` ~D O ~ --~ I
_~ o ~ o o _I
o ,~
o~l ~ O ~ --~ I -~ D ~ O O O
¢
E~ _Io~
C~ o ~o o ~ _I I
`D ~ O O_I
~o ~Dl ~ O ~ --I I ---11 ~ ~ o o o _I ~
~ ~ o U~ ~ o ~_I . .
_~ ~o ~ o o _I
_Io~ _I
~`D O ~ --I
_I ~o ~ o o o o ~r ~O O ~ --I
_l~o ~ o o_~
H O
H H ~ O
O ,1 _I ~ 0 0 ~I) 0 1~ O ~ `
O
H ~ ~ H ~Z;C:l ~ p~
The wet laid nonwoven material with the thermoplastic polymer produced in Table 2 were molded under conditions similar to that of Example 1. The molded samples were tested in a manner similar to those of example 1 for tensile, flexural and impact properties.
5 These test results are presented in Table 3.
EXPERIMENTAL RESULTS
10 COMPOSITETEN STR. FLEX STR. FLEX MOD. IZOD IMP.
FORMULATION MD/CMD MD/CMD MD/CMD MD/CMD
(PSI) (PSI) (PSI) (FT-LBS/IN) 1 13,700 16,700 697,000 15.2 8,100 16,000 610,900 9.9 AVG lO,9OO 16,400 654,000 12.6 2 15,800 18,400 692,300 16.0 11,100 16,600 597,000 10.0 AVG 13,500 17,500 644,700 13.0 3 18,600 20,900 816,000 15.6 11,900 17,300 642,800 AVG 15,300 19,100 729,400 12.6 4 18,400 24,900 887,500 7.1 12,200 18,700 653,000 5.6 AVG 15,300 21,800 770,300 6.4 17,000 22,100 816,800 6.9 13,300 17,400 616,300 5.5 AVG 15,200 19,800 716,600 6.4 6 18,000 23,200 814,900 7.6 11,100 17,000 626,300 5.5 AVG 14,600 20,100 720,600 6.6 7 17,600 22,000 775,100 7.5 16,700 18,700 656,100 5.7 AVG 17,200 20,400 715,600 6.2 8 13,800 19,300 798,200 6.81 9,400 16,600 589,500 5.60 AVG 11,600 17,900 693,800 6.20 ~~ - 22 - 2 0 5 67 20 9 13,000 18,400 754,600 5.80 8,800 11,900 448,200 4.40 AVG 10,900 15,200 601,400 5.10 5 10 10,300 16,200 717,500 6.60 8,600 14,200 548,000 5.20 AVG 9,500 15,200 632,700 5.90 11 11,100 15,400 730,800 9.90 7,400 11,900 503,500 6.50 AVG 9,300 13,600 617,200 8.20 12 10,100 18,500 791,700 9.20 8,900 12,600 496,700 ~ Q
15 AVG 9,500 15,600 644,200 8.20 13 9,500 16,400 737,100 8.80 7,100 13,5Q0 531,800 6.80 AVG 8,300 15,000 634,500 7.80 1 13,700 16,700 697,000 15.20 8,100 16,000 610,900 9.90 AVG 10,900 16,400 654,000 12.60 Ad.iusted PhYsical Pro~erties TEN STR. FLEX STR. FLEX MOD. IZOD IMP.
TRIAL # MD/CMD MD/CMD MD/CMD MD/CMD
14 13,200 17,100 681,400 8.20 8,700 17,000 698,400 5.90 AVG 11,000 17,100 689,000 7.10 35 15 15,200 20,800 838,900 10.10 8,000 13,140 534,600 6.50 AVG 11,600 17,000 681,800 8.30 16 13,000 18,900 822,300 8.20 8,600 13,700 548,500 7.30 AVG 10,800 16,300 685,400 7.80 17 13,500 21,700 863,900 10.30 8,500 15,000 637,100 6.20 45 AVG 11,000 18,400 750,500 8.30 18 14,500 21,900 897,400 6.90 10,300 18,400 671,600 5.80 AVG 12,400 20,200 784,500 6.40 ~ - 23 - 20 56 7 2 0 19 14,100 25,800 990,100 7.40 8,200 16,100 596,800 5.50 AVG 11,200 21,000 793,500 6.50 16,700 22,000 890,300 5.30 7,400 13,300 515,200 5.10 AVG 12,100 17,700 702,800 5.20 10 21 15,600 22,700 951,400 8.80 9,100 13,600 506,300 6.50 AVG 12,400 18,200 728,900 7.70 9.751 15 22 12,600 19,800 866,700 7.709 6.808 7,300 17,100 645,900 5.909 AVG 10,000 18,500 756,300 7.60 20 23 14,400 18,200 791,900 10.02 7,900 14,900 584,800 6.20 AVG 11,200 16,600 688,400 8.10 It can be concluded from the study that composite physical properties improve as the melt flow index of the resin matrix is increased and that strength and modulus properties improve but impact performance decreases with the addition of 4 percent maleic anhydride modified polypropylene. The impact performance is reduced 30 significantly because the low molecular weight additive tends to imbrittle the resin matrix thereby reducing the composites ability to absorb energy during impact. At a 1 percent loading the maleic anhydride modified polypropylene additive offers benefits to all performance criteria. It can also be concluded from the study that 35 chemical formulation III gives the best properties of any chemical formulation studied plus the lower the level of carbon black present the better the overall physical properties performance will be.
Finally, it was determined that maleic acid and maleic anhydride modified polypropylene could be used interchangeable as part of the 40 composite formulations,
Claims (16)
1. A process of forming a wet-laid, non-woven, glass fiber containing thermoplastic polymer web that is moldable as a fiber reinforced thermoplastic laminate, comprising:
A. forming an aqueous dispersion containing:
1) a particulate or particulate powder thermoplastic matrix polymer selected from the group consisting of polyolefins, polyesters, polyamides, polyphenylene oxide andpolycarbonate, the matrix polymer constituting from 50 to 99 percent of the wet-laid web and present throughout and on the fibers of the web;
A. forming an aqueous dispersion containing:
1) a particulate or particulate powder thermoplastic matrix polymer selected from the group consisting of polyolefins, polyesters, polyamides, polyphenylene oxide andpolycarbonate, the matrix polymer constituting from 50 to 99 percent of the wet-laid web and present throughout and on the fibers of the web;
2) glass fibers of non-continuous lengths treated with a forming size containing a film forming polymer compatible with the matrix polymer, an organo coupling agent andcationic lubricant, wherein the size allows the glass fibers to disperse in the aqueous dispersion from which the wet laid web is formed, the glass fibers constituting from 1 to 50 percent of the wet-laid web;
B. depositing the aqueous dispersion onto a screen and removing water to form a non-woven, sheet-like, fiber containing thermoplastic polymer mat; and C. applying to the non-woven mat a mat binder having a solids content from around 0.1 to 32 weight percent and comprising:
1) a chemically modified thermoplastic polymer, constituting from around 0.01 toaround 20 weight percent of the wet-laid web, containing chemically reactive moieties for addition, condensation or free radical reaction to allow for coupling of the fibers to the matrix polymer, selected from the group consisting of carboxylic acid modified polyolefins, carboxylic anhydride modified polyolefins, mixtures and blends of these;
2) film forming polymer in a positive amount not exceeding 4 weight percent of the wet-laid web selected from the group consisting of polyurethane, epoxy, epoxy-polyurethane and polyoxyalkylene;
B. depositing the aqueous dispersion onto a screen and removing water to form a non-woven, sheet-like, fiber containing thermoplastic polymer mat; and C. applying to the non-woven mat a mat binder having a solids content from around 0.1 to 32 weight percent and comprising:
1) a chemically modified thermoplastic polymer, constituting from around 0.01 toaround 20 weight percent of the wet-laid web, containing chemically reactive moieties for addition, condensation or free radical reaction to allow for coupling of the fibers to the matrix polymer, selected from the group consisting of carboxylic acid modified polyolefins, carboxylic anhydride modified polyolefins, mixtures and blends of these;
2) film forming polymer in a positive amount not exceeding 4 weight percent of the wet-laid web selected from the group consisting of polyurethane, epoxy, epoxy-polyurethane and polyoxyalkylene;
3) from 0 to about 5 weight percent of the wet-laid web of an electron donating organo coupling agent; and
4) from 0 to about 3 weight percent of the wet-laid web of a compound selected from aliphatic or cyclic mono- or polycarboxylic acids and anhydrides thereof;
D. drying the sheet-like web to form the wet-laid, non-woven fiber containing thermoplastic polymer web.
2. The process of claim 1 wherein the thermoplastic matrix polymer is polypropylene.
3. The process of claim 1 wherein the film-forming polymer of the mat binder is a thermoplastic polymer.
4. The process of claim 1 wherein the mat binder additionally contains an effective stabilizing amount of a stabilizing agent selected from metal deactivating agents and antioxidants.
D. drying the sheet-like web to form the wet-laid, non-woven fiber containing thermoplastic polymer web.
2. The process of claim 1 wherein the thermoplastic matrix polymer is polypropylene.
3. The process of claim 1 wherein the film-forming polymer of the mat binder is a thermoplastic polymer.
4. The process of claim 1 wherein the mat binder additionally contains an effective stabilizing amount of a stabilizing agent selected from metal deactivating agents and antioxidants.
5. The process of claim 4 wherein the stabilizing agent is an antioxidant selected from thioester type antioxidants, phosphite type antioxidants, aromatic amine type antioxidants and combinations of these.
6. The process of claim 1 wherein the aqueous dispersion is a foamed aqueous dispersion of the glass fibers and matrix polymer with surfactant.
7. The wet-laid web of claim 1 wherein the chemically modified thermoplastic polymer is present as an emulsion or dispersion in the mat binder.
8. The process of claim 7 wherein, in the mat binder, the organo coupling agent is an amine organo coupling agent having a primary amine with basicity (pKb) greater than diethyl ethanolamine; the chemically modified thermoplastic polymer is an aqueous emulsion of surfactant and maleic acid or maleic anhydride modified polypropylene, the acid neutralized with amine having basicity similar to diethyl ethanolamine, the emulsion of maleic acid or maleic anhydride modified polypropylene present in an amount such that polypropylene constitutes the predominant solids of the mat binder; and the film former is an aqueous dispersion selected from water soluble, dispersible or emulsifiable polyurethane, epoxy, and epoxy-polyurethane, present in the mat binder in an amount less than the polypropylene emulsion.
9. The process of claim 1 wherein the film forming polymer of the glass fiber forming size is a crosslinkable polyurethane, the organo coupling agent is an organofunctional silane or its hydrolysis products and the forming size further contains an effective film forming amount of a copolymer of an acrylic type monomer that is addition polymerizable, matrix resin-miscible and matrix resin-reactable.
10. The process of claim 1 wherein the glass fiber forming size contains:
1) water soluble film forming polymer having an intrinsic viscosity of less thanabout 150 centipoise selected from poly(vinyl alcohol) polymer with weight average molecular weight ranging from about 22,000 to greater than 105,000, poly(vinyl-pyrrolidone), poly(hydroxy alkyl cellulose) and copolymers of monomers for preparing these polymers, wherein the polymer is present in an amount up to about 98 weight percent of the solids of the composition;
2) ureido organo-functional trialkoxy silane, its hydrolysis products and mixtures thereof, wherein the organo functionality is resin compatible and wherein the silane in all of its forms is present in an amount in the range of about 0.4 to about 20 weight percent of the solids of the composition;
3) cationic lubricant in an amount in the range of about 0.1 to about 15 weight percent of the solids of the composition; and 4) epichlorohydrin polyamide reaction product present in an amount in the range from about 0.4 to an amount not detrimental to the dispersibility of the treated fibers in water.
1) water soluble film forming polymer having an intrinsic viscosity of less thanabout 150 centipoise selected from poly(vinyl alcohol) polymer with weight average molecular weight ranging from about 22,000 to greater than 105,000, poly(vinyl-pyrrolidone), poly(hydroxy alkyl cellulose) and copolymers of monomers for preparing these polymers, wherein the polymer is present in an amount up to about 98 weight percent of the solids of the composition;
2) ureido organo-functional trialkoxy silane, its hydrolysis products and mixtures thereof, wherein the organo functionality is resin compatible and wherein the silane in all of its forms is present in an amount in the range of about 0.4 to about 20 weight percent of the solids of the composition;
3) cationic lubricant in an amount in the range of about 0.1 to about 15 weight percent of the solids of the composition; and 4) epichlorohydrin polyamide reaction product present in an amount in the range from about 0.4 to an amount not detrimental to the dispersibility of the treated fibers in water.
11. The process of claim 1 wherein the glass fiber forming size contains:
1) water soluble film forming polymer having an intrinsic viscosity of less thanabout 150 centipoise selected from poly(vinyl alcohol) polymer having weight average molecular weight ranging from about 22,000 to greater than 105,000, poly(vinylpyrrolidone), poly(hydroxy alkyl cellulose) and copolymers of monomers for preparing these polymers, wherein the polymer is present in an amount up to about 98 weight percent of the solids of the composition;
2) vinyl organo-functional trialkoxy silane, its hydrolysis products and mixtures thereof, wherein the organo functionality is resin compatible and wherein the silane in all of its forms is present in an amount in the range of about 0.4 to about 20 weight percent of the solids of the composition;
3) cationic lubricant in an amount in the range of about 0.1 to about 15 weight percent of the solids of the composition; and 4) epoxy functional polyamide present in an amount in the range from about 0.4 to an amount not detrimental to the dispersibility of the treated fibers in water.
1) water soluble film forming polymer having an intrinsic viscosity of less thanabout 150 centipoise selected from poly(vinyl alcohol) polymer having weight average molecular weight ranging from about 22,000 to greater than 105,000, poly(vinylpyrrolidone), poly(hydroxy alkyl cellulose) and copolymers of monomers for preparing these polymers, wherein the polymer is present in an amount up to about 98 weight percent of the solids of the composition;
2) vinyl organo-functional trialkoxy silane, its hydrolysis products and mixtures thereof, wherein the organo functionality is resin compatible and wherein the silane in all of its forms is present in an amount in the range of about 0.4 to about 20 weight percent of the solids of the composition;
3) cationic lubricant in an amount in the range of about 0.1 to about 15 weight percent of the solids of the composition; and 4) epoxy functional polyamide present in an amount in the range from about 0.4 to an amount not detrimental to the dispersibility of the treated fibers in water.
12. The process of claim 1 wherein the forming size of the glass fiber is present in an amount in the range of about 0.15 to about 0.45 weight percent of the strand.
13. A wet-laid, non-woven, glass fiber containing thermoplastic polymer web prepared according to the process of claim 1.
14. A wet-laid, nonwoven, glass fiber containing thermoplastic polymer web prepared by the process of claim 6.
15. A wet-laid, non-woven, glass fiber containing thermoplastic polymer web prepared by the process of claim 11.
16. A wet-laid, non-woven, glass fiber containing thermoplastic polymer web prepared by the process of claim 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62267190A | 1990-12-05 | 1990-12-05 | |
| US622,671 | 1990-12-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2056720A1 CA2056720A1 (en) | 1992-06-06 |
| CA2056720C true CA2056720C (en) | 1996-05-14 |
Family
ID=24495056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002056720A Expired - Fee Related CA2056720C (en) | 1990-12-05 | 1991-12-03 | Wet laid fiberous thermoplastic material and aqueous dispersion for producing same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5393379A (en) |
| EP (1) | EP0491204B1 (en) |
| JP (2) | JPH0791394B2 (en) |
| CA (1) | CA2056720C (en) |
| DE (1) | DE69124214T2 (en) |
| ES (1) | ES2099119T3 (en) |
Families Citing this family (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69124214T2 (en) * | 1990-12-05 | 1997-08-07 | Ppg Industries Inc | Wet-laid fibrous thermoplastic material and aqueous dispersion for its production |
| EP0696609B1 (en) * | 1994-03-03 | 2002-12-04 | Kawasaki Steel Corporation | Stampable glass fiber reinforced thermoplastic resin and method of producing the same |
| FR2707976B1 (en) * | 1993-07-22 | 1995-09-22 | Vetrotex France Sa | Glass fibers intended for the reinforcement of organic matrices. |
| US5678502A (en) * | 1994-03-17 | 1997-10-21 | Porter Sewing Machines, Inc. | Variable walking foot apparatus for a sewing machine for mattresses |
| CN1082885C (en) * | 1994-08-15 | 2002-04-17 | 川崎制铁株式会社 | Punched material with good mechanical performance |
| US5935879A (en) * | 1994-09-21 | 1999-08-10 | Owens Corning Fiberglas Technology, Inc. | Non-woven fiber mat and method for forming same |
| US6267843B1 (en) | 1996-03-20 | 2001-07-31 | Owens Corning Fiberglas Technology, Inc. | Wet-laid nonwoven mat and a process for making same |
| US5824413A (en) * | 1996-07-15 | 1998-10-20 | Ppg Industries, Inc. | Secondary coating for fiber strands, coated strand reinforcements, reinforced polymeric composites and a method of reinforcing a polymeric material |
| US5804313A (en) * | 1996-07-15 | 1998-09-08 | Ppg Industries, Inc. | Polyamide and acrylic polymer coated glass fiber reinforcements, reinforced polymeric composites and a method of reinforcing a polymeric material |
| US6054022A (en) * | 1996-09-12 | 2000-04-25 | Owens-Corning Veil U.K. Ltd. | Method for producing a non-woven glass fiber mat comprising bundles of fibers |
| US6093359A (en) * | 1997-11-06 | 2000-07-25 | Gauchel; James V. | Reinforced thermoplastic composite systems |
| US6315865B1 (en) * | 1998-02-27 | 2001-11-13 | Hercules Incorporated | Silyl-linked polyamidoamine and their preparation |
| US6008147A (en) * | 1998-05-28 | 1999-12-28 | Johns Manville International, Inc. | Fiber glass mat for laminating to foam, foam laminate precursor, foam laminate, and methods of making the mat and the foam laminate |
| US6537614B1 (en) | 1998-12-18 | 2003-03-25 | Kimberly-Clark Worldwide, Inc. | Cationically charged coating on hydrophobic polymer fibers with poly (vinyl alcohol) assist |
| US6274041B1 (en) | 1998-12-18 | 2001-08-14 | Kimberly-Clark Worldwide, Inc. | Integrated filter combining physical adsorption and electrokinetic adsorption |
| US6517676B1 (en) * | 1999-01-08 | 2003-02-11 | Ahlstrom Mount Holly Springs, Llc | Recyclable thermoplastic moldable nonwoven liner for office partition and method for its manufacture |
| US6251224B1 (en) | 1999-08-05 | 2001-06-26 | Owens Corning Fiberglass Technology, Inc. | Bicomponent mats of glass fibers and pulp fibers and their method of manufacture |
| US20030008586A1 (en) * | 1999-10-27 | 2003-01-09 | Johns Manville International, Inc. | Low binder nonwoven fiber mats, laminates containing fibrous mat and methods of making |
| US6645388B2 (en) | 1999-12-22 | 2003-11-11 | Kimberly-Clark Corporation | Leukocyte depletion filter media, filter produced therefrom, method of making same and method of using same |
| US6296795B1 (en) | 2000-05-19 | 2001-10-02 | George S. Buck | Non-woven fibrous batts, shaped articles, fiber binders and related processes |
| US6548155B1 (en) | 2000-07-19 | 2003-04-15 | Johns Manville International, Inc. | Fiber glass mat |
| US6572736B2 (en) | 2000-10-10 | 2003-06-03 | Atlas Roofing Corporation | Non-woven web made with untreated clarifier sludge |
| US6488811B1 (en) | 2001-04-30 | 2002-12-03 | Owens Corning Fiberglas Technology, Inc. | Multicomponent mats of glass fibers and natural fibers and their method of manufacture |
| US20030031854A1 (en) * | 2001-08-07 | 2003-02-13 | Kajander Richard Emil | Method of making coated mat online and coated mat products |
| US20030109190A1 (en) * | 2001-12-12 | 2003-06-12 | Geel Paul A. | Wet-laid nonwoven reinforcing mat |
| US6852259B2 (en) | 2002-09-18 | 2005-02-08 | Owens Corning Fiberglas Technology, Inc. | Moldable preform with B-stage thermoset polymer powder binder |
| US20040121680A1 (en) * | 2002-12-23 | 2004-06-24 | Kimberly-Clark Worldwide, Inc. | Compositions and methods for treating lofty nonwoven substrates |
| US20050136242A1 (en) * | 2003-12-22 | 2005-06-23 | Kimberly-Clark Worldwide, Inc. | Porous substrates having one side treated at a higher concentration and methods of treating porous substrates |
| US8129018B2 (en) * | 2004-06-18 | 2012-03-06 | Ocv Intellectual Capital, Llc | Sizing for high performance glass fibers and composite materials incorporating same |
| WO2006039465A1 (en) * | 2004-09-29 | 2006-04-13 | Eastman Chemical Company | Heat stable functionalized polyolefin emulsions |
| US20070185003A1 (en) * | 2006-01-18 | 2007-08-09 | Invista North America S.A.R.L. | Non-textile polymer compositions and methods |
| US20070082199A1 (en) * | 2005-10-11 | 2007-04-12 | Schweizer Robert A | Fiber size, sized reinforcements, and articles reinforced with such reinforcements |
| US20080142178A1 (en) * | 2006-12-14 | 2008-06-19 | Daphne Haubrich | Wet layed bundled fiber mat with binder fiber |
| DE102007018579B4 (en) * | 2007-04-18 | 2012-03-15 | Abts- Advanced Bag Technology & Service Gmbh | Cement bag and manufacturing process |
| CA2686755A1 (en) * | 2007-05-16 | 2008-11-27 | Nova Chemicals, Inc. | Plastic-cellulosic composite articles |
| US8348604B2 (en) * | 2008-03-17 | 2013-01-08 | Rolls-Royce Corporation | Airfoil assembly and method of forming same |
| FI126046B (en) | 2009-04-20 | 2016-06-15 | Elastopoli Oy | Composite intermediate and process for its preparation |
| US8084378B2 (en) * | 2009-04-24 | 2011-12-27 | Johns Manville | Fiber glass mat, method and laminate |
| JP5704165B2 (en) * | 2010-03-26 | 2015-04-22 | 凸版印刷株式会社 | Film-forming composition and sheet |
| WO2013118605A1 (en) * | 2012-02-08 | 2013-08-15 | 東レ株式会社 | Stimuli-responsive material and medical material comprising same |
| US9144955B2 (en) | 2013-09-04 | 2015-09-29 | Johns Manville | Blended thermoplastic and thermoset materials and methods |
| KR101548279B1 (en) * | 2013-12-20 | 2015-08-28 | 주식회사 불스원신소재 | Non-Woven Fabric for Shielding and Absorbing of Electromagnetic Waves or Non-Woven Fabric Composite Comprising the Same |
| FI127679B (en) * | 2015-01-29 | 2018-11-30 | Teknologian Tutkimuskeskus Vtt Oy | Thermoplastic fibrous materials and a method of producing the same |
| JP6544033B2 (en) * | 2015-05-12 | 2019-07-17 | 王子ホールディングス株式会社 | Nonwoven fabric, method for producing the same, and fiber-reinforced plastic molding |
| CN107849822B (en) * | 2015-07-06 | 2023-09-12 | 斯道拉恩索公司 | Formation and dewatering of compounds using twin-wire presses |
| KR20180064535A (en) | 2015-11-03 | 2018-06-14 | 킴벌리-클라크 월드와이드, 인크. | Paper tissue with high bulk and low lint |
| BR112018009470B1 (en) * | 2015-11-12 | 2022-04-12 | Cytec Industries Inc | Hybrid veil, composite laminate, fibrous preform configured for liquid resin infusion, prepreg, fibrous tape suitable for use in an automated tape laying (ATL) or automated fiber laying (AFP) process, fabric that can be infused with a liquid resin, woven fabric that is permeable to liquid and gas |
| JP6520662B2 (en) * | 2015-11-24 | 2019-05-29 | 王子ホールディングス株式会社 | Base material for fiber reinforced plastic molded body and fiber reinforced plastic molded body |
| US11718934B2 (en) | 2017-03-21 | 2023-08-08 | Dow Global Technologies Llc | Manufacture of composite dispersion based resin-infused random fiber mat |
| US11255051B2 (en) | 2017-11-29 | 2022-02-22 | Kimberly-Clark Worldwide, Inc. | Fibrous sheet with improved properties |
| GB2590316B (en) | 2018-07-25 | 2022-06-01 | Kimberly Clark Co | Process for making three-dimensional foam-laid nonwovens |
| EP3825351A1 (en) * | 2019-11-21 | 2021-05-26 | SABIC Global Technologies B.V. | Composites with improved adhesion and mechanical performance |
| EP3825350A1 (en) * | 2019-11-21 | 2021-05-26 | SHPP Global Technologies B.V. | Composites with reduced weight and improved interfacial strength |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2200815A (en) * | 1940-05-14 | Imidazoline derivatives and process | ||
| US2268273A (en) * | 1939-05-27 | 1941-12-30 | Carbide & Carbon Chem Corp | Textile finishing |
| US2267965A (en) * | 1939-07-18 | 1941-12-30 | Carbide & Carbon Chem Corp | Hydroxyalkyl glyoxalidines |
| US2355837A (en) * | 1942-03-17 | 1944-08-15 | Carbide & Carbon Chem Corp | Substituted glyoxalidines |
| US2694633A (en) * | 1950-02-23 | 1954-11-16 | Talbott Dev Associates | Affixing organic and inorganic additaments to cellulosic materials |
| US2728972A (en) * | 1951-04-10 | 1956-01-03 | Owens Corning Fiberglass Corp | Method and apparatus for coating fibers |
| US3016325A (en) * | 1955-11-01 | 1962-01-09 | Electro Chem Fiber Seal Corp | Process of combining water-insoluble additament with organic fibrous material |
| BE452797A (en) * | 1955-12-19 | |||
| US3036950A (en) * | 1959-06-22 | 1962-05-29 | Burgess Cellulose Company | Process for incorporating resins into paper |
| US3109769A (en) * | 1961-07-27 | 1963-11-05 | Ray C Martin | Process for incorporating resins into paper |
| US3328234A (en) * | 1961-08-07 | 1967-06-27 | Hawley Products Co | Bonding anionic fibers to anionic and non-ionic materials by treating the fibers with a cationic altering resin containing an oxirane ring |
| US3269860A (en) * | 1963-04-03 | 1966-08-30 | Grace W R & Co | Treatment of paper with latex composition |
| US3483276A (en) * | 1964-12-04 | 1969-12-09 | Hercules Inc | Blends of modified and unmodified polypropylene |
| US3416990A (en) * | 1965-08-06 | 1968-12-17 | Hercules Inc | Glass fiber-reinforced polymers |
| US3437550A (en) * | 1966-01-07 | 1969-04-08 | Hercules Inc | Glass fiber reinforced crystalline polypropylene composition and laminate |
| GB1129757A (en) * | 1966-05-31 | 1968-10-09 | Wiggins Teape Res Dev | Method of producing a thixotropic liquid suspending medium particularly for the forming of non-woven fibrous webs |
| US3597265A (en) * | 1968-05-06 | 1971-08-03 | Emery Industries Inc | Fiber lubricants |
| JPS5614778B2 (en) * | 1972-02-07 | 1981-04-06 | ||
| GB1329409A (en) * | 1972-04-06 | 1973-09-05 | Wiggins Teape Research Dev Ltd | Method of and apparatus for manufacturing paper or other non- woven fibrous material |
| FI65459C (en) * | 1972-04-07 | 1984-05-10 | Wiggins Teape Res Dev | FRAMEWORK FOR THE FRAMEWORK OF FIXED FIBERS |
| US4179331A (en) * | 1977-11-15 | 1979-12-18 | Gaf Corporation | Glass fiber dispersions for making uniform glass fiber mats by the wet-laid process |
| US4265704A (en) * | 1979-03-30 | 1981-05-05 | Gaf Corporation | Method of dispersing bundles of glass fibers for making glass fiber mats by the wet-laid process |
| BE884712A (en) * | 1979-07-10 | 1981-02-11 | Arjomari Prioux | NEW SHEET PRODUCTS CONTAINING THERMOPLASTIC AND CELLULOSIC FIBERS, PROCESS FOR THEIR PREPARATION AND APPLICATION THEREOF |
| US4308093A (en) * | 1979-12-03 | 1981-12-29 | Texon, Inc. | High temperature resistant compressible sheet material for gasketing and the like |
| US4395306A (en) * | 1980-01-31 | 1983-07-26 | The Dow Chemical Company | Method for preparing fibrous mats from a fibrous suspension |
| FR2481707B1 (en) * | 1980-04-30 | 1985-07-26 | Arjomari Prioux | NOVEL SHEET MATERIAL COMPRISING REINFORCING FIBERS AND THERMOPLASTIC POWDER MATERIAL, AND METHOD FOR PREPARING THE SAME |
| US4426470A (en) * | 1981-07-27 | 1984-01-17 | The Dow Chemical Company | Aqueous method of making reinforced composite material from latex, solid polymer and reinforcing material |
| EP0071219B2 (en) * | 1981-07-27 | 1991-06-19 | The Dow Chemical Company | Aqueous method of making reinforced composite material from latex, solid polymer and reinforcing material |
| JPS5869047A (en) * | 1981-10-22 | 1983-04-25 | 株式会社クラレ | Sheet-shaped body, its manufacture and heat insulating material |
| US4358502A (en) * | 1981-12-14 | 1982-11-09 | Owens-Corning Fiberglas Corporation | Glass fiber mat for reinforcing polyamides |
| US4618401A (en) * | 1982-02-02 | 1986-10-21 | Texon, Inc. | Battery separator material |
| US4442138A (en) * | 1982-02-22 | 1984-04-10 | Westinghouse Electric Corp. | Substrate pretreatment with a metal-beta keto ester complex in the method of curing an anaerobic resin |
| JPS59105053A (en) * | 1982-12-09 | 1984-06-18 | Karupu Kogyo Kk | Thermoplastic resin composition and production thereof |
| GB8400294D0 (en) * | 1984-01-06 | 1984-02-08 | Wiggins Teape Group Ltd | Fibre reinforced composite plastics material |
| US4882114A (en) * | 1984-01-06 | 1989-11-21 | The Wiggins Teape Group Limited | Molding of fiber reinforced plastic articles |
| US4728573A (en) * | 1985-03-25 | 1988-03-01 | Ppg Industries, Inc. | Glass fibers for reinforcing polymers |
| US4680223A (en) * | 1985-11-22 | 1987-07-14 | Hercules Incorporated | Fibrous inner web for sheet vinyl flooring goods |
| US4681805A (en) * | 1985-12-23 | 1987-07-21 | Ppg Industries, Inc. | Strands of chemically treated glass fibers having a reduced tendency to give gumming deposits |
| GB8612813D0 (en) * | 1986-05-27 | 1986-07-02 | Wiggins Teape Group Ltd | Layer forming technique |
| EP0281475A3 (en) * | 1987-03-05 | 1990-09-12 | Exxon Chemical Patents Inc. | Reinforced thermoplastic material and process for its manufacture |
| FR2618373B1 (en) * | 1987-07-23 | 1990-03-23 | Arjomari Prioux | REINFORCED THERMOPLASTIC SHEET AND MANUFACTURING METHOD THEREOF |
| FR2620079B1 (en) * | 1987-09-04 | 1990-01-19 | Arjomari Prioux | HIGH-MOULDABILITY REINFORCED THERMOPLASTIC SHEET |
| FR2620968B1 (en) * | 1987-09-29 | 1990-04-27 | Arjomari Prioux | SEMI-PRODUCTS IN THE FORM OF ENHANCED THERMOPLASTIC SHEETS WITH IMPROVED HOT FLUIDITY |
| JPH01318045A (en) * | 1988-05-10 | 1989-12-22 | E I Du Pont De Nemours & Co | Composite material composed of wet molding mixture of glass fiber and thermoplastic fiber |
| CA1330284C (en) * | 1988-07-15 | 1994-06-21 | Luciano Michael Parrinello | Chemically treated shapes, fillers and reinforcement for polymer matrices |
| GB9000865D0 (en) * | 1990-01-15 | 1990-03-14 | Exxon Chemical Patents Inc | Polymer composition |
| DE69124214T2 (en) * | 1990-12-05 | 1997-08-07 | Ppg Industries Inc | Wet-laid fibrous thermoplastic material and aqueous dispersion for its production |
-
1991
- 1991-11-29 DE DE69124214T patent/DE69124214T2/en not_active Expired - Fee Related
- 1991-11-29 EP EP91120540A patent/EP0491204B1/en not_active Expired - Lifetime
- 1991-11-29 ES ES91120540T patent/ES2099119T3/en not_active Expired - Lifetime
- 1991-12-03 CA CA002056720A patent/CA2056720C/en not_active Expired - Fee Related
- 1991-12-05 JP JP3322173A patent/JPH0791394B2/en not_active Expired - Lifetime
-
1993
- 1993-04-22 US US08/052,296 patent/US5393379A/en not_active Expired - Lifetime
-
1997
- 1997-01-30 JP JP9017231A patent/JPH09310296A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ES2099119T3 (en) | 1997-05-16 |
| EP0491204B1 (en) | 1997-01-15 |
| DE69124214D1 (en) | 1997-02-27 |
| EP0491204A2 (en) | 1992-06-24 |
| JPH09310296A (en) | 1997-12-02 |
| JPH0791394B2 (en) | 1995-10-04 |
| EP0491204A3 (en) | 1992-12-09 |
| DE69124214T2 (en) | 1997-08-07 |
| US5393379A (en) | 1995-02-28 |
| CA2056720A1 (en) | 1992-06-06 |
| JPH04300923A (en) | 1992-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2056720C (en) | Wet laid fiberous thermoplastic material and aqueous dispersion for producing same | |
| JP3003705B2 (en) | Size and mat for glass fiber | |
| US4394418A (en) | Aqueous sizing composition and glass fibers made therewith for reinforcing thermosetting polymers | |
| AU740119B2 (en) | Reinforced thermoplastic composite systems | |
| US4810576A (en) | Treated glass fibers and aqueous dispersion and nonwoven mat of the glass fibers | |
| US5656366A (en) | Urea-formaldehyde binder for high tear strength glass mat | |
| EP1544352B1 (en) | Method of making fibrous mats and fibrous mats | |
| KR20060011958A (en) | Mineral fibre sizing composition containing a carboxylic polyacid and a polyamine, preparation method thereof and resulting products | |
| US5085938A (en) | Chemically treated fibers and method of preparing and method of using to reinforce polymers | |
| KR950004062B1 (en) | Chemical composition to produce water soluble curable films on fibrous surfaces and said treated fibers | |
| US8283266B2 (en) | Method of making tough, flexible mats and tough, flexible mats | |
| EP0511235B1 (en) | Polymer composition | |
| CN103717670A (en) | Sizing composition for charges used in thermoplastic polymeric material reinforcement, reinforced polymeric materials and method of manufacture | |
| US5141802A (en) | Chemically treated shapes, fillers and reinforcement for polymer matrices | |
| EP0304837B1 (en) | Chemically treated fibers and method of preparing and method of using to reinforce polymers | |
| JPH0643501B2 (en) | Chemically treated moldings, fillers and reinforcements for polymer matrices | |
| US3922472A (en) | Glass fiber reinforced elastomers | |
| CA1285434C (en) | Treated glass fibers and aqueous dispersion and nonwoven mat of theglass fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |