DE1912466A1 - Processes and mixtures for the production of molded parts by pressing - Google Patents

Description

Processes and equipment for the manufacture of porcelain parts by pressing

The invention relates to the production of molded parts by pressing mixtures that have a binder on

one

Base / thermosetting synthetic resin, inventory activators,
parts such as catalysts / crosslinking agents and a predominant proportion of an inert filler and are then cured.

The invention is primarily directed to the production of molded parts from a material, the natural stone imitated like marble and granite, being a thermosetting Binders and fragments and waste of natural stone and other materials are used.

It has surprisingly been found that molded parts are obtained whose hardness, impact and shock resistance and abrasion resistance have the corresponding properties of natural stones are at least equivalent and even superior if the one exerted on the mixture Pressure is at least 100 kg / cm and, as resins, unsaturated polyester resins, ally resins, epoxy resins and their mixtures are used,

309845/0889

The press, for example, can be in a punch press careful production of plates or in a row with rotating mandrel for example for Herateil mg of hollow. Columns take place, presses can be used for this already known for similar purposes.

According to the invention, the inert filler consists of Parts and residues from animals, Pfiar-aen and natural and / or synthetic minerals such as shells of animals and plants ", natural or artificial Mother of pearl, Marnor-y 'granite, glass, metals -na others similar I'fatefialien, at least a part of aea filler is in For:.: of an ata bfine powder. normally the maximum size of the grain is 7 nm. It is also possible that all of the inert filler

1i) the forr. of a fine powder. It irjt be noted that the mixture used contained the less binder mu3 _f the higher the pressure is. To carry out the shaping by pressing, the binder and the filler must be in such. Hengenverhäit-

20 must be present so that an at least partially dry powdery mixture is formed.

ψ In the pressing process geniä.3 of the invention, the

best results obtained when the mixture used contains about 2.5 to 14 ^ thermosetting resin, which is preferably is an unsaturated polyester resin, in particular a potassium acid-phthalic acid ester of propyl glycol.

In a particular embodiment of the invention "" ■ "' serves as a crosslinking agent, a monomer that is associated with the Resin is able to form a copolymer, preferably an ITinyl monomer, e.g. styrene. In this case it is the proportion of styrenes about 10 to 60> & of the resin weight without any other ingredient or filler.,

Peroxides or organic persalts are used as catalysts used. If the mixture is at a low tempe-

909845/0809

BATH ORIGINAL

temperature, d-.hc at a temperature between 20 and 60 ° C, methyl ethyl ketone peroxide is preferably used (as a 50% solution in diethyl phthalate). For example, a modified technical methyl ethyl ketone peroxide is suitable. If the mixture is to harden at an elevated temperature, ie at 60 to 180 ^° C., one of the following catalysts is preferably used: methyl ethyl ketone peroxide, benzoyl peroxide (if the hardening or polymer solution

10 tion temperature of the mixture is above TO. "C),

tert-butyl diperphthalate (if the curing or polymerization temperature of the mixture is above 95 ° C), a-cumyl peroxide (if the mixture is hardened or polymerized at between 100 and 150 C) and tert-butyl peroxide and cumyl peroxide (if the mixture is hardened) or polymerization temperature of the mixture between 120 and 180 ⁰ C). The proportion of the catalyst is generally Yfo, based on the weight of the mixture of resin and styrene. In the case of α-cumyl peroxide, this proportion can reach 1.5 # _f based on the mixture of resin and styrene. Of course, the curing or polymerization time is ao shorter, the higher the proportion of catalyst.

If Methyläthylketonperoxyd is used at a low temperature (20 to 60 ⁰ C) as the catalyst, are manνvorzugsweise an accelerator which consists of a metal salt such as cobalt octoate, cobalt naphthenate, magnesium naphthenate or, in an amount of 0.1 to 0.3 $, to the Weight of the maleic acid-phthalic acid ester of propylene glycol, as a solution in the styrene monomer to,

The decomposition time of the catalyst after its addition to the resin-styrene mixture must also be taken into account. For example, the benzoyl peroxide-catalyzed mixture of polyester resin and styrene has a useful

909845/0889

- 4 - ■■■ '■ -.

period of 24 hours at .2O ⁰ C ₀ When the mixture of polyester resin and styrene contains as catalyst tert-butyl diperphthalate, the service life is 10 days at 20 ⁰ C. The mixture of polyester resin, styrene and ct-Curiiylperoxyd has a service life of 30 iuty tert to 100 days at 20 C and the mixture of polyester resin, styrene, and Cumylperoxyd! peroxide a useful life of 180 days at 2O ⁰ Co

The invention further comprises a molding compound for production of molded parts by pressing according to the method described above.

In the following examples the percentages are based on the weight measurements of the physilcalischen properties were carried out at 20 ⁰ C.

example 1

A binder is made by mixing the following ingredients at 20 ⁰ G under a pressure of 5 mm Hg:

Binder A B-C

Paint in acid-phthalic acid eh
ester of propylene glycol
kol, io 73,340 68.260 56,580 Monomeric styrene, ^ 25,670 30.716 42,460 terto-butyl peroxide
and cumyl peroxide, '^ 0.990 1.024 0.960 Effective volume weight,
g / cm- ⁵ • 1.141 1.136 1.124 Example 2

To produce the molding compounds according to the invention, the binders produced according to Example 1 are used given an inert filler. The inert filler has the following grain sizes:

9098 /, 5/08 8 9

'ORIGINAL

Powder # 000:

Powder No. 00:

Powder No. 0:

Marble with grain size no.1s

Marble with grain size # 2:

Marble with grain size # 3:

Granite with grain size # 1:

Granite with grain size 2s

Granite with grain size 3s Dust-fine powder, its particles

a sieve with at least 1100 meshes /

cm happen.

Grain fraction with a sieve

810 meshes / cm happened.

Grain fraction with a sieve

ο 140 stitches / cm happened.

1.5 to 2.5 mm 2.5 to 3 mm 3 to 6 mm 1 to 2.8 mm 2.8 to 4.8mm 4.8 to 7 now

The table below shows the percentages of the constituents of the masses to be pressed according to the invention called. These mixtures are numbered 6701, 6702, 6704, 6705, 6708 to 6714, 6716 to 6718, 67100 to 67102, 6620 and 6628. This table also shows the properties of the mixtures.

909845/0889 ^8AD ORIGINAL

(O O (O

θ »

cn

»Χ» O 00 Ο> (O

Binder B Powder # 000 Powder # 00 Powder # 0, grain # 1, grain # 2, grain Nf.3

Properties of the G ^ miscHe

Type of powder used as inert filler

Physical condition, structure of the mixture

Bulk density, g / cm3 b, 20 ° 0 Effective rauo weight, g / esp] 3 _e 2O ° C

6620 8.334

41.667

8.333

16,666

25,000

Gran.

1.575 2.310

6704 6701

13,000 87,000

KaIk (I) lime

powder

1.070

2.205 (4) 2.163 (5)

6705
6702

13.793
66.207

lime

powder

1.054
2.160

6710 6708

10.715

69.285

Sacc (2)

powder

1.C70

2.1d7 2.229

6711 6709

11.505

bö, 495

bacc.

powder

1.130 2.187

2,293

6716 6712

12.200

87,800

0fical (3)

powder

O.si-C

2.227

2.083

CTn

oo * · * cn * ■ »» ο

cc co

6717 6713

6718 6714

67101 67100

67102

6628

Binder. B.

Powder # 000

Powder # 00

Powder I \ ⁽ r. C

Grain no

Grain # 2

Grain number 3

Properties of the mixtures

Type of powder used as inert filler

Physical state, structure of the mixture Bulk density, g / cm ^{5 at} 20 ° C Effective volume weight, g / cm 'at 20 °

13,000 87,000

13.795
66.207

14.035

28.655
2b, 655

3, ö46

48.07b

Limestone, marble

Saccaroid: powdered microcrystalline marble

7,072

4.6,4t4

Ofical Sacc lime 11.616 powder Gran. Gran. 11.616 Ofical 0.905 1,700 1.268 lime powder 2.180
2.073 1,900
2.041 2.023 Gran 0.930 ί, 600 2.143
2.122 2,200

Oficalce: naturally pigmented mixture of asbestos fibers and limestone in powder form In each column, the first value for the effective volume weight applies to 106 kg / cm pressed mixture.

5) In each column the second value applies to the effective volume weight of a ^{mixture pressed at 305 kg / cm "5.} If this value is lower than the first value, this means that the pressure was too high.

Example 3

The following table shows the percentages
of the components of equipment specified, which according to the invention can be pressed with or without simultaneous rotation. The table also lists the properties of the mixtures.

909845/0889

6721

6725

6726

6727

6728

6729

6730

6738

6739

, Binder B 12.678 11.504 8,756 7.319 12,280 ♦ Saccaroid: powdered microcrystalline marble 10 , 873 , 300 8.108 8.108 10.714 VO
I. CD Powder No. 000 10,524 ♦ »Limestone, marble , 522 5.004 5.406 NO Powder # 00 87,322 88,496 35,100 59.654 87.720 89 , 127 43,444 43.243 89.286 CT)
CD Grain No. 1 45.620 43,444 43.246 Powder 00 Sacc. * 29.646 Binder B 3.381 9098 / Properties of the
Mixtures »5/088 Kind of as fill
fabric serving
Powder Lime ** lime lime Lime/
Sacc lime lime lime Lime sacc to Physical condition and
Structure of the
Mixture Powder powder Gran. powder powder powder Gran. Gran. Powder Bulk density,
g / cm ^ 1.422 1.575 1.575 1.282 1.242 1 1,238 1.346 1.142 Effective haul
weight, g / cm * 2,200 2,327 2,420 2.264 2.256 2 2,300 2.192 2.021

Example 4

The mixture ITr mentioned in the table of Example 2. 6620 is also suitable for the pressing process with equilateral rotation (press with rotating mandrel).

5 Example 5

ö62G 7392 g of that described in Example 2. Mixtures ^ are produced. After <? Uter homogenization by mixing in a homogenizer, optionally with; a device is provided which creates a vacuum of 5 mm Hg, at a temperature of 20 ⁰ C for about 5 minutes, the mixture is poured into the die of a Jrresae up to a layer height of 3.2 cm. The die has a cavity in the shape of a parallelepiped measuring 40 cm 40 cm 3.5 cm. The mixture is pressed for 15 seconds at 20 ° C. under a pressure of 200 kg / cm. In this way a sheet 2 cm thick is obtained. This plate is lifted out of the mold and cured in an oven for 30 minutes at 80 to 150 ^° C. by polymerization.

Example 6

35.23 kg of the mixture No. 6721 described in Example 3 are produced. After good homogenization, the mixture is poured into the funnel of a rotating press Cast mandrel. The mandrel, which is in our part, i.e. at the end of its stroke, is set in rotation, whereupon the mixture above is allowed to fall down. During the rotation, the moves Pin up until it is above the mixture, creating a column. The device has the following dimensions: outer diameter of the gut 140 mm;

30 inner diameter of the cylindrical body of the press 200 mm; Length of the stroke of the mandrel 1000 mm.

The completion time of the column is 4 minutes at 20 ⁰ C under a theoretical pressure ^ calculated on

909845/0889

1912A66

the density intended for the hardened material) vot; about 100 kg / cm "

After shaping, the device is opened over a carriage on which the well-pressed hollow column rests and remains upright. The column is transported into an oven where it is cured for 30 minutes at 80 big 15O ⁰ C by polymerization.

90984 5/086 3

Claims (54)

Claims 1) Process for the production of molded parts by pressing 'Mixtures that have a binder based on a synthetic thermosetting resin, components such as catalysts, activators, crosslinking agents and a predominant one Containing portion of an inert filler, and hardening the deformed mass, characterized in that one is on the mixture exerts a pressure of at least 100 kg / cm and as synthetic thermosetting resins, unsaturated polyester resins, allyl resins, epoxy resins, and mixtures of these kinds of resins used. 2) Method according to claim 1, characterized in that the inert filler consists of parts and residues of animals, Plants and natural and / or synthetic minerals, such as the shells of animals and plants, natural or artificial Made of mother-of-pearl, marble, granite, glass, metals and other similar materials. 3) Method according to claims 1 and 2, characterized in that that at least part of the filler is in the form of a dust-proof Powder is present. 4) Process according to claims 1 to 3, characterized in that the maximum grain size of the filler is normally 7 mm. 5) Method according to claim 3 »characterized in that the entire filler is in the form of a fine powder. 6) Process according to claims 1 to 5, characterized. 909845/0889 that the mixture used contains the less binding agent the higher the preflow pressure is. 7) Method according to claims 1 to 6, characterized in that that binder and filler are present in such proportions that an at least partially dry powdery Mixture is formed. 8) Process according to claims 1 to 7 »characterized in that the starting mixture is about 2.5 to 14 wt .- # thermosetting contains synthetic resin. 9) Process according to claims 1 to 8, characterized in that the starting mixture is about 2.5 to 14 wt .- # unsaturated Contains polyester resin as a solution in monomeric styrene. 10) Process according to claims 1 to 7 »characterized in that the starting mixture is approximately 2.5 to 14 wt .- # allyl Contains 15 resin. 11) Process according to claims 1 to 7, characterized in that the starting mixture is about 2.5 to 14 wt .- # epoxy resin
contains. 12) Process according to claims 1 to 7 »characterized in that the starting mixture is about 2.5 to 14 wt .- ^ of a mixture of unsaturated polyester resin, allyl resin and / or epoxy resin. 13) Method according to claim 8, characterized in that the Starting mixture 2.5 to 14% by weight maleic acid-phthalic acid-propylene glycol resin contains in solution of monomeric styrene. 9098 * 5/086 9 originally inspected 14) Process according to claims 8 to 12, characterized in that the crosslinking agent consists of a monomer, which can form copolymers with the resins. 15) Method according to claim 14, characterized in that as a crosslinking agent vinyl mono-ware, preferably styrene, used. 16) Method according to claim 15 * thereby eekerjr ^ elohnet that the amount of the styrene is about 10 to 60 percent by weight of the resin without any other ingredient or filler matter. 17) Process according to Claims 8 to 1.3, characterized in that it is kerxizelehnet, that the starting mixture acts as a catalyst, a peroxide or contains organic persalt. 18) Method according to claim 17j, characterized in that the starting mixture as a catalyst is tert-butyl peroxide and cumyl peroxide. 19) Method according to claim 17 *, characterized in that the starting mixture contains Benseyl peroxide as a catalyst. 20) Method according to claim 17 »characterized in that the catalyst is methyl ethyl ketone peroxide. 21) Method according to claim 17, characterized in that the catalyst is tert-butyl diperphthalate » 22) Method according to claim 17 *, characterized in that the catalyst is α-cumyl peroxide. 0984570880 BADORiQINAL 23). Process according to Claims 17 to 22, characterized in that the catalyst is used in an amount of about 1% by weight, based on the total amount of polyester resin and monomers . 2.4) Method according to claim 20, characterized in that the outlet mixture used also includes an accelerator contains, which is made from a metal salt, such as the Ootoat or Naphthenate consists of cobalt or the naphthenate of magnesium 25) Method according to claim 24, characterized in that a cobalt salt is used as an accelerator and methyl ethyl ketone peroxide is used as a catalyst. 26) Method according to claim 25, characterized in that an accelerator based on cobalt in amounts of 0.1 to 0.3 wt .- ^, based on that as a solution in monomer Maleic acid-phthalic resin of propylene glycol used in styrene is used. 27) Process according to Claims 18, 19, 21 and 22, characterized in that a catalyst is used without an accelerator. 28) Process according to Claims 1 to 27 #, characterized in that the pressing is carried out at ambient temperatures, preferably at about 20 ° C. 29) Process according to claims 20 ·, 24 to 2.6 and 28, characterized in that the polymerization or the final curing at 20 to 60 ° C is carried out. 909845/0869 '- 16 - 30) Method according to claims 18 to 22, 23, 27 and 28, characterized characterized in that the final curing is carried out at temperatures of 60 to 180 ° C. Mixtures for the production of molded parts by pressing with a content of a binder based on a synthetic thermosetting resin, components such as catalysts, Activators, wetting agents and a predominant amount of an inert filler, characterized in that that the synthetic thermosetting resins are unsaturated polyester resins, allyl resins, epoxy resins and mixtures thereof Are resins and that the binder and inert filler are present in such proportions that the mixture is at least is partially a dry powder. Mixtures according to Claim Jl, characterized in that the inert filler consists of parts and residues from animals, plants and natural and / or synthetic minerals, such as shells from animals and plants, natural or artificial mother-of-pearl, marble, granite, glass, metals and other similar Materials. 33) Mixtures according to Claims 31 to 32, characterized in that that at least part of the filler is in the form of a fine powder. 34) mixtures according to claims 32 and 33 * characterized in that that the maximum grain size of the inert filler is usually 7 mm. 35) Mixtures according to claim Jk, characterized in that the entire inert filler is in the form of a fine powder. 909845/0889 36) Mixtures according to Claims 3I to 35 * characterized by a content of about 2.5 to 14 wt .- ^ unsaturated polyester resin in solution of monomeric styrene, 37) Mixtures according to claims 31 to 35 * characterized by a content of the mixture to about 2.5 to 14 wt -.% Allyl resin. ■ -, ... 38) Mixtures according to claims 3I to 35 * characterized by a content of about 2.5 to 14 wt -.% Epoxy resin. 39) Mixtures according to claims pi to 36 "characterized by a content of about 2.5 to 14 wt -.% Of a mixture of unsaturated polyester resin and / or allyl resin and / or epoxy resin. 40) mixture according to claim 37, characterized by a content of 2.5 to 14 wt -.% Of maleic acid-phthalic acid-propylene glycol Esterharz as Lö'sung in monomeric styrene. 41) Mixtures according to Claims 36 to 40, characterized by a content of a crosslinking agent consisting of a monomer capable of forming copolymers with the resin. 42) Mixtures according to claim 41, characterized by a content on vinyl monomers as crosslinking agents » 43) Mixtures according to claim 42 * characterized by a content of monomeric styrene as a crosslinking agent. 44) Mixtures according to claim 43 * characterized by a content of styrene from about 10 to 6 % by weight of the resins _{: none} other ingredient or filler * BATH ORIGINAL 1912468 45) Mixtures naoh claims 36 and 40 to 4-t, characterized in that that it orkanisohe peroxides as a catalyst Contains persalts. 46) mixture naoh claim 45, characterized by a Gehelt of tert-butyl peroxide and cumyl peroxide. 47) mixture according to claim 46, characterized by a content of benzoyl peroxide. 48) Mixture according to claim 46, characterized by a content of methyl ethyl ketone peroxide. 49) Mixture according to claim 45, characterized by a content of tert-butyl diperphthalate. 50) mixture according to claim 45, characterized by a content of α-Cuiiiylperoxid. 51) mixture according to claims 45 to 50 characterized by a Catalyst content of about 1 wt .- ^ based on the Total weight of polyester resin and monomers.,. 52) mixture according to claim 48, characterized by an additional Content of an accelerator that consists of a Metal salt such as cobalt octcrate, cobalt naphthenic or magnesium naphthenate consists. 53) mixture according to claim 52, characterized by a content of cobalt sal as an accelerator and of methyl ethyl ketone peroxide as a catalyst. 54) mixture according to claim 53, characterized by a Ge Holds 0.1 to 0.3 wt% accelerator on the base from K-: »old, based on the weight of the maleic acid phthal · acid propylene glycol ester resin ala solution in monomers Styrene. ORIGINAL 909845 / 088'ä