DE2350424A1 - PLASTIC MOLDED BODY WITH RELIEF-LIKE SURFACE - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basel

CIBA-GEIGY

Case 3-8453 GERMANY

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr.FLKoenigsfasrger - Dipl. Phys. R. Holzhauer

Dr. F. Zumstein jun.

Patent attorneys

8 Munich 2, Bräuhaussfraße 4 / III

Plastic molded body with a relief-like surface

Tableware, vessels and the like made of thermoset Plastics, in particular made from melamine resins, are known and have proven themselves because of their breaking strength, low heat conduction and easy cleaning. Such Articles are sold monochrome, with a large selection of colors and decorated in a variety of patterns.

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The production of tableware and similar moldings is carried out using the hot-pressing process. Pressing tools in connection with hot presses are mainly used. Often, however, the injection molding process and the transfer pressing process are also used. The molding compound used is known to consist of a mixture of the curable thermoset resin with fillers, pigments waxes like dyes _s optionally curing agents, accelerators and the like.

Especially when working with a heating press, it is possible to place a printed on a pre-pressed press part Paper, which has been impregnated with melamine resins and dried, is to be applied and replaced by another final hot-pressing process to produce a shaped body with very specific decoration. This kind of Decoration is very popular because it offers many possibilities in the tableware sector and for promotional items.

Single-colored pressed bodies are often remunerated in the following way. Here, too, the pigmented molding compound is used first briefly pre-pressed under pressure and heat in the mold until the molding compound no longer throws bubbles. Then the mold is opened, a pure melamine resin brought to the surface of the preform and then hot pressed again. In this way, a glaze is formed on the outer layer of the body.

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pers, which gives the body a pleasing appearance and at the same time makes it more resistant to chemical attack power.

The molding compounds containing thermosets as the base resin according to the state of the art and their processing according to the conventional hot-pressing process still have not relevant to a satisfactory solution of all Problems led. For example, it has not yet been possible to make tableware and, in particular, vessels to produce from thermosetting materials, which have the typical appearance of ceramic bodies, preferably of stone ^ exhibit bodies. It is typical of stoneware that coarse-grained particles of the hardened mass protrude more or less on the surface of the object. This stoneware character is underlined by the different color of the base material and the protruding particles.

Since stoneware vessels and similar rustic items in have become very fashionable again in recent years, there has been no lack of attempts to find similar-looking objects, in particular to produce from melamine resin molding compounds. For example, coarse stoneware particles were mixed into the thermoset mass as a filler. One got but not to the desired success, as the work

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testify to a very high level of wear and tear due to friction and Was exposed to impressions. In addition, the stoneware particles are not like real stoneware items partially protrude from the surface of the molded body, but that they are completely in the mold the matrix material is pressed into it and thus into the same are embedded. Ultimately, the result is a smooth one Surface without rustic stoneware character.

Pressing tools have also already been produced which have an uneven, relief-like surface. Under However, using such tools does not lead to molded articles with a rustic appearance. The reason for that is that either the color of the individual depressions and elevations in the molded body surface is too even or that color coordination, as is the case with real stoneware, is not achieved can be.

The above-mentioned problem is solved by the present invention in a simple and elegant manner, by processing molding compounds, which hardened thermoset compounds or high-melting thermoplastic compounds in Contain in the form of powders or granules.

The invention therefore relates to a molding compound for the production of moldings, such as dishes, ashtrays,

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Sanitary articles or the like with a relief-like, uneven surface according to known hot-pressing processes, such as injection molding processes, transfer-pressing processes or processes using a heating press, containing a curable thermoset and conventional mixing additives, which are characterized in that they contain 5 to 50% by weight. a hardened thermoset compound or a thermoplastic compound with a softening temperature of at least 200 ^° C. in the form of powders or granules with a grain size between 0.1 and 3 mm.

Surprisingly, after processing, the compounds according to the invention are obtained Molding compounds according to the known hot-pressing process are not molded bodies with a smooth surface, rather, moldings with a relief-like, uneven surface result. The effect also occurs if according to One preferred form of the invention is the molding compound as a curable base resin and as a hardened thermoset in the powdered or granulated, hardened thermoset mass contains the same thermoset. Because of the same mechanical and physical properties as in particular Thermal expansion behavior, shrinkage properties and elasticity were particularly in the case of these In the preferred form of the invention, such an uneven surface is not to be expected at all. From a nice surprise effect but must also be spoken

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if the base resin and that contained therein according to the invention Plastic powder or granulate consists of different plastics, as there are also deviations here are low in the mechanical or physical properties mentioned.

The rustic, stoneware-like appearance of the. through commitment the articles produced according to the invention can only be fully achieved if either the basic molding compound or the plastic powder it contains or granulate has the typical color of ceramics or stoneware. The rest of the molding compound must be appropriately matched in color.

However, the invention is not limited to molding compounds for the production of articles with the appearance of stoneware. You can also make articles with a completely different appearance, for example if you have base resins and the ones in them containing plastic powder or granules with so-called pop colors. To the striking "topographical" Effect (relief surface) there is also the shock effect of such color compositions. In principle, however, the invention is in no way limited to multicolored molding compounds; the "topographical" The effect is also fully apparent when synthetic resin

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The base mass and the plastic powder or granulate it contains are of the same color.

As a further technical advance to which the invention leads, it should be noted that the one obtained is not smooth surface especially for bathtubs, sinks, tiles and similar sanitary facilities means a slip resistance. Such slip resistance could be found in corresponding articles from conventional Molding mass cannot be achieved.

Moldings, which are produced by the hot-press processing of the molding compositions according to the invention are produced, also advantageously differ in the following respects of molded bodies which are manufactured with the use of pressing tools with a relief-like surface. While the pressing tools with a relief-like surface always provide identical shaped bodies, each pressed part from the composition according to the invention relates each represents a very individual look on the surface structure. This fact is psychological in terms of sales. to evaluate positively.

As curable base resins for the molding compositions according to the invention aminoplasts such as melamine, benzoguanamine, acetoguanamine, urea and phenol-formaldehyde resins are preferred, Epoxy resins, unsaturated polyester resins, iso-diallyl phthalate resins

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and mixed polyester-isodiallyl phthalate resins. If the molding compound according to the invention contains a hardened, powdery or granulated thermoset compound, the thermoset contained therein can either be the same resin as the hardenable base resin, or it can be any other thermoset. If it is in the plastic powder or granules in the present invention measured molding compound is a thermoplastic mass having a softening temperature of at least 200 ⁰ C., are, in particular saturated polyester resins such as polyethylene terephthalate, and polyamides such as nylon 6 and nylon 6,6, in question.

The plastic powder contained in the molding compound according to the invention or granulate is not limited to a material made from a corresponding thermoset mixture or thermoplastic mixture, but rather the The topographical effect and the color effect of the molded body can also be particularly pronounced when the powder or granulate consists of the pure hardened thermosetting plastic or of the pure thermoplastic.

The powder or granules can be in the form of a grain fraction or as a mixture of several grain fractions. It can also be used in the form of a grain mixture a statistical distribution of the grain sizes in the

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Molding compound are present. In the latter case it is the case Production of the molding compound according to the invention is not absolutely necessary that the powder of particles with grain, Grb'ssen below 0.1 mm is removed. It can, in principle There are cases in which the inventive Compression compound additionally also the fine dust of the hardened May contain thermosetting or thermoplastic mass.

A special effect can also be achieved in that the powdered or granulated hardened thermosetting plastics contained in the molding compound according to the invention Thermoplastic mass colorless or colored particles made of glass, ceramic or the like, in particular glass spheres contains.

The molding compound according to the invention can be made by known methods can be produced using suitable mixing equipment. So-called tumble mixers are particularly suitable. In general, the mixing process is followed by a compression stage and finally a granulation process at. A kneader with a nozzle can advantageously be used for the last two stages. The so extruded strands (spaghetti) of the finished invention ' masses of molding material become short cylinders as usual, cut.

In addition to this granulate, which is very cheap for further processing,

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Other methods can also be used for the molding compound get the "build-up granulation"; for example by tabletting and briquetting the mass Cold pressing. Is the molding compound according to the invention from the outset fairly due to its composition compact, dense texture, it is also conceivable that the powder obtained by the mixture directly is pressed.

The invention also encompasses the use of the molding compounds for the production of corresponding shaped bodies. Another subject matter is thus also a process for the production of moldings, such as dishes, ashtrays, sanitary articles or the like, from plastics with a relief-like, uneven surface by processing thermoset molding compounds according to the known hot-pressing processes, such as injection molding processes, transfer molding processes , Method using a heating press or the like, which is characterized in that a thermosetting molding compound is used which contains 5 to 50% by weight of a hardened thermosetting compound or a thermoplastic compound with a softening temperature of at least 200 ^° C. in the form of powders or granules with a grain size between about 0.1 and 3 mm.

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Example 1 - '

a) Production of a powder from a hardened melamine resin composition

370 g of a powdery melamine resin are placed in a taurine mixer (with an M: F weight ratio of 1: 1.8, flexibilized with 5% f.-CaproTactam, precondensed on a water compatibility (g resin: g water) of 1: 2.8 and accelerated with 2% diethylethanolamine acetate) with

77.8 g cellulose powder
499.0 grams of barium sulfate
49.6 g white pigment (Lithopone ¹¹ Dy lia ")

2.0 g release agent zinc stearate

0.01g Russ Printex V (10% in Lithopone "Dylia")

0.15g iron oxide yellow 0 1362 (this is a synthetic Iron (III) trihydrate)

premixed in a tumbling shear for 1 h.

This mixture is dissolved in a 75-80 ⁰ C Ko-kneader preheated Fa. Buss, Pratteln, trade name PR-46, melted and compressed. The plastic mass is "pressed via a discharge screw through a perforated nozzle, where the emerging" spaghetti "is cut to a uniform length with a rotating knife. The resulting granulate is ^{hardened for 3 h at 150 °} C. and then ground a screening plant divided into the different grain sizes "

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b) Production and further processing of a molding compound according to the invention

The ingredients listed under a) for the cured melamine resin composition are added together in the same mixing ratio (as under a)) in a total amount of 1000 g. Then 250 g of a sieve fraction between 0.5 and 0.8 mm of the hardened, ground product according to a) are added. After mixing in the tumble mixer, the mixture is melted by the kneader as described under a), compressed, pressed through the nozzle and the emerging "spaghetti" cut to a uniform length of about 20.2 cm. A part of this granulate is processed into plates under a heating press. Another part is used for the production of test bars of dimensions 120x15x10 mm (at 150 ⁰ C, 8 min.).

The plate has a decidedly "gritty" surface on.

The following test values resulted, which are definitely can be described well and normally:

Flexural strength (DIN 53452) 856 kp / cm ²

Impact strength (DIN 53453) 4.9 cmkp / cm ²

Dimensional stability in the heat

according to Martens (DIN 53458) 122 ⁰ C

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Example 2

In a porcelain ball mill of 4.5 1 content

150 g of a styrene-free, unsaturated polyester resin of BASF (brand name: Palatal P 10 M)

with
50 g iso-diäUylphthälat "prepolymer"

2.5 g of lauric acid
341.5 g chalk flour OMYA BSH
50 g titanium dioxide RN-56
6 g tert-butyl benzoate 80% in dioctyl phthalate

Balled together with 1.25 kg porcelain balls for 4 hours.

The balls are then removed from the ball mill and 400 g of the synthetic resin powder prepared according to Example la) (grain fraction 0.5-0.8 mm) were added. Thereafter the ball mill is rotated again for 1 hour and then emptied.

After compression and granulation of the molding compound in the kneader According to the description in Example 1, part of this granulate becomes a plate and another part becomes Test rods under the same conditions as in example 1, processed. The plate is characterized by a relief-like surface. The following test values are determined:

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Flexural strength (DIN 53452) 432 kp / cm ²

Impact strength (DIN 53453) 2.85 cmkp / cm ²

Dimensional stability in the heat

according to Martens (DIN 53458) 153 ⁰ C

Example 3

In a porcelain ball mill with a capacity of 4.5 liters

154 grams of triglycidyl isocyanurate

146 g of a hardener, which is prepared as specified below,

493 g of barium sulfate powder
5 g zinc stearate

5 g surgical wax (trade name of the Farbwerke

Hoechst A.G. for a partially saponified ester wax)

5 g of a red monoazo dye (coupling of di- 'azotized 2-methyl-4-chloroaniline to 2,3-hydroxynaphthoic ^{acid (2'-methyl-4 1} -chloranilide)

ground together with 1.25 kg porcelain balls for 8 hours.

The balls are then taken out of the mill and 400 g of the synthetic resin powder produced according to Example la) (grain fraction 0.5-0.8 mm) were added. The ball mill is rotated again for 1 hour and then unloaded.

The resulting molding compound is processed further as described in Example 1. One made from the crowd Plate has a decidedly rustic, ceramic-like look

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Appearance. .

Particles protrude partially from the surface, and these particles are different from the color of the Base mass of the plate.

The following properties were measured on DIN bars:

Flexural strength (DIN 53452) 516 kp / cm ² impact strength (DIN 53453) 3.85 cmkp / cm

Dimensional stability in the heat
.according to Martens (DIN 53458) 117 ⁰ G

Manufacture of the hardener

340.6 g (2 mol) of 3-aminomethyl-3,5,5-trimethylcyciohexylamin are heated in a 1 Lt reaction vessel at 120 ⁰ C and under continuous stirring for 30 minutes. 377.3 g of bisphenol-A-Epoxidharζ (5 , 3 epoxy group equivalents / kg) was added dropwise and mixed in. The solid adduct obtained after cooling is pulverized.

Properties: softening point 63 ⁰ C

Melting point 78 ⁰ C

Amino group equivalents / kg 4.18.

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Example 4

Put in a porcelain jug with a capacity of 4.5 liters, together with 2.5 kg porcelain balls. ''.

370 g of the melamine resin described in Example 1

76 g cellulose powder

500 g of barium sulfate

50 g white pigment (Lithopone Dylia)

2 g zinc stearate

2 g of the red monoazo dye used according to Example 3

Globular for 8 hours.

The powder thus obtained is then placed in a tumble mixer and 250 g of uncolored crastin (polybutylene terephthalate; Grain size approx. 2 χ 2.5 mm) added and twisted.

The molding compound obtained in this way can be used as described under Example 1 be pressed.

Plates pressed from it show a similar decorative effect as the samples according to the patent examples 1-3 are produced. What is particularly impressive here is that the particles protruding in relief form a have a different color (namely yellowish) than the red matrix. This creates the rustic ceramic appearance underlined.

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Example 5 Mixture A
The following mixture is prepared in an agitator:

1520 g of diallyl phthalate prepolymer (Dapön 35 from the company Food Machinery Corp.)

40 g diallyl phthalate monomer 60 g tert. Butyl perbenzoate 40 g calcium stearate

20 g carnauba wax (consisting of cerotic acid myricyl ether, free cerotic acid and myricyl alcohol)

180 g of antimony trioxide

60 g Cereclorwax 70 (trade name, the company ICI for a chlorinated paraffin)

2036 g glass fibers (ground)

This premix is Buss, plasticized at about 80 ⁰ C by a co-kneader PR-46, shaped by a die to form spaghetti and cut mm at DUsenaustritt with a knife to a lens-shaped pellets of about 2x1. These granules are hardened under the same conditions as the granules according to example la). (These granules are referred to herein as "Granules G" ).

Part of the granulate G is ground in a hammer mill. The resulting powder is referred to here as "Granulate F" . The sieve analysis gives the following values:

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-ClOO micron 25th 7th
/ ο 2350424 < 600 micron 17th 7th
/ ο > 100 <: i6oo micron 27 7th
la > 600 > 16OO micron 31 7th
/ ο -

Mixture B

Mixture B corresponds to the powder as it is produced according to Example 4, without crastin.

To 1000 g of this mixture B, 100 g of the granules G and
200 g of the granules F are given.

The molding compound obtained in this way is mixed well in a tumble mixer as described in Example 1, by means of of the co-kneader compacted and granulated and finally processed into a plate under the heating press. Even Because of the different color, this plate is similar to the particles that partially protrude from the surface and the base mass is a plate made of ceramic material.

The following properties are measured on DIN bars:

Flexural strength (DIN 53452) 283 kp / cm ² impact strength (DIN 53453) 20 cmkp / cm ²

. Dimensional stability under heat according to Martens (DIN 53458) 99 ⁰ C.

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Claims (22)

CLSA-GElGY AG - 19 - patent claims 1. molding compound for the production of molded bodies, such as dishes, Ashtrays, sanitary ware odt_ * the like with a relief-like, uneven surface according to known Hot pressing processes, such as injection molding processes, transfer pressing processes or processes using a heating press containing a curable thermoset and usual.Mix additives, characterized in that, • that it contains 5 to 50% by weight of a hardened thermoset compound or a thermoplastic compound with a softening temperature of at least 200 ^° C. in the form of powders or granules with a grain size between 0.1 and 3 mm. 2. molding compound according to claim 1, characterized in that it contains 10 to 35% by weight of the powdery or granulated, hardened thermosetting or thermoplastic mass contains. 3. molding compound according to claim 1, characterized in that it contains 5 to 50 wt .-% of a hardened thermoset compound in the form of powders or granules. 409817 / 1.01 5 CIBA-GEIGY AG - 20 - 4. molding compound according to claim 3, characterized in that it is used as a hardenable base resin and as a hardened one Duroplast in the powdery or granulated, hardened thermoset compound contains the same thermoset. 5. molding compound according to claim 3, characterized in that it is used as a curable base resin and as a hardened one Duroplast in the powdered or granulated, hardened Thermosetting compound contains various thermosetting plastics. 6. molding compound according to claim 1, characterized in that the powdery or granulated contained in it, hardened thermoset or thermoplastic mass, in addition to the pure plastic component, known additives, such as dyes, fillers, release agents, stabilizers, waxes or the like. 7. molding compound according to claim 1, characterized in that the powdery or granulated contained in it, hardened thermosetting or thermoplastic mass is present in the form of one or more grain fractions. 8. molding compound according to claim 1, characterized in that the powdery or granular contained in it £ 09817/101 5 C1BA-G £ IGYÄG - 21 - lined, hardened thermoset or thermoplastic mass is in the form of a grain mixture with a statistical distribution of grain size. 9. molding compound according to claim 1, characterized in that the powdery or granulated, hardened thermosetting or thermoplastic compound contained therein contains colorless or colored particles of glass, ceramic or the like, in particular glass spheres. 10. molding compound according to claim 1, characterized in that it is a MeIarainharz as the curable base resin (thermoset) contains. 11. molding compound according to claim 1, characterized in that that it is an epoxy resin, an unsaturated polyester resin, as the curable base resin (thermoset) Iso-diallyl phthalate resin or a mixed polyester-iso-diallyl phthalate resin contains. 12. Process for the production of moldings, such as dishes, Ashtrays, sanitary articles or the like, made of plastics with a relief-like, uneven surface by processing thermoset molding compounds according to the well-known hot-pressing process, such as injection molding 409817 / 1.0 1 5 molding method, transfer molding method, method using a hot press or the like, characterized in that use a thermosetting molding compound comprising 5 to 50 wt .-% of a cured Duroplastenmasse or Therraoplastenmasse having a softening temperature of at least 200 ⁰ C in Contains the form of powders or granules with a grain size between about 0.1 and 3 mm. 13. The method according to claim 12, characterized in that that a thermoset molding compound is used, which contains 10 to 35% by weight of the powdered or granulated, contains hardened thermoset or thermoplastic mass. 14. The method according to claim 12, characterized in that that you use a thermosetting molding compound, which Contains 5 to 50% by weight of a hardened thermoset mass in the form of powders or granules. 15. The method according to claim 14, characterized in that that a thermoset molding compound is used, which is used as a hardenable base resin and as a hardened thermoset in the powdered or granulated, hardened Thermoset compound contains the same thermoset. 409817/1015 CiDA-GcIGYAG - 23 - 16. The method according to claim 14, characterized in that a thermosetting molding compound is used which as a hardenable base resin and as a hardened thermoset in the powdered or granulated, hardened form Thermosetting compound contains various thermosetting plastics. 17. The method according to claim 12, characterized in that that the powdery or granulated, hardened thermosets or Thermoplastic mass apart from the pure plastic component known additives such as dyes, fillers, leveling agents, stabilizers, waxes or contains the like. . 18. The method according to claim 12, characterized in that the contained in the thermosetting molding compound powdery or granulated, hardened duro- ρlast or ■ thermoplastic mass in the form of an or several grain fractions is present. 19. The method according to claim 12, characterized in that that the powdery or granulated, hardened thermosets or Thermoplastic mass in the form of a grain mixture with a statistical distribution of the grain size is present. AO9817 / 1016 CiBA-GEiGYAG - 24 - 2350A24 20. Procedure according to. Claim 12, characterized in that the contained in the thermosetting molding compound powdered or granulated, hardened thermosetting plastics or thermoplastic mass colorless or colored particles of glass or the like, in particular Contains glass balls. 21. The method according to claim 12, characterized in that a thermosetting molding compound is used, "which contains a melamine resin as the curable base resin (thermoset). 22. The method according to claim 12, characterized in that a thermosetting molding compound is used which . as the curable base resin (thermoset) an epoxy resin, an unsaturated polyester resin, an iso-3iallyl phthalate resin or a mixed polyester-Iβόα contains iallyl phthalate resin. 409817/1015