DE2207754A1 - Plastic matnze and resin compound for use in their manufacture - Google Patents

Description

A-8

Nippon Paint Co ", Ltd. No. 1-1, Kita 2-chome, Oyodo-cho, Oyodo-ku, Osaka-shi, Osaka-fu / japan

Plastic mold and resin compound for use therefor

Manufacturing

The invention relates to a plastic die and a resin composition for use in their manufacture In particular, the invention relates to a plastic matrix for producing a relief pattern on the Surface of a resin material and a resin composition for use in their manufacture

The creation of a relief pattern on the surface of a resin material has hitherto been used in a variety of fields such as plastic production as well as in the manufacture of printing plates using a die, as a material for the manufacture of a A metal or a plastic is usually used for the die. In the case of using a metal, this is

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Manufacture of the die is extremely complicated and very expensive. In the case of using a plastic, the manufacture is Although the die is simple, it is necessary to use high temperatures for molding an original plate made of a material that is not thermally stable, such as plastic, for damage or deformation subsceptible. Therefore, only a metal engraving or a relief can be used as the original plate. If a plastic matrix, which is capable of producing a pattern from an original plate made of a heat-stable material, for example made of metal or a thermally unstable material, such as plastic, is able to transfer, such a die can be extremely valuable. In the effort to find an ideal plastic matrix it was found that the use of some polymerizable Resin with a polymerization catalyst decomposable at lower temperature and one at higher temperature Temperature decomposable polymerization catalyst enables the creation of such a plastic matrix. It it should be noted that for the production of a plastic matrix two types of catalysts as mentioned above have never been used in combination.

According to the invention, there is thus a plastic matrix provided that are molded at a relatively low temperature for a relatively short time so that an original plate cannot be

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is damaged or deformed, even if it is made of a material with poor thermal stability «

The plastic matrix according to the invention is prepared by a resin composition consisting of (a) a thermosetting, polymerizable, modified 1,2-polybutadiene diol resin, (b) at least one polymerisation catalyst which decomposes at a lower temperature, (c) at least one polymerisation catalyst which can be decomposed at a higher temperature and (d) a filler a film is formed, the film is formed in contact with an original plate and after removing the Original plate is completely hardened.

The resin composition used for the preparation of the plastic matrix according to the invention contains (a) a thermosetting, polymerizable, modified 1,2-polybutadiene diol resin, (b) at least one polymerization catalyst which is decomposable at a lower temperature, (c) at least a polymerisation catalyst decomposable at elevated temperature and (d) a filler.

As the modified 1,2-polybutadiene diol resin, a that can be used which can be described by the following formula:

CII = CH ₂ χ OH = CH ₂

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wherein A is an extender group, such as a diisocyanate residue (for example 2,4-toluene diisocyanate residue, 2,6-toluene diisocyanate residue, 1 _t h benzene diisocyanate residue, diphenylmethane diisocyanate residue, 1,5-naphthalene ^{diisocyanate residue), A 1 is} a modifier group, for example a hydrogen atom or a

+
olefinically unsaturated alkanoyl group, preferably with 3 to 5 carbon atoms (for example acryloyl, methacryloyl) and η is a natural number from 7 to ^ k . The symbol χ means a natural number which is such as to keep the modified 1,2-polybutadiene diol resin liquid. Namely, the modified 1,2-polybutadiene diol resin to be used according to the invention must be liquid. Among the various resins covered by this formula, the resin extended with a toluene diisocyanate radical is particularly preferable. Other examples of the resin are, for example, in Chetn. & Eng. News, Vol. ^ 7, No. 14, page ^ 3 (1969).

By using the modified 1,2-polybutadiene diol resin According to the information above, curing can be achieved in a short time during the manufacture of the plastic matrix will. In addition, the plastic matrix obtained in this way is quite heat-stable

The polymerization catalyst decomposable at a lower temperature may be one which operates at about 50%

+ (ethylenic uneaturation containing)

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is decomposed up to 100 C, specific examples are benzoyl peroxide, Lauroyl peroxide, t-butyl peroxyisobutyrate, azobisisobutyronitrile etc. The polymerization catalyst decomposable at a higher temperature may be one used in about 100 to 150 C is decomposed. Specific examples are dicumyl peroxide, t-butyl peroxybenzoate, cyclohexanone peroxide, t-butyl peroxylaurate, etc. If these catalysts are solid, such as benzoyl peroxide or dicumyl peroxide it is preferably in the form of a dispersion in a conventional plasticizer (e.g. dioctyl phthalate, Dibutyl phthalate) The polymerization catalyst decomposable at the lower temperature and that at the higher temperature used Temperature-decomposing polymerization catalysts are normally each in an amount of about 0.5 wt · - ^ », related based on the weight of the modified 1,2-polybutadiene diol resin used.

By using the two kinds of catalysts in common, molding can be carried out in one enables semi-hardened state or final hardening in a short time

Be used as filler may be silica (silica), clay, talc, calcium carbonate, glass wool (glass flake) zinc white, alumina, magnesia, calcium, etc. _e The addition of filler is usually from about "100 to 500 wt .- $, based on the Weight of the modified

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1,2-polybutadlenediol resin "

The purpose of adding the filler is to give the resulting resin composition the flowability required for molding to lend »It also serves to reduce the shrinkage of the plastic matrix made from the resin compound when it hardens to prevent.

The resin composition can contain any additives, such as a fiber reinforcing material, in addition to the four essential components mentioned (e.g. glass fiber, rayon fiber, tungsten fiber, molybdenum fiber, boron fiber), a surface active agent based on silane (for example 7-methacryloxypropyltrimethoxysilane, Vinyltriethoxysilane, vinyltris (ß-methoxyttthoxy) silane), a polymerization inhibitor (e.g. 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (6-t-butyl-m-cresol), ^, 4 "-butylidene-bis (6-t-butyl-m-cresol) and / or a Contain pigment (e.g. iron oxide pigment, chrome green)

The fiber reinforcement material is used to mechanical strength of the finished plastic matrix increase, and its proportion by weight is about 5 to 30 wt .- ^, based on the weight of the modified 1,2-polybutadiene diol resin. Among various fiber reinforcement materials, for the examples given above, glass fibers, especially short-cut ones

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Glass strands (glass chopped strand) from approx. 3 to 13 mm Length, preferable.

The function of the silane surfactant (silane coupling agent) consists in increasing the compatibility of the modified 1,2-polybutadiene diol resin with any fiber reinforcement material and filler, so that the mechanical strength and the separability the molded sheet or sheet is improved "usually the amount of the surface-active agent based on silane is approx. from 1 to 10% by weight based on the Weight of modified 1,2-polybutadiene diol resin.

The polymerization inhibitor is used to prevent unfavorable hardening or excessive hardening of the modified 1,2-polybutadiene diol resin on storage or to prevent when molding; the amount used is usually about 0.1 to 1 wt .- ^, based on the Weight of modified 1,2-polybutadiene diol resin.

The addition of the pigment, usually in amounts of about 0.5 to 5 wt .- ^, based on the weight of the modified 1,2-polybutadiene diol resin, is used to improve the workability when molding letters.

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The resin composition can also contain any other additives, such as an internal release agent (e.g. zinc stearate, calcium stearate, powdered polyethylene) or a metal powder (e.g. aluminum powder, iron powder), The internal release agent is used to facilitate the loosening of the molded Foil or board from an original plate ο »the like · to facilitate and can normally in proportions of about 1 to 10 wt .- ^, based on the weight of the modified 1,2-polybutadiene diol resin be used. The metal powder effectively prevents the finished ones from shrinking Plastic matrix, if it is in proportions of approx · 1 to Wt .- ^ b, based on the weight of the modified 1,2-polybutadiene diol resin is used.

If the resin mass contains an electrically conductive pigment (for example, red iron oxide, graphite) or metal powder (e.g. aluminum powder, iron powder), the finished plastic matrix made from it can be methods known per se are treated galvanically.

The essential and optional components according to the above list are mixed using a conventional mixer, for example a kneader, mixed to obtain a uniform resin composition. The mixing temperature need not be higher than the decomposition temperature of the one at the lower temperature

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decomposable polymerization catalyst and can usually be from about 40 to 100 ° C.

The resin composition thus obtained is then, usually at low temperature, on a conventional molding machine, for example a molding press, a natural roller, in an extruder or by means of an injection molding or Transfer molding machine processed into a resin sheet or sheet. Since this resin sheet or sheet turns into a rubber-like State, it can be replaced by placing it on a supporting material such as a metal plate (e.g. steel plate, Aluminum plate) or stiffened on a plastic plate, if necessary, by means of an adhesive.

The resin sheet or sheet thus obtained can be molded as it is or after being half-cured. To the Half of the hardening is achieved when the resin film or sheet is in the region of the decomposition temperature of the Held lower temperature decomposable polymerization catalyst. Such half-curing is advantageous, because it prevents the formation of voids in the molded sheet or sheet, which occasionally can occur when the resin composition is highly flowable, and because it causes the peeling of the molded sheet or Plate relieved from an original plate, so that molding is possible at low temperature. Also will

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half hardening means the time for post-hardening shortened. From a practical point of view, the degree of half or partial curing in a suitable manner using a Shore hardness meter (durometer) A. Be determined »Particularly advantageous, but not the decisive factor is a hardness in the range of values from 20 to 80 (20 ° C).

The molding of the resin sheet or sheet in contact with an original plate may be with heating or with Room temperature can be carried out · In the latter case, curing is carried out by heating to a temperature equal to or greater than the decomposition temperature of the at a higher temperature decomposable polymerization catalyst brought to an end.

According to the invention, the molding temperature is usually about 110 to 140 C. If the original plate is too large or sensitive to heat, molding can be carried out at room temperature. A comparison with the Molding temperature using a conventional resin sheet or sheet shown in Table 1 shows that the Molding temperature when using a resin sheet or sheet according to the invention is considerably lower.

The process for manufacturing the die consists of two stages, namely the molding of the die

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and that of post-curing. At the stage of forming the Die, the hardening is interrupted at a state in which the product is not yet in a solid state but remains in a gel state. This condition is referred to as "half hardening" in the present description designated. After removing the original plate, the hardening of the molded film is carried out in the post-hardening stage completed by heating to approx. 160 to 200 C, a plastic matrix being obtained.

Since the production of the die takes place in two work stages in the manner described, the original plate is used never damaged or deformed. Furthermore, the plastic matrix carries that which has been faithfully transferred from the original plate Image because the resin sheet has excellent flowability after molding. The plastic matrix also stands out characterized by excellent thermal stability and mechanical strength.

If desired, the plastic matrix can be made with curved Surface to be produced. In order to achieve this, the film or sheet is used after molding and before post-curing curved in a corresponding manner and only then post-cured.

It can also increase the abrasion resistance and the

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mechanical strength of the plastic matrix on their Surface can be provided with a galvanic coating, this can be done by making the resin compound Plastic matrix, which contains an electrically conductive material, after post-curing in an electrolyte bath, for example in an aqueous copper sulphate solution, in a conventional manner under electroplating conditions is treated «By using such a metallic coated die, it is possible to produce a far greater number of making duplicate plastic sheets by molding · This is particularly useful when making reliefs (Embossing) on a plastic material

As examples of suitable polymers for casting plastic duplicates using the plastic matrix according to the invention can be named! Polyolefins (e.g. polyethylene, polypropylene), polyvinylidene chloride, Polyether, polyacrylate, polymethacrylate, polyamide, polycarbonate, Polyhydroxy ethers, etc. Other vinyl polymers, copolymers (Copolymers) as well as mixtures thereof can also be used.

Practical and currently preferred examples of implementation of the invention are illustrated in FIGS The following examples are given in which proportions are expressed in parts by weight

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example 1

(1) Production of the resin tub:

A modified 1,2-Polybutadiendiolharz (molecular weight of 1,2-polybutadiene diol: 2000; diluent: 2,4-Toluoldiisocyanatj "Nisso PB TE2000" from ₀ Nippon Soda Co., Ltd.) (100 parts), 2,6- Di-t-butyl-p-cresol (0.1 part), '»A'-methacryloxypropyltrimethoxysilane (4.5 parts), silica (350 parts), zinc stearate (4.5 parts) and iron oxide pigment (1 part) are in mixed in a pressure kneader at a temperature of 55 to <50 C for one hour. After the addition of t-butyl peroxybenzoate (4 parts), benzoyl peroxide (1 part), dispersed in dioctyl phthalate (14 parts), and chopped glass fiber strands of 3 mm in length (15 parts) ₄ , mixing is carried out at a temperature of

_o + -

55 to 60 C to obtain a resin composition continued

(2) Production of the resin film or sheet:

On a lower platen of a flexographic compression molding press a release paper and on both sides of the same spacer strips (bearers) of 3 mm thickness are placed. A 0.3 mm thick tin plate is placed on the release paper as a base plate, and the resin composition is applied thereon. After placing a release paper on the resin compound, the lower plate is lifted for molding in 10 seconds.

- for 13 + 5 minutes

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The molding takes place at room temperature under a pressure of 20 kp / ctn and takes one minute. The release paper is removed from the thus formed film, and the formed film is heated with the tin plate at 80 ° C. for 10 minutes. A resin film 2.7 mm thick and with a Shore A hardness of 20 to 8O (20 ° C.) is obtained.

(3) making the plastic die;

A flexographic molding press is used for molding, its lower plate at 130 C and its upper plate 125 ° C. A release paper and spacers (bearers) 2.7 mm thick are placed on both sides of the release sheet on the lower plate. On the release paper the resin film, and a photopolymer engraving is placed on it. The photopolymer engraving and the spacers are covered with a release paper, and then the bottom plate is raised in 10 seconds for molding · The Forming takes place for 1.5 minutes at a pressure of 20 kgf / cm. The photopolymer engraving is removed · The Shaped film is then heated using a temperature of 180 ° C heated flexographic compression molding press for one minute and this gives a plastic die of 2.5 mm Thickness · The plastic matrix can be used to create a plastic duplicate plate by pouring it with polypropylene «

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Example 2

(1) Making the resin mass:

A resin composition is prepared as described in Example 1 (1), but using dicumyl peroxide (k parts) instead of t-butyl peroxybenzoate (k parts).

(2) Making the resin sheet:

The resin composition thus produced is as in Example 1

(2) Formed under pressure into a resin sheet of 3 mm thick supported on a tin plate.

(3) Production of the plastic matrix:

Using this resin sheet, a plastic die is produced as in Example 1 (3). These Plastic die can be used for molding polypropylene to make a duplicate plastic sheet.

Example 3

(1) Making the resin mass:

Am modified 1,2-polybutadiene diol resin (molecular

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weight of the 1,2-polybutadiene diol: 2000; Extender:

2, ^ - toluene diisocyanate "Nisso PD TE2000" from Nippon Soda Co., Ltd.) (100 parts), 2,6-di-t-butyl-p-cresol (0.1 part), T'-methacryloxypropyltrimethoxysilane ( 4.5 parts), silica (100 parts), clay (250 parts), zinc stearate (4.5 parts) and iron oxide pigment (1 part) are in a pressure kneader at a temperature of 55 bi. ⁸ Mixed at 60 C for one hour After adding t-butyl peroxybenzoate (k parts) and benzoyl peroxide (0.5 part) dispersed in dioctyl phthalate (7 parts), mixing is continued at a temperature of 55 to 60 C for 5 minutes, whereby a resin mass is produced.

(2) Making the resin sheet:

Shaping is carried out using a T-shaped extruder with a diameter of 76 mm and the ratio L / D = 16. The lip width and the distance between the T-dies are 400 mm and 3 mm, respectively. The resin mass obtained in the manner described is extruded at room temperature with a screw speed of 20 rpm.The extruded film is stacked on a 0.3 mm thick tin plate with an adhesive in between and gives a 3 mm thick resin sheet carried on the tin plate. The Shore hardness A is k0 to 80 (20 ° c).

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(3) Production of the plastic matrix:

The molding is done using a flexographic molding press at room temperature. A release paper is placed on the lower plate and on both sides of the release paper now 3 thick spacers are attached »The one according to the above The resin film produced in the description is placed on the release paper, and a photopolymer engraving is made on this placed · After covering the photopolymer engraving and the spacer with a release paper, the bottom plate lifted in 10 seconds for molding. The molding takes place for 5 seconds under a pressure of 20 kp / cm at room temperature. The photopolymer engraving is removed. The molded sheet is then 1.5 minutes heated at 180 ° C. for a long time using a flexographic compression molding press, and a plastic die is obtained of 3 mm thickness «The plastic matrix can be used for casting of polypropylene to make a duplicate board made of plastic can be used »

Example 4

(1) Production of the Ilarz mass:

A modified 1,2-polybutadiene diol resin (molecular weight of 1,2-polybutadiene diol: 2000; Extender: 2,4-toluene diisocyanate; "Nisso PB TE2000" from Nippon

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Soda Co., Ltd.) (100 parts), 2,6-di-t-butyl-p-c: resol

(0.1 parts), ^ - methacryloxypropyltrimethoxysilane (^, 5 parts),

Clay (350 parts), zinc stearate (k, 5 parts) and iron oxide

pigment (i part) are in a pressure kneader at a

Mixed at a temperature of 75 to 100 C for two hours « After cooling to 70 ° C., t-butyl peroxybenzoate is obtained

(k parts), glass fiber strands cut to a length of 3 mm (10 parts) and dispersed in dioctyl phthalate (7 parts)

Benzoyl peroxide (0.5 part) added. Further mixing

takes place at a temperature of 60 to 70 ° C for 10 minutes long and results in a resin mass

(2) Making the resin sheet:

Shaping is done using a T-extruder with a diameter of 76 mm and the ratio L / D = The gap width and the distance of the T-nozzle are 100 mm and 2.5 mm, respectively. The resin composition obtained in the above manner is extruded at room temperature at a screw speed of 20 rpm. The extruded sheet is laid (stacked) on a 0.3 mm thick polyester sheet, and a resin sheet of 2 mm thick superposed on the polyester sheet is obtained .

(3) Manufacture of the plastic matrix

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The resin film produced in the manner described is, however, as in Example 1 (3) ι using 2 mm thick spacers to a 2 mm thick plastic matrix shaped. The plastic matrix can be used for casting polypropylene to create a duplicate panel Plastic can be used.

Example 5

In the production of a plastic matrix according to Example 3 (3) is the shaped film after half curing on the outer surface of an iron pipe or hollow cylinder 200 mm in diameter and heated to 200 C for 1.5 minutes to fully cure. The one so prepared Plastic mattress has a curved surface. You can make a plastic duplicate plate for pouring off Polypropylene can be used.

Example 6

A plastic matrix is produced as in Example h (2) and (3) using the same resin composition as in Example k (1), but with an additional content of reduced iron powder (5 parts). The plastic matrix is cleaned with gasoline and galvanically copper-plated under the following conditions to achieve a copper-plated matrix.

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20 22G7754

Concentration of the aqueous copper sulfate solution:

250 g / L

Concentration of the hydrogen sulfide acid 60 to ¹ JO

ε / h

O.

Temperature: 20 C Anode current density: 2 to 5 A / dni

The conditions under which the plastic matrices made in accordance with the invention and conventional methods are in the following comparative table summarized:

Tables

lir. Piastil; -Matrizo

Forming Forimings Time Usable

temperature time *) may be changed to the original

Ilerstel-]) latte

lung * *)

(J enie ß 110 ... ΐΛθ " C 1 , 5 J Metal tables the I]] in min 1 l'Jrf i n- Photopoly manure Kauiiitetn- 5 lake 2, 5 "ι η merisat- pora tui ' engravings

was standing

1 <3e huik uJl «I (, on- y.00 1 ■, () "( 1' dl y; ₅ II, j] < S. JS t «! 1- J ' t : i ta lid in) I. V. C in the (I ' hf IJO ;; 3 · ' 1 (>

2.5 im j π J) mi η

Metal sticks

1 ') min

2Ü9Ü37 / 1

(y in y n

Me taJ1-s ti ehe

BATH ORIGINAL

*) Time required for molding when the resin film and the original plate come into contact;

**) Time required for shaping, post-curing and cooling in case no.1 and for shaping and cooling in case no, Z and 3.

From the table above it can be seen that the plastic matrix according to the invention can be molded at a temperature significantly lower than the temperature required for molding according to conventional methods (for example at room temperature). The original plate is therefore hardly damaged or deformed. It also emerges from this that the time required for dividing the plastic matrix according to the invention is considerably shorter than according to conventional methods. The operational efficiency is therefore largely increased. In addition, it can be seen that the usability of the original plate in the method according to the invention is not subject to such restrictions as in the conventional Vex methods. According to the invention, an original plate can be used to produce the plastic matrix, which is made of a material with far less thermal stability ₀

Vix the invention eliminates various disadvantages of conventional methods, it takes into account the modern endeavors in the field of printing technology by one

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Papiermaohfc ^ matrizen-halide plate process to one Plastic die-plastic duplicate plate process to pass over. In addition, the invention makes it possible to produce a plastic matrix with a curved surface, by curving the shaped sheet or sheet and post-curing this curved product. Such a plastic matrix Can be used as a roller for molding a plastic decorative panel or as a textile printing roller

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Claims (1)

Claims 1. iiarziiiasse, characterized in that it consists of (a) a thermosetting, polymerizable, liiodii'isiert 1,2-polybutadiene diol resin, (b) at least one decomposable at a lower temperature
Polymerization catalyst, (c) at least one at
a higher temperature decomposable polymerization catalyst and 2 resin composition according to claim 1, characterized in that the heat-insulating, polymerizable, modified 1,2-polyhydric diol resin is a polymerizable liquid
Resin is that with an elongated 1,2-Polybulafliendiülkpl te with intermediate stretching group and a modi iiz i erendcu group at each of the two ends of the Ke t 1 ν i \ uhi 1 de L is. j, iiarümuij.'io narh / iiisprucli I, characterized in that dci at ii a temperature
νου ri "i <i I j 8 10O C ^ is replaceable .. ■ 'ι. ii;! rzin; * HSi>n; u Ii, insjiruch 1 _V thereby gpkeimzeichne t, dni .. (1 ( ¹ J "bi'i liiili'MPi j '« MnjH'i * a t-ui "zei'sot zliaro Polymerisa t J huh— Iwi ι aJ λ ■ -? <t ι ·· »in soldier is, (1 ( ¹ I 'at a temperature 2 0 9 8 3 7/1 U 7 h from about 100 to 15O C is decomposable. 5. Resin composition according to claim 1, characterized in that the filler silica, clay, talc, calcium carbonate, glass flakes (glass wool), zinc white, clay, talc earth or calcium silicate. 6, resin composition according to opposition 1, characterized in that they also have fiber reinforcement material, a surface-active one * Silane coupling agent contains a polymerization inhibitor and a pigment. 7 · Resin composition according to claim 1, characterized in that the ratio between the thermosetting, polymerizable modified 1,2-polybutadiene diol resin, the at the lower temperature decomposable polymerization catalyst, the higher temperature decomposable Polymerization catalyst and the filler approx. 100 j 0.5 to 10: 0.5 to 10: 100 to 500 in parts by weight amounts to. 8. Resin film, sheet or sheet produced from the resin composition according to claim 1. 9. Resin film produced from the resin composition according to claim 7, board or track. - 24 - 209837/1076 10, Resin film made from the resin composition according to FIG. 1, -board or sheet, which is supported on a carrier material. 11, resin film, sheet or sheet according to claim 10, characterized in that characterized in that the supporting material is a metal or Plastic plate is. 12, a method of making a plastic matrix, thereby characterized in that the product according to claim is molded on an original plate and after removal the original plate is post-cured. 13 · Method according to claim 12, characterized in that molding at a temperature of around 110 to 14O C. he follows. 14. The method according to claim 12, characterized in that molding after half (partial) hardening at 50 takes place up to 100 C at room temperature. 15 »Method according to claim 12, characterized in that the molding after half (partial) hardening at a temperature of approx. 50 to 100 C at a temperature of approx. 110 to 14O ° C is carried out. - 25 - 209837/1076 16. The method according to claim 12, characterized in that that the post-curing is carried out at a temperature of about 16O to 200 ° C. 17 · The method according to claim 12, characterized in that the shaped film, sheet or web is curved after shaping and then subjected to post-curing. 18. The method according to claim 12, characterized in that the plastic matrix is electroplated to produce a coating on its surface. 209837/1076