JPS6178807A - Production of synthetic resin molding having surface excellent in scratch resistance and antistaticity - Google Patents

Abstract

PURPOSE:To produce a synthetic resin molding excellent in scratch resistance and antistaticity, by forming a specified resin film on the molding surface of a mold, pouring a base resin material into the mold and polymerizing the material to transfer the film to the material. CONSTITUTION:A film-forming resin material is obtained by mixing 90-99.8wt% polymerizable compound having at least two (meth)acryloyl groups in the mole cule [e.g., diethylene glycol di(meth)acrylate] with 10-0.2wt% polymerizable acidic phosphate of formula I (wherein R1 and R3 are each H or methyl, R2 is H or a group of formula II, and m and n are each 1-5). Said resin material is applied to the molding surface of a glass or meallic mold and cured by polym erization to form a 1-100mum-thick film, and a base resin material comprising a polymerizable unsaturated monomer containing at least 80wt% methyl methacrylate is poured into the mold and polymerized to transfer the preformed film to the side of the base resin. In this way, a synthetic resin molding of a thickness of 0.2-20mm can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a synthetic resin molded article having a surface with excellent scratch resistance and antistatic properties.

[Prior art]

Currently, many synthetic m-finger molded products are on the market, and although they have many excellent properties, they generally have low surface hardness and low scratch resistance, so when processing or transporting the product: Scratches easily occur on the surface of plastic products, which not only damages the product value, but also removes dirt such as dust and chips that adhere to the surface of plastic products during use with a cloth. This has the fatal disadvantage that it is easy to cause abrasion scratches due to collisions with other objects, and in extreme cases, these scratches can cause the optical properties to be lost, making it completely unusable.

To address this problem, several methods have already been used industrially to form a scratch-resistant film on the surface of synthetic resin molded products, and the problem has been practically solved in many application fields. ing.

However, in applications such as instrument dials and see-through panels, there is an extremely strong demand for synthetic resin molded products that have not only scratch resistance but also antistatic properties. However, with the prior art, a synthetic resin molded product having both scratch resistance and antistatic ability that satisfies market requirements has not been obtained industrially.

That is, for example, in Japanese Patent Application Laid-open No. 55-86848,
Three or more (meth)acryloyloxy groups in one molecule (
Irradiation with active energy rays in air consisting of a compound having an acryloyloxy group or a methacryloyloxy group (the same shall apply hereinafter), a polymerizable acidic phosphate ester having 7 (meth)acryloyloxy groups, and an ethanolamine-based compound. A coating composition is disclosed that forms a film having both scratch resistance and antistatic properties.

However, the above method has the problem that when a large amount of compound is added in order to impart sufficient antistatic ability, cloudiness tends to occur due to what is considered to be bleeding on the surface. There is a need for improvement.

[Problem that the invention seeks to solve]

Under the current situation as described above, we conducted a series of discussions with the aim of providing synthetic resin molded products with sufficient scratch resistance and antistatic properties. A synthetic resin molded product that meets the above purpose can be obtained by forming a cured film on a synthetic resin molded product using a film-forming resin raw material consisting of an acid ester and a mold made of glass or metal. We have discovered this and arrived at the present invention.

[Means for solving problems]

The method for producing a synthetic resin molded article having a surface with excellent scratch resistance and antistatic properties according to the present invention uses a polymerizable compound (A) having at least two acryloyloxy groups and/or methacryloyloxy groups in the molecule (90). ~99
．． 8% by weight and the following general formula CI"I hydrogen or CH, = C-CC-C-0- (C group, R3II" is hydrogen or methyl group, m and n are integers of 1 to 5 Polymerizable acidic phosphate ester (B) represented by
A film-forming resin raw material of 0.2 to 10 weight percent by weight is applied to the molding surface of a glass or metal mold, and the film is sufficiently polymerized and cured to the extent that it will not swell or dissolve with the base resin raw material that is injected later. The method is characterized in that after forming in advance, a base resin raw material is injected and polymerized to transfer the previously formed film to the base resin side.

An enjoyable and important feature of the present invention is that on the surface of the synthetic resin molded product,
When providing a cured film with excellent scratch resistance and antistatic properties, the above-mentioned specific mold and specific film-forming resin raw material are used in combination.

Therefore, the synthetic resin molded product obtained by the present invention is
It has significantly better antistatic properties than synthetic resin molded products produced using similar film-forming resin raw material compositions in a gas such as air or in contact with a polymer film.

For this reason, in the method of the present invention, the amount of polymerizable acidic phosphate ester added is small compared to other methods, and other defects in surface properties are less likely to occur.

Specific examples of the mold used in the present invention include inorganic glass such as tempered glass, stainless steel, aluminum, and metal such as chrome plating. Glass and metal mold surfaces are generally instantaneous surfaces, but in some cases, surfaces with minute irregularities and a song glare treatment can also be used depending on the purpose.

The polymerizable compound (A) having at least two acryloyloxy groups and/or methacryloyloxy groups in the molecule constituting the film-forming resin raw material of the present invention includes polyhydric alcohol, (meth)acrylic acid, or their combinations. Specific examples include esterified products obtained from derivatives, or esterified products obtained from polyhydric alcohols, polyhydric carboxylic acids, (meth)acrylic acids, or derivatives thereof. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, and triethylene glycol.

Tetraethylene glycol, a polyethylene glycol having an average molecular weight of about 300 to about 1000.

Propylene glycol, siglopylene glycol, 1,
3-propanediol, i, 3-butanediol, 2,
3-butanediol, 1,4-butanediol, 1,5
-bentanediol, 1,6-hexanediol, neopentyl glycol (2゜2-dimethyl-1,3-propanediol), 2-ethyl-1,3-hexanediol, 2,2'-thiodietanol, 1 , 4-cyclohexane dimetatool, other dihydric alcohols, trimethylolpropane (1,1,1-trimethylolgloban), pentaglycerol (1,1,1-) IJ
methylolethane), glycerol, pentaerythritol (2,2-bishydroxymethyl-1°3-propanediol), diglycerol, dipentaglycerol, etc.

Particularly preferred compounds obtained from these and (meth)acrylic acid include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. Acrylate.

1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate.

Examples include pentaglycerol tetoxide (meth)acrylate, dipentaglycerol penta(meth)acrylate, and dipentaglycerol hexa(meth)acrylate.

Additionally, polymerizable compounds obtained from polyhydric alcohols, polyhydric carboxylic acids, and (meth)acrylic acids or their derivatives are basically the hydroxyl groups of polyhydric alcohols, polyhydric carboxylic acids, and (meth)acrylic acids. It is obtained by reacting a mixture such that both carboxyl groups are ultimately equivalent.

Preferred compounds include esterified products obtained by using dihydric alcohol, trihydric alcohol, or a mixture of dihydric alcohol and trihydric alcohol as the polyhydric alcohol, and using a dihydric carboxylic acid as the polyhydric carboxylic acid. can be given. When using a mixture of trihydric alcohol and dihydric alcohol, the molar ratio of trihydric alcohol to dihydric alcohol can be arbitrarily selected. Further, the molar ratio of divalent carboxylic acid and (meth)acrylic acid is such that the equivalent ratio of the carboxyl group of the divalent carboxylic acid to the carboxyl group of (meth)acrylic acid is in the range of 2:1 to 0:1. It is preferable. If the divalent carboxylic acid is in excess of the above range, the viscosity of the resulting ester will become too high, making it difficult to form a smear.

Examples of divalent carboxylic acids include succinic acid.

aliphatic dicarboxylic acids such as adipic acid and sebacic acid; alicyclic dicarboxylic acids such as tetrahydrophthalic acid and 3,6-nindomethylenetetrahydrophthalic acid; aromatic dicarboxylic acids such as hepthalic acid, isophthalic acid, and terephthalic acid;
Thiodiglycolic acid, thiodivaleric acid, diglycolic acid or maleic acid, fumaric acid, itaconic acid, etc. or their chlorides, anhydrides and esters can be used.

The polymerizable acidic phosphate ester (B) represented by the general formula CI which constitutes the film-forming resin raw material of the present invention is (
meth) acryloxyethyl phosphate, di(meth)
Acryloxyethyl phosphate, (meth)acryloxyglobyl phosphate, di(meth)acryloxyglobyl phosphate, (meth)acryloxybutyl phosphate, di(meth)acryloxybutyl phosphate, etc. It will be done. Among these, (meth)acryloxyethyl phosphate and (meth)acryloxyethyl phosphate contain two OH groups in the molecule.

(Meth)acryloxybutyl phosphate is particularly preferred since it exhibits excellent antistatic properties even when added in a relatively small amount.

In the present invention, a polymerizable compound (A) having a small number of traps in the molecule (both having two acryloyloxy groups and/or methacryloyloxy groups) and a polymerizable acidic phosphate ester (
The mixing ratio with B) is 90 to 99% of the polymerizable compound (A).
．． Polymerizable acidic phosphate ester (B) 0 to 8% by weight
．． It is 2 to 10% by weight.

If the amount of the compoundable acidic phosphate ester (B) added is less than 0.2% by weight, the antistatic properties of the resulting skin surface will not be sufficient, while if it exceeds 10% by weight, the antistatic properties will generally be poor. ′+
Although the anti-Z property is sufficient, the surface tends to become cloudy due to being left unattended, which is not preferable.

The film-forming resin raw material of the present invention essentially consists of both the above compound (A) having at least two acryloyloxy groups and/or methacryloyloxy groups in the molecule and the polymerizable acidic phosphorus ester (B). However, in carrying out the present invention, it is preferable to add a polymerization initiator, and in some cases, it is preferable to add a polymerization initiator, and in some cases, the development of antistatic properties by offshore acidic phosphate ester (B) may be necessary. Encourage! A compound having the property "'I" may be further added.

In carrying out the present invention, polymerization and curing of the film-forming resin raw material is not particularly limited, but photopolymerization using ultraviolet irradiation is preferred because the equipment is relatively simple and productivity is high. Therefore, as the polymerization initiator added to the film-forming resin raw material, a photosensitizer is preferable. Examples of such photosensitizers include, for example, Pentwin,
Benzin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetoin, benzyl, benzophenone.

carbonyl compounds such as p-methoxybenzophenone,
Tetramethylthiuram monosulfide.

Examples include sulfur compounds such as tetramethylthiuram disulfide. These can also be used in combination of two or more instead of just one type. Further, sources of ultraviolet rays include mercury lamps, arc lamps, xenon lamps, and the like.

The amount of these photosensitizers added is 0.1 to 10 parts by weight (preferably 1 part) per 100 parts by weight of the film-forming resin raw material. If the amount of photosensitizers added is too small, Polymerization and curing of the film is slow, resulting in low productivity, and on the other hand, if the amount added is too large, the weather resistance of the cured film is likely to deteriorate.

Examples of compounds that promote the antistatic properties of the polymerizable acidic phosphate ester (B) include (meth)acrylic acid.

Ethylene glycol mono(meth)acrylate.

Diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylic acid ester with an average molecular weight of about 300 to about 1000, glycerin mono(
Polyhydric alcohol mono(meth) such as acrylate
Examples include acrylate, or ethanolamine compounds such as N-laurylgetanolamine and N-stearylgetanolamine, and these compounds can be added in large amounts (both polymerizable acidic phosphate esters (B)
It is preferable that the amount is equal to .

Other copolymerizable monomers that can be mixed with the polymerizable compound (A) of the present invention include, for example, acrylic acid,
methacrylic acid, their esters, acrylonitrile,
Metacyclonitrile.

Examples include styrene and its derivatives.

Further, the viscosity of the film-forming resin raw material is preferably in the range of 1 to 1000 centivoise, and more preferably 5 to 1000 centivoise.
More preferably, it is 1000 centivoise.

Further, the thickness of the film imparting scratch resistance and antistatic properties of the present invention is preferably in the range of 1 to 100 μm. When the film thickness is less than 1 μm, it is not preferable because, in some cases, sufficient scratch resistance may not be provided. On the other hand, when the film thickness exceeds 100 μm, the synthetic resin molded product having the film on its surface often becomes brittle.

The base resin raw material used in the present invention is methyl methacrylate, a mixture of polymerizable unsaturated monomers containing 80% by weight or more of methyl methacrylate, or a partial polymer thereof.

Examples of polymerizable unsaturated monomers that can be copolymerized with methyl methacrylate include acrylic esters such as methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate, and methacrylic esters such as ethyl methacrylate.

Examples include styrene and its derivatives.

Examples of the polymerization initiator for the base resin raw material include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, isopropyl peroxydicarbonate, and initiator. Butyl peroxide.

Free radical initiators such as acetylcyclohexylsulfonyl peroxide can be used. It is also possible to use a redox polymerization initiator, such as a combination of peroxides and amines. Furthermore, the base resin raw material may contain various additives, such as stabilizers,
yll fuel, plasticizer, bipolymer network binding agent, dye/pigment, etc. may be added.

In addition, as a release agent that facilitates the release of synthetic resin from the mold, the following general formula [■] (wherein R3 is an alkyl group or aryl group having 30 or less carbon atoms, R9 is hydrogen or R, - 0-(CH,0H20
).

(R1 is an alkyl group or aryl group having 30 or less carbon atoms, and q and γ are integers of 0 to 5°)
A non-polymerizable acid ester represented by can be added.

Examples of the compound represented by the general formula [II] include ethyl phosphate and diethyl 7-phosphate.

Butyl phosphate, dibutyl phosphate, 2-
Ethylhexyl phosphate, his(2-ethylhexyl) phosphate, hexaoxyethylene nonyl ether phosphate, bis(hexaoxyethylene nonyl ether) phosphate, hexaoxyethylene phenyl ether phosphate, bis(hexaoxine ethylene phenyl) ether) phosphate, octaoxyethylene nonyl ether phosphate, bis(octaoxyethylene nonyl ether) phosphate,
Examples include octaoxyethylene phenyl ether phosphate and his(octaoxyethylene phenyl ether) phosphate.

0.001 to 1 volume part of the non-polymerizable acidic phosphoric acid ester represented by the general formula [■] is added to 100 parts by weight of the polymerizable monomer or its partial polymer as the base resin raw material. Even if injection polymerization of the base resin raw material is performed in a state where the film-forming resin raw material is not sufficiently polymerized and cured, no problem arises in peeling the synthetic resin from the mold.

On the other hand, if the amount of the non-polymerizable acidic phosphoric acid ester represented by the above general formula [■] in the base resin raw material is less than 0.001 parts by weight, the film-forming resin raw material will not be sufficiently polymerized and cured. If injection and polymerization of the base resin raw material are carried out without proper procedures, the synthetic resin will not be easily peeled from the mold, and moderate product defects or mold breakage will likely occur.

On the other hand, when the amount added exceeds 1 part by weight, the strength of the synthetic resin tends to decrease.

The shape of the synthetic resin molded product produced by the present invention is not particularly limited, but specific examples include plate crystals with a thickness of 0, 2 to 20 mm, more preferably 0.5 to 10 layers. It can be given as

The method for manufacturing a synthetic resin molded article having a surface with excellent scratch resistance according to the present invention using the above-mentioned sticky film-forming resin raw material and base resin raw material is described in
No. 7, No. 49-36829, No. 49-36830,
It can be applied to the methods described in Japanese Patent Nos. 54-14617, 54-14618, and 56-53488. Of these, from the point of view of productivity,
No. 488, the resin raw material forming the above-mentioned film is continuously applied to endless stainless steel belts with single-sided mirror polishing that move in the same direction and at the same speed, and is sufficiently polymerized and cured. After that, the periphery is sealed with a gasket to form a molding space, and the base resin raw material is injected from the upstream end of the molding space, polymerized and cured, and the previously formed film is transferred. Preferred for application.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. Parts in the examples represent parts by weight.

The scratch resistance is evaluated by the increase in haze value determined by the falling sand method shown below. That is, the test piece was tilted in advance at an angle of 45° with respect to the horizontal direction, and around the vertical axis K 11 R, P,
60 meshes of carborundum 3001 from 70CTL above the test piece.
The increase in haze value is calculated by subtracting the glue value before sand fall from the haze value after sand fall.

The haze value is expressed by the following formula.

- The smaller the increase in haze value, the better the scratch resistance.

Moreover, the antistatic property was expressed by the value of charge half-life measured under the following conditions.

That is, under constant temperature and humidity conditions of 20°C and 50% relative humidity.
After holding the sample for 4 hours, a voltage of 10 KV was applied for 10 seconds using an honest meter (Shishido Shokai!!1) to measure the half-life.

In addition, changes in the appearance of synthetic resin molded products after being left unused were determined by observing the appearance after the samples were left under constant temperature and humidity conditions of 20° C. and 50% relative humidity for 24 hours after manufacture.

Example 1 1.6-hexanediol diacrylate 95 parts Kayamer PM, 5
(manufactured by Nihon Yakuyaku Co., Ltd., monomethacryloxyethyl phosphate) pentwin ethyl ether
610 m of film-forming resin raw material mixed with 1.5 parts of
z It was cast onto one side of a tempered glass plate measuring 460 mm x 6 mm (thickness), covered with a 20 μm thick polypropylene film cover with tension on all four sides, and air bubbles were created between the film and the glass plate using a roller from above. It was spread so that no residue remained, and the thickness of the coating material was about 20 μm. First, the objects in such a state are separated at intervals of 75
00 fluorescent chemical lamps (manufactured by Toshiba, FL
-20BL) for 15 seconds from a height of 6 cm. After that, the cover film was peeled off from the pre-cured film, and then: Two high-pressure mercury lamps arranged at 400 mm intervals (
The film was post-cured by irradiating it for 30 seconds with a Toshiba H2O0OL) from a height of 201. The thus treated glass plate was placed facing untreated glass with the cured film on the inside to form a cell, and the cell was filled with 100 parts of methyl methacrylate partial polymer and 0 parts of Tinupin P (ultraviolet absorber). Base resin consisting of .01 parts 2.2'-azobisisobutyronitrile o, oss manufactured by Nippon Chemical Industry Co., Ltd., trade name "E A PJ O, 05 parts (mixture of monoethyl phosphate and diethyl phosphate)" Inject the raw materials, seal the surrounding area with a soft vinyl chloride gasket, adjust the spacing between the glass molds so that the resin plates are arranged in three order, and heat at 60°C for 6 hours, then at 120°C.
Polymerization was carried out by heating for 2 hours.

After cooling, the scratch resistance of the surface on the non-coated side of the resin plate obtained by peeling it off from the glass plate showed that the haze value increased by 55% using the sand drop method, and the charge half-life was 120 seconds. As mentioned above, regarding the scratch resistance of the surface on which the film was formed, the increase in glue value by the sand drop method was 12%, the charge half-life was 1 second, and the scratch resistance and antistatic properties were excellent. No change in appearance was observed after being left alone.

Comparative Example 1 The same film-forming resin raw material as in Example 1 was heated to 45°C to produce a methacrylic resin plate (thickness) of 6 x 10 mm x 460 silk x 3 (thickness) (Mitsubishi Rayon Co., Ltd., Acrylai E).
The coating material was then polymerized and cured under the polypropylene film cover and in the absence of the cover film in the same manner as in Example 1 to form a coating similar to that in Example 1 on one side. A resin plate was obtained.

The abrasion resistance of the surface of the resin plate thus obtained on which the film was formed was an increase in haze value by sand drop method of 12%, and the charge half-life was 45 seconds.

Comparative Example 2 The same film-forming resin raw material as in Example 1 was heated to 45°C. 6 10 mm x 460 mm x 3 mwt (thickness)
It was cast onto one side of a methacrylic resin plate (Mitsubishi Rayon Co., Ltd., Acrylite E), and placed in a nitrogen stream at 9 traps for 400 min.
Two high-pressure mercury lamps arranged at mm intervals (manufactured by Toshiba, H2)
The surface side coated with the coating material was irradiated for 30 seconds from a height of 20 crrL) to obtain a resin plate on which a coating similar to that of Example 1 was formed on one side.

Regarding the scratch resistance of the surface of the resin plate thus obtained on which the film was formed, the haze value increased by 12% by the sand drop method, and the charge half-life was 53 seconds.

Examples 2 to 4, Comparative Example 3 The film-forming resin raw materials were listed in Table 1; resin plates were obtained by repeating the same operations as in Example 1, except that the film-forming resin raw materials were changed.

Table 1 shows the results of measuring the scratch resistance and charge half-life of the coated surface of the resin plate thus obtained, as well as the results of observing changes in appearance after standing.

Comparative Examples 4 and 5 A resin plate on which a film was formed was obtained by repeating the same operations as in Comparative Example 1 except that the film-forming resin raw materials were changed to those listed in Table 2.

Table 2 shows the results of measuring the scratch resistance and half-life of the charge on the surface of the thus obtained resin plate on which the film was formed, as well as the results of observing changes in appearance after standing.

Table-1 Table-2 Example 5 The experiment was carried out using the continuous manufacturing apparatus shown in FIG. 1.

In Figure 1, belts (1) and (1') have a width of 1.57
It is an endless mirror-polished stainless steel belt with a thickness of 1, and the lower belt is 12 meters longer than the upper belt. The belt is the main boo! J-(2
The initial tension of the belt is given by a hydraulic cylinder provided on the tension pulley, and is set to 10 kg per cross section of the belt.

Trimethylolpropane triacrylate 97.
Part 5 “JPA-514” manufactured by Johoku Kagaku Kogyo 2
．． Film-forming resin raw material (5) + (5') consisting of 5 parts (mixture of monomethacryloyloxyethyl phosphate and dimethacrylokydiethyl phosphate 1ate) and 5.0 parts of benzoin ethyl ether was prepared using a roll coater (6 ), (6')・After being applied to the polyester film (7)l (7') with a thickness of 12 μm, the belt (1) was applied with press rolls (8), (8').
), (1') with a thickness of 18 μm.

The film-forming resin raw material (5) thus applied.

(5'n continues to be a fluorescent chemical lamp (manufactured by Toshiba).

F1. -408 L) (12), (12')
After being pre-cured with a polyester film, the polyester film is peeled off and subsequently post-cured with a high-pressure mercury lamp (13), (13').

The film-treated belts were placed facing each other, and both sides were sealed with polyvinyl chloride hollow pipes (15) containing a considerable amount of pikaner, and between them 100 parts of methyl methacrylate partial polymer (average polymerization Polymer content 21%) 2.2'
-Azobis(2,4-dimethylvaleronitrile) 0
．． Part 05 Tinupin P
O, 01 part Dai-ichi Kogyo Seiyaku Co., Ltd. Pricesurf A-2
Base resin raw material consisting of 0.05 part of 17E (acidic phosphoric acid ester of polyoxyethylene alkyl ether) (
14) is delivered through the infusion device by a metering pump.

The polymerization area has a total length of 96m, and the first half of the 66nZ section has idle rollers arranged at 15c7rL intervals (4)
, In group (4'), the distance between the belt surfaces is regulated, and 80°C warm water is sprayed from a nozzle from the outer surface of the belt to heat it, and the second half 307? In section l, the belt is supported by idle rollers arranged at 1 m intervals, and an infrared heater (17
) to about 130°C and then cooled. After cooling, the resin plate was peeled off from the belt to continuously obtain a resin plate having a thickness of 2 mm.

The scratch resistance of the resin plate obtained in this way is such that the haze value increases by 11% by the sand drop method, the charge half-life is 2 seconds, it has excellent scratch resistance and antistatic properties, and the appearance after irradiation. No changes were observed.

[Brief explanation of drawings]

FIG. 1 shows an example of a continuous manufacturing apparatus in which a cover having no affinity with the film is used to cure the film-forming resin raw material. (1), (1')... Endless belt (2)
, (3), (2'), (3')
... Puri - Puri - (4), (4'
)...Idle roller (5)l (5')...
...Film-forming resin raw material (6), (6')...
・Roll coater (7), (7')...Cover integrated (s) + (g')...Press roll (9)l
(9')...Nip roll (1o), Qo'
)・・・・・・Cover integrated unwinding roller (n), (n
')...Take-up roller with integral cover (12)j
(12'), (13), (13')...Curing device (+4) ""°Base resin raw material (15)...Gasket ([6)...Heater

Claims (1)

[Scope of Claims] 1. 90 to 99.8% by weight of a polymerizable compound (A) having at least two acryloyloxy groups and/or methacryloyloxy groups in the molecule, and the following general formula [
I 〕▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I 〕 (In the formula, R_1 is hydrogen or a methyl group, R_2 is hydrogen or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group, and R_3 is hydrogen or It is a methyl group, and m and n are 1 to
A film-forming resin raw material consisting of 0.2 to 10% by weight of polymerizable acidic phosphoric acid ester (B) represented by (an integer of 5) is applied to the molding surface of a glass or metal mold, and the base to be injected later is applied. After sufficiently polymerizing and curing to the extent that it does not swell or dissolve with the base resin raw material and forming a film on the molding surface in advance, the base resin raw material is injected and polymerized.
A method for producing a synthetic resin molded article having a surface with excellent scratch resistance and antistatic properties, characterized by transferring the above-mentioned pre-formed film to the base resin side. 2. The film-forming resin material having excellent scratch resistance and antistatic properties as set forth in claim 1, wherein the polymerization and curing of the film-forming resin raw material is carried out by irradiation with ultraviolet rays in the presence of a photosensitizer. A method for manufacturing a synthetic resin molded product having a surface. 3. Base resin raw material is methyl methacrylate or 80
Claim 1, characterized in that it is a mixture of methyl methacrylate or more and 20 weight % or less of an unsaturated polymerizable monomer copolymerizable therewith, or a partial polymer thereof. A method for producing a synthetic resin molded product having a surface with excellent scratch resistance and antistatic properties. 4. Scratch resistance and antistatic properties as claimed in claim 1, characterized in that the molds are endless stainless steel belts that are mirror-polished on one side and move in the same direction and at the same speed. A method for producing a synthetic resin molded product having a surface with excellent properties.