JPH04292638A - Synthetic resin molded article having surface with excellent scratch resistance and antistaticity and its production - Google Patents

Abstract

PURPOSE:To obtain a synthetic resin molded article having excellent scratch resistance and antistaticity by placing a cross-linkable and curable resin raw material containing a specific compound between a mold and a synthetic resin molded article, polymerizing and curing the material and releasing the product from the mold. CONSTITUTION:The curable resin raw material to be used in the subject molded article is obtained by mixing (A) 30-99.5 pts.wt. of a polymerizable compound having >=2 (meth)acryloyloxy groups in one molecule, (B) 0-69.5 pts.wt. of a compound having one alpha,beta-ethylenic unsaturated bond in one molecule and (C) 0.5-40 pts.wt. of a (co)polymer produced by (co)polymerizing (C1) 20-99wt.% of a compound having quaternary ammonium base and expressed by formula (R1 is H or methyl ; R2 to R4 are H or 1-9C alkyl; m is integer of 1-10; X<-> is anion of quaternarizing agent) and (C2) 80-1wt.% of a compound having one copolymerizable unsaturated double bond. The curable resin raw material is placed between a mold (e.g. inorganic glass) and a synthetic resin molded article (e.g. polystyrene) and cured by polymerization to form a cross- linked and hardened film on the surface. The produced molded article is released from the mold.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is characterized by wear resistance, solvent resistance,
and a resin molded product having a surface protective layer made of a resin with excellent antistatic properties.

0002

2. Description of the Related Art In general, synthetic resins are easily damaged by various frictional effects, and are charged with static electricity, making them easy to attract dust. Many attempts have been made to improve these shortcomings in the past, but effective means for solving both of these shortcomings regarding wear resistance and antistatic properties are hardly known. A method is already known in which a resin film of a polyfunctional monomer such as ethylene glycol dimethacrylate is adhered to the surface of a base resin to improve the wear resistance of the base material, but these resin films are completely free of charge. Does not have preventive properties.

As seen in Japanese Patent Publication No. 54-15074, a resin film formed by polymerizing a monomer having a quaternary ammonium base and a polyfunctional monomer such as ethylene glycol dimethacrylate is used as a base material. Methods for improving the abrasion resistance and antistatic properties of substrates by adhering them to resin surfaces are already known. According to the method described in the specification shown in this publication, the hygroscopicity of the monomer having a quaternary ammonium base is so high that a large amount of water is contained in the resin raw material forming the film. Therefore, uneven polymerization and curing and uneven quality occur during polymerization of the film. Furthermore, even if an attempt is made to remove water in a monomer having a quaternary ammonium base, due to the high polymerizability of a monomer having a quaternary ammonium base, a polymerization reaction will occur during heating and depressurization operations, resulting in a substantial It is not possible to obtain monomers with anhydrous quaternary ammonium bases.

0004

[Problem to be solved by the invention] As explained above,
To date, no effective method for imparting scratch resistance, solvent resistance, and antistatic properties to synthetic resin surfaces is known.

[0005]

[Means for Solving the Problem] As a result of intensive studies on the above-mentioned problems, the present inventors have devised a method to interpose a poly(co)polymer having a specific quaternary ammonium base between the mold and the synthetic resin molded product. It has been discovered that by mixing it with a functional monomer and polymerizing and curing this mixture with a crosslinked curable resin raw material interposed, it is possible to simultaneously impart scratch resistance, solvent resistance, and antistatic properties to the surface of the synthetic resin. .

That is, the present invention provides a method for adding a polymerizable compound (A )
30 to 99.5 parts by weight, 0 to 69.5 parts by weight of a compound (B) having one α,β-ethylenically unsaturated bond in the molecule, and general formula (I)

[Chemical formula 5] (However, R1 is a hydrogen atom or a methyl group, R2 to R
4 is a hydrogen atom or an alkyl group optionally containing a substituent having 1 to 9 carbon atoms, m is an integer of 1 to 10, and X-
is an anion of a quaternizing agent) A compound having a quaternary ammonium base (a) 20 to 99% by weight and a compound (b) having one unsaturated double bond copolymerizable with 80 to 99% by weight
(co)polymer (C) obtained by polymerizing 1% by weight of 0.
5 to 40 parts by weight, this mixture is polymerized and cured with a cross-linked curable resin raw material interposed, and then the synthetic resin molded product with the cross-linked cured film integrally formed on the surface is separated from the mold. The present invention relates to a synthetic resin molded product having a surface with excellent scratch resistance and antistatic properties, and a method for producing the same.

[0007] Since the present invention uses a (co)polymer having a specific quaternary ammonium base, it can be completely dehydrated without the risk of polymerization reaction, and water in the coating composition can be removed. It is possible to eliminate various defects that occur due to

In the present invention, the monomer (a) having a quaternary ammonium base constituting the (co)polymer (C) is
General formula (I)

[Chemical formula 6] (However, R1 is a hydrogen atom or a methyl group, R2 to R
4 is a hydrogen atom or an alkyl group optionally containing a substituent having 1 to 9 carbon atoms, m is an integer of 1 to 10, and X-
is an anion of a quaternizing agent), which is obtained by quaternizing an acrylate or methacrylate having an amino group with a quaternizing agent. Acrylates or methacrylates having an amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminobutyl methacrylate, dihydroxyethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, Examples include dibutylaminoethyl methacrylate.

Examples of the quaternizing agent include dimethyl sulfate,
Alkyl sulfates such as diethyl sulfate and dipropyl sulfate, p
- Sulfonic acid esters such as methyl toluenesulfonate and methyl benzenesulfonate, alkylphosphoric acids such as trimethylphosphite, various halides such as alkylbenzyl chloride, benzyl chloride, alkyl chloride, and alkyl bromide are used, especially alkyl sulfates. Considering the thermal decomposition resistance of sulfonic acid esters,
This is more preferable. m in the general formula is an integer of 1 to 10, particularly preferably an integer of 2 to 6.

Various known compounds can be used as the copolymerizable compound (b) having one unsaturated double bond. For example, methacrylic esters such as methyl methacrylate and ethyl methacrylate, acrylic esters such as methyl acrylate and ethyl acrylate, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and acid anhydrides such as maleic anhydride and itaconic anhydride. , maleimides such as N-phenylmaleimide, hydroxy group-containing monomers such as 2-hydroxyethyl acrylate and 2-hydroxypropyl methacrylate, nitrogen-containing monomers such as acrylamide and acrylonitrile, and epoxies such as allyl glycidyl ether and glycidyl methacrylate. Group-containing monomers, macromonomers such as terminal methacrylate polymethyl methacrylate, terminal styryl polymethyl methacrylate, terminal methacrylate polystyrene, terminal methacrylate polyethylene glycol, terminal methacrylate acrylonitrile styrene copolymer, etc. can be used.

These copolymerizable compounds (b) having one unsaturated double bond include general formula (II)

embedded image (However, R5 is a hydrogen atom or a methyl group, R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, A is an alkylene group having 2 to 4 carbon atoms, and n is an integer from 0 to 500).

In the general formula (II), compounds represented by an integer of n=0 or 1 include methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, ethylhexyl methacrylate,
Examples include stearyl methacrylate, methyl acrylate, ethyl acrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, and 2-hydroxyethyl methacrylate.

In general formula (II), n=2 to 500
Examples of compounds represented by an integer include polyethylene glycol (4) monomethacrylate, polyethylene glycol (23) monomethacrylate, polyethylene glycol (300) monomethacrylate, polyethylene glycol (23) monoacrylate, and polypropylene glycol (23) monomethacrylate. , polybutylene glycol (23) monomethacrylate, polyethylene glycol (23) monomethacrylate monomethyl ether, polyethylene glycol (23) monomethacrylate monobutyl ether, polyethylene glycol (23) monomethacrylate monostearyl ether,
Polyethylene glycol (23) Monomethacrylate monophenyl ether, polyethylene glycol (23)
Examples include monomethacrylate monobenzyl ether, polyethylene glycol (23) monomethacrylate monooleyl ether, etc. (the number in parentheses is the number of polyalkylene glycol units).

In the general formula (II), it is particularly preferable to use a compound represented by an integer of n=0 or 1, since the adhesiveness between the crosslinked curable resin and the base synthetic resin is good. In general formula (II), when using a compound represented by an integer of n = 2 to 500, the (co)polymer (C)
This is more preferable because the compatibility between the compound and the polymerizable compounds (A) and (B) is improved, and the crosslinked curable resin can be uniformly cured.

The (co)polymer (C) in the present invention comprises 20 to 99% by weight of the compound (a) represented by the general formula (I),
Preferably 20 to 90% by weight, and 80 to 1% by weight of compound (b) represented by general formula (II), preferably 80 to 1% by weight.
It consists of 10% by weight. If the amount of compound (a) is less than 20% by weight, good antistatic properties cannot be imparted. Further, the compound (b) is used to improve the uniformity of the crosslinked curable resin and its adhesion to the base synthetic resin.

The polymerizable compound (A) used in the present invention has at least two (meth)acryloyloxy groups (meaning acryloyloxy group and/or methacryloyloxy group, the same applies hereinafter) in the molecule. ), in which the residue bonding each (meth)acryloyloxy group is a hydrocarbon or a derivative thereof, and the molecule contains, for example, an ether bond, thioether bond, ester bond, or amide bond. , a urethane bond, and the like.

[0017] Main examples of these compounds include esterified products obtained from polyhydric alcohols and (meth)acrylic acid (meaning acrylic acid and/or methacrylic acid, the same shall apply hereinafter) or derivatives thereof. or a linear esterified product obtained from a polyhydric alcohol, a polyhydric carboxylic acid, and (meth)acrylic acid or a derivative thereof.

Examples of the former polyhydric alcohol used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 300 to 1000, propylene glycol, dipropylene glycol, , 3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2-dimethyl 1,3-propanediol, 2-ethyl 1,3-hexanediol, 2,2'-thiodiethanol, 1,4
- dihydric alcohol such as cyclohexanedimethanol,
Other trimethylolpropane (1,1,1-trimethylolpropane), pentaglycerol (1,1,1-
trimethylolethane), glycerol, 1,2,4-
There are butanetriol, pentaerythritol (2,2-bishydroxymethyl 1,3-propanediol), etc., and particularly preferred crosslinking polymerizable compounds obtained from these and (meth)acrylic acid include diethylene glycol di(meth) Acrylate (meaning acrylate or methacrylate, the same shall apply hereinafter), triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaglycerol (
Examples include meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

[0019] In addition, the latter is basically such that the hydroxyl group of the polyhydric alcohol and the carboxyl group of both the polyhydric carboxylic acid and (meth)acrylic acid are ultimately equal in amount. Although it can be obtained by reacting a mixture, particularly preferred products of the present invention have the general formula
Glycols or derivatives thereof (α) represented by HO-R9 -OH, general formula HOCO-R10-COO
dicarboxylic acids represented by H, chlorides, anhydrides or esters of these acids (β), and (meth)acrylic acid or chlorides or esters of these acids (γ), for example (α): (β):(γ)=q+1:q:2~2
．． It is a compound expressed by the following general formula, obtained by reacting at a ratio of 2 (molar ratio).

[0020]

[Formula 8] (wherein, R8 is a hydrogen atom or a methyl group, R9 is 2
a group of an aliphatic hydrocarbon group or a derivative thereof having ~20 carbon atoms, R10 is a group of an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms or a derivative thereof, and q is 1 to (represents an integer of 20).
As α), for example, the dihydric alcohols mentioned above can be used, and as compounds (β), for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid, tetrahydrophthalic acid, 3, Alicyclic dicarboxylic acids such as 6-endomethylenetetrahydrophthalic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, thiodiglycolic acid, thiodivaleric acid, diglycolic acid, etc., which contain heteroatoms in the main chain dicarboxylic acids, etc.
or their chlorides, anhydrides and esters, and particularly preferred compounds obtained from these and (meth)acrylic acid or chlorides or esters of these acids include ethylene glycol, phthalic acid or acrylic acid. acid or methacrylic acid and whose q is an integer of 1 to 10, especially a di(meth) integer of 1 to 5.
It is acrylate.

Other examples of compounds containing urethane bonds include di(meth)acrylate obtained by reacting organic diisocyanate and 2-hydroxyethyl (meth)acrylate.
2-hydroxyethyl (meth)acrylate derivative and a diisocyanate intermediate obtained by reacting polyethylene glycol with an organic diisocyanate.
Examples include di(meth)acrylate derivatives obtained by reacting acrylates.

The compound (B) used in the present invention is as follows:
A commonly used compound having one α,β-ethylenically unsaturated bond in the molecule is used. In particular, a compound having compatibility with both the polymerizable compound (A) and the (co)polymer (C) and having a polar group in the molecule is preferred. It can be selected as appropriate depending on the type and amount of the polymerizable compound (A) and (co)polymer (C), but generally acrylic acid, methacrylic acid, amides thereof, methylolated products of amides, and 2-hydroxy (meth)acrylates are used. ,
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. are preferred.

The proportions of the polymerizable compound (A), compound (B), and (co)polymer (C) used in the present invention are determined depending on the desired degree of wear resistance and antistatic property. Generally, the polymerizable compound (A) is 30 to 99.5 parts by weight, preferably 60 to 95 parts by weight, and the compound (B) is 0 to 69.5 parts by weight.
5 parts by weight, preferably 0 to 20 parts by weight, and 0.5 to 40 parts by weight, preferably 5 to 2 parts by weight of the (co)polymer (C).
It is 0 parts by weight. If the amount of the polymerizable compound (A) is less than 30 parts by weight, good abrasion resistance cannot be imparted, and (
If the amount of co)polymer (C) is less than 0.5 parts by weight, good antistatic properties cannot be imparted.

Methods for curing these crosslinked polymerizable resin raw materials include a method of adding a thermally decomposable polymerization initiator and heating, a method of adding a compound having a photosensitizing effect and irradiating with ultraviolet rays, and There are also methods of irradiating ionizing radiation, methods of combining these methods, and the like. Among these methods, particularly preferred is a method in which a compound having a photosensitizing effect is added and ultraviolet rays are irradiated.

Examples of thermal decomposition type polymerization initiators include known radical polymerization initiators, such as oil-soluble peroxides or azo compounds; examples of compounds having a photosensitizing effect include wavelengths of 20
Radical generators that can be activated in the range of 00 to 5000 Å are effective, and generally carbonyl compounds, azo compounds, peroxides, sulfur compounds, halides, quinone compounds, etc. can be used. or 2
More than one species can be used in combination. In the case of polymerization by ionizing radiation, the total absorbed dose is 0.1 to 1
A range of 00 Mrad is utilized, preferably 1 to 50
Mrad range. As the ionizing radiation, for example, electron beams obtained from an accelerator, other accelerated particles, neutron beams, α rays, β rays, etc. are used, and accelerated electron beams are particularly preferred.

[0026] In the present invention, a cross-linked polymerizable resin raw material is interposed between the molding surface of a glass or metal mold and a synthetic resin molded product, polymerized and cured, and then a cross-linked cured film is integrally formed on the surface. This includes separating the synthetic resin molded product from the mold. In this method, a cross-linked polymerizable resin raw material is first applied to the surface of a mold such as a glass or mirror-finished metal plate, and/or the surface of a synthetic resin molded product as a base material, and then between coated surfaces,
It is polymerized and cured while being pressed into a sandwich shape. Methods for applying the crosslinked polymerizable resin raw material to the mold and/or the surface of the synthetic resin molded product include roller coating, bar coating, spray coating, air knife coating, dipping, etc. It's not limited either.

As the synthetic resin molded article used in the present invention, known synthetic resin molded articles can be used, but in particular, polymethyl methacrylate or a copolymer containing methyl methacrylate as a main component, polystyrene, and styrene-methacrylate copolymer are used. Preferred are polymers, styrene-acrylonitrile copolymers, polycarbonates, and cellulose acetate butyrate resins. The most preferred among these are polymethyl methacrylate or a copolymer containing methyl methacrylate as a main component.

[0028] A copolymer containing methyl methacrylate as a main component is 50% by weight or more of methyl methacrylate and 50% by weight of a monomer copolymerizable with methyl methacrylate.
It means a copolymer consisting of: Monomers copolymerizable with methyl methacrylate include methacrylic esters such as ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; acrylic esters such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid; Unsaturated carboxylic acids such as methacrylic acid, maleic acid, itaconic acid, acid anhydrides such as maleic anhydride, itaconic anhydride, N
- Maleimide derivatives such as phenylmaleimide, N-cyclohexylmaleimide, N-t-butylmaleimide, etc., 2
- Hydroxy group-containing monomers such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, dimethylaminoethyl methacrylate Nitrogen-containing monomers such as allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, styrene monomers such as styrene, α-methylstyrene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Allyl acrylate, allyl methacrylate, divinylbenzene,
Examples include cross-linking agents such as trimethylolpropane triacrylate, but these are not particularly limited. The type and amount of the copolymerizable monomer can be determined depending on the desired synthetic resin molded product.

[0029] The template used in the present invention is as follows:
Specific examples include those made of inorganic glass such as tempered glass, stainless steel, metals such as aluminum and chrome plating, and resins such as polyester resin. The surfaces of molds such as glass and metal are generally mirror surfaces, but
Depending on the case, a material whose surface has been subjected to a matte treatment with minute irregularities may also be used if necessary.

[0030]

[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. The electrical properties of all samples were measured at 20° C. and 65% relative humidity for one day. To measure the charge half-life time, use a static honest meter (manufactured by Shishido Shokai).
Applied voltage 10000 V, sample rotation speed 1550 rpm
The measurement was carried out under the conditions of an application time of 30 seconds, a measurement temperature of 20° C., and a measurement humidity of 65%, and the time required for the sample voltage during voltage application to be halved after the applied voltage was cut off was defined as the charge half-life time (sec). The surface resistivity was measured using a super insulation resistance meter (manufactured by Takeda Riken, TR-
8601), measurement temperature 20℃, measurement humidity 65%
Under the conditions, the surface resistivity after 1 minute with an applied voltage of 500 V (
Ω) was measured.

Abrasion resistance was determined by tilting the test piece at an angle of 45° with respect to the horizontal direction, rotating it around the vertical axis at a speed of 11 rpm, and dropping 200 g of 60 mesh carborundum from 70 cm above. The surface reflectance was measured before and after the sand fell, and expressed as the rate of decrease in reflectance. (In the examples, parts and % represent parts by weight and % by weight, respectively)

[Example 1] In a glass flask equipped with a stirring blade, 187 parts of diethylaminoethyl methacrylate,
and 220 parts of methanol, and while stirring, a mixture of 126.2 parts of dimethyl sulfuric acid and 80 parts of methanol was added dropwise to keep the internal temperature below 30°C.
Stirring was continued for a minute to obtain a monomer (M-1) solution containing a quaternary ammonium base. To this solution were added 3 parts of azobisisobutyronitrile, 2.5 parts of n-octyl mercaptan, 243 parts of methanol, and 311 parts of polyethylene glycol (23) monomethacrylate monomethyl ether (the number of polyethylene glycol units is in parentheses).
4 parts were added and polymerized by reacting for 6 hours at 60° C. under a nitrogen atmosphere, followed by vacuum drying at 70° C. for 1 day to obtain a copolymer having electrostatic properties.

85 parts of trimethylolpropane triacrylate as compound (A), 5 parts of methacrylic acid as compound (B), 10 parts of the above copolymer as (co)polymer (C), and as a photosensitizer. , 1.5 parts of benzoisobutyl ether were mixed to prepare a crosslinked curable resin raw material. This cross-linked curable resin raw material mixture was coated on a tempered glass plate to a thickness of 50 μm, and the coated surface was coated with a thickness of 3 mm.
A methacrylic resin plate (Acrylite manufactured by Mitsubishi Rayon) was pressed against the plate to prevent air from being drawn in, and the glass side was irradiated with ultraviolet rays for 30 minutes using an ultraviolet irradiation device equipped with an array of high-pressure mercury lamps, and then heat treated in a hot air oven at 120 °C to polymerize. Hardened. After polymerization and hardening, it was cooled and peeled off from the glass plate to obtain a methacrylic resin plate with a thickness of about 3 mm. The surface resistivity of the obtained methacrylic resin plate was 4.1 × 101
1Ω, charge half-life time is 1.3 seconds, and wear resistance is 9
It was 4%.

[Examples 2 to 15] The types of compound (a) in copolymer (C) are as shown in Table 1.
As shown in Table 2, the monomer type, composition and amount added in C), and the type and amount added of compound (A) and compound (B) were changed as shown in Table 2, but otherwise the same as in Example 1. A methacrylic resin plate with a thickness of about 3 mm was obtained. Table 2 shows the evaluation results of the obtained resin plate.

[Comparative Examples 1 to 5] Similarly, the compound (A
) or without copolymer (C) are also shown in Table 2 for comparison. It can be seen that if the crosslinked curable resin composition in Comparative Examples 1 to 5 is outside the range used in the present invention, good abrasion resistance or antistatic properties cannot be obtained.

[Table 1]

[Table 2]

[Table 3]

[Examples 16 to 20] As the base synthetic resin molded product, instead of the methacrylic resin plate, a polystyrene resin plate, a polycarbonate resin plate, an ABS resin (acrylonitrile-butadiene-styrene resin) plate, and an AS resin plate were used, respectively.
Using a resin (acrylonitrile-styrene resin) plate and a phenol resin plate, the thickness was approximately 3 m according to Example 1.
A resin plate of m was obtained. Table 4 shows the evaluation results of the obtained resin plate.

[Comparative Examples 6 to 10] Similarly, the results when no crosslinked curable resin was used are also shown in Table 4 for comparison.

[Table 4]

[Example 21] In this example, the crosslinked curable resin raw material mixture obtained in Example 1 was applied to a 3 mm thick methacrylic resin plate (Acrylite manufactured by Mitsubishi Rayon) to a thickness of 50 μm. Then, a tempered glass plate was pressed onto the coated surface without entraining air, and ultraviolet rays were irradiated from the glass side for 30 minutes using an ultraviolet irradiation device equipped with high-pressure mercury lamps, and then heat treated in a hot air oven at 120 °C to polymerize and harden. . After polymerization and hardening, it was cooled and peeled off from the glass plate to obtain a methacrylic resin plate with a thickness of about 3 mm. The surface resistivity of the obtained methacrylic resin plate was 5.7 × 101
1Ω, charge half-life time is 1.3 seconds, and wear resistance is 9
It was 3%.

[Comparative Example 11] The monomer (M-1) solution containing the quaternary ammonium base obtained in Example 1 was
The mixture was concentrated under reduced pressure at °C to obtain a monomer (M-1). A mixture of 10 parts of the obtained monomer (M-1), 75 parts of trimethylolpropane triacrylate, and 15 parts of methacrylic acid was used as a crosslinked curable resin raw material, and the same method as in Example 1 was used to prepare a material with a thickness of about 3 mm. A methacrylic resin plate was obtained. The surface resistivity of the obtained methacrylic resin plate was 5.3 × 10 11 Ω, the charge half-life time was 1.0 seconds, and the antistatic property was good. The abrasion resistance was mostly good and the rate of decrease in reflectance was about 93%, but there were some scratches due to uneven curing and some areas where the reflectance decreased.

[Comparative Example 12] The monomer (M-1) solution containing the quaternary ammonium base obtained in Example 1 was heated to 80%
An attempt was made to obtain monomer (M-1) by concentrating under reduced pressure at °C, but
Since the monomer (M-1) was polymerized and solidified, the monomer (M-1
) could not be isolated.

[0041]

[Effects of the Invention] According to the present invention, a resin molded product having good abrasion resistance and good antistatic properties can be obtained, and problems caused by static electricity, which have conventionally been a problem when using synthetic resins, can be obtained. It can be expected to eliminate the deterioration in aesthetics due to scratches.

Claims (11)

[Claims] Claim: 1. A polymerizable compound (A) having at least two acryloyloxy groups and/or methacryloyloxy groups in its molecule, 30-99. 5 parts by weight,
0 to 69.5 parts by weight of a compound (B) having one α,β-ethylenically unsaturated bond in the molecule, and general formula (I)
[Formula 1] (However, R1 is a hydrogen atom or a methyl group, R2 to R
4 is a hydrogen atom or an alkyl group optionally containing a substituent having 1 to 9 carbon atoms, m is an integer of 1 to 10, and X-
is an anion of a quaternizing agent) A compound having a quaternary ammonium base (a) 20 to 99% by weight and a compound (b) having one unsaturated double bond copolymerizable with 80 to 99% by weight
(co)polymer (C) obtained by polymerizing 1% by weight of 0.
A composition consisting of 5 to 40 parts by weight, which is polymerized and cured with a crosslinked curable resin raw material interposed therebetween, and then a synthetic resin molded article with a crosslinked cured film integrally formed on the surface is used as a mold. A synthetic resin molded product that is characterized by its ability to separate. Claim 2: The compound (b) having one copolymerizable unsaturated double bond has the general formula (II) [Formula 2] (wherein, R5 is a hydrogen atom or a methyl group, and R6 is a hydrogen atom or a carbon number 1-18 alkyl, aryl, or aralkyl group, A is an alkylene group having 2-4 carbon atoms, and n is an integer of 0-500. Resin molded product. 3. The synthetic resin molded article is polymethyl methacrylate or a copolymer containing methyl methacrylate as a main component, polystyrene, styrene-methyl methacrylate copolymer, styrene-acronitrile copolymer,
The synthetic resin molded article according to claim 1, which is selected from the group consisting of polycarbonate and cellulose acetate butyrate resin. [Claim 4] The counter anion of the quaternary ammonium base has the general formula R7 SO3 − or R7 OSO3 −
The synthetic resin molded article according to claim 1, wherein R7 is a hydrogen atom or an alkyl group, an aryl group, or an aralkyl group which may contain a substituent having 1 to 20 carbon atoms. 5. The synthetic resin molded article according to claim 1, wherein a glass plate or a metal plate with minute irregularities formed on the surface is used as the mold. 6. A polymerizable compound (A) 30-99. having at least two acryloyloxy groups and/or methacryloyloxy groups in the molecule is placed between the mold made of inorganic glass or metal and the synthetic resin molded article. 5 parts by weight,
0 to 69.5 parts by weight of a compound (B) having one α,β-ethylenically unsaturated bond in the molecule, and general formula (I)
[Chemical formula 3] (However, R1 is a hydrogen atom or a methyl group, R2 to R
4 is a hydrogen atom or an alkyl group optionally containing a substituent having 1 to 9 carbon atoms, m is an integer of 1 to 10, and X-
is an anion of a quaternizing agent) A compound having a quaternary ammonium base (a) 20 to 99% by weight and a compound (b) having one unsaturated double bond copolymerizable with 80 to 99% by weight
(co)polymer (C) obtained by polymerizing 1% by weight of 0.
5 to 40 parts by weight of a cross-linked curable resin raw material is interposed, polymerized and cured, and then the synthetic resin molded product having a cross-linked cured film integrally formed on its surface is separated from the mold. A method for producing a synthetic resin molded product having a surface with excellent scratch resistance and antistatic properties. 7. The compound (b) having one copolymerizable unsaturated double bond is represented by the general formula (II) [Claim 4] (wherein, R5 is a hydrogen atom or a methyl group, and R6 is a hydrogen atom or a carbon number 7. The synthesis according to claim 6, which uses a compound represented by an alkyl group, an aryl group, or an aralkyl group having 1 to 18 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 0 to 500. Method for manufacturing resin molded products. 8. The synthetic resin molded article is polymethyl methacrylate or a copolymer containing methyl methacrylate as a main component, polystyrene, styrene-methyl methacrylate copolymer, styrene-acronitrile copolymer,
7. The method for producing a synthetic resin molded article according to claim 6, wherein the resin is selected from the group consisting of polycarbonate and cellulose acetate butyrate resin. [Claim 9] The counter anion of the quaternary ammonium base has the general formula R7 SO3 − or R7
OSO3 − (However, R7 is a hydrogen atom or an alkyl group which may contain a substituent having 1 to 20 carbon atoms,
Claim 6 represented by an aryl group or an aralkyl group)
A method for manufacturing the synthetic resin molded product described above. 10. The method for producing a synthetic resin molded article according to claim 6, wherein a glass plate or a metal plate with minute irregularities formed on the surface is used as the mold. 11. Polymerization and curing of the crosslinked curable resin raw material comprises:
7. The method for producing a synthetic resin molded article according to claim 6, wherein the method is carried out by irradiating ultraviolet rays in the presence of a photosensitizer.