JPS62169833A - Production of synthetic resin molding having improved abrasion resistance - Google Patents

Abstract

PURPOSE:To increase the abrasion resistance of a synthetic resin molding, by coating the surface of the molding with a composition comprising a monomer mixture of a specified polyfunctional monomer and a monofunctional (meth) acrylate, a photosensitizer, an alkyl ester of a linear higher saturated fatty acid and an organic solvent and irradiating it with ultraviolet rays. CONSTITUTION:A coasting composition comprising the following four components (a)-(d) is applied to the surface of a synthetic resin molding and irradiated in air with ultraviolet rays to form a 1-30mu-thick crosslinked cured film on the surface of the molding (a): 100pts.wt. monomer mixture comprising 30-90wt% polyfunctional monomer of the formula (wherein at least three of the X's are CH2=CR-COO- groups and the rests are OH groups, n is an integer of 1-5 and R is H or methyl) and 70-10wt% monofunctional (meth) acrylate having at least one ether bond in the molecule, (b): 0.01-10pts.wt. photosensitizer, (c): 0.05-3pts.wt. linear higher saturated fatty acid alkyl ester and (d): 10-1,900pts.wt. organic solvent which can be mixed with the monomer mixture to form a hamogeneous solution of the monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention produces transparent materials with excellent abrasion resistance, surface smoothness, flexibility, heat resistance, solvent resistance, durability, and adhesion to substrates by ultraviolet irradiation in the air. The present invention relates to a method for producing a synthetic resin molded article having improved wear resistance using a coating composition capable of forming a crosslinked cured film.

Synthetic resin molded products made from polymethyl methacrylate resin, polycargenate resin, polycarbonate resin, etc. are not only lighter and more impact resistant than glass products, but also inexpensive and easy to mold. It has various advantages such as organic plate glass.

Optical uses such as lighting equipment covers, optical lenses, eyeglass lenses, reflectors, m, decorative uses such as signboards and displays, name plates, dust cover cases,
It is used in many fields such as automobile parts.

However, these synthetic resin molded products lack surface abrasion resistance, so the surface may be damaged by contact with other objects, impact, scratches, etc. during transport, installation, or use of the molded product. Damage may reduce product yield or
The aesthetic appearance is ruined and I sip on it.

Various methods have been studied in the past to improve these drawbacks of synthetic resin molded products. For example, silicone-based coating materials or melamine-based breakage materials have been applied to the surface of plastic products. : Methods of painting and curing have been proposed, but although products manufactured by these methods have improved surface abrasion resistance, they are not fully satisfactory. For example, since both methods are based on a thermosetting method, they require high temperature and long curing conditions until complete curing, resulting in large equipment, poor productivity, and high manufacturing costs.

In addition, in terms of performance, the former has insufficient adhesion to the base material, and cracks are likely to occur during processing or use. In the latter case, the abrasion resistance of the coating is insufficient and the adhesion to the substrate is poor.

In addition to the above examples, a polyfunctional acrylate or methacrylate monomer having t-3 or more polymerizable (meth)acryloyloxy groups in one molecule may be applied as a crosslinked cured coating material to the surface of a synthetic resin molded product. There is a method in which a crosslinked cured film is formed by radical polymerization on the surface of a synthetic resin molded article by irradiating active energy rays.

Conventionally, such polyfunctional (meth)acrylate (acrylate or methacrylate, hereinafter the same) monomer has excellent polymerization activity when irradiated with one dose of active energy, so it has been used as a quick-drying ink material in U.S. Patent No. 3. .661.
No. 614, No. 3, No. 551,311, No. 4551.
No. 246, or British Patent Nos. 1.19 & 259, etc., and the application of these polyfunctional (meth)acrylate monomers as surface modifying materials for synthetic resin molded products has been proposed in the United States. Patent No. 4552, 986,
Same No. 2,413,973 or No. 4770,4
This is proposed in Specification No. 90, etc.

U.S. Patent No. 496a505 or U.S. Patent No. 496&5
(No. 19 proposes a method for improving the abrasion resistance of the surface of synthetic resin molded products using the aforementioned polyfunctional (meth)acrylates having three or more (meth)acryloyloxy groups. These methods form a film without using an organic solvent and cure it by irradiating it with active energy rays in an inert gas atmosphere.

The present applicants also found that a polyfunctional (meth)acrylate monomer has excellent crosslinking and curing polymerizability upon irradiation with active energy rays1, and that it is a crosslinked cured film that can improve the abrasion resistance of the surface of synthetic resin molded products. discovered that it is effective as a forming material,
For example, it has been filed as Japanese Unexamined Patent Publication No. 5λ-102936.

By the way, the pencil hardness or steel wool hardness, which represents the abrasion resistance or surface hardness of synthetic resin molded products with excellent abrasion resistance manufactured by the above-mentioned method etc., is conventionally measured under high load (1509
7 cm" or more) and evaluated it.1 For example, for things like surface-hardened plastic lenses used in glasses, the abrasion resistance measured under the above-mentioned high load does not always match the results of practical use. It may not be possible to harden the surface of a synthetic resin molded product.Depending on its use or usage conditions, the load range and load condition of the frictional force during wear or abrasion vary greatly; This is because it is dangerous to make a comparative evaluation of the gender).

For the surface-hardened plastic lenses used in the above-mentioned glasses, we conducted a low-load continuous reciprocating friction test using minute silicon carbide, which is assumed to be rubbed with a handkerchief, tissue paper, etc. that has foreign objects, dust, etc. attached. It was found that the method is very good and matches the practical wear resistance quite well.

The present inventors have conducted intensive studies on coating compositions that exhibit excellent abrasion resistance (scratch resistance) under such low loads, and have found that the following composition meets the purpose of the present invention. The present invention was completed based on the findings.

In other words, the present invention is based on (a) the following general formula % formula % (1) (where xtt l xtz l xts + X2!
rX2! + ” ' ” + Xn2 r Xn3
*At least 3 of X14 are OH2-0R-Coo
- group and the rest are 10H groups. n is an integer from 1 to 5. R represents hydrogen or a methyl group. ) at least one polyfunctional monomer selected from poly(meth)acrylates of mono- or polypentaerythritol having three or more (meth)acryloyloxy groups in one molecule and 30-90% by weight; , has at least one ether bond in one molecule, and has a boiling point of 150°C or higher at normal pressure,
Monofunctional acrylic (v-) or methacrylate having a viscosity at 20°C of 20 centiboise or less from 14 to 70
a monomer mixture consisting of 10 parts by weight, (b) 0 photosensitizer per 100 parts by weight of the monomer mixture;
．． 01 to 10 parts by weight, (c) 005 to 3 parts by weight of linear higher saturated fatty acid alkyl ester based on 100 polymerized parts of the monomer mixture;
and (d) a coating composition comprising 10 to 1900 parts by weight of at least one organic solvent mixed with the #monomer mixture to form a homogeneous solution per 100 parts by weight of the monomer mixture. Improved abrasion resistance characterized by coating the surface of a synthetic resin molded product and then irradiating it with 5c ultraviolet rays to form a crosslinked cured film on the surface of the synthetic resin molded product? The present invention relates to a method for manufacturing a synthetic resin molded article having the following.

The feature of the present invention is that a specific trifunctional or higher functional (meth)ac IJL
/-1-monomer, a specific monomer having one or two (meth)acryloyloxy groups, and a specific linear higher saturated fatty acid alkyl ester are blended in a predetermined Jl1 combination, A coating material that can form a transparent crosslinked cured film with excellent wear resistance, reboilability, water resistance, heat resistance, chemical resistance, and adhesion to substrates when exposed to ultraviolet rays in the air. The composition and its use to create synthetic resin molded products with improved abrasion resistance and smoothness are the most important features, including the fact that it can be cured in air and the fact that it can be cured in the air. By adding a small amount of alkyl ester,
The abrasion resistance (scratch resistance) under low loads is significantly improved.

The poly(meth)acrylate of mono- or pentaerythritol represented by the general formula (1) used in the present invention has very good polymerization activity when irradiated with ultraviolet rays even in an air atmosphere.

It also crosslinks and cures to form a highly crosslinked and cured polymer that exhibits a high degree of abrasion resistance. In the present invention, the polyfunctional monomer represented by the above general formula (1) is 1, for example, pentaerythritol tri(meth)acrylate (beta/
taerythritol triacrylate and pentaerythritol trimethacrylate (the same hereinafter), pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate , dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate,
tripentaerythritol tetra(meth)acryle), tripentaerythritol penta(meth)acrylic V-), tripentaerythritol hexa(meth)acrylic V-), etc., and the use of these monomers is sufficient. Achieving that purpose, the vine, among others, dipentaerythritol tri(meth)acrylate 2 dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate has active energy in the air. It is particularly preferable from the aspect of polymerization activity by radiation irradiation and the aspect of ease of handling. The polyfunctional monomers represented by the general formula (1) may be used alone or in combination of two or more.

The proportion of the polyfunctional monomer used is 30 to 90 parts by weight, preferably 35 to 88 parts by weight, based on 100 parts by weight of the monomer mixture. If the amount of the polyfunctional monomer in the monomer mixture is less than 30 parts by weight, a cured film with sufficient layer resistance cannot be obtained, and if the amount exceeds 90 parts by weight, This is not preferred because the smoothness of the film is poor.

In the present invention, for example, three or more (
Even if a polyfunctional monomer has a meth)acryloyloxy group, a polyfunctional monomer that does not satisfy the general formula (1) t-, such as trimethylolpropane tri(meth)acry'
) h) Polyfunctional (meth)acrylates such as limethylolethane tri(meth)acrylate and pentaglycerol tri(meth)acrylate have poor polymerization activity when exposed to ultraviolet rays in the air, and do not sufficiently crosslink and cure the applied film. I don't like it because I can't do much.

At least one ether bond in one molecule used in combination with a polyfunctional monomer represented by the general formula <1), and a boiling point of 150°C or higher at normal pressure, Monofunctional acrylates or methacrylates having an ape of 20 ape or less are essential components for imparting flexibility, adhesion, and smoothness to crosslinked cured coatings, and specific examples include 2-ethoxyethyl (meth) Acrylate, 5-ethoxypropyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, phenoyaethyl (meth)
Acrylic V-), 2-(2-methoxyethoyac)ethyl (
meth)acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate (ethylcarpitol(meth)acrylate), 2-(2-butoxyethoxy)ethyl(meth)acrylate(butylcarpitol(meth)acrylate)
acrylate), 2-(2-chloroethoxy)ethyl (
meth) Acrynaut, Tetrahydrofurfuryl (meth)
Acrylic v-), 2-tetrahydrofurfuryloxyethyl (meth)acrylate, 2-glycisiloxyethyl (meth)acrynaute, 2-(2-(2-hydroxyethoxy)ethoxy)ethyl (meth)azirylate, etc. However, among these monomers, the ether bond contained in one molecule has a cyclic ether bond or an ether bond of H211/j or more and is an acryloyloxy group, such as tetrahydrofurfuryl acrylate, 2-
Tetrahydrofurfuryloxyethyl acrylate, 2-
(2-ethoxyethoxy)ethyl acrylate V-to(ethylcarpitol acrylate), 2-(2-butoxyethoxy)ethyl acrylate (butylcarpitol acrylate), 2-(2-(2-hydroxyethoxy)ethoxy)ethyl acrylate, etc. When used in combination with a polyfunctional monomer represented by the general formula (+), the curability is particularly excellent when irradiated with external radiation in an air atmosphere, which is desirable.

These monomers may be used alone or in combination of two or more within the composition range. The proportion of monomers used is 10 to 70 parts by weight per 100 parts by weight of the monomer mixture. This blue color is 10 in the monomer mixture.
7fF; If it is less than T%, the flexibility of the crosslinked cured film,
Adhesion and smoothness are poor, and on the other hand, if the weight exceeds 70:4, it is not preferable because a crosslinked cured film with sufficient abrasion resistance cannot be obtained.

The bifunctional monomer of the general formula (■), which is used in combination with a polyfunctional (meth)acrylate monomer if necessary, can add flexibility to the crosslinked cured film without reducing its abrasion resistance. The monomer is a bifunctional (meth)acrylate monomer represented by the following general formula (■), which imparts air curability when activated energy is applied and activated energy is irradiated.

■ o-C-xno---x, o-x, o+c-a-cHt
---([+) (in the formula, R is hydrogen or a methyl group -xl*x, +...

X is the same or different alkynone group having 6 or less carbon atoms, or a structure in which one hydrogen atom of the alkynone group is replaced with a hydroxyl group, and n is an integer from 0 to 5) represented by this general formula (■) Even in compounds, if the number of carbon atoms in xn is 7 or more, or if the number of n is 6 or more, the wear resistance of the crosslinked cured film may be poor, or the adhesion to the substrate may be reduced. I don't like it. More preferred monomers include those in which xn has 3 or less carbon atoms and n has 3 or less carbon atoms.

Specific examples of the bifunctional monomer represented by the above general formula (II) include 2.2-bis(4-acryloyloxyphenyl)propane, 2.2-bis(4-methacryloyloxyphenyl)propane, .2.2-bis(4-acryloyloxyethoxyphenyl)propane, 2.2
-bis(4-methacryloyloxyethoxyphenyl)
Propane, 2.2-his(4-acryloyloxyjetoxyphenyl)propane, 2.2-bis(4-methacryloyloxyjetoxyphenyl)propane, 2.
2-bis(4-acryloyloxypropoxyphenyl)propane, 2.2-bis(4-methacryloyloxypropoxyphenyl)propane, 2,2-bis[4-acryloyloxy(2-hydroxypropoxy)phenyl]propane, 2. 2-bis[4-methacryloyloxy(2-hydroxypropoxy)phenyl]propane,
2.2-bis[4-acryloyloxy(2-hydroxypropoxyethoxy)phenyl]propane, 2,2-
Examples include bisCd-J31)royloxy(2-hydroxypropoxyethoxy)phenyl]propane.

One type of monomer can be used alone,
Moreover, within the composition range, two or more kinds may be used in combination.

The usage ratio of these bifunctional (meth)acrylate monomers represented by the general formula (■) in the monomer mixture is 0 to 0.
Must be in the range of 60% by weight, more preferably 0
-40 weight range. When the proportion used exceeds 60% by weight, the wear resistance of the crosslinked cured coating decreases.

The linear higher saturated fatty acid alkyl ester used in the present invention is an essential component for improving wear resistance (scratch resistance) under low loads, which is the objective of the present invention.

As mentioned above, surface-hardened synthetic resin molded products vary greatly in the load range and load condition of the frictional force that damages the surface of the synthetic resin molded product, depending on its application or usage conditions, and may damage the surface and damage the shape and shape of the object. The size also changes greatly. Therefore.

The abrasion resistance (scratch resistance) of surface-hardened plastic molded products cannot be uniformly evaluated using the same test method.

For example, in the case of surface-hardened plastic molded products used in prescription glasses, fashion glasses, etc., scratches on the surface are not caused by strong frictional force, but rather by the adhesion of foreign matter, dust, etc. In most cases, it is lightly rubbed with tissue paper, etc., and for such applications, we use fine silicon carbide (+100a), which is a test method that assumes the case of being rubbed with a small object with a strong force. It was found that the continuous reciprocating friction test under low load using fi-matched the wear resistance (scratch resistance) results when plastic molded products were actually used.

Based on this knowledge, the present inventor investigated a coating composition that has excellent wear resistance (scratch resistance) under low loads, and found that linear higher saturated fatty acid argyl ester We discovered that by adding a small amount to a coating composition, abrasion resistance (scratch resistance) under low loads can be significantly improved.

These linear higher saturated fatty acid argyl esters include inbutyl myristate, n-butyl palmitate,
Examples include inbutyl stearate, inbutyl palmitate, isooctyl palmitate, methineoneate, and the like. Among them, esters of linear higher saturated fatty acids having 14 to 18 carbon atoms and monohydric alcohols having 3 to 10 carbon atoms and having side chains, such as isobutyl palmitate and inoctyl palmitate. etc. are particularly preferred for their effectiveness.

The amount added to 100 parts by weight of the monomer mixture is LL05~
The amount is preferably 3 parts by weight, and if it exceeds 3 parts by weight, the cured film may become hazy. On the other hand, if the amount added is too small, the effect will be small. If a compound other than a linear higher saturated fatty acid alkyl is used, it may not be effective, or it may reduce the abrasion resistance (scratch resistance) or the smoothness of the surface-hardened coating. Although the blending of these low-load scratch resistance improvers is not particularly effective for high-load scratch resistance and surface pencil hardness, it does not impede these effects.

In the present invention, id: has a very favorable effect on the coating processability and the ability to form a uniform heavy coating when the coating material composition is applied to the surface of a synthetic resin molded article.

In addition, an organic solvent is required to ensure excellent adhesion of the crosslinked cured coating to the substrate.

In the present invention, the organic solvent used is 1) mixed with the polyfunctional (meth)ac IJL'-) monomer mixture to form a homogeneous solution.

2) The boiling point at normal pressure is 50°C or more and 20Qt: or less.

3) The viscosity at room temperature is 10 centivoise or less.

4) Polyfunctional (meth)ac IJL/-to monomer mixture 1
00 parts by weight to 10 to 1900 parts by weight.

It is necessary to satisfy the following conditions. First of all, multi-sensual (meta)
The first condition is to form a homogeneous solution with the acrylate monomer mixture; for example, saturated hydrocarbon organic solvents such as n-hexane, n-hebutane, and cyclohexane cannot be used because they do not form a homogeneous solution. . The second condition is that the boiling point at normal pressure is 50℃μ or higher and 200℃ or lower, in order to form a cross-linked cured coating with excellent uniform coating properties or surface smoothness when applied to the surface of a synthetic resin molded product. This is an important and necessary requirement.

If the boiling point at normal pressure is less than 50°C, after the coating composition is applied, the surface of the substrate is cooled by the latent heat of the organic solvent that evaporates from the coating, and moisture in the air condenses there, causing the coating to deteriorate. The surface smoothness of the film is lost, and if the temperature exceeds 200°C, the organic solvent evaporates from the coating film very slowly, resulting in workability problems, and the residual organic solvent evaporates during the ultraviolet irradiation process. Uniformity of cross-linked cured film due to lack of balance between escape and formation of cross-linked cured film by polymerization.

This is undesirable because the surface smoothness may be lost or the organic solvent may remain in the cross-linked cured film, resulting in whitening of the film. Therefore, the boiling point of the organic solvent used must be 50°C or more and 200°C or less at normal pressure, and more preferably 60 to 150°C.

The viscosity of the organic solvent used must also be 10 cmVoice or less at room temperature, and if it exceeds 10 cmVoice, it will have little effect on the coating workability or the smoothness of the coating.

Use of an organic solvent, 1 is preferably in the range of 10 to 1900 parts by weight based on 100 parts by weight of the above-mentioned tilt body mixture;
If the part by weight is unskinned, the viscosity of the coating material composition is high, resulting in insufficient coating workability by dipping, difficulty in controlling the thickness of the applied film, and poor uniform film formation. .

On the other hand, if it exceeds 1900 parts by weight, it is difficult to control the thickness of the crosslinked cured film, resulting in loss of surface smoothness and poor abrasion resistance, which is not preferable.

The type of organic solvent used must satisfy the conditions mentioned above, and specifically, ethanol, impropatol, normanpropanol, isophthyl alcohol, n-butyl alcohol, benzene,
Aromatic hydrocarbons such as tonene, glycylene, and ethylbenzene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, ethyl acetate, and acetic acid n-
Examples include esters such as butyl and ethyl propionate. These organic solvents may be used alone or in combination of two or more, as long as the N18 point of the mixture and the component ratio are within the range that satisfies the above requirements. Good too.

In addition, polymerizable monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and stinone can be used as a type of organic solvent if they have a specific purpose, meet the same conditions, and have the same effects as organic solvents. You can also use

Depending on the type of synthetic resin that is used as the base material, these organic solvents may cloud the material used for transparent purposes, elute dyes and pigments from the colored base material, causing discoloration, or may cause cracks in the base material itself. Therefore, it is desirable to select the type of organic solvent to be used depending on the purpose of thickening the substrate on which a crosslinked cured film is to be formed.

In the present invention, in order to apply the coating material composition to the surface of the synthetic resin molded product and form a crosslinked cured film, ultraviolet light,
It is necessary to irradiate active energy rays such as beams, electron beams, or radiation. Among them, wavelength 2000~8000A
The method using ultraviolet irradiation is the most preferred crosslinking and curing method from a practical standpoint.

When ultraviolet rays are used as energy rays for crosslinking and curing coatings, it is necessary to add a photosensitizer that initiates polymerization initiation reactions upon irradiation with ultraviolet rays to the coating material composition.

Specific examples of such photosensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, pencil/isopropyl ether, acetoin, butyroin, toluoin, and benzyl.

Benzophenone, P-chlorobenzophenone, P-methoxybenzophenone, methylphenylglyoxy V-)
, carbonyl compounds such as ethylphenylglyoxylate and n-butylphenylglyoxinto, sulfur compounds such as tetramethylthiuram monosulfite and tetramethylthiuram disulfide, azobisisobutyronitrile, azohis-2,4-dimethyl Examples include azo compounds such as valeronitrile, and peroxide compounds such as benzoyl peroxide and di-tert-butyl peroxide. These photosensitizers may be used alone or in combination of two or more.

Among these, the following general formula (in the formula, R is an alkyl group having 1 to 10 carbon atoms)
It is particularly preferable to use an alkyl phenylglyoxylate represented by: By using phenylglyoxylic acid in combination, the effect of improving the scratch resistance under low loads due to the linear higher saturated fatty acid alkyl becomes more pronounced.

The amount of these photosensitizers added to the monomer mixture is in the range of 101 to 10 parts by weight per 100 parts by weight of the monomer mixture in total; adding too much may cause coloring of the crosslinked cured film. This is undesirable because it causes problems such as drying and a decrease in weather resistance.

Furthermore, additives such as antistatic agents, ultraviolet absorbers, and storage stabilizers may be appropriately added to the coating material composition used in the present invention, if necessary.

The above are the essential components of the covering material composition used in the present invention, and in order to produce a wear-resistant synthetic resin molded product with excellent surface smoothness, the covering material composition can be molded with synthetic resin. After coating the surface of the product, it is molded by irradiating it with ultraviolet light in an air atmosphere.

In the present invention, it is preferable to use a dip coating method as a method for applying a coating composition to a synthetic resin molded article.

In order to form a film with excellent surface smoothness, it is preferable to use a dipping method.If a coating method other than the dipping method, such as a spray coater method, curtain coater method, or roll coater method, is used, the surface smoothness may not be improved. Unable to form an excellent secondary coating. Of course, in the case of synthetic resin molded articles that do not particularly require surface smoothness or uniformity, it is of course possible to employ a coating method other than the dipping method.

The amount of the coating material composition applied to the surface of the synthetic resin molded article varies depending on the purpose and location of the monomer mixture contained in the coating material composition. Cured film thickness range 1J to 30μ
It is necessary to apply it so that it becomes I4rC. If the thickness of the cross-linked cured film formed on the surface of a synthetic resin molded product is less than 1 μm, the wear resistance will be poor, and if it exceeds 30 μm, the cured film will have poor reclosability and cracks will easily occur. This is not preferable because it may cause a decrease in the strength of the molded product itself.

If the immersion method is used, the film thickness can be adjusted and the uniformity and smoothness of the film can be freely achieved by arbitrarily changing the monomer content of the curing liquid, liquid viscosity, lifting speed from the immersion tank, etc. . In addition, although there are some restrictions depending on the shape of the synthetic resin molded product, the coating process is simple, there is little loss of the coating material composition, and it has excellent workability and productivity as well as excellent reproducibility. There are advantages such as:

In order to crosslink and cure the coated film, as mentioned above, ultraviolet rays with a wavelength of 200 to AOOOX are most preferable, and the irradiation atmosphere is sufficient in normal air, but of course nitrogen can be used if it is easily available. Of course, it can be carried out in an inert gas such as gas, carbon dioxide, or helium, or in an atmosphere with a reduced oxygen concentration. The temperature of the irradiation atmosphere may be room temperature, or may be an atmosphere heated to such an extent that no harmful deformation occurs to the base synthetic resin molded product.

In the present invention, synthetic resin molded products used in the production of wear-resistant synthetic resin molded products include various synthetic resin molded products 1, regardless of thermoplastic resin or thermosetting resin, such as polymethyl methacrylate resin, polycarbonate resin, polycarbonate resin, etc. Allyl diglycol carbonate resin, Boristin resin,
Acrylonitrile-styrene copolymer resin (AS resin),
Polyvinyl chloride resin, acetate resin, ABI3 resin,
Specific examples include plate glass manufactured from polyester resin, sheet-shaped molded products such as mirrors, film-shaped molded products, rod-shaped molded products, various lens molded products, and various injection molded products such as lighting equipment covers.

Among these molded products, molded products manufactured from polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol cargenate resin, etc. take advantage of their optical properties, heat resistance, YE impact resistance, etc. Because it is often used and there is a strong demand for improved wear resistance.

This is particularly preferred.

Each of the above-mentioned Afi molded products used in the present invention can be used as is, but if necessary, pretreatments such as cleaning, etching, corona discharge, active energy ray irradiation, dyeing, and printing may be performed. can also be used.

The coating material composition of the present invention and the synthetic resin molded product having a crosslinked cured coating on the surface produced using the same have excellent surface smoothness and aesthetic appearance, and have extremely excellent surface hardness, abrasion resistance, and scratch resistance. It is something that Furthermore, the cross-linked cured film formed on the surface is a transparent, flexible, and uniform film that has extremely good adhesion to the base material and does not cause peeling or cracking even under harsh conditions or environments. It is extremely useful for applications such as organic window glass, lighting equipment covers, reflectors, mirrors, eyeglass lenses, sunglass lenses, and optical lenses.

The content of the present invention will be further described below by actual/m 14J f:P
As explained in the following, parts in the examples represent parts by weight.

The measurements and evaluations in the column were carried out in the following manner.

(1) Abrasion resistance a) Surface hardness: Pencil hardness according to JXB K-5400 b) High load abrasion test Attach steel wool of ≠000 to the tip of a load cylinder with a diameter of 20 m and place it on the test product with a load of 5001. Press and rotate 5 times (at a speed of 20 rpm). The degree of damage is then evaluated using the following criteria.

○: There is almost no field attached to the sample surface.

Δ...The sample surface is slightly biased.

×...The sample surface is severely damaged.

C) Low-load abrasion test (Hardness measurement method using silicon carbide with low-load continuous reciprocating vibration method) Measurement method [A wool felt tread with +1000 mesh of silicon carbide attached is attached to the tip of a load cylinder with an α diameter of 20 m, and it is held constant. It is pressed against the sample surface under a load (13 or) and reciprocated. The degree of adhesion of scratches at that time is measured with a 'Hazemeter, and evaluated by the number of reciprocations when the Haze becomes 3%.

Here, sample detergent before testing Method A is a method of cleaning using water and water. Method B is to not wash.

(2) Cross-cut cellophane tape peeling test on adhesive crosslinked cured film. In other words, there are 11,111 film cutting lines in the film that reach the base material, and 11 film cutting lines are inserted vertically and horizontally.
Make a total of 100 pieces of 2, paste a cellophane tape on top of it, and then peel it off quickly. Repeat this cellophane tape operation three times at the same location.

O... No peeling marks in the crosslinked cured film even after repeating 3 times Δ... Number of peeling marks after repeating 3 times 1 to 50 x... Number of peeling marks after repeating 3 times 51 - 100 pieces (3) Flexibility (maximum bending angle) A cross-linked cured film is formed on the surface of a sheet-shaped molded product with a thickness of 2 to 3 mm, and a strip-shaped test piece with a width of 6 cm and a length of 5 mm is cut out from it. Apply force from both ends of this strip to give it bending deformation strain, and find the angle from the horizontal plane of the test piece when a crack occurs in the coating. This is the "maximum bending angle", and the larger the angle, the better the flexibility of the seed coating.

(4) Surface smoothness measurement Visual method ○...The surface smoothness of the coating is good.

X: The surface is disturbed and the smoothness is poor.

Examples 1 to 4, Comparative Examples 1 to 3 20 parts of dipentaerythritol hexaacrylate, 13 parts of dipentaerythritol pentaacrylic V-), tetrahydrofurfuryl acrylic V-door part, 4' parts of inpropyl alcohol - 10 parts of isobutyl alcohol A smooth methacrylic resin plate with a thickness of 3-3 was placed in each coating material made by uniformly mixing 10 parts of toluene, 12 parts of the photosensitizer O and a shown in Table 1, and 12 parts of the wear resistance improver α. Soaked and α5 c!
A film was formed by pulling at a speed of R/8ec. The resin plate was then left to stand for 3 minutes, and then irradiated with a 2 KW high-pressure mercury lamp in the air for 10 seconds to obtain a resin plate with a surface-cured film.

Table 1 shows the test results of the abrasion resistance (test method (a), test method (C)) and smoothness of the obtained resin plate.

BiP: Penzoin isopropyl ether BNP:
Benzophenone IPG: Ethylphenylglyoxylate iBP:
Isobutyl palmitate nBP: n-butyl palmitate MO: Methyl oleate 8A Ni-stearin monoglyceride DME Nidimethyl polysiloxane (manufactured by Matsumoto Yushi, viscosity 20 centistokes) Example 5 45 parts of dipentaerythritol hexaacrylate, dipentaerythritol tetra Acrylate sa# 25 parts of tetrahydrofurfuryl acrylate, 4 parts of benzoin ethyl ether, 100 parts of isopropyl alcohol,
) An optical lens made of polyallyl diglycol carbonate is immersed in a coating material prepared by mixing 50 parts of Chef and 25 parts of isooctyl palmitate α, which is a low-load scratch resistance improver, (L 5 cm /
Pulled up at sea speed and received 1! Please form rJ. After being left for 3 minutes, it was irradiated with a 2 KW high-pressure mercury lamp for 10 seconds in an air atmosphere to produce a surface-hardened V-lens.

When the abrasion resistance of the obtained V-lens was measured, the pencil hardness was ○ in the 8H1 high-load abrasion test and 150 in the low-low-load abrasion soot B method. When used, there was no change in pencil hardness and abrasion resistance in the high load scratch test, but it was 95 in the low load scratch test E method.

Example 6, Comparative Examples 4 to 5, Reference Example 1 A pre-hardening solution shown in Table 2 was prepared, a methacrylic resin plate (3-) was immersed in it, and the plate was pulled up at a speed of [1L75I/θec]. A film was formed.

After being left as is for 10 minutes, both sides of the plate were irradiated with a 2 KW high-pressure mercury lamp for 15 seconds in the atmosphere listed in Table 2.

The expected results are shown in Table 2.

Actual #1 rows 7 to 8, comparison row 6 A curing solution as shown in Table 3 was prepared, and a 2wR thick methacrylic resin plate fc was immersed in it and pulled up at a speed of 0.5m788C to form a film. After leaving it for 5 minutes, irradiate both sides of the plate with a 2KH high-pressure mercury lamp for 10 seconds in an air atmosphere. The thickness of each cured film was 4μ.

The results obtained are shown in Table 5VC.

Claims (1)

[Claims] 1. (a) The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (wherein the formulas X_1_1, X_1_2, X_1_3, X_2_
2, X_2_3, ..., X_n_2, X_n_3, X
At least 3 of _1_4 are CH_2=CR-COO
- group and the rest are -OH groups. n is an integer from 1 to 5. R represents hydrogen or a methyl group. 30 to 90% by weight of at least one polyfunctional monomer selected from poly(meth)acrylates of mono- or polypentaerythritol having three or more (meth)acryloyloxy groups in one molecule represented by and has at least ether bonds in one molecule, and has a boiling point of 150°C or higher at normal pressure,
A monomer mixture consisting of 70 to 10% by weight of one or more monofunctional acrylates or methacrylates having a viscosity of 20 cps or less at 20°C; (b) a photosensitizer based on 100 parts by weight of the monomer mixture; 0
．． 01 to 10 parts by weight, (c) 0.05 to 3 parts by weight of linear higher saturated fatty acid alkyl ester per 100 parts by weight of the monomer mixture, (d) homogeneous by mixing with the monomer mixture. A coating material composition comprising 10 to 1900 parts by weight of at least one organic solvent that forms a solution, based on 100 parts by weight of the monomer mixture, is uniformly applied to the surface of a synthetic resin molded article, and then air is applied. UV rays are irradiated inside to create a film thickness of 1 to 3 on the surface of the synthetic resin molded product.
A method for producing a synthetic resin molded article having improved abrasion resistance, characterized by forming a crosslinked cured film of 0μ. 2. The polyfunctional monomer represented by general formula (1) is dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2.) The method for producing a synthetic resin molded article according to claim 1, wherein the compound is at least one compound selected from the group consisting of acrylates. 3. Linear higher saturated fatty acid alkyl ester is 14-1
Linear higher saturated fatty acids having 8 carbon atoms and 3 to 10
2. The method for producing a synthetic resin molded article according to claim 1, wherein the synthetic resin molded article is an ester with a hydric alcohol having a carbon number of 1 and a side chain. 4. The method for producing a synthetic resin molded article according to claim 1, wherein the synthetic resin molded article is polymethyl methacrylate, polycarbonate resin, or polyallyl diglycol carbonate resin.