JPS59133268A - Matte coating material composition having excellent wear resistance - Google Patents

Abstract

PURPOSE:To provide a coating material compsn. having excellent resistance to wear and marring, flatting and dispersion stability, consisting of a specified monomer mixture, a specified composite material of an inorg. compd. and an org. polymer, a photosensitizer and an org. solvent. CONSTITUTION:A compsn. consists of 100pts.wt. monomer mixture (a) consisting of at least 30wt% compd. having at least three (meth)acryloyloxy groups per molecule and not more than 70wt% compd. having 1-2 alpha,beta-ethylenically unsaturated bonds per molecule, 0.01-20pts.wt. composite material (b) obtd. by polymerizing a vinyl monomer in a polymn. system contg. a sulfonic acid monomer or a sulfate salt monomer of formula I (wherein R1 is a 1-15C alkyl group, etc.; X is NH4, etc.) or a carboxylic acid monomer of formula II or III (wherein R2 is halogen, etc.; R3 is phenyl, etc.; R4, R5 are each H, etc.) and fine inorg. particles dispersed therein, 0.1-6.0pts.wt. photosensitizer (c), and 100-2,000pts.wt. org. solvent (d).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a matte coating composition with excellent wear resistance.

Molded products of thermoplastic resins such as polymethyl methacrylate resin, polycarbonate resin, ABS resin, nylon/resin, and PET resin are generally glossy, which is considered an important characteristic depending on the application, but on the other hand, this There are many applications in which matte plates are preferred, but in recent years there have also been many applications such as matte plates and non-glare plates that scatter single reflected rays and eliminate gloss without compromising optical properties such as total light transmittance. It has become.

Conventionally, methods for achieving matteness on molded products include adding fine particles of silica, titanium oxide, aluminum oxide, etc. to paint, or adding these particles to resin and applying them to the surface during molding. It was produced by raising the surface of the material and eliminating its luster, or by molding it in a mold with a finely textured surface, or by performing cast l-polymerization in a cell with a finely textured surface.

However, with paints that simply contain silica, titanium oxide, aluminum oxide, etc., when the paint is stored, the dispersion stability deteriorates over time, resulting in hard sedimentation that is difficult to redisperse.
Or the degree of matteness may change. Also, there are methods to obtain matte molded products using molds or cell cast transfer.

Careful attention must be paid to the maintenance and management of molds and cells. However, in any case, with this method, even if a matte molded product is temporarily obtained, the wear resistance of the two surfaces,
Because it has poor scratch resistance, scratches easily occur and damage the matte surface.

In order to improve these shortcomings, the present inventors continued intensive studies and found that radical It was discovered that a composite in which an inorganic compound and an organic polymer are strongly united can be obtained by a method of bringing a polymerized vine vinyl monomer into contact with inorganic fine particles. When the coating material composition obtained by blending the mixture in a specific proportion with the mixture was applied to a plastic molded product and cured, the coating material composition showed not only excellent dispersion stability but also excellent abrasion resistance and scratch resistance. The present inventors have discovered that it is possible to produce plastic molded products that also have extremely excellent matte properties, and have thus arrived at the present invention.

jYr That is, the gist of the present invention is as follows.

(a) A 70 weight plate of a compound having at least 3 (meth)acryloyloxy groups in one molecule and a compound having 301 weight or more and 1 to 2 α,β-ethylene thread unsaturated bonds in one molecule A monomer mixture consisting of:

(bl Based on 100 parts by weight of the monomer mixture, the following general formula % formula % [:] (wherein r R1 is H2 an alkyl group having 1 to 20 carbon atoms, a phenyl group and its derivatives, or 2) a halogen atom, X is -CONH-, -CONH-C-R
,-.

3 -〇〇〇(CH2)rrl- or -(CH2)n-.

R2 and R are each H or an alkyl group having 1 to 15 carbon atoms, R4 is an alkyref group having 0 to 15 carbon atoms, and 2m is 1 to 15 carbon atoms.
an integer of 20, n is an integer of O to 20, Y represents H, NH, or an alkali metal atom) following the general formula (wherein, RI is an alkyl group having 1 to 15 carbon atoms,
cooy, halogen atom or phenyl group and derivatives thereof, R2 is H2 alkyl group having 1 to 15 carbon atoms,
cooz, halogen atom or phenyl group and its derivatives, R8 is H2 alkyl group having 1 to 15 carbon atoms,
Halogen atom or phenyl group and its derivatives, X,
Y, Z+! (each represents H, NH, or an alkali metal atom) or the following general formula (in the formula + R4 + R1 each represents H2 carbon number 1-15
at least one monomer selected from the group consisting of sulfo/acid monomers, sulfonate monomers, or carboxylic acid monomers represented by j) and inorganic fine particles. 0.01 to 20 parts by weight of a composite of an inorganic compound and an organic polymer obtained by polymerizing at least one radically polymerizable vinyl monomer in a dispersed polymerization system.

(cl 0.01 to 6.0 parts by weight of at least one photosensitizer per 100 parts by weight of the monomer mixture.

and (dl) A matte liquid covering material composition having excellent abrasion resistance and comprising 100 to 2000 parts by weight of an organic solvent per 100 parts by weight of the monomer mixture.

In the present invention, the compound having at least three (meth)acryloyloxy groups in one molecule is an essential component in order to improve the scratch resistance and abrasion resistance of the coating material composition,
In order to obtain better abrasion resistance and scratch resistance, these trifunctional or more functional compounds should be contained in the monomer mixture in an amount of 30% by weight or more, and the trifunctional or more functional compound should be present in an amount of 1 to 2 in one molecule. It is necessary that the average molecular weight per polymerizable unsaturated group in the monomer mixture having α,β-ethylenically unsaturated bonds is 300 or less. The content of compounds having three or more (meth)acryloyloxy groups in one molecule is 3O
When the N amount is less than 100%, or when the average molecular weight of one polymerizable unsaturated group in the monomer mixture exceeds 300 even if the amount of these compounds exceeds 300 parts by weight, sufficient abrasion resistance and scratch resistance are obtained. may not be obtained.

Compounds having three or more (meth)acryloyloxy groups in one molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)
Acrylate, pentaglycerol tri(meth)acrylate.

Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate.

Poly(meth)acrylates of polyhydric alcohols such as tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate;
Malonic acid/trimethylolethane/(meth)acrylic acid.

Maron! /)! J Methylolpropane/(meth)acrylic acid, malonic acid/glycerin/(meth)acrylic acid, malonic acid/pentaerythritol/(meth)atalylic acid,
Succinic acid/trimethylol emme//(methanoacrylic acid, succinic acid/trimethylolpropane/(meth)acrylic acid.

Succinic acid/glycerin/(meth)acrylic acid.

Succinic acid/pentaerythritol/(meth)acrylic acid, adipic acid/trimethylolethane/(meth)acrylic acid, adipic acid/trimethylolpropane/(meth)
Acrylic acid, adipic acid/pentaerythritol/(meth)acrylic acid, adipic acid/glycerin/(meth)acrylic acid, glutaric acid/trimethylolethane/(meth)acrylic acid, glutaric acid/trimethylolgloban/
(meth)acrylic acid, glutaric acid/glycerin/(meth)acrylic acid, glutaric acid/pentaerythritol/(
meth)acrylic acid, sepacifrll/)limethylolethane/(methaneacrylic acid, sebacic acid/trimethylolpropane/(meth)acrylic acid, sebacic acid/glycerin/(meth)acrylic acid, sebacic acid/pentaerythritol/(meth) ) acrylic acid, fumaric acid/trimethylolethane/(meth)acrylic acid, 7malic acid/trimethylolpropane/(meth)acrylic acid, fumaric acid/chrycerin/(meth)acrylic acid, fumaric acid/pentaerythritol/(meth) ) Acrylic acid, itaconic acid/trimethylolethane/(meth)acrylic acid, itaconic acid/trimethylolpropa//(meth)acrylic acid, itaconic acid/pentaerythritol/(meth)acrylic acid, maleic anhydride/trimethylolethane /(meth)acrylic acid, maleic anhydride/glycerin/(meth)acrylic acid, etc. saturated or unsaturated polyester poly(meth)ac υL/-) ;) IJ methylolpropane toluylene diisocyanate, or The following general formula (wherein Rbahexamethylene diisocyanate.

4.4'
- Methylenebis(cyclohexyl incyanate), inphorone diisocyanate.

2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy- Urethane (meth)acrylate obtained by reacting 3-methoxypropyl (meth)acrylate, N-methylol (meth)acrylamide, N-hydroxy (meth)acrylamide, etc. with 93 or more molecules per incyanate molecule by a conventional method; Tris +2-hydroxyethyl±isocyanuric acid tri(meth)acrylate and the like can be mentioned.

As the compound having 1 to 2 α,β-ethylenically unsaturated bonds in one molecule, any ordinary monomer with radical polymerization activity can be used, but the polymerizable unsaturated group A compound having a (meth)acryloyloxy group is preferable because it has excellent polymerization activity by ultraviolet rays. Specific examples of these compounds include ethylene glycol di(meth)acrylate as a compound having two (meth)acryloyloxy groups in one molecule;
Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene/glycol di(meth)acrylate, polyethylene/
Cricol di(meth)acrylate, 1,4-geta/diol di(meth)acrylate, 1°6-hexanethiol di(meth)acrylate.

Unskilled Pe/Tyl glycol di(meth)acrylate, Globylene glycol di(meth)acrylate, Diprobi V
/Glycol di(meth)acrylate; tolylene diisocyanate, xylylene diisocyanate, naphthalene/
diincyanate, hexamethylene diincyanate,
Acrylic monomers having diincyanates such as tetramethine/diisocyanate, lysine diisocyanate, 4,4'-diphenylmethane diincyanate and active hydrogen, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
2-Hydroxy-3-methoxyfurovir (meth)acrylate, N-methylol (meth)acrylamide.

Urethane acrylate obtained by reacting N-hydroxy(meth)acrylamide etc. with 92 incyanate molecules per molecule by a conventional method; or the following general formula (wherein R1 is hydrogen or a methyl group, Xl, X2...・
Xn is the same or different alkyrev group having 6 or less carbon atoms, or one hydrogen atom thereof is replaced with a hydroxyl group and has a structure of 1, where n is an integer from O to 5).
For example, 2,2-bis+4 acryloxyphenyl±propane, 2,2-bis+4 methacryloxyphenylnabroban, 2,2-bis+4 acryloxyethoxyphenyltipropay, 2,2-bis+4 methacryloxy Ethoxyphenylthipropane, 2,2-bis+4acryloxydiethoxyphenyl±propane, 2.2-bis+4methacryloxydiethoxyphenylnapropane, 2,2-bis+4acryloxyglopoxyphenylnapropane, 2
, 2-bis+4methacryloxyf''roboxyphenyltyflopane, 2,2-bis+4acryloxy(2hydroxypropoxy)phenylproha'+ 212-bismo4methacryloxy(2hydroxypropoxy)phenylpropane, 2,2-bis 4 Acryloxy(2hydroxypropoxyethoxy)phenylpropane, 2,
Examples include 2-bis(-4methacryloxy(2hydroxygloboxyethoxy)phenyl)furopane.

Examples of compounds having one (meth)acryloyl group in one molecule include methyl (meth)acrylate and propyl (meth)acrylate.

Butyl acrylate, inbutyl acrylate.

t-7-f acrylate, 2-ethylhexyl acrylate acrylate, cyclohexyl acrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyglobyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate) t
1 r 4-7-ethylene glycol monoacrylate, ethoxyethyl acrylate, ethylcarpitol acrylate), 2-hydroxy-3-chloropropyl acrylate, acrylamide, N-hydroxymethyl (
meth)acrylamide, N-hydroxyethyl(meth)
Acrylamide, N-hydroxypropyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, hydroxymethyl diacetone acrylamide, N
-Hydroxyethyl-N-(methyl)acrylamide, etc. can be mentioned.

Among these compounds, compounds having three or more (meth)acryloyloxy groups in one molecule have the following general formula (wherein, Xll, X12, Xl3, X22
, X23''・Xn2, Xn3, X14, at least three of them are CH, = CM -Coo- groups, and the rest are hydroxyl groups, ε groups, alkylene groups, substituted alkylene groups, etc. Q, n&!2~ Compound 2 represented by (an integer of 5) such as dipentaerythritol triacrylate, dipentaerythritol tetraacrylate,
Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. are particularly preferred because they have excellent curing properties with ultraviolet rays in the air.
When considering cost and the like, it is preferable to use at least one compound having at least three (meth)acryloyloxy groups in one molecule of these compounds in an amount of 20 weight percent or more.

Further, for the same purpose, compounds having 1 to 2 (meth)acryloyloxy groups in one molecule used in combination with these include compounds 2 represented by the general formula [V], such as 2,2-bis+4 -Acryloxethoxyphenylnapropane, 2,2-bis+4-acryloxyjethoxyphenyl±7"O huff, 2,2-bis+4-acryloxyglopoxyphenylnapropane p zt2-
his(-4-acryloxy-(2-hydroxypropoxy)phenyl÷propane, 2.2-bis-E-4-
Acryloxy (2-hydroxypropoxyethoxy)
Preferred bifunctional monomers include phenyl÷propane, and monofunctional monomers include 2-hydroxyethyl acrylate, 2-hydroxyglohylacrylate, and glycidyl acrylate.

Is there a hydroxyl group in the side chain of a compound like tetrahydrofurfuryl acrylate, ethoxyethyl acrylate, ethyl carpitol acrylate, butoxyethyl acrylate, 1゜4-butylene glycol monoacrylate?
Acrylates having a cyclic ether bond and/or a chain ether bond are particularly preferred because they have excellent polymerization activity with ultraviolet rays in normal atmosphere.

The complex of an inorganic compound and an organic polymer has the general formula CD,
In a polymerization system in which at least one monomer selected from the group consisting of sulfonic acid monomers, sulfonate monomers, or carboxylic acid monomers represented by (1:) or [I] and inorganic fine particles are dispersed, at least one
It is obtained by polymerizing various radically polymerizable monomers. These composites are essential components for obtaining a matte molded article, which is the object of the present invention.

By blending a small amount of these into the composition, a plastic molded article with excellent uniformity and mattness, as well as excellent wear resistance and surface hardness can be obtained. Of course, a matte molded product may be obtained by blending only inorganic fine particles, but since the viscosity of the composition of the present invention is as low as 100 cps/20°C or less, 2% of the inorganic fine particles in the coating material composition may be obtained. The dispersion stability of inorganic fine particles is poor, and if left for a long time, they may solidify in the form of a cake at the bottom and may not be redispersed. Furthermore, because the dispersibility of the inorganic fine particles in the coating material composition is poor, a matte pattern with good uniformity cannot be obtained at all.

However, when a composite of inorganic fine particles and an organic polymer is used, these drawbacks are solved at once, and the dispersibility and dispersion stability in the coating material composition are also very good. Glass molded products with excellent matte pattern uniformity can be easily obtained.

The detailed mechanisms of the dispersibility and dispersion stability of the composite in the coating material composition as well as the ability to develop a uniform matte pattern have not been fully elucidated.

In a composite having an organic polymer in the outer layer, the organic polymer is interposed between the inorganic substance, the organic polyfunctional (meth)acrylate, and the organic solvent, and the above-mentioned excellent effects are due to this inorganic polymer. This is thought to be due to the organic polymer strongly integrated into the outer layer of the fine particles.

Sulfo/acid monomers, sulfonate monomers or carboxylic acid monomers represented by the general formula CI], (:Il) or CI) used to produce composites of inorganic compounds and organic polymers include inorganic substances and The presence of a sulfonic acid group or a carboxylic acid group, which has a unique polymerization activity with organic substances, and a dil bond, which develops a strong bond between the resulting polymer and the inorganic substance, is essential. All compounds that have the following can be applied. For example, 2-acrylamide-2-methylpropane/L/phonic acid (hereinafter abbreviated as AMPS), sodium 2-methacrylethanesulfonate (hereinafter abbreviated as AMPS).

SEM-Na), 3-sodium methacrylicpropanesulfonate (hereinafter abbreviated as sps), 2-
Prope/sodium sulfonate (hereinafter abbreviated as NaAS), 2-methyl-2-prope/sodium sulfonate (hereinafter abbreviated as NaMS), acrylic acid, methacrylic acid, crotonic acid, tiglic acid, cinnamic acid, anhydride Maleic acid.

Examples include citraconic anhydride, but especially AMPS containing an amide bond and SEM 7Na containing an ester bond.
M and sps, or acrylic acid.

Methacrylic acid R and crotonic acid have high polymerization activity and are preferred.

The inorganic fine particles used in the present invention have a particle size of 1 mμ to 1
It is preferable to adjust the polymerization so that the particle size of the composite of inorganic fine particles and organic matter is 1 mμ to 100 μm, and it is preferable to adjust the polymerization so that the particle size is 1 μm to 100 μm. More preferably, the particle size is 5 mμ to 50μ.

As an inorganic compound, it is listed in the first periodic table.　　I[,I.

■ Group V, transition metals and their oxides, hydroxides, chlorides, sulfates, sulfites, carbonates.

Phosphates, silicates 8 and mixtures thereof, complex salts are effective, especially calcium sulfite.

Calcium sulfate, silicon dioxide, titanium oxide.

Antimony trioxide, Merck, clay, aluminum oxide, calcium back acid, carbon black.

Nickel powder, iron powder, zinc powder, copper powder, ferric oxide.

Zinc oxide and aluminum hydroxide are preferred because they have a particularly remarkable effect of activating the vinyl monomer and strongly integrating it with the polymer. Moreover, these can also be used in the form of organosol or aqueous sol. Among these, silicon dioxide has good transparency and is therefore particularly preferred when optical properties of molded articles, particularly transparency and low haze value, are required.

The vinyl monomer used in the present invention includes:

Although any of the ordinary vinyl monomers that undergo radical grouping are applicable, methyl methacrylate has a particularly high polymerization activity and good compatibility between the resulting polymer and inorganic compounds. Therefore, it is particularly preferable. When using a mixture of two or more types of monomers, using methyl methacrylate as one component can be said to be a preferable application method, especially from the viewpoint of polymerization activity.

According to the invention, the concentration of sulfonic acid monomers, sulfo/acid acid monomers or carboxylic acid monomers is used in an amount of about 0.05 to 100 parts by weight, based on the total weight of inorganic compound and monomer. .

In most cases, it is preferred to increase the amount of sulfo/acid monomer, sulfonate monomer, or carboxylic acid monomer as the monomer content increases. The weight ratio of monomer or monomer mixture to inorganic compound used can vary within a wide range and may range from about 500:1 to 1:5. Preferably the ratio is from about 50:1 to about 1:1.

The polymerization reaction medium may be aqueous, organic solvent, or a mixture thereof, but it is preferable to use water in combination. In some cases, a small amount of a polymerization regulator, dispersant, etc. such as mercaptan may be used in combination. The amount of reaction medium is about 1 to several hundred times the total weight of the inorganic fine particles and monomer.

The reaction is preferably carried out at a temperature of about 10-100°C under an atmosphere of an inert gas, such as nitrogen.

Preferably it is carried out at 20-80°C. The specific reaction temperature here is selected as appropriate depending on the vinyl monomer used, but it is important to carry out the reaction at a temperature at which thermal polymerization is suppressed to a non-ignorable degree, and at a temperature so high that thermal polymerization is extremely difficult. When this is done, the integrity and homogeneity of the resulting conjugate is inhibited. Reaction time is 30 minutes to about 15 hours. The resulting complex is heated to about 10-300°C, preferably about 50-20°C.
Although it can be used after being dried in a temperature range of 0° C., it is preferable to use the mixture of the two complexes and the reaction medium as it is because a redispersion step using a homomixer or the like is not necessary. However, care must be taken to ensure that the solid content of the composite falls within the range of 0.01 to 20 parts by weight per 100 N parts of the monomer mixture. If the amount of the composite is less than 0.01, the matting properties will be poor, and if it exceeds 20 parts by weight, the amount of the composite will be too large and the surface uniformity will be poor.

The interaction between the surface of the inorganic compound and the polymer goes beyond adhesion in a physical sense due to simple adsorption or van der Waals forces, and this fact can be extracted using a good solvent for vinyl polymers. It is clear from the fact that a large amount of unextracted polymer is observed even after treatment, that this polymer and the inorganic compound have strong compatibility and that the polymer has a significantly high molecular weight. The characteristic of this complex is that

The means for curing the coating composition of the present invention is usually 20 to
Although it is possible to irradiate active energy rays such as electron beams extracted from a 2000 KV electron beam accelerator or radiation such as α rays, β rays, and γ rays, in order to easily and economically cure the material, a wavelength of 100 KV is required. UV radiation in the range from nm to 500 nm is preferred. Of course, UV irradiation can be carried out in an inert gas such as nitrogen, carbon dioxide, or argon, but if a compound containing the specific acryloyloxy group mentioned above is used, it can be cured efficiently even in normal air. possible and economically the most preferable.

When ultraviolet rays are used as active energy rays, it is preferable to add a photosensitizer (photocatalyst) to the monomer mixture. Examples of these photosensitizers include benzoin, benzoin/methyl ether, Benzoin ethyl ether, benzoin propyl ether, acetoin.

butyroin, toluoin, benzyl, benzophenone,
p-methoxybenzophenone, jetoxyacetophenone/, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxin-toethylphenylglyoxyle), 4,4'-bis(dimethylaminebenzophenone), 2-hydroxy -2-methyl-1-
Carbonyl compounds such as phenylpropan-1-one.

Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide.

Azo compounds such as azobisinbutyronitrile and azobis-2,4-dimethylvaleronitrile.

Examples include peroxide compounds such as bennoyl peroxide and di-tertiary butyl peroxide. The amount added to 10'O parts by weight of the monomer mixture is 0.0
It is preferably 1 to 6 parts by weight, and if it is added in too large a quantity, the cross-linked cured film will be colored or the weather resistance will be deteriorated, which is undesirable. If the quantity added is too small, the curability by ultraviolet rays will deteriorate.

The above are the essential components constituting the present invention, but if necessary, the crosslinked cured film formed may have antistatic properties,
At least one other vinyl monomer having polymerization activity under ultraviolet rays may be used in combination for the purpose of imparting antifogging properties or other functions. In addition, stabilizers such as antioxidants, light stabilizers, thermal polymerization inhibitors, and ultraviolet absorbers are added as necessary.

A small amount of coloring agent may be added as appropriate.

The smoothness of the coating on the surface of the obtained molded product.

When uniformity is particularly required, the silicone-based leveling agent is preferably one whose molecular structure consists of polydimethylsiloxane units, a part of which is modified with polyoxyalkylene groups, and the degree of modification is is at least one oxyalkylene group (-0CH
2CH2-.

-QCH2CH-, etc.) within the range of 0.1 to 10.0 units.

Preferably, those bonded with If the degree of modification by oxyalkylene groups is less than 0.1, the smoothness of the film will be worse than when no silicone surfactant is added, whereas if the degree of modification by oxyalkylene groups exceeds 10, the smoothness of the film will be worse. This is not preferable because it reduces smoothness. In some cases, if a silicone leveling agent is not used, the resulting matte molded product may become white (cloudy), but this can be prevented by adding a small amount.

The coating composition of the present invention may be coated by brush coating, flow coating, spray coating, dipping coating, dipping coating, etc.;
Smoothness and uniformity of coating.

From the viewpoint of improving the adhesion of the cured film to the substrate, the most preferred method is to apply by dipping using a suitable organic solvent.

The amount of organic solvent used is 100 to 2000 parts by weight per 100 parts by weight of the monomer mixture, but when the composite is used in a mixed state with the reaction medium, the amount of organic solvent used in the coating material composition is 100 to 2000 parts by weight. Alternatively, it is necessary that the proportion of the mixed organic solvent with water does not exceed the above range. When the amount of organic solvent or organic solvent containing water used is less than 100 parts by weight.

It was not possible to obtain a film with good smoothness and uniformity, and on the other hand, 2000! If the amount exceeds 3 parts, the film thickness will become too thin and the abrasion resistance and scratch resistance will decrease. Further, when the reaction medium for producing the composite is an organic solvent containing water, it is necessary that water does not exceed 10% of the 100 to 2000 parts by weight of the organic solvent in the coating composition. If it exceeds 10%, water becomes a phase component in the coating composition! Please be careful as it may cause damage.

Yes! Specific examples of solvents include ethanol, inpropatol, normalprono< / -/L'+ iso7'
Chylalcohol nato alcohol/l' class 1 Bense/.

Aromatic hydrocarbons such as toluene/, xylene, and ethylbenzene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, ethyl acetate, and acetic acid n-
These include esters such as butyl and ethyl propionate. One or more of these organic solvents can be used in combination.

Care must be taken in selecting the solvent 2 and in the mixing ratio so that the coating composition does not undergo phase separation. In this respect, when a small amount of water is used, it is preferable to use an alfur solvent together.

The coating amount of the coating material composition on the surface of the synthetic resin molded product is such that the thickness of the cured film is 1 to 30 μm.

Preferably, it is necessary to apply the coating so that the thickness is in the range of 1.5μ to 20μ. If the thickness of the cross-linked cured film is less than 1μ, the abrasion resistance or surface hardness of the obtained molded product will decrease, and if it exceeds 30μ, the adhesion to the base material will decrease or cracks will occur. may be more likely to occur.

Synthetic resin molded products used to produce matte synthetic resin molded products with excellent abrasion resistance and scratch resistance using the composition of the present invention include thermoplastic resins and thermosetting resins. First, various synthetic resin molded products 2, such as polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, and polystyrene resin.

Acrylonitrile-styrene copolymer resin (AS resin),
Polyvinyl chloride resin, acetate resin.

A B S '41J]L Specific examples include sheet-like molded products, film-like molded products, rond-like molded products, and various injection molded products manufactured from polyester resin and the like. Among these molded products, molded products manufactured from polymethyl metagelylate, polycarbonate resin, etc. are often used mainly for their optical properties, heat resistance, impact resistance, etc. These molded products are particularly preferred as synthetic resin molded products used in the present invention, since there is a strong demand for improved abrasion resistance and weather resistance.

The matte synthetic resin molded product with excellent wear resistance and scratch resistance produced using the coating material composition of the present invention having the above-mentioned sticky composition has the following properties: smoothness, chemical resistance, and durability. Two examples of fields that require matte properties are CRT filters and TV filters.

Display related items such as taxi meters or digital display boards, lighting, optical related items, filters for fluorescent display tubes, f
It is extremely useful for applications such as product filters.

The present invention will be explained in more detail below with reference to Examples. Parts in Examples indicate parts by weight.

Note that the measurement and evaluation in the examples were performed in the following manner.

(1) Attach steel wool with scratch resistance #000 to the tip of a cylinder with a diameter of 25 mm, bring it into contact with the sample surface placed horizontally, and
Rotate 5 times (2 Or, p, m) with P load and visually observe the degree of scratch adhesion.

○...The sample surface is hardly scratched.

△・・・The sample surface is slightly scratched.

×...Equivalent value is attached to the sample surface.

(2) Uniformity of matte surface Based on visual judgment.

○・・・Good uniformity.

△...There is some unevenness.

×: Poor uniformity.

Examples 1-6. Comparative Examples 1 to 2 Monomers (S E M -N a ) and two of the compounds in Table 1 were placed in an 11 four-ring flask reactor equipped with a cooling tube, a nitrogen introduction tube, a stirring rod, and a thermocouple for internal temperature detection. The compound from which water had been removed was added and dispersed, followed by nitrogen displacement for 30 minutes with continued stirring. Then the remaining water and S E M -N
The mixture of (a) was added to the reactor and reacted for 5 hours at a reaction temperature of 50°C to obtain a composite.

40 parts of dipentaerythritol tetraacrylate, 40 parts of dipentaerythritol pentaacrylate, per 100N parts of the mixture of the obtained complex and reaction medium;
dipentaerythritol hexaacrylic L/-) 40 parts,
30 parts of tetrahydrofurfuryl acrylate, 125 parts of Improvil alcohol, 125 parts of toluene, α.

Composition consisting of 78 parts of α-dimethoxy-α-phenylacetophenol and 11 parts of silicone leveling agent (E-1
) were mixed to prepare various dressing compositions.

2 mm of each of these dressing compositions were then added to the immersion solution.
1. Thick acrylic plate (part name: Acrylite L manufactured by Mitsubishi Rayon Co., Ltd.). It was immersed at a pulling speed of Ocr/L/see to form a film, and then heated under a 2KW high pressure mercury lamp.
Irradiation was performed for 10 seconds at an irradiation distance of 200 m. The results obtained are shown in Table 2.

Table 1 Reaction composition of composite (parts) (1) Silica, average particle size 365μ, Fuji Devin Co., Ltd.
Made of (2) Silica 2. Average particle size: 1.6 mμ2 Manufactured by Nippon Aerosil Co., Ltd. (3) For comparison, one reaction was performed just by dispersing silica (4) Sodium 2-methacrylethanesulfonate (5) Methyl methacrylate (6) Ethyl Methacrylate Table 2 Examples 7 to 12 For 100 parts of a mixture of the complex shown in Table 1 and the reaction medium, dipentaerythritol tetraac') 3
0 parts g 40 parts dipentaerythritol pentaacrylate, 30 parts dipentaerythritol hexaacrylate y 10 parts 2,2-his±4-acryloxyjethoxyphenyltyphropa, 10 parts 2-hydroxyethyl acrylate, tetrahydrofur Furyl acrylate 30m, Inglovir alcohol 125m
) Composition consisting of 125 parts of toluene, 10 parts of 2-hydroxy-2-'-f-1-phenylpropane, and 0.57 parts of a silicone leveling agent (E-11)
A suitable dressing composition was prepared by mixing. Acrylic plates similar to those used in Examples 1 to 6 were immersed in these compositions and cured. The results obtained are shown in Table 3.

Table 3 Examples 13-21 Mixtures of composites and reaction medium were obtained in the same manner as in Examples 1-6 using the reaction compositions shown in Table 4. The same amount of the composition (E-■) used in Examples 7 to 12 was mixed with 100 parts by weight of these mixtures to prepare various coating material compositions.

Acrylic plates similar to those in Examples 1 to 6 were immersed in these compositions and cured. The results obtained are shown in Table 5.

Table 4 Reaction composition of complex (parts)

Claims (1)

[Scope of Claims] (1) (a) 30% by weight or more of a compound having at least three (meth)acryloyloxy groups in one molecule and one to two α,β-ethylene groups in one molecule A monomer mixture consisting of 70% or less of a compound having an unsaturated bond. (bl) General formula % formula % [1 (wherein, R1 is H1 an alkyl group having 1 to 20 carbon atoms, a phenyl group and its derivatives, or a halogen atom, and X is - C
ONH-'. 2 -CONH-C-R, -, -Coo(CH2)-m 3 or -(CH2)n-, p R2F R3 is each H or an alkyl group having 1 to 15 carbon atoms. R, ha is an alkyref group having 0 to 15 carbon atoms, 2m is an integer of 1 to 20, and n is an integer of 0 to 20. Y represents H, NH, or an alkali metal atom) The following general formula (wherein, R is H2 an alkyl group having 1 to 15 carbon atoms,
C00Y, halogen atom or phenyl group and its derivatives, R2 is H1 alkyl group having 1 to 15 carbon atoms,
cooz, halogen atom or phenyl group and derivative thereof p R3 is H1 alkyl group having 1 to 15 carbon atoms, halogen atom or phenyl group and derivative thereof, x
, y, and z each represent H, NH, or an alkali metal atom) or the general formula 10 of the arrow (in the formula, + R4 + R, each represents H2 carbon number 1 to 15
Polymerization in which at least one monomer selected from the group consisting of sulfonic acid monomers, sulfonate monomers, or carboxylic acid monomers (representing alkyl groups, halogen atoms, or phenyl groups, and derivatives thereof) and inorganic fine particles are dispersed. 0.01 to 20 parts by weight of a composite of an inorganic compound and an organic polymer obtained by polymerizing at least a vinyl monomer that undergoes radical polymerization of IPJ in the system. (c) 0.01 to 6.0 parts by weight of at least one photosensitizer per 100 parts by weight of the monomer mixture, and (d) 1 part by weight of an organic solvent per 100 N parts of the #monomer mixture.
00-200 A matte coating material composition with excellent abrasion resistance. (2) In a monomer mixture consisting of a compound having at least three (meth)acryloyloxy groups in one molecule and a compound having one to two α,β-ethylenically unsaturated bonds in one molecule. A matte coating material composition with excellent wear resistance according to claim (1), characterized in that the average molecular weight per polymerizable unsaturated group is 300 or less. (3) A compound having at least one or three methaneacryloyloxy groups in one molecule has the following general formula (wherein, Xll, X12. Xss, X22.
X2j-xn2. , Xns, at least three of X14 are 0H3=CH-'Coo- groups and the rest are hydroxyl groups,
An amino group, an alkylene group, a substituted alkylene group, etc., and n is an integer of 2 to 5. Claim No. (
1) A matte coating material composition with excellent wear resistance as described in item 1). (4) A compound having at least three (meth)acryloyloxy groups in one molecule is from dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaarylate, or dipentaerythritol hexaacrylate. A matte coating material composition with excellent abrasion resistance as set forth in claim 1, 2, or 3, characterized in that the composition is made of a selected material. (511 Compounds with 1 to 2 α, β-ethylenically unsaturated bonds in the molecule have 1 acryloyloxy group in the molecule, and the side chain has a hydroxyl group and/or a cyclic ether bond and/or A matte coating material composition with excellent abrasion resistance according to claim (1), which is a compound having a chain ether bond. (61 Sulfonic acid monomer, sulfonate monomer or The carboxylic acid monomer is 2-acrylamido-2-methylpropa/sulfonic acid. Sodium 2-methacrylethanesulfonate, sodium 3-methacrylethanesulfonate, acrylic acid,
The matte coating material composition with excellent wear resistance according to claim (1), characterized in that it contains at least one selected from methacrylic acid and crotonic acid. (7) A matte coating material composition with excellent wear resistance according to claim (1), characterized in that the main component of the vinyl monomer is methyl methacrylate. (8) Inorganic fine particles include calcium sulfite, calcium sulfate, silicon dioxide, titanium oxide, armonium trioxide, talc, clay, aluminum oxide, calcium carbonate, and carbon black. The wear-resistant material according to claim (1) is at least one selected from nickel powder, iron powder, zinc powder, copper powder, ferric oxide, zinc oxide, and aluminum hydroxide. A matte coating material composition with excellent properties. (9) Claim (1) or (8) characterized in that the inorganic fine particles have a particle size of 1 mμ to 100μ.
A matte coating material composition with excellent wear resistance as described in 2. (10) Claims (1), (8), or (1) characterized in that the inorganic fine particles are silicon dioxide.
9) A matte coating material composition with excellent wear resistance as described in item 9). (11) A matte coating material composition with excellent abrasion resistance according to claim (1), wherein the organic solvent contains water in an amount of 10% by weight or less.