JPH0219859B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an erasable coating material composition with excellent wear resistance. Molded products of thermoplastic resins such as polymethyl methacrylate resin, polycarbonate resin, ABS resin, nylon resin, and PET resin generally have ridges, which are considered to be an important characteristic depending on the application. There are many applications where it is preferable not to have a light beam, and in recent years, it has become possible to scatter reflected light without sacrificing optical properties such as total light transmittance.
The use of pine boards, non-glare boards, etc. that eliminate slats is also increasing. Conventionally, the methods for achieving this kind of erasure of molded products include adding fine particles of silica, titanium oxide, aluminum oxide, etc. to paint, or mixing them with resin, and then applying some method to the surface during molding. The methods used were to precipitate these materials and eliminate the ridges, or to mold them in a mold that already had a finely textured surface, or to perform cast polymerization in a cell that had a finely textured surface. However, when paints containing silica, titanium oxide, aluminum oxide, etc. are stored, the dispersion stability becomes poor over time, resulting in hard sedimentation that is difficult to redisperse, or the degree of dispersion changes. or Furthermore, the method of obtaining a matte molded product using a mold or cell cast transfer requires careful attention to the maintenance and management of the mold and cells, and is not necessarily an advantageous method. However, in any case, with these methods, even if a matted molded product is temporarily obtained, the surface has poor abrasion resistance and scratch resistance, so it is easily scratched, and the matted surface is easily damaged. often results in damage. In order to improve these shortcomings, the present inventors continued their intensive studies and found that a coating material composition containing a cross-linked fine particulate emulsion polymer and a specific polyfunctional methacrylate as the main components has excellent anti-friction properties. The present invention has been achieved based on the discovery that the resulting molded article has excellent abrasion resistance and scratch resistance, and the storage stability of the coating composition is also extremely excellent. That is, the present invention provides (a) 30% by weight or more of a compound having at least three acryloyloxy and/or methacryloyloxy groups in one molecule and one to two α,β-ethylenically unsaturated compounds in one molecule. A monomer mixture (A) consisting of 70% by weight or less of a compound having a bond, and (b) for 100 parts by weight of the mixture (A).
0.01 to 6.0 parts by weight of at least one photosensitizer; and (c) 0.5 to 30 parts by weight of a reactive monomer having one α,β-ethylenically unsaturated bond in one molecule. 75-99% by weight and 2 or more α, β in one molecule
- Reactive monomer 1 with ethylenically unsaturation
~25% by weight of an emulsifying crosslinked polymer or copolymer, and 85~99.9% by weight of a reactive monomer having one α,β-ethylenically unsaturated bond per molecule. Graft crosslinking agent having two or more α,β-ethylenically unsaturated bonds in 0.1 to 15
75-99% by weight of a reactive monomer having one α,β-ethylenically unsaturated bond in one molecule and two or more α,β-ethylenically unsaturated bonds in one molecule. , a crosslinked copolymer consisting of 1 to 25% by weight of a reactive monomer having a β-ethylenically unsaturated bond, and a multistage emulsion crosslinked polymer or copolymer in which the outermost layer is provided. The present invention provides a coating material composition which is cured by active energy rays, has excellent abrasion resistance and scratch resistance, and has erasable properties. In the present invention, the compound having at least three acryloyloxy and/or methacryloyloxy groups in one molecule is essential for improving the scratch resistance and abrasion resistance of the coating material composition, and provides better abrasion resistance. In order to obtain properties and abrasion resistance, these trifunctional or higher functional compounds should be present in the monomer mixture (A) at 30%
It is necessary for the compound to account for at least % by weight, and to contain a trifunctional or higher functional compound and 1 to 2 α, β-
Mixtures with compounds having ethylenically unsaturated bonds
The average molecular weight per polymerizable unsaturated group of (A) is 300
The following is desirable. If the content of compounds having three or more acryloyloxy and/or methacryloyloxy groups in one molecule is less than 30% by weight, or even if these compounds are 30% by weight or more, the polymerizability of monomer mixture (A) If the average molecular weight per unsaturated group exceeds 300, sufficient abrasion resistance and scratch resistance may not be obtained. Examples of compounds having three or more acryloyloxy and/or methacryloyloxy groups in one molecule include trimethylolpropane triacrylate or trimethacrylate, trimethylolethane triacrylate or trimethacrylate, pentaglycerol triacrylate or trimethacrylate, and pentaerythritol. triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, glycerin triacrylate or trimethacrylate, dipentaerythritol triacrylate or trimethacrylate, dipentaerythritol tetraacrylate or tetramethacrylate, dipentaerythritol pentaacrylate or pentamethacrylate, dipenta Polyacrylates of polyhydric alcohols such as erythritol hexaacrylate or hexamethacrylate, tripentaerythritol tetraacrylate or tetramethacrylate, tripentaerythritol pentaacrylate or pentamethacrylate, tripentaerythritol hexaacrylate or hexamethacrylate, tripentaerythritol heptaacrylate or heptamethacrylate or polymethacrylate; malonic acid/trimethylolethane/acrylic acid or methacrylic acid, malonic acid/trimethylolpropane/acrylic acid or methacrylic acid, malonic acid/glycerin/acrylic acid or methacrylic acid, malonic acid/pentaerythritol/acrylic acid or Methacrylic acid, succinic acid/trimethylolethane/acrylic acid or methacrylic acid, succinic acid/trimethylolpropane/acrylic acid or methacrylic acid, succinic acid/glycerin/acrylic acid or methacrylic acid, succinic acid/pentaerythritol/acrylic acid or methacrylic acid Acid, adipic acid/trimethylolethane/acrylic acid or methacrylic acid, adipic acid/trimethylolpropane/acrylic acid or methacrylic acid, adipic acid/
Pentaerythritol/acrylic acid or methacrylic acid, adipic acid/glycerin/acrylic acid or methacrylic acid, glutaric acid/trimethylolethane/acrylic acid or methacrylic acid, glutaric acid/
Trimethylolpropane/acrylic acid or methacrylic acid, glutaric acid/glycerin/acrylic acid or methacrylic acid, glutaric acid/pentaerythritol/acrylic acid or methacrylic acid, sebacic acid/trimethylolethane/acrylic acid or methacrylic acid, sebacic acid/tri Methylolpropane/acrylic acid or methacrylic acid, sebacic acid/
Glycerin/acrylic acid or methacrylic acid, sebacic acid/pentaerythritol/acrylic acid or methacrylic acid, fumaric acid/trimethylolethane/acrylic acid or methacrylic acid, fumaric acid/trimethylolpropane/acrylic acid or methacrylic acid, fumaric acid/glycerin /Acrylic acid or methacrylic acid, fumaric acid/Pentaerythritol/
Acrylic acid or methacrylic acid, itaconic acid/trimethylolethane/acrylic acid or methacrylic acid, itaconic acid/trimethylolpropane/acrylic acid or methacrylic acid, itaconic acid/pentaerythritol/acrylic acid or methacrylic acid, maleic anhydride/trimethylol Saturated or unsaturated polyester polyacrylates or polymethacrylates with combinations of compounds such as ethane/acrylic acid or methacrylic acid, maleic anhydride/glycerin/acrylic acid or methacrylic acid; trimethylolpropane toluylene diisocyanate; polyisocyanate, (In the formula, R is hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate,
Represents a residue of 4,4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate or trimethylhexamethylene diisocyanate. ) and acrylic monomers having active hydrogen, such as 2-hydroxyethyl acrylate or methacrylate, 2
-Hydroxypropyl acrylate or methacrylate, 2-hydroxy-3-methoxypropyl acrylate or methacrylate, N-
methylol acrylamide or methacrylamide, N-hydroxyacrylamide or methacrylamide, etc., per molecule of isocyanate.
Urethane acrylate obtained by reacting a molar or more amount by a conventional method; other examples include triacrylate or trimethacrylate of tris(-2-hydroxyethyl)-isocyanuric acid. 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 an acryloyloxy or methacryloyloxy group is preferable because it has excellent polymerization activity by ultraviolet rays. Specific examples of these compounds include ethylene glycol diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, triethylene glycol diacrylate or dimethacrylate, as compounds having two acryloyloxy or methacryloyloxy groups in one molecule.
Tetraethylene glycol diacrylate or dimethacrylate, polyethylene glycol diacrylate or dimethacrylate, 1,4
- butanediol acrylate or dimethacrylate, 1,6-hexanediol diacrylate or dimethacrylate, neopentyl glycol diacrylate or dimethacrylate, propylene glycol diacrylate or dimethacrylate, dipropylene glycol diacrylate or dimethacrylate; tolylene diisocyanate, Diisocyanates such as xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, 4,4'-diphenylmethane diisocyanate and acrylic monomers having active hydrogen, such as 2-hydroxyethyl acrylate or methacrylate, 2- Obtained by reacting hydroxypropyl acrylate or methacrylate, 2-hydroxy-3-methoxypropyl acrylate or methacrylate, N-methylolacrylamide or methacrylamide, N-hydroxyacrylamide or methacrylamide, etc. with 2 moles per isocyanate molecule in a conventional manner. Urethane acrylate; or the following general formula (In the formula, R ₁ is hydrogen or a methyl group, X ₁ , X ₂ ...,
Xn is the same or different alkylene group having 6 or less carbon atoms or has a structure in which one hydrogen atom thereof is replaced with a hydroxyl group, and n is an integer of 0 to 5. ), for example, 2,2-bis(-4-acryloxyphenyl)-propane, 2,
2-bis(-4-methacryloxyphenyl)-propane, 2,2-bis(-4-methacryloxyethoxyphenyl)-propane, 2,2-bis(-4-methacryloxyethoxyphenyl)-propane ,2,
2-bis(-4-acryloxydiethoxyphenyl)-propane, 2,2-bis(-4-methacryloxydiethoxyphenyl)-propane, 2,2-bis(-4-acryloxypropoxyphenyl) )-propane, 2,2-bis(-4-methacryloxypropoxyphenyl)-propane, 2,2-bis[-4-acryloxy(2-hydroxypropoxy)phenyl]-propane, 2,2-bis[ -4-methacryloxy(2-hydroxypropoxy)phenyl]-
Propane, 2,2-bis[-4-acryloxy(2-hydroxypropoxyethoxy)phenyl]-propane, 2,2-bis[-4-methacryloxy(2-hydroxypropoxyethoxy)phenyl]-propane, etc. be able to. Compounds having one acryloyl or methacryloyl group in one molecule include methyl acrylate or methacrylate, propyl acrylate or methacrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate,
Cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, 1,4-butylene glycol monoacrylate, ethoxyethyl acrylate, ethyl carbitol acrylate, 2-hydroxy-3- Chloropropyl acrylate, acrylamide, N-
Hydroxymethylacrylamide or methacrylamide, N-hydroxyethylacrylamide or methacrylamide, N-hydroxypropylacrylamide or methacrylamide, N-hydroxybutylacrylamide or methacrylamide, hydroxymethyldiacetoneacrylamide, N-hydroxyethyl-N-
(Methyl)acrylamide and the like can be mentioned. Among the compounds having three or more acryloyloxy and/or methacryloyloxy groups in one molecule as described above, the general formula (): (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ...X _o2 , X _o3 ,
At least three of X ₁₄ are CH ₂ =CH-COO- groups, the rest are hydroxyl groups, amino groups, alkylene groups, substituted alkylene groups, etc., and n = an integer of 2 to 5. ), such as dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc., have excellent curability with ultraviolet rays in air and are particularly preferred. When used in combination with the compound represented by the general formula (), it has excellent curing properties by ultraviolet rays in the air.
As a compound having ~2 acryloyloxy or methacryloyloxy groups, the general formula (): (In the formula, X ₁ , X ₂ ..., Xn are the same or different alkylene groups having 6 or less atoms, or 1
It has a structure in which each of these is substituted with a hydroxyl group, and n is an integer of 0 to 5. ), such as 2,2-bis(-4-acryloxyethoxyphenyl)-propane, 2,2-bis(-4-acryloxydiethoxyphenyl)-propane, 2,2-bis(-4-acryloxypropoxyphenyl)-propane,
2,2-bis[-4-acryloxy(-2-hydroxypropoxy)phenyl]-propane, 2,2-
Bis[-4-acryloxy-(2-hydroxypropoxyethoxy)phenyl]-propane and the like are preferred, and monofunctional monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, and tetrahydrofuryl acrylate. Acrylates having a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond in the side chain of the compound, such as furyl acrylate, ethoxyethyl acrylate, ethyl carbitol acrylate, butoxyethyl acrylate, 1,4-butylene glycol monoacrylate, etc. is particularly preferable because it has excellent polymerization activity by ultraviolet rays in normal atmosphere. The polyfunctional acrylate represented by the general formula () has the following general formula (): (In the formula, at least three R are CH ₂ =CH-COO-
The remainder is -H, a hydroxyl group, an amino group, an alkylene group, or a substituted alkylene group,
n ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ , and m ₄ are 0,
Takes either 1 or 2, and x is 1 to 10
is a positive integer up to . ), such as malonic acid/trimethylolethane/acrylic acid, malonic acid/trimethylolpropane/acrylic acid, succinic acid/trimethylolethane/acrylic acid, succinic acid/trimethylolpropane/acrylic acid, adipic acid / trimethylolethane / acrylic acid, or an esterification reaction product synthesized from a combination of compounds such as adipic acid / trimethylolpropane / acrylic acid, and compound () / compound () = 5 to 1/5
When used in combination at a ratio of 1, it is particularly preferable because it prevents the weather resistance of the resulting overmolded product, especially changes in appearance such as rough skin, cracks, peeling of the film, and poor adhesion due to accelerated exposure and natural exposure. When used in combination with the above monomer mixture (A), the emulsifying crosslinked polymer or copolymer that makes the resulting molded product obsolete has one α,β-ethylenically unsaturated bond in one molecule. Reactive monomers with 75-99% by weight
and 1 to 25% by weight of a reactive monomer having two or more α,β-ethylenically unsaturated bonds in one molecule;
Reactive monomers with ethylenically unsaturated bonds 85~
Graft crosslinking agent with 99.9% by weight and two or more α,β-ethylenically unsaturated bonds in one molecule
The inner layer is a copolymer consisting of 0.1 to 15% by weight, 1
75-99% by weight of reactive monomers with one α,β-ethylenically unsaturated bond in the molecule and 2% in one molecule.
It is a mixture of crosslinked microparticles in which the outermost layer is a crosslinked copolymer consisting of 1 to 25% by weight of a reactive monomer having at least 10 α,β-ethylenically unsaturated bonds. It can be produced by emulsion polymerization of Of course, the crosslinked polymer having a multilayer structure may have three or four layers, but a two-layer structure consisting of an inner layer and an outer layer is sufficient in terms of the erasing effect of the present invention and the workability of polymerization. The need to use micro cross-linked polymers or copolymers in combination with single-layer structure fine particles and multi-layer structure fine particles in order to obtain erasing in this way is explained later, although the former has a slightly inferior erasing effect. The latter has contradictory properties in that it has an excellent fader effect but is slightly inferior in resolution, so if the two are used together, it will be possible to achieve the superiority of both. This is because it becomes possible to harmonize well with almost no deterioration in performance. Therefore, the optimal ratio of both is in the range of 9 to 1/9, and if it deviates from this range, it will not be possible to achieve both the erasing property and the erasing effect, which are the objects of the present invention. In addition, especially as fine particles with a single layer structure, from 0.05μ
Uses 0.3 μ as fine particles with a two-layer structure.
When a material having a particle size of 0.3 μ to 3.0 μ is used within the above-mentioned ratio range, the contradictory properties of the fade effect and resolution can be most conveniently achieved. The graft cross-linking agent that connects the inner and outer layers is
Of course, there is no particular problem as long as it is a reactive monomer having two or more α,β-ethylenically unsaturated bonds in one molecule, as described below, but copolymerizable α,β-unsaturated carboxylic acids or Allyl, methallyl or crotyl esters of dicarboxylic acids, preferably allyl esters of acrylic acid, methacrylic acid, maleic acid and fumaric acid, are mentioned, with allyl methacrylate being particularly effective. Other effective examples include triallyl cyanurate and triallyl isocyanurate. Such graft cross-agents mainly have conjugated unsaturated bonds of their esters as allyl groups,
Reacts and chemically bonds much faster than methallyl or crotyl groups. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group acts effectively during the polymerization of the next layer to provide a graft bond between two adjacent layers. Therefore, in order to produce fine particles having a multilayer structure, a graft crosslinking agent is essential, and the lower limit of the amount used is especially important. If the amount used is less than 0.1% of the inner layer copolymer, the effective amount of graft bonding will be small and desired fine particles will not be obtained. A reactive monomer having two or more α,β-ethylenically unsaturated bonds in one molecule of the outermost layer is also essential for the present invention, and the amount of the crosslinking agent is one molecule of the outermost layer copolymer. %, the microparticles are a monomer mixture
(A) or the organic solvent used in combination may swell or dissolve, and the viscosity of the coating material composition system may become abnormally large, or the particle size may become too large due to swelling, making it impossible to obtain a desired elongated molded product. I won't be able to do it.
Conversely, if the amount of crosslinking agent exceeds 25% by weight,
It becomes difficult to polymerize the microparticles, and the particles may not adhere evenly and uniformly to the obtained molded product. The preferred range is 2 to 20% by weight. Regarding the particle size of the microparticles, if the particle size is less than 0.05 μ, the gloss will be strong and an excellent erasing effect will not be obtained, whereas if the particle size exceeds 3 μ, the dispersion stability of the coating material composition of the present invention will be affected. becomes defective, and if the coating material composition is left standing for several days, the fine particles will settle to the bottom. The most preferable particle size in terms of gloss reduction effect and static stability of the coating material composition is
It is in the range of 0.1μ to 2.0μ. As the reactive monomer having one α,β-ethylenically unsaturated bond in one molecule, any polymerizable monomer can be used, but monomer mixtures (A) reduces haze value by matching the refractive index of the cured film made of the monomer mixture (A) and the microparticles made of the emulsified crosslinked polymer or copolymer. If necessary, use an acrylic acid alkyl ester with an alkyl group of 1 to 13 carbon atoms, a methacrylic acid alkyl ester with an alkyl group of 1 to 4 carbon atoms, and an aromatic vinyl monomer as the reactive monomer. Among them, the ratio of methacrylic acid alkyl ester and/or aromatic vinyl monomer to acrylic acid alkyl ester is 99.5/2.5-40/
60 is preferable, and if even a small amount of acrylic acid alkyl ester is copolymerized, the adhesion to the base resin will be better. Examples of such monomers include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, t-butyl acrylate or methacrylate, 2-ethylhexyl acrylate. , cyclohexyl acrylate, lauryl acrylate, n-octyl acrylate, styrene, α-methylstyrene, etc., and these can be used alone or in combination. As the reactive monomer having two or more α,β-ethylenically unsaturated bonds in one molecule, if it is a monomer with polymerization activity, the above-mentioned acryloyl having two or more in one molecule can be used. Of course, polyfunctional monomers having oxy and/or methacryloyloxy groups are acceptable, but ethylene glycol diacrylate or dimethacrylate,
Alkylene glycol diacrylates or dimethacrylates such as 1,3-butylene glycol diacrylate or dimethacrylate, 1,4-butylene glycol diacrylate or dimethacrylate and propylene glycol diacrylate or dimethacrylate; divinylbenzene, trivinylbenzene, etc. Polyvinylbenzene; allyl compounds such as allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate are preferred. During polymerization to obtain an emulsion crosslinked polymer or copolymer using these reactive monomers,
It is possible to use polymerization degree regulators such as n-octyl mercaptan and t-dodecyl mercaptan, and it is often preferable to use them to control the molecular weight distribution. The amount of microparticles made of emulsifying crosslinked polymer or copolymer is 0.5% of the monomer mixture (A).
~30 parts by weight, preferably 2 to 20 parts by weight. If the amount added to the mixture (A) is less than 0.5 parts by weight, a sufficient erasing effect will not be obtained, and if it exceeds 30 parts by weight, the abrasion resistance and scratch resistance of the erasing crosslinked cured film will decrease. It becomes like this. As a means for curing the coating material composition consisting of the monomer mixture (A) and the micro crosslinked polymer or copolymer, electron beams, α rays, β rays, γ rays, which are usually taken out from a 20 to 2000 kV electron beam accelerator, are used. Although it is possible to irradiate active energy rays such as radiation such as rays, in order to cure economically and easily, it is necessary to
UV radiation in the range 100nm to 500nm 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. This is the most preferred method. When using ultraviolet rays as active energy rays, it is preferable to add a photocatalyst or photosensitizer to the monomer mixture (A), and these photocatalysts or photosensitizers include, for example, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α,α-dimethoxy-α-
Phenylacetophenone, methyl phenyl glyoxylate, ethyl phenyl oxylate, 4,
4'-bis(dimethylaminobenzophenone), 2
- Carbonyl compounds such as hydroxy-2-methyl-1-phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, azobisisobutyronitrile, azobis-2 , 4-dimethylvaleronitrile, and peroxide compounds such as benzoyl peroxide and ditertiarybutyl peroxide.
The amount added to 100 parts by weight of monomer mixture (A) is 0.01
The amount is preferably 6 parts by weight. If too much is added, the crosslinked cured film will be colored or the weather resistance will be deteriorated, which is undesirable. If the amount is too small, curability with ultraviolet rays will deteriorate. The above are the essential components constituting the present invention. At least one other vinyl monomer may be used in combination. Further, if necessary, stabilizers such as antioxidants, light stabilizers, thermal polymerization inhibitors, and ultraviolet absorbers, colorants, and the like may be added in small amounts as appropriate. In addition, the smoothness of the coating on the surface of the obtained molded product,
If uniformity is particularly required, it is advisable to add a small amount of silicone leveling agent. Preferably, the molecular structure is composed of polydimethylsiloxane units, a part of which is modified with polyoxyalkylene groups, and the degree of modification is 1 unit of methylsiloxane group CH ₃ (SiO) ₁ ^- _/2 . at least one oxyalkylene group (-
OCH ₂ CH ₂ −,

[Formula], etc.) are preferably bonded within a range of 0.1 to 10.0 units. 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, while 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 the If a silicone leveling agent is not used, the resulting erasable molded product may become cloudy in some cases, but this phenomenon can be prevented by adding a small amount of this agent. Methods for applying this composition include brushing,
Methods such as flow coating, spray coating, spin coating, or dip coating are adopted, but from the viewpoint of improving the coating workability of the coating material composition, the smoothness and uniformity of the coating, and the adhesion of the cured coating to the substrate, The most preferred method is to apply by dipping using a suitable organic solvent. The amount of organic solvent used is preferably 100 to 2000 parts by weight per 100 parts by weight of the monomer mixture (A).
If the amount of organic solvent used is less than 100 parts by weight,
A film with excellent smoothness and uniformity cannot be obtained, and on the other hand, if it exceeds 2000 parts by weight, the film thickness may become too thin and the abrasion resistance and scratch resistance may deteriorate. The coating amount of the coating composition on the surface of the synthetic resin molded article is preferably such that the thickness of the cured film is in the range of 1 to 30 microns, preferably 1.5 to 20 microns. If the thickness of the cross-linked cured film is less than 1 μm, the effect of improving weather resistance will be poor, and if it exceeds 30 μm, the adhesion to the substrate will decrease and cracks, haze, etc. will be more likely to occur. In the present invention, synthetic resin molded products used in the production of erasable synthetic resin molded products with excellent wear resistance and scratch resistance include various synthetic resin molded products, regardless of thermoplastic resin or thermosetting resin, such as Polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin,
Sheet-shaped molded products, film-shaped molded products, rod-shaped molded products, and various injection molded products manufactured from polystyrene resin, acrylonitrile-styrene copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, etc. Specific examples include products. Among these molded products, molded products made from polymethyl methacrylate resin, polycarbonate resin, etc. are often used to take advantage of their optical properties, heat resistance, impact resistance, etc., and are also wear resistant. Since there is also a strong demand for improved weather resistance, these molded products are particularly preferred as synthetic resin molded products used in the present invention. As described above, the coating material composition of the present invention and the erasable synthetic resin molded product manufactured using the same with excellent wear resistance and scratch resistance are characterized by its smoothness, chemical resistance,
It has excellent durability and is used in fields where erasability is required, such as CRT filters, TV filters, display-related displays such as taximeters and digital display boards, lighting, etc.
It is extremely useful for optical applications, filters for fluorescent display tubes, filters for liquid crystals, etc. The present invention will be explained in more detail below using Examples. Parts in Examples indicate parts by weight. In addition, the measurement evaluation in the examples was performed by the following method. (1) Scratch resistance Attach #000 steel wool to the tip of a cylinder with a diameter of 25 mm, contact it with the horizontally placed sample surface, rotate it 5 times (20 rpm) with a load of 100 g, and visually observe the extent of scratches. . 〇…There is almost no scratch on the sample surface. △...The sample surface is scratched. ×...The sample surface is considerably scratched. (2) Resolution The front 1 /
If you can clearly see the Γ250L/in line when observing with a 10x magnifying glass through the erasing board at a distance of 2 inches → 〇 When you place it closely against the erasing board instead of in front of Γ
If the 250L/in line can be clearly seen → △ Γ If it cannot be seen → ×. ○ has better resolution. Examples 1 to 3, Comparative Examples 1 to 4 In order to produce a crosslinked copolymer with a single layer structure, 250 parts of water was added to a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, etc. as shown in the table. Monomer parts,
Add 2 parts of emulsifier and 0.3 parts of potassium persulfate,
After the inside of the container was sufficiently purged with nitrogen gas, polymerization was carried out at 75° C. for 5 hours with stirring to obtain a latex with a polymerization rate of about 96%. According to the light transmission method, this latex is 0.2~
It had a particle size of 0.3μ. 5 for this latex
of calcium chloride was added for salting out, followed by dehydration, washing with water, and drying to obtain a powdery polymer.

[Table] For double crosslinked polymer particles, add 250 parts of water, each part of the monomers shown in the table as the first stage monomer, 0.06 part of emulsifier, and potassium persulfate in the same reaction vessel as above.
After adding 0.1 part and replacing the inside of the container with nitrogen,
Polymerization was carried out at 75°C for 2 hours with stirring, and then each part of the monomers shown as the second stage monomer in the table and an emulsifier were added.
0.7 parts of benzoyl peroxide and 0.4 parts of benzoyl peroxide were fed into the container, and polymerization was further continued for 5 hours. Polymerization rate is 96%
According to the light transmission method, the particles in the latex are
It had a particle size of 0.5-0.6μ. Five parts of calcium chloride was added to this latex for salting out, followed by dehydration, washing with water, and drying to obtain a powdery polymer.

[Table] Dipentaerythritol pentaacrylate 10
Dipentaerythritol hexaacrylate
10 parts, 8 parts of tetrahydrofurfuryl acrylate
1 mole of succinic acid/2 moles of trimethylolethane/4 moles of acrylic acid (TAS) 7 parts, isopropyl alcohol 35 parts, toluene 30 parts, 2-hydroxy-2-methyl-1-
To a composition consisting of 2 parts of phenylpropan-1-one and 0.2 parts of a silicone leveling agent, a mixture of micro crosslinked polymers consisting of the compounds shown in the table was added and blended in the parts by weight shown in the table, and coated. A material composition was prepared. A 2 mm thick acrylic plate (Acrylite L manufactured by Mitsubishi Rayon) was dip-coated on this at a dipping speed of 1.0 cm/sec, and after air-drying for 3 minutes, a 2 kW high-pressure mercury lamp was used to irradiate the film at a distance of 20 cm in air for 13 min. Irradiated for seconds.
The results obtained are shown in the table.

【table】

[Table] Examples 4 to 11 Dipentaerythritol tetraacrylate 5
parts, dipentaerythritol pentaacrylate 8 parts, dipentaerythritol hexaacrylate 7 parts, tetrahydrofurfuryl acrylate 5 parts
parts, TAS 5 parts, isobutyl alcohol 35 parts, xylene 35 parts, 1-(4-isopropylphenyl)-2
-Hydroxy-2-methylpropan-1-one 2
A coating material composition was prepared by adding the mixture of the microcrosslinked polymer shown in the table in the weight part shown in the table to a composition consisting of 1 part and 0.1 part of a silicone-based leveling agent. An acrylic plate was immersed in this in the same manner as in Examples 1 to 3 and cured. The results obtained are shown in the table.

[Table] Body particles.

Claims (1)

[Scope of Claims] 1 (a) 30% by weight or more of a compound having at least 3 acryloyloxy and/or methacryloyloxy groups in one molecule and 1 to 2 in one molecule
Monomer mixture (A) consisting of 70% by weight or less of a compound having α,β-ethylenically unsaturated bonds
and, based on 100 parts by weight of the mixture (A), (b) 0.01 to 6.0 parts by weight of at least one photosensitizer, and (c) 0.5 to 30 parts by weight of 1 per molecule. α,β
-Reactive monomer with ethylenically unsaturated bonds
75-99% by weight and 2 or more α, β- in one molecule
Reactive monomer 1 having an ethylenically unsaturated bond
An emulsifying crosslinked polymer or copolymer consisting of ~25% by weight and a reactive monomer having one α,β-ethylenically unsaturated bond in one molecule 85~
A copolymer consisting of 99.9% by weight and 0.1 to 15% by weight of a graft crosslinking agent having two or more α,β-ethylenically unsaturated bonds in one molecule as an inner layer,
75-99% by weight of reactive monomers having one α,β-ethylenically unsaturated bond in one molecule and reactive monomers having two or more α,β-ethylenically unsaturated bonds in one molecule By active energy rays, it is made by blending microparticles made by mixing a multi-stage emulsion crosslinked polymer or copolymer with a crosslinked copolymer consisting of 1 to 25% by weight of a monomer in the outermost layer. Curable coating composition. 2. The coating material according to claim 1, wherein the multi-stage emulsion crosslinked polymer or copolymer is a two-stage type polymer or copolymer having one inner layer and one outermost layer. Composition. 3. The ratio of fine particles made of a single-stage emulsion crosslinked polymer or copolymer to fine particles made of a multistage emulsion crosslinked polymer or copolymer is 9 to 1/9.
The coating material composition according to claim 1, characterized in that the composition has a composition in the following range. 4 The particle size of the microparticles made of the one-stage emulsion crosslinked polymer or copolymer is 0.05 to 0.3μ, and the particle size of the microparticles made of the multistage emulsion crosslinked polymer or copolymer is 0.3 to 3.0μ. The coating material composition according to claim 1, characterized in that it has a size of μ. 5 A reactive monomer having one α,β-ethylenically unsaturated bond in one molecule is an acrylic acid alkyl ester whose alkyl group has 1 to 13 carbon atoms and/or
The coating material composition according to claim 1, wherein the coating material composition is a methacrylic acid alkyl ester and/or an aromatic vinyl monomer whose alkyl group has 1 to 4 carbon atoms. 6. A patent characterized in that the ratio of methacrylic acid alkyl ester and/or aromatic vinyl monomer to acrylic acid alkyl ester in the outermost layer of a multi-stage emulsion crosslinked polymer or copolymer is 99.5/0.5 to 40/60. The coating material composition according to claim 5. 7. Claim 1, wherein the graft crosslinking agent having two or more α,β-ethylenically unsaturated bonds in one molecule is allyl methacrylate, triallyl cyanurate, or triallyl isocyanurate. The coating material composition described in Section 1. 8 The reactive monomer having two or more α,β-ethylenically unsaturated bonds in one molecule is ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3- Alkylene glycol diacrylates or alkylene glycol dimethacrylates such as butylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol diacrylate or propylene glycol dimethacrylate; divinylbenzene or trivinyl The coating material composition according to claim 1, which is polyvinylbenzene such as benzene; an allyl compound such as allyl methacrylate, triallyl cyanurate, or triallyl isocyanurate. 9 Polymerization of a mixture (A) consisting of a compound having at least three acryloyloxy and/or methacryloyloxy groups in one molecule and a compound having one to two α,β-ethylenically unsaturated bonds in one molecule 2. The coating material composition according to claim 1, wherein the average molecular weight per sexually unsaturated group is 300 or less. 10 100 parts by weight of organic solvent for 100 parts by weight of mixture (A)
2. The coating material composition according to claim 1, which is used by mixing up to 2000 parts by weight. 11. The compound according to claim 1, wherein the compound having at least three acryloyloxy and/or methacryloyloxy groups in one molecule is a single compound or a mixture of compounds represented by the general formula (). Dressing composition. (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ...X _o2 , X _o3 ,
At least three of _X14 are _CH2 =CH-COO- groups, the rest are hydroxyl groups, amino groups, alkylene groups, substituted alkylene groups, etc., and n is an integer of 2 to 5. ) 12 A compound having at least three acryloyloxy and/or methacryloyloxy groups in one molecule is a mixture of a compound represented by the general formula () and a compound represented by the general formula (), and the compound ()/compound Claim 1 characterized in that the ratio of () is in the range of 5 to 1/5.
The coating material composition described in Section 1. (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ...X _o2 , X _o3 ,
At least three of _X14 are _CH2 =CH-COO- groups, the rest are hydroxyl groups, amino groups, alkylene groups, substituted alkylene groups, etc., and n is an integer of 2 to 5. ) (In the formula, at least three R are CH ₂ =CH-COO-
The remainder is -H, a hydroxyl group, an amino group, an alkylene group, or a substituted alkylene group,
n ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ and m ₄ are 0 and 1
or 2, and x is a positive integer from 1 to 10. ) 13 A compound having 1 to 2 α,β-ethylenically unsaturated bonds in one molecule has one acryloyloxy group in one molecule, and has a hydroxyl group and/or a cyclic ether bond in the side chain. The coating material composition according to claim 1, which is a compound having/or a chain ether bond. 14 A patent characterized in that the polyfunctional monomer represented by the general formula () is selected from dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate The coating material composition according to claim 11 or 12. 15 An ester compound in which the polyfunctional monomer represented by the general formula () is a reaction product of malonic acid, trimethylolethane and acrylic acid, an ester compound consisting of a reaction product of malonic acid, trimethylolpropane and acrylic acid, and succinic acid. an ester compound consisting of a reaction product of succinic acid, trimethylolpropane and acrylic acid, an ester compound consisting of a reaction product of adipic acid, trimethylolethane and acrylic acid, or 13. The coating material composition according to claim 12, wherein the coating material composition is selected from ester compounds consisting of a reaction product of adipic acid, trimethylolpropane, and acrylic acid. 16. The coating material composition according to claim 1, wherein the active energy rays are ultraviolet rays with a wavelength in the range of 100 nm to 500 nm.