JPS6383117A - Coating agent composition which can give cured coating - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a crosslinked cured coating excellent in surface properties such as abrasion resistance, scratch resistance, surface hardness, heat resistance, etc., by mixing a specified monomer mixture with an ultraviolet absorber, an alkyl (meth)acrylate polymer and a photopolymerization initiator. CONSTITUTION:A monomer mixture (A) is obtained by mixing 30-80wt% compound (a) of formula I [wherein at least three of X11-13, X22-23...Xn2-3 and X14 are groups of formula II, the rests are hydroxyl, amino or (substituted) alkylene groups and n is 2-5] with 5-40mol% compound (b) of formula III (wherein R is X11... or X14, n1-4 and m1-4 are each 0-2 and x is 1-10), 10-50wt% compound (c) of formula IV [wherein R1 is (meth)acryloyloxy, R2 is H or methyl, l, m and n are each 1-8 and y is 0-10] and 10-50wt% compound (d) having one acryloyloxy group in the molecule and having at least one member selected from among a hydroxyl group and cyclic and linear ether bonds in a side chain. 100pts.wt. component A is mixed with 0.5-8pts.wt. alkyl (meth)acrylate polymer (B), 3-35pts.wt. ultraviolet absorber (C) and 0.01-6pts. wt. photopolymerization initiator (D).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is based on active energy ray irradiation in an air atmosphere.
A coating material composition that can form a crosslinked cured film with excellent surface properties such as abrasion resistance, scratch resistance, surface hardness, heat resistance, solvent resistance, removability, adhesion to synthetic resin substrates, and weather resistance. relating to things.

[Prior art] Polymethyl methacrylate resin, polycarbonate tree
Synthetic resin molded products made from resin, polystyrene 9J resin, As resin, ABe resin, etc. are not only lightweight and have excellent impact resistance, but also have advantages such as being inexpensive and easy to mold. Since it has mild advantages, its use is being developed in many fields. However, on the other hand, these synthetic resin molded products have insufficient surface wear resistance, so they are easily damaged by contact with other hard objects, friction, scratches, etc. There is a strong demand for improving the abrasion resistance of the surface because it can significantly reduce its commercial value or make it unusable in a short period of time. In addition, synthetic resin molded products with improved surface abrasion resistance using coating materials may be used outdoors depending on their intended use, such as aircraft windshields, outdoor signs, street signs, and automobile parts. Since it is used for such purposes, its +11 weatherability is strongly required.

Various methods have been studied in the past to improve these drawbacks of synthetic resin molded products. By coating and heating, a cross-linked cured film is formed and
A method for improving 1it abrasion resistance and by applying a polyfunctional monomer having one or more polymerizable groups in one molecule to the surface of a synthetic resin molded product and irradiating it with active energy rays in an inert gas. , a method for manufacturing synthetic resin molded products with excellent abrasion resistance by forming a cross-linked cured film on the surface of synthetic resin molded products by radical polymerization has been proposed (Japanese Patent Publication No. 4Q-42211 and No. 49-2295).
No. 1).

[Problem that the invention seeks to solve]

Although these methods have improved the abrasion resistance of synthetic resin molded product surfaces to some extent, the former has insufficient durability against heat shock, hot water, etc., and chemical resistance, while the latter has insufficient durability against heat shock, hot water, etc. Although it has excellent durability and chemical resistance, it has various drawbacks such as the need for expensive inert gas when manufacturing wear-resistant synthetic resin molded products, and it is also unsatisfactory in terms of weather resistance. It wasn't a kimono. In particular, if the weather resistance of the synthetic resin molded product is poor due to the quality of the wood, such as polycarbonate resin, even if the weather resistance of the cross-linked cured coating is excellent, the synthetic resin molding may be performed using active energy rays such as ultraviolet rays that have passed through the coating. The surface of the product deteriorates, resulting in severe yellowing of the molded product, cracks in the cross-linked cured coating, and in the past, there have been problems in which the coating peels off from the surface of the molded product.

In view of this situation, the present inventors have been making proposals for improving wear resistance and weather resistance (Japanese Patent Application No.
27088, 55-51017), certain polyfunctional acrylates, ultraviolet absorbers and (meth)acrylic/
It has been discovered that a coating composition containing an alkyl L' acid polymer as a main component provides excellent wear resistance and weather resistance. However, even with these proposals, the level of weather resistance is still insufficient, and it has become clear that the heat resistance is also somewhat insufficient when used under severe conditions.

The inventors of the present invention have intensively investigated ways to significantly improve weather resistance and improve heat resistance. As a result, the inventors have found that by using a special acrylic monomer in combination with some of the polyfunctional acrylates used in the above-mentioned proposal, weather resistance can be improved. The inventors have completed the present invention by discovering that they have excellent properties and improved heat resistance.

[Means to solve the problem]

That is, the present invention is based on the following general formula % (wherein x11, XI!, xts, Coo- group,
The remainder is a hydroxyl group, an amino group, an alkylene group, a substituted alkylene group, etc., and n is an integer of 2 to 5.

) 50 to 80% by weight of the compound (a) represented by the following general formula (% formula %) (in the formula, at least 3 R's are CH!-CH-Coo- groups, and the remainder are hydrogen, hydroxyl group, An amino group, an alkylene group, a substituted alkylene group, etc., "1, T1
2, n3, n4, ml %ml, ml and m
4 takes a value of either 0.1 or 2, and X takes a value of 1 to 2.
A positive integer up to 10. ) Compound (b)
5 to 40% by weight, and the following general formula % formula % CH-CH, - formula...
・(m) (In the formula, R1 is an acryloyloxy group or a methacryloyloxy group, horse is hydrogen or a methyl group, 11m and n are positive integers from 1 to 8, and y
is a positive integer from 0 to 10. ) Compound (c
) 10 to 50 weight i% and one acryloyl y per molecule
A monomer mixture (g) consisting of 10 to 60% by weight of a compound (d) having an oxyV group and having a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond in the side chain in the molecule; , 3 to 35 parts by weight of at least one type of ultraviolet absorber (B) per 100 parts by weight of the monomer mixture (A), and at least one type of ultraviolet absorber (B) per 100 parts by weight of the monomer mixture (A). meth) acrylic acid alkyl μ polymer (C) 0.5 to 8 parts by weight and photopolymerization initiator ■) α0 1 to 6 parts by weight based on 100 parts by weight of the monomer mixture (A), activity. Can be cured in air with energy rays,
The present invention relates to a coating composition that forms a crosslinked cured film with excellent surface properties such as abrasion resistance and weather resistance.

The polyfunctional monomer having five or more acryloyloxy groups in one molecule represented by the general formula (I) used in the present invention exhibits very good polymerization activity when irradiated with ultraviolet rays, and also exhibits crosslinking and curing. It exhibits high wear resistance. In the present invention, the purpose can be sufficiently achieved by using the monomer represented by the general formula (I), but dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, diventaerythrit-μ
Hexaacrylate and the like are particularly preferred monomers because they have excellent polymerization activity when irradiated with ultraviolet rays in an air atmosphere. The monomers represented by the general formula CI) may be used alone or in combination of two or more.

The proportion of the monomer used is 30 to 80% in the monomer mixture.
weight, preferably in the range of 40 to 70 weight. If the amount of the monomer is less than 50 parts by weight, curing in an air atmosphere may be insufficient and the product may remain uncured, or even if it is cured, the P# abrasion resistance may not be sufficient. The adhesion to the base material is also poor, and conversely, when it is used in excess of 80% by weight,
Although abrasion resistance and hardenability are improved, the film's removability is reduced, which may cause cracks when heated at high temperatures, and may cause cracks during molding, resulting in poor heat resistance. This is a problem, and the weather resistance is not a desirable condition since the film becomes susceptible to scratches.

In addition, in the present invention, even if the monomer has three or more acryloyl μoxy groups in one molecule, polyfunctional monomers that do not satisfy the general formula CI), such as trimethylo-μpropane triacrylate , pentaglycero-μ
Triacrylic V-) and the like have poor polymerization activity when exposed to ultraviolet rays in the air, and therefore cannot be used for the purpose of the present invention.

The polyfunctional monomer (+)) represented by general formula (II) is -
By using in combination with a polyfunctional monomer represented by general formula (I),
It is a preferred monomer because it imparts excellent wear resistance to the film without reducing the hardenability of the film in an air atmosphere, and has a large effect on improving weather resistance and heat resistance. .

Among the polyfunctional monomers represented by general formula (II), totrimethylolethane malonate and acrylic/l/acid,
malonic acid and trimethylo-μ propane and acrylic acid,
Esthetics consisting of reactants such as succinic acid and trimethylolethane and acrylic acid, succinic acid and trimethylolpropane and acrylic acid, adipic acid and trimethylolethane and acrylic/l/acid, adipic acid and trimethylo-μpropane and acrylic acid. μ compounds are particularly preferred because they are excellent in improving the weather resistance of the coating. The polyfunctional monomers represented by general formula (II) may be used alone or in combination of two or more.

The proportion of the monomer used is in the range of 5 to 40% by weight, preferably 5 to 30% by weight, in the monomer mixture. If the amount of the monomer is less than 5% by weight, the effect of improving weather resistance and heat resistance may not be obtained, and if it is used in excess of 40% by weight, the curability of the film in air may deteriorate. This is not preferable because it may reduce the adhesion of the film or the adhesion of the film.

The bifunctional monomer represented by the general formula (III) used in combination with the general formula CI) and the general formula (II) in the present invention has good curability by ultraviolet irradiation in an air atmosphere, and forms a crosslinked cured film. Since it imparts excellent weather resistance and flexibility to the film, it is an essential component for preventing the occurrence of scratches, improving adhesion to substrates, and improving weather resistance and heat resistance.

The bifunctional monomer is a urethane acrylate having a polyester μ structure in its main chain, as shown by the general formula (III), and its constituent components include a dibasic acid, a dihydric alcohol, and a divalent isocyanate. It is an acrylic ester containing a hydroxyl group.

Specific examples of dibasic acids include anhydrous futa A/acid, isophtha μ acid, terephtha A/acid, succinic anhydride, azobic acid, azefinic acid, cepacic acid, tetofhydro fugu anhydride μ acid,
Hexahydrophthalic anhydride, tetofurom phthalic anhydride, tetofuclo phthalic anhydride, het acid anhydride, himic anhydride, maleic anhydride, fumaric acid, itaconic acid, succinic acid, tetofhydrofuccinic acid, hexahydrofuclic acid, etc. As dihydric alcohols, ethylene glycol, propylene glyco-μ, 1.5-butylene glyco-A/, 1.4-butanedio-/I/, 1.6-hexanedio-, diethylene glycol, Propylene glyco-μ, neopentyl glycol, polyethylene glycol, polypropylene glyco-μ, hydrogenated bisphenol
A/A, Binuphenol dihydroxybrobiate~
Divalent isocyanates include tolylene diisocyanate, 4.4'-diphenylmethane diisocyanate, xylylene diisocyanate, 4.4'-methylenebis(cyclohexylisonanate), and methylcyclohexane 2.4 (2,6). diisocyanate,
Examples of hydroxyl group-containing acrylic esters include hexamethylene diisocyanate, isophorone diisocyanate, and trimethylhexamethylene diisocyanate.
Examples of the dibasic acid include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, but in the present invention, as shown by the general formula (Tll), the dibasic acid includes a saturated dibasic acid with a methylene group having 1 to 8 carbon atoms, Bivalent aμ
For the coal, an aliphatic divalent alcohol-μ having a methylene group of 1 to 8 carbon atoms is used, and for the divalent isocyanate, an aliphatic divalent isocyanate having a methylene group of 1 to 8 carbon atoms is used, and 2-hydroxyethyl acrylate or 2 synthesized by conventional methods using 2-hydroxypropyl acrylate
Functional polyester urethane acrylate with general formula CI)
It is preferable to use it in combination with a polyfunctional monomer represented by general formula (II). Among them, the saturated dibasic acids include succinic acid, adipic acid, and sepacic acid, the aliphatic dihydric alcohols include 1,4-butanedio-μ or 1,6-hexanediol, and the aliphatic divalent isocyanates include hexamethylene diisocyanate and 2 Bifunctional polyester μ urethane acrylate synthesized from -hydroxyethyl acrylate or 2-hydroxypropyl acrylate by a conventional method is preferred because it is particularly effective in improving the weather resistance and heat resistance of the coating, which is the object of the present invention.

Furthermore, even if the compound is represented by the general formula (III), y
If the value exceeds 10, the viscosity of the polyester urethane acrylate becomes very high, which is not a preferable condition because the coating workability and solubility of the coating material composition or the smoothness of the coating decrease.

One polyester urethane acrylate represented by the general formula (■) may be used alone, or two or more may be used in combination.

Urethane monomers other than polyester urethane acrylate represented by general formula ([11), for example, polyether urethane acrylate V-) whose structure is polyether type, or aromatic type such as tolylene diisocyanate as divalent isocyanate. Urethane acrylate and the like are monomers other than those of the present invention, and the former has insufficient weather resistance and has been found to cause clouding of the film during exposure, and the latter also has weather resistance problems. However, since the coating has a yellowish yellow color, it cannot be used for the purpose of the present invention.

The proportion of the monomer represented by the general formula (■) is 10 to 50% by weight, preferably 10 to 50% by weight of the monomer mixture.
It is in the range of 40% by weight. If the amount of the monomer used is less than 10% by weight, the effect of weather resistance and heat resistance of the coating will decrease several times as described in 11f. If it is used in excess of 50% by weight, the resistance of the coating will decrease. This is not preferable because it reduces abrasion resistance.

It also has one acryloyloxy group in one molecule used with the polyfunctional monomer consisting of general formulas (I), (II) and (III), and has a hydroxyl group and/or a cyclic group in the side chain of the molecule. The compound (d) having an ether bond and/or a chain ether bond is a monofunctional monomer (hereinafter simply referred to as a monofunctional monomer) having one polymerization active group in one molecule. After applying the coating composition to the molded product, it is an essential component for imparting properties such as smoothness, adhesion to the substrate, and removability to the formed coating. .

Specific examples of monofunctional monomers include butyl acrylate, isobutyl μ acrylate, 1-butyl acrylate, 2-ethylhexyl acrylate, furyl acrylate, tridenyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, glycidiacrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, 1,4-butylene glycol monoacrylate, ethoxyethyl acrylate, ethyl μ pitot p
Acrylic V-to, 2-hydroxy-3-chloropropyl acrylate, phenoxyethyl acrylate, noniμ phenoquinethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, cabrocton modified tetrahydrofurfuryl acrylate, 1.3- Dioxane alcohol ε-cabrofuctone adduct acrylate, phenoquine diethylene glycol acrylate, ethylene oxide modified phthalocylate acrylate, butquine ethyl acrylate, dicyclopentenyl acrylate, N-
Dimethy-aminoethyl acrylate, N-diethylaminoethyl acrylate, isopolonyl acrylate,
Examples include nony-phenoxy polyethyl glycol acrylate, N-vinylpyrrolidone, and the like.

Among these monomers, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetofhydrofurfuryl acrylate, ethoxyethyl acrylate, ethylcarpitole acrylate, tetofhydrofurfuryloxyethyl acrylate, caprocton modified Monofunctional monomers having a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond in the monomer side chain, such as tetrahydrofurfuryric acid and acrylate, have excellent polymerization activity by ultraviolet rays in an air atmosphere. Therefore, it is particularly preferable. The monofunctional monomer preferably has a boiling point of 150'C or more at normal pressure and a viscosity of 100 cp or less at 20C. If the boiling point is too low, the film will evaporate and scatter during the process of forming the film and curing with ultraviolet rays, resulting in a large difference in film performance between the undried state and the cured state. Therefore, the boiling point of the monomer should be as high as possible. Regarding the viscosity, the viscosity of the aforementioned polyfunctional monomers is relatively high in many cases, and the viscosity of monofunctional monomers is 1.
If it is relatively high, exceeding 00 cp,
Because the viscosity of the monomer mixture becomes high, problems often arise with smoothness during film formation, so it is recommended to use monofunctional monomers with as low a viscosity as possible to increase the dilution effect. This is the preferred direction.

The specific examples of monofunctional monomers mentioned above all have a boiling point of 150°C or higher at normal pressure and a viscosity of 1 at 20°C.
00 cp It is a preferable monomer as it satisfies the following conditions.

These monofunctional monomers may be used alone or
Moreover, two or more types may be used in combination. The proportion of monofunctional monomer used is 10 to 60% by weight based on the monomer mixture, preferably 1
It ranges from 0 to 40% by weight. If it is less than 10% by weight, the dilution efficiency will decrease and the viscosity of the monomer mixture will increase, the smoothness of the coating will decrease, or the r
8! The adhesion and even the removability of the film may deteriorate. On the other hand, if the thickness exceeds 60", it is not preferable because a coating having sufficient wear resistance cannot be obtained.

The (meth)acrylic acid polymer (C) used by being added to the monomer mixture (4) does not reduce the appearance of the crosslinked cured film such as transparency or smoothness.
It improves the adhesion of the coating to the base material and has the effect of a dispersion aid that can uniformly disperse a large amount of ultraviolet absorber in the coating, improving the weather resistance of synthetic resin molded products with excellent wear resistance. It is an essential ingredient for improving.

Methods for improving the weather resistance of coatings by incorporating ultraviolet absorbers into paints are known, but in order to form coatings with a highly crosslinked structure as in the present invention, ultraviolet absorbers are often included in the composition. It was impossible to disperse the In other words, even if a large amount of ultraviolet absorber is added to the coating composition, when the coating composition is cured, the large amount of ultraviolet absorber is not sufficiently uniformly retained in the crosslinked cured coating, and the crosslinked cured coating is They either aggregate in the form of small islands or ooze out onto the hardened surface, turning the entire film milky white (the surface hardness and abrasion resistance of the hardened film have significantly decreased).

In fact, only a small amount of ultraviolet absorber is included in the crosslinked cured coating formed from the monomer mixing dynamics of the present invention. If a large amount of UV absorber is added in excess of this amount, various defects as mentioned above will occur, and if the amount of UV absorber added is reduced, the above problems will disappear, but the weather resistance will be affected. The improvement effect will be insufficient.

However, it has been found that by adding a small amount of the above-mentioned alkyl (meth)acrylate polymer to the coating material composition of the present invention, the above problems can be solved at once.

The (meth)acrylic acid polymer used in the present invention has an intrinsic viscosity [η) (g/l), which is a guideline for the average molecular weight of the polymer, in the range of α01 to 0.30, A homopolymer of a monomer selected from alkyl having 1 to 8 carbon atoms/(meth)acrylic having an L' group/l/acid alkyl or a copolymer thereof is preferable.

When the intrinsic viscosity [η] of the (meth)acrylic acid alkyl μ polymer is less than 101, the ultraviolet absorber is sufficiently dispersed into the crosslinked cured film by the (meth)acrylic acid alkyl μA/polymer. On the other hand, if it exceeds 0.30, the solubility of the (meth)acrylic/acyl L' acid polymer in the coating material composition of the present invention is insufficient9, and the smoothness of the cured film Sexuality may decrease. Alki/l/1&
Even when the number of carbon atoms in is 9 or more, the solubility of the (meth)acrylic acid Apki/L' polymer in the coating material composition is poor. Examples include Methyl/I/(meth)acrylate, Methylv(meth)acrylate, Propy/L/(meth)acrylate, Buty/L/(meth)acrylate,
I/(meth)acrylate, iso-butyl(meth)acrylate, amyl methacrylate, Pekin p methacrylate V
-t, heptyl methacrylate, octyl methacrylate V-
Total, 2-methy/l/-1-hexy/l/(meth)acrylate, 3-bench! Acrylic V-to, 3-methyl-1-
Examples include homopolymers of butyl acrylate, 2-methyA/-1-butylacrylate, or 2-hebutyl acrylate, or copolymers thereof. These polymers may be used alone or in combination of two or more.

The amount of alkyl (meth)acrylate μ to 100 parts by weight of the monomer mixing motive force of the polymer is α5 to 8 parts by weight,
Preferably it is in the range of 1 to 5 parts by weight. (If the amount is less than 5 parts by weight, the ultraviolet absorber cannot be contained in a large amount, and if the amount exceeds 8 parts by weight, the smoothness and abrasion resistance of the crosslinked cured film will decrease. .

Further, the ultraviolet absorber used in the present invention is not particularly limited, and in a broad sense includes light stabilizers for polymers, such as hindered amine type, and is uniformly contained in the coating material composition of the present invention. However, from the viewpoint of improving the solubility and weather resistance of the composition of the present invention, benzophenone-based, benzotriacyic μ-based, A compound derived from phenyl salicylate or phenyl benzoate, with a maximum absorption wavelength of 240 to 380.
UV absorbers in the nanometer range are preferred.

Specific examples of ultraviolet absorbers include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
-fi-octoxybenzophenone, 4-dobucyloxy-2-hydroxybenzophenone, 2-hydroxy-4
-octadecyloxybenzophenone, 2,2'-dihydroxy-V-4-methoxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone, phenysalicylate, p-tert-buty-phenysalicylate, p-( 1,1,S, 3-tetofumethypguti/L/) phenyl salicylate, 3-hydroxyphenylbenzoate, phenynon-1,3-dipenzoate, 2-(2-hydroxy-5-methylpheny, 11/)
Benzotriacy7+/,2-(2-hydroxy-5-
tert-butyphenylene/l/)-5-chlorobenzotriacyp.

2-(2-hydroxy-5-5'-tert-butylphenyl)benzotriazole, 2-(2-hy)'
Examples include cl xy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxypheni/l/)benzotriazole, and the like.

These ultraviolet absorbers may be used alone or in combination with
You may use more than one species in combination.

The amount of the ultraviolet absorber added to the monomer mixture is preferably in the range of 3 to 35 parts by weight, more preferably 8 to 30 parts by weight, based on 100 parts by weight of the monomer mixture.

If it is less than 3 parts by weight, the effect of improving the weather resistance of the synthetic resin molded product as described above will not be sufficient, and if it exceeds 35 parts by weight, the severe abrasion resistance of the crosslinked cured coating will be insufficient, and This is not preferable because it also reduces curability.

As a means for curing the coating material composition consisting of a monomer mixture, a (meth)acrylic acid μ polymer, and an ultraviolet absorber, an electron beam, α, taken out from an electron beam accelerator of 20 to 2000 kV, Although it is possible to irradiate active energy rays such as rays, β rays, and γ rays, ultraviolet rays with a wavelength in the range of 100 to 500 nm are preferred for economical and easy curing. Regarding ultraviolet irradiation in an elevated atmosphere, it is of course possible to irradiate in an inert gas such as nitrogen, carbon dioxide, or argon, but if the above-mentioned compound having a specific acryloyloxy group is used, it can be efficiently performed even in normal air. Curing is possible and is the most preferred method.

When using ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator to the monomer mixture (4), and specific examples of these compounds include benzoin,
Benzoin methyl ether 1 Penzoin ethyl ether μ
, benzoin propyl ether p, penzoin isobutyl ether p1 acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone,
2.2-Jethoxyacetophenone, α-dimethoxy-α-phenylacetophenone, methylμ phenylglyoxy V-), ethyl phenylglyoxylate, 4.4
'-Bis(dimethylaminobenzophenone), 2-hydroxy-2-methy/l/-1-phenylpropane-1-
sulfur compounds such as pboniμ compounds, tetofmethyltihummonosulfide, tetramethylthiuram disulfide, azo compounds such as azobisisobutyronitrile 1 azobis-2,4-dimethyμvaleronitriμ,
Examples include peroxide compounds such as benzoyl peroxide and di-tert-butyl peroxide.

The amount of the photopolymerization initiator to be added to 100 parts by weight of the monomer mixture (A) is preferably cL01 to 6 parts, and if it is added too much, yellowing of the film may occur, or the weather resistance may be deteriorated. This is not preferable because it causes a decrease in the amount of UV rays, and if the amount added is too small, curing by ultraviolet rays becomes worse.

The coating composition can be applied by brushing, flow coating, spray coating, word-of-mouth coating, or dip coating, but depending on the workability of the coating, the smoothness of the coating, From the viewpoint of uniformity and improved adhesion of the cured film to the substrate, the most preferred method is to apply by dipping using an appropriate organic solvent.

The organic solvent is not particularly limited, and any organic solvent that can uniformly dissolve the coating composition of the present invention can be used.

Specific examples of organic solvents include alcohols such as ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, and normal butyl alcohol, and aromatic hydrocarbons such as benzene, toluene, and xylene. , acetone, ketones such as methyl ethyl ketone, ether plA such as dioxane, vinegar rtl
Examples include esters such as ethymu, n-butymu acetate, iso-amylacetic acid mu, and polyacrylic apco/l/derivatives such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve. These organic solvents may be used alone or in combination of 2a or more. The amount of these organic solvents used is in the range of 100 to 2000 parts by weight per 100 parts by weight of the monodisperse 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 if it is used in excess of 2,000 parts by weight, the film thickness will be too thin. This is not preferable because it reduces abrasion resistance and weather resistance.

Regarding the coating amount of the coating material composition on the surface of the synthetic resin molded product, the thickness of the cured film is 1 to 30 μm, preferably 1
．． It is preferable to apply the coating to a thickness in the range of 5 to 20 μm.

If the thickness of the cured film is less than 1 μm, the effect of improving abrasion resistance and weather resistance will be poor; if it exceeds 30 μm, the hardness of the film will decrease, and the adhesion to the substrate or appearance will tend to deteriorate. or If smoothness and uniformity of the coating on the surface of the obtained molded product are particularly required, it is best to add a small amount of silicone surfactant, and the amount added should be within the monomer mixture. For 100 parts by weight (L
It is in the range of 0001 to 1.0 parts by weight. Its usage is 0
．． If the amount is less than 1.0001 parts by weight, the effect of improving smoothness and uniformity will be small, while if it is used in excess of 1.0 parts by weight, the transparency of the film will deteriorate, which is undesirable. The silicone-based surfactant is not particularly limited, but it is preferably a silicone surfactant whose molecular structure is composed of polydimethyl to sylogisane units, as described in Japanese Patent Application No. 54-4569.
-17) Those partially modified with polyoxyalkylene groups are preferable, and the degree of modification is less than 1 unit of methylsiloxane group CH, (Sin). −
1-OCH, CH-, etc.) is [L1-1 (CH in the range of LO units).

Preferably, they are bonded. If the degree of modification by oxyalkylene groups is less than α1, the smoothness of the coating will be worse than when no silicone surfactant is added, while if the degree of modification by oxyalkylene groups exceeds 110, the smoothness of the coating will be poor. This is not preferable because it lowers the temperature.

Synthetic resin molded products that can be used to produce synthetic resin molded products with excellent surface properties such as iItM abrasion resistance and weather resistance using the coating composition of the present invention include thermoplastic resins, thermosetting resins, etc. Various synthetic resin molded products, such as polymethymu methacrylate resin, polycarbonate resin,
Polyaryl diglyco μ carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin (As
resin), polyvinyl chloride resin, acetate resin, ABS
Specific examples include sheet-like molded products, film-like molded products, rod-like molded products, and various injection molded products manufactured from resins, polyester resins, and the like. Among these molded products, molded products made from polymethacrylate resin, polycarbonate resin, etc. are often used to take advantage of their optical properties, heat resistance, impact resistance, etc., and are also highly wear resistant. Since there is also a strong demand for improvement in weather resistance (particularly for polycarbonate resins with insufficient weather resistance), these molded articles are particularly preferred as synthetic resin molded articles to which the composition of the present invention is applied.

The content of the present invention will be explained in more detail below with reference to Examples. In the examples, the numerical values representing the proportions of each component in the coating material composition indicate parts by weight of each component. Moreover, the measurement evaluation in Examples was performed by the following method.

(1) Steel wool with abrasion resistance ÷ 000 is attached to the tip of a cylinder with a diameter of 25 + m, and brought into contact with the sample surface placed on a horizontal surface.
The film was rotated 5 times (20 rpm) under a load of 0 g, and the degree of scratch adhesion was visually observed and evaluated based on the following criteria.

○: Almost no scratches are observed on the sample surface.

Δ...There are some scratches on the surface of the sump μ.

×: The surface of the sump μ is severely scratched.

(2) Adhesion Cross Cut Gopan Eye C Crimp it and peel it off quickly.

○...No number of cracks in the cured film Δ...Number of boxes 1 to 50 ×...Number of stingers 51 to 100 (3) Smoothness of the film O: The surface of the coating has good smoothness.

Δ: Smoothness of the surface of the coating is slightly insufficient.

×: The surface smoothness of the film is poor.

(4) Appearance (a) Discoloration or cloudiness ○...No discoloration (yellowing or cloudiness) or cloudiness Δ...Slight discoloration or cloudiness ×...Discoloration or cloudiness (b) Conspicuous cracks, film peeling O... None x... Yes The weather resistance test was conducted using a Sunshine Carbon Weather-Ometer (Suga Test Instruments Model WE-8UN-DC). Test conditions were black spring μ temperature 63±3℃, rainfall 12
minutes/60 minutes cycle μ.

In the heat resistance test, the sample μ was left in an atmosphere at 130° C. for 24 hours, and after being taken out, the appearance was observed.

Examples 1 to 3, Comparative Examples 1 to 7 A coating material composition shown in Table 1 was prepared, and a 2-inch thick polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical, trade name: Kneepilon) was immersed in it, and the pulling rate was set to α5. cryt/81
A film was formed with 9C. Leave this as is for 3 minutes,
Next, a high-pressure mercury lamp (HOZ- manufactured by Iwasaki Electric) was heated in an air atmosphere.
Ultraviolet rays were irradiated from both sides of the sump for 20 seconds at an irradiation distance of 12crP1 using UV rays (trade name: L21).

The results obtained are shown in Table-1.

DPHA Nidipentaerythritol hexaacrylate 'I'AS: Ester compound consisting of succinic acid, trimethylolethane and acrylic acid U-108A: 1,6-hexanedio-/L//adipic acid/hexamethylene diisocyanate/2- Polyester urethane diacrylate consisting of hydroxyethyl acrylate (average molecular weight 1500-1600), manufactured by Shin Nakamura Chemical 'rHp-A: AtowohydrofuFriP acrylate MP (): Methylphene μglyoxylate BNP
:benzophenone tinuvin-PS:2-(hydroxy-5-tertiary-
Buchi μ Feni/I/) Benzotriacy/I/(Chipa・
(trade name manufactured by Geigy) Sano) vLS-770: Bis(2,2,6,6-titramethy!lepivelidini μm4) Separate (trade name manufactured by Sankyo) MAl: Methyl methacrylate/I//Butymethacrylate 1
v-50150 (weight ratio) copolymer ([η]-α04
) MA2: Polyethyl methacrylate ([η] = 109) MA? 1m polyiso-butyl methacrylate ([η)-
0,03) MA4: Boristine ((17)-(L 10 )M
A5: Polydodecyl methacrylate ([η)-CL13) MA6: Polyisobutyl methacrylate ([η)-0
,002) MA7: Polyisobutymu methacrylate ([η)-0
, 50) Example 4, Comparative Examples 8 to 16 The coating material compositions shown in Table 2 were prepared and treated under the same treatment conditions as in Example 1. The results obtained are shown in Table-2.

Examples 5 to 11, Comparative Examples 17 to 19 Coating material compositions shown in Table 3 were prepared and treated under the same treatment conditions as in Example 1. The results obtained are shown in Table 3.

TAA: Adivic acid and trimethylolethane Viscoat: Viscoatna 825, V-tan diacrylate using tolylene diisocyanate as the diisocyanate (trade name manufactured by Osaka Organic Co., Ltd.) TC-110S: ε-caderofucton modified tetofhydrofufurip acrylate (Japan) (trade name manufactured by Kayaku) 2-HEA: z-hydroxyethyl acrylate 2-ERA: 2-ethylhexyl acrylate D-
1175: 2-hydroxy-2-methyl-1-phenyp
Propan-1-one (trade name manufactured by Meuri) I-184: Irgacure 184 (trade name manufactured by Chipa Geigy) Sanol LS-292: Bis(1,2, Muhe 6-bentamethyl/l/-4 -Piperidi/L/) Separate (Sankyo brand name) Examples 12 to 14 In Example 12, the ultraviolet absorber used in Example 1 (Tinuvin-P810 parts by weight, Sano/L/L8-7701.0
The same formulation as in Example 1 was used, except that the weight part of Tinupin-P812 was changed from the weight part of the compound. In Examples 13 and 14, the photopolymerization initiator used in Example 1 (MPG2.4
parts by weight, B N P t 6 parts by weight) respectively MP (
) 4 parts by weight (Example 13) and D-11734 parts by weight (Example 14), the same formulation as in Example 1 was used.

Using these, ABS resin plate 3cm thick (manufactured by Mitsubishi Rayon,
Diapet (trade name: AB S13001MR) was immersed and a film was formed at a pulling rate of 0.4 sub/S8C. This was left as it was for 5 minutes, and then ultraviolet rays were irradiated from both sides of the sample for 18 seconds at an irradiation distance of 912 cIn using a high-pressure mercury lamp (the one used in Example 1 (B)) in an air atmosphere. The abrasion resistance, adhesion, appearance, and smoothness of the resin plate were good, and the appearance and adhesion after a 2000-hour weather test were also good.

In addition, the results of the heat resistance test were also good, and no occurrence of cracks or the like was observed.

Example 15, Comparative Example 20 In Example 15, a 2-fi thick Mekkuri P resin board (manufactured by Sanshi Rayon, trade name Acrylite-L) was immersed using the recipe shown in Example 5, and the same method as in Example 5 was used. Processed. The abrasion resistance, adhesion, appearance, and smoothness of the obtained resin plate were good, and the appearance and adhesion after 2000 hours (weather resistance test) were also good. Further, in a heat resistance test at 80° C. for 24 hours, no particular change in appearance was observed and the result was good.

In Comparative Example 20, the polyfunctional acrylate (DPHA 50 parts by weight, 'I'A 310 parts by weight) used in Example 5 was TM
PTA()IJ methylo-propane triacrylate)
The formulation was changed to 60 parts by weight, and the other ingredients were the same as in Example 5.

Using this, dip a polycarbonate resin plate 2,
The coating was formed at a pulling rate of 0.5 an/56c. After this was left as it was for 3 minutes, it was irradiated with ultraviolet rays for 20 seconds at an irradiation distance of 1[]c1rt using a high-pressure mercury lamp in an air atmosphere. The resulting coating was insufficiently cured and remained sticky.

〔Effect of the invention〕

The synthetic resin molded product manufactured using the coating composition of the present invention has not only wear resistance and weather resistance, but also smoothness, water resistance,
It has excellent chemical resistance and durability, and is resistant to gas, oxygen, ozone,
Its performance hardly deteriorates even under harsh conditions and environments such as rainwater, heat, and various gases in the atmosphere, making it extremely useful in fields where wear resistance and weather resistance are required.

Claims (9)

[Claims] (1) The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, X_1_1, X_1_2, X_1_3, X_2_
2, X_2_3, ...Xn_2, Xn_3, X_1_4
At least three of them are CH_2=CH-COO- groups, the rest are hydroxyl groups, amino groups, alkylene groups, or substituted alkylene groups, and n is an integer of 2 to 5. ) 30 to 80% by weight of compound (a) represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) (In the formula, at least three R's are CH_2=CH-COO-
group, and the rest are hydrogen, hydroxyl group, amino group, alkylene group, or substituted alkylene group, n_1, n_
2, n_3, n_4, m_1, m_2, m_3 and m
_4 takes the value of 0, 1 or 2, and x is 1
A positive integer between ~10. ) 5 to 40% by weight of compound (b) represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (III) (In the formula, R_1 is an acryloyloxy group or a methacryloyloxy group, , R_2 is hydrogen or a methyl group, l, m and n are positive integers of 1 to 8, and y is a positive integer of 0 to 10.) Compound (c) 10 to 50 weight %, and a compound (d) having one acryloyloxy group in one molecule and having a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond in the side chain in the molecule (d) 10 to 60
% by weight of a monomer mixture (A); 3 to 35 parts by weight of at least one ultraviolet absorber (B) per 100 parts by weight of the monomer mixture (A); (A) At least one type of (per 100 parts by weight)
Consists of 0.5 to 8 parts by weight of an alkyl meth)acrylate polymer (C) and 0.01 to 6 parts by weight of a photopolymerization initiator (D) per 100 parts by weight of the monomer mixture (A). Cured film-forming coating composition. (2) A patent claim in which the compound (a) represented by general formula (I) is selected from dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. A cured film-forming coating material composition according to item 1. (3) Compound (b) represented by general formula (II) is an ester compound consisting of a reaction product of malonic acid, trimethylolethane and acrylic acid, or an ester compound consisting of a reaction product of malonic acid, trimethylolpropane and acrylic acid. , an ester compound consisting of a reaction product of succinic acid, trimethylolethane and acrylic 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 The cured film-forming coating material composition according to claim 1, which is selected from compounds and ester compounds consisting of a reaction product of adipic acid, trimethylolpropane, and acrylic acid. (4) The compound (c) represented by the general formula (III) is a bifunctional polyester urethane acrylate synthesized by a conventional method from a saturated dibasic acid, a dihydric alcohol, a divalent isocyanate, and a hydroxyl group-containing acrylic ester,
The saturated dibasic acid is selected from succinic acid, adipic acid and sebacic acid, the dihydric alcohol is selected from 1,4-butanediol and 1,6-hexanediol, and the dihydric isocyanate is selected from 1,4-butanediol and 1,6-hexanediol. The cured film-forming coating material composition according to claim 1, wherein is hexamethylene diisocyanate, and the hydroxyl group-containing acrylic ester is 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate. (5) has one acryloyloxy group in one molecule,
and a compound having a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond in the side chain in the molecule (
The cured film-forming coating material composition according to claim 1, wherein d) has a boiling point at normal pressure of 150°C or higher and a viscosity at 20°C of 100 cps or lower. (6) The cured film-forming coating material composition according to claim 1, which additionally contains 100 to 2000 parts by weight of an organic solvent based on 100 parts by weight of the monomer mixture (A). (7) 0.0001 to 1.0 parts by weight of at least one silicone surfactant modified with a polyoxyalkylene group is additionally contained based on 100 parts by weight of the monomer mixture (A). A cured film-forming coating material composition according to claim 1. (8) A patent claim in which the ultraviolet absorber (B) is a compound derived from a benzophenone type, a benzotriazole type, a phenyl salicylate type, or a phenyl benzoate type, and its maximum absorption wavelength is in the range of 240 to 380 nm. The cured film-forming coating material composition according to item 1. (9) The alkyl (meth)acrylate polymer (C) is a homopolymer or copolymer of a monomer selected from alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms. and its limiting viscosity [η] is 0.01 to 0.30
A cured film-forming coating material composition according to claim 1.