JPH0141649B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to radiation-curable coating compositions containing copolymerizable ultraviolet absorber compounds capable of providing polymeric materials with improved photodegradability. Coating compositions which can be cured under the influence of radiation in general, particularly ultraviolet radiation as well as electron beams, are well known.
Typical examples of conventional paints include U.S. Patent No.
No. 3782961, No. 3829531, No. 3850770, No.
No. 3874906, No. 3864133, No. 3891523, No.
No. 3895171, No. 3899611, No. 3907574, No.
Includes paints disclosed in Nos. 3912516, 3932356 and 3989609. Unfortunately, these coating compositions have a number of drawbacks and do not include UV absorbers in the composition. Many of these coating compositions are not flexible enough to cause cracks in the coating when applied to flexible supports such as polyvinyl chloride. Other compositions have the undesirable result of not adhering well to the substrate and becoming susceptible to migration or delamination. Still other coating compositions require the use of solvents, which must be evaporated during the curing process. Evaporation of such solvents consumes energy and causes air pollution problems. Other compositions produce coatings that are yellow, have poor weather resistance, and have insufficient scratch, stain, abrasion, and/or solvent resistance. It is known to use UV absorbers in plastics or paints. The absorber absorbs the radiation and dissipates the energy, thus protecting the coating from structural deterioration. Significant economic savings are achieved by incorporating the UV absorber into the surface of the plastic article rather than incorporating it throughout, as is conventionally done. Additionally, conventional surface applications such as using solvents or paint vehicles are undesirable due to pollution risks and large volume processing requirements. Although radiation curing can produce paint films that are easier to handle, until now UV absorbers have consumed energy from the radiation source, resulting in either too high energy requirements for curing or a slow curing rate. It was too late. If a small amount of UV photoinitiator is used to facilitate curing, the addition of most UV stabilizers will interfere with curing. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a superior coating composition that is substantially free of one or more of the disadvantages of conventional radiation-curable coating compositions. Another object of the present invention is to provide a coating composition that produces a coating that is weather resistant, scratch resistant, stain resistant, abrasion resistant, solvent resistant and non-yellowing. Another object of the present invention is to obtain a coating composition that does not contain volatile solvents. Another object of the invention is to provide an improved method for coating substrates such as natural leather, synthetic leather, polyvinyl chloride, polyurethane and polycarbonate. Another object of the present invention is to obtain a coating composition containing a copolymerizable ultraviolet absorber that can be cured by radiation. The above and other objects are achieved in the present invention by the following formula: (In the formula, R ¹ is a hydrogen atom or a methyl group, and Y is a divalent urethane residue); and B (where (Ar) ₁ and (Ar) ₂ are benzene-based and naphthalene-based aromatic carbocyclic nuclei, independently of the others, phenyl groups, or alkyl, halo,
alkoxy, carboxy, carbalkoxy,
selected from phenyl and naphthyl groups substituted with cyano, acetyl, benzoyl, phenyl, alkylphenyl, phenoxyphenyl, alkyl-substituted phenoxy or alkoxyphenyl-substituted phenyl groups, X is unsubstituted or halo, cyano, _C1 ～ _C6
alkyl, _C1 - _C6 alkoxy, _C2 - _{C17 alkylene group substituted with C1-C6 alkoxyalkyl} or _C1 - _C6 alkoxyalkyleneoxy _, Y is _C3 - _C12 selected from the group consisting of acryloyl, _C3 - _C12 alkyl acryloyl, _C3 - _C12 acryloxyalkyl, _{C3 - C12} acryloxyhydroxyalkyl, C3- _C12 alkylacryloxyhydroxyalkyl A copolymerizable group or -RCR'-CHR'', where R is unsubstituted or substituted with a hydroxyl group
_C1 - _C10 phenylene, _C1 - _C10 alkylene,
C ₁ -C ₁₀ oxyalkylene or C ₁ -C ₁₀ alkyleneoxyalkylene group, R′ and R″ are independently hydrogen atoms or
This is achieved by providing a coating composition containing a copolymerizable (2-cyano-3,3-diphenylacryloxy)alkylene acrylic ester ultraviolet absorber represented by (representing a _C1 to _C6 alkyl group) be done. In the most preferred compositions of the invention, (Ar) ₁ and (Ar) ₂ are phenyl groups, X is -C ₂ H ₄ ,
R is alkylene--CH ₂ --, and R' and R'' both represent hydrogen atoms. The one or more vinyl monomers that can be copolymerized with the oligomer in the composition are N-vinyl-2-pyrrolidone and acrylic ester. Formula oligomers having acrylic or methacrylic components are well known in the industry. Oligomers of this type are described in U.S. Pat.
No. 3989609 and No. 3895171.
A preferred form of oligomer has both an acrylic component and a urethane moiety in the Y group. Examples of these compounds are U.S. Pat.
It is published in No. 3864133 and No. 3850770. A preferred new form of acrylic urethane is represented by the following formula and formula: However, in the above formula, R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkylene group, R ³ is an aliphatic group or an alicyclic group, X is -O- or -NH-, and n is an integer from 2 to 50. show. These oligomers are made by reacting polytetrahydrofuran, polycaprolactone polyols, and other polyols with diisocyanates to form isocyanate-terminated prepolymers. The isocyanate-terminated prepolymer is then capped with a capping agent to produce oligomers of formula and formula. Preferred oligomers of the formula are of the formula; preferred oligomers of the formula are of the formula: However, in the above formula, n represents an integer of 5 to 20. Polytetrahydrofuran is available from DuPont under the trade names ``Telecor-650'', ``Telecor-1000'' and ``Telecor-2000'', and from Quaker Coats Company under the trade names ``Polymegu-650'' and ``Polymegu-650''.
It is available on the market under the trade names "Polymegu-1000" and "Polymegu-2000". The numerical value in the above trade name indicates the approximate molecular weight of polytetrafuran. The most preferred polytetrahydrofuran is
Consistent with the definition of "n" in the formula and formula
It has a molecular weight of 650. At higher molecular weights, where "n" exceeds about 50, the resulting oligomers are too viscous. Caprolactone polyol is "NIAX Caprolactone Polyols" from Union Carbide Corporation.
PCP-200, PCP-0210, PCP-0230, PCP-
0240, PCP―0300, PCP―0301 and PCP―
It is available on the market under the trade name 0310. The 0200 series are diols with molecular weights of 530, 830, 1250 and 2000, respectively. The 0300 series are triols with molecular weights of 540, 300 and 900, respectively. , , and the oligomers of formula U.S. Patent No.
It can be manufactured according to No. 4129709. Capping agents useful in the present invention are those that react with the isocyanate-terminated prepolymer to form oligomers of the formula. Generally, any capping agent having a terminal amine or hydroxyl group and having an acrylic or methacrylic acid moiety is suitable. Suitable capping agents include, among others, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl, methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, hydroxypentyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate. , aminoethyl acrylate and aminoethyl methacrylate. Diisocyanates useful in preparing oligomers of formula are aliphatic and cycloaliphatic diisocyanates that react with the terminal hydroxyl groups present in polytetrahydrofuran. Aromatic diisocyanates, of course, perform the same reaction, but do not produce products as satisfactory as those obtained by the use of aliphatic diisocyanates. Examples of suitable diisocyanates include, among others, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, sold under the trade name "Hexylene W" by Dubon, and trimethyl-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate. ,2,4,4-triethyl-
These include 1,6-hexylene diisocyanate, octadecylene diisocyanate and 1,4-cyclohexylene diisocyanate. A preferred diisocyanate is isophorone diisocyanate (3-
isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate) and 4,4'-dicyclohexylmethane-diisocyanate. The vinyl monomer copolymerizable with the oligomer can be one or more monomers that are compatible with the selected oligomer. Acrylic acid esters and N-vinyl-2-pyrrolidone having a boiling point of at least 200° C. at 760 mm Hg are preferred. These monomers make it possible to adjust the viscosity and facilitate the coating operation, and N-vinyl-2-pyrrolidone increases the curing rate. The weight ratio of oligomer to N-vinyl-2-pyrrolidone can vary within a range without adversely affecting the properties of the resulting cured coating composition, but generally the oligomer and N-vinyl-2-pyrrolidone are 1:9. Weight ratio of ~9:1, preferably ~1:3
Present in a weight ratio of 3:1. The ratio is even greater.
For example, when enriched in oligomers, uncured coating compositions tend to become too viscous. Such high viscosity makes it difficult to apply the uncured coating composition to a support. As the ratio becomes smaller, the resulting uncured coating composition tends to become too hard and undeformable. Acrylic ester is 760mmHg and at least 200
It should have a boiling point of °C. Low boiling acrylic esters tend to evaporate during curing. When such evaporation occurs, undesirable changes occur in the coating composition. Furthermore, vaporized acrylic esters tend to polymerize at radiation sources, such as ultraviolet lamps or electron beam windows. This evaporation also causes unwanted air pollution. Acrylic esters useful in this invention include monoesters, diesters, and higher esters of both acrylic and methacrylic acids, among others. Examples of suitable acrylic acids include, among others, 1,4-butanediol diacrylate;
These include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol-tetramethacrylate, trimethylolpropane triacrylate, ethylhexyl-acrylate, ethylhexyl-methacrylate, pentyl-acrylate, hexyl-acrylate and cyclohexyl-methacrylate. 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate are the preferred acrylic esters. The acrylic ester can be present in the coating composition in a wide range of amounts, but in a weight ratio of 1:9 to 9:1, preferably 1:3 to 3:1, compared to the formula or oligomer of the formula. Make it exist. The copolymerizable (2-cyano-3,3-diphenylacryloxy) alkylene acrylate ultraviolet absorber has the following formula. In the above formula, (Ar) ₁ and (Ar) ₂ are benzene-based and naphthalene-based aromatic carbocyclic nuclei, and are phenyl groups or alkyl, halo, alkoxy, carboxy, carboalkoxy, cyano, acetyl, selected from phenyl and naphthyl groups substituted with benzoyl, phenyl, alkylphenyl, phenoxyphenyl, alkyl-substituted phenoxy, or alkoxyphenoxy-substituted phenyl, and X is unsubstituted or halo, cyano, C ₁ - _C6 alkyl, _C1 -C6 alkoxy, C1 _{- C6} alkoxyalkyl or _C1 - _{C6 alkoxyalkyleneoxy} -substituted alkylene group, Y is _C3 - _C12 acryloyl, _C3 -C6 a copolymerizable group selected from the group consisting of _C12 alkyl acryloyl, _C3 to _C12 alkyloxyalkyl, _C3 to _C12 acryloxyhydroxyalkyl, _C3 to _C12 alkylacryloxyhydroxyalkyl; or -RCR′=CHR″, where R is unsubstituted or hydroxyl-substituted C ₁ to C ₁₀ phenylene;
_C1 - _C10 alkylene, _C1 - _C10 oxyalkylene or _C1 - _C10 alkyleneoxyalkylene, R′ and R″ are independently hydrogen atoms or _C1
~ _C6 alkyl group. Suitable (Ar) ₁ and (Ar) ₂ groups are described in U.S. Pat.
No. 3,644,466, which includes representative starting benzophenone compounds. In the most preferred embodiment of the invention, (Ar) ₁ and (Ar) ₂ are both phenyl groups. The X group is a _C2 - _C17 unsubstituted or substituted alkylene group. Preferred groups are _C2 - _C6 unsubstituted lower alkylene groups synthetically derived from ethylene glycol, propylene glycol, butanediol, and the like. Representative X groups are -CH ₂ CH ₂ -,, -
CH ₂ CH ₂ CH ₂ ―, ―CH ₂ CH ₂ CH ₂ CH ₂ ―, etc. Most preferred is --CH ₂ CH ₂ --. The Y group can be copolymerized with the vinyl monomer so that the UV absorber becomes an essential part of the polymer.
Suitable Y groups are derived from acryloyl, alkylacryloyl, acryloxyalkyl, acryloxyhydroxyalkyl and alkylacryloxyhydroxyalkyl having from _C3 to _C12 carbon atoms. Preferred groups are acryloyl, methacryloyl, glycidyl acryloyl and glycidyl methacryloyl. A typical Y group is

[Formula] (acryloyl),

[Formula] (methacryloyl),

[Formula] (3-acryloxy-2-hydroxypropyl),

[Formula] CH ₂ (3-methacryloxy-2-hydroxypropyl). The most preferred group is acryloyl or methacryloyl. The compounds of the formula contain a group copolymerizable with a UV absorber moiety in the same molecule. These groups are effectively separated by the X group so that each can perform its own function without interference from the others. Therefore, the absorbent part does not interfere with the copolymerization and Y
The groups do not affect the light absorption properties of the molecule. -RCR'=CHR'' groups can be copolymerized with vinyl monomers and the UV absorber becomes an essential part of the polymer.Suitable groups are allyl, crotyl, methylpropenyl, vinylbenzyl, vinyloxyether, allyloxy-2- Hydroxypropyl and 2-hydroxy-3-butenyl. Most preferred is allyl. The absorbent compound is 2-hydroxyalkyl (2
It can be produced by esterifying -cyano-3,3-diphenyl)acrylate with acryloyl halide or acrylic acid. In this synthesis, it is preferable to first protect the hydroxyl group of the hydroxyalkylcyanoacetate by acylation with a group convertible to a hydroxyl group by hydrolysis, for example, by acylation using acetyl chloride to obtain the corresponding acetoxyalkylcyanoacetate. The protected compound is then condensed with benzophenone by Knoeffenagel reaction to obtain acetoxyalkyl (2-cyano-3,3-diphenyl) acrylate in high yield. Acid hydrolysis of the protected acetyl group then yields the corresponding hydroxy intermediate, which is then directly esterified with the appropriate acryloyl halide or acrylic acid to yield the desired compound. The absorbent compound is 2-hydroxyalkyl-2-
It can be produced by alkylating cyano-3,3-diphenyl acrylate with an ethylene halide. In this synthesis, it is preferred to first protect the hydroxyl group of the hydroxyalkylcyanoacetate by acylation with a group convertible to a hydroxyl group by hydrolysis, for example, by acylation using acetyl chloride to obtain the corresponding acetoxyalkylcyanoacetate. The protected compound is then condensed with benzophenone by Knoeffenagel reaction to obtain acetoxyalkyl (2-cyano-3,3-diphenyl) acrylate in high yield. Acid hydrolysis of the protected acetyl group then yields the corresponding hydroquine intermediate, which is then directly alkylated with a suitable ethylene halide to yield the desired compound. The amount of UV absorber of the above formula in the coating composition for radiation curing is 0.5% to 5%, preferably 0.75% to 2%, most preferably about 1.5% by weight of the composition.
It is. If the amount is less than this, a coating that maintains light transmission or low yellowing cannot be obtained. Above the above amounts, curing will be unacceptably slow. If curing is carried out with ultraviolet light, a photoinitiator is used. Suitable photoinitiators include vicinal keto aldonyl compounds (i.e. compounds having ketone and aldehyde groups) such as diacetyl, benzyl;
3-pentanedione, 2,3-octanedione,
1-phenyl-1,2-butanedione, 2,2-
Dimethyl-4-phenyl-3,4-butanedione, phenyl-glyoxal, diphenyl-triketone; aromatic diketones, such as anthraquinone; acryloin, such as benzoin; pivaloin-acryloin ether, such as benzoin-methyl-ether, benzoin-ethyl- Ethers, benzoin-butyl-ether, benzoin-isobutyl-ether, benzoin-phenyl-ether; including alpha-methyl-benzoin, alpha-alkylbenzoin, and even phenylbenzoin as described in U.S. Pat. No. 2,722,512. Included are alpha hydrocarbon substituted aromatic acryloins; diaryl ketones such as benzophenone and dinaphthyl ketone; and organic disulfides such as diphenyl disulfide. The photoinitiator may also contain a synergist, such as a tertiary amine, to facilitate the conversion of light absorption energy to polymerization initiating free radicals. Dimethoxyphenylacetophenones such as diethoxyacetophenone available from Union Carbide Corporation, IRGACURE 651 available from Ciba Geigy or Vicure available from Stauffer Chemical Company. Benzoin ethers such as No. 10 are preferred. The photoinitiator is present in the coating composition in an amount sufficient to initiate the desired polymerization under the influence of the amount of actinic energy absorbed. Generally, the coating composition contains from 0.01 to 5% by weight of photoinitiator, based on the weight of the coating composition. Additionally, addition polymerization initiators can be included in the coating composition to prevent undesirable autopolymerization of the coating composition during storage prior to use. Examples of suitable addition polymerization initiators include, among others, di(1,4-sec butylamino)benzene, available from DuPont under the tradename "Anti-Oxidant 22" and phenothiazine, available from Tefuenco Chemical Company. . The addition polymerization initiator is present in an amount sufficient to avoid autopolymerization and is generally present in an amount of 100 to 300 ppm based on the weight of the coating composition. The coating composition can also contain surfactants. Preferred surfactants are silicone surfactants such as those available from Dow Corning Corporation under the trade name "DC-193." The surfactant is present in an amount necessary to reduce the surface tension of the coating composition. Generally, the surfactant is present in an amount of 0.1 to 5% by weight based on the weight of the coating composition. The coating compositions of the present invention may contain, for example, flow control agents, leveling agents, organic and inorganic dyes and pigments, fillers, plasticizers, lubricants and reinforcing agents, such as alumina, silica, clay, talc, glass powder, carbon. May contain black and glass fibers. The coating compositions of this invention can be applied and cured as a 0.5 mil thick film onto a substrate. Curing is preferably carried out under an inert atmosphere of nitrogen. The coating composition can be applied as a thin film by any conventional method, such as by brush spraying, brushing, dipping, roll coating, and the like. Typically, the film on the support is conveyed on a conveyor and passed under a source of free radical generators in a radial manner. The coated side of the support is exposed to radiation for a sufficient time to polymerize, converting the film into a tough, flexible adhesive coating. Reference herein to radiation shall mean a radiation source that generates free radicals and induces addition polymerization of vinyl bonds. Actinic radiation is 2000-7500A, preferably
A wavelength of 2000-4000A is suitable. One of the actinic radiations useful in the present invention is ultraviolet radiation; other forms of actinic radiation include solar and artificial sources such as RS solar lamps, carbon arc lamps, xenon arc lamps, mercury vapor lamps, tungsten halide lamps, lasers, and ultraviolet radiation. It comes from a fluorescent lamp that uses phosphorescent substances. For commercial acceptance it is necessary to obtain UV curing rates of 6 m (20 ft)/min/lamp or higher. Coating compositions employing UV absorbers of the formula present in amounts of 0.5 to 3% by weight of the composition, if fairly thick (10 mils or less),
Can be cured at 25-50 ft/min/ramp speed. A preferred electron beam system produces a wide beam of electrons (electron curtain) directly from a linear cathode. Broad electrons accelerated to high speed by a 200 KV potential from the cathode of the electron gun are emitted from the chamber through a foil window onto the coated support (Electron Curtain TM, by Energy Sciences, Inc.). As mentioned above, electron beam curing of the coating composition is less than 5 megarads, and curing is usually carried out at 2 megarads. Curing above 8 megarads is expensive and appears to be unacceptable. A laminate consisting of a thin film of a coating based on acrylic urethane with the UV absorber (2-cyano-3,3-diphenyl acryloyloxy)alkylene ethylene ether on transparent polyvinyl chloride has shown surprising results. In particular, it is not leached and does not yellow. The invention will be illustrated with reference to the following examples. Unless otherwise specified, "parts" and "%" mean "parts by weight" and "% by weight." Example 1 Production of radiation-cured coatings 1 dry resin kettle 300.8 with air inlet tube, stirrer, thermometer and dropping funnel.
g (1.3 mol) of isophorone diisocyanate and 10% (W/
V) 4.8 ml of ethylhexyl acrylate solution was fed. Dry air was bubbled through the solution while stirring, and 322.1 g (0.61 mol) of polyol caprolactone (PCP-200) was added dropwise over 45 minutes. The solution was then heated to 80°C and the reactants were maintained at this temperature for 30 minutes. After cooling to 55℃,
160ml of phenothiazine was mixed. 151.9 g (1.3 moles) of hydroxyethyl acrylate were then rapidly added. The temperature was raised to 80°C and maintained for 2 hours. The resulting oligomer (58.1 g) was mixed with 25.4 g ethylhexyl acrylate, 16.8 g vinylpyrrolidone, 14.2 g hexanediol diacrylate, 1.8 g DC-193 silicone surfactant, 2.4 g
g of Bikiure 10 photoinitiator and 2.5 g of 2-
A paint was made by mixing with (2-cyano-3,3-diphenylacryloxy)ethyl acrylate. The resulting syrup was coated onto polyvinyl chloride to form a film having a thickness of 1.5 mils. This film was then cured with ultraviolet light in an inert atmosphere to obtain a tough transparent coating containing a copolymerized ultraviolet absorber compound. The polyvinyl chloride plate thus protected showed only a slight tendency to yellowing even after being tested in a weatherometer for 734 hours. Example 2 The produced oligomer (58.1 g) was mixed with 25.4 g ethylhexyl acrylate, 16.8 g vinylpyrrolidone, 14.2 g hexanediol diacrylate, 1.8 g DC-193 silicone surfactant, 2.4 g
g of Bikiure 10 photoinitiator and 2.5 g of 2-
(2-cyano-3,3-diphenylacryloxy)ethyl was mixed with allyl ether to make a paint. The resulting syrup was coated onto a polyvinyl chloride plate to form a film having a thickness of 1.5 mils. The film was then cured with ultraviolet light under an inert atmosphere to yield a tough transparent coating containing the copolymerized ultraviolet absorber compound of the present invention. The protected polyvinyl chloride film had less tendency to yellow than the unprotected film in the Weatherometer test.

Claims (1)

[Claims] 1 A The following formula (In the formula, R ¹ is a hydrogen atom or a methyl group, and Y is a divalent urethane residue); and B (where (Ar) ₁ and (Ar) ₂ are benzene-based and naphthalene-based aromatic carbocyclic nuclei, independently of the others, phenyl groups, or alkyl, halo,
alkoxy, carboxy, carbalkoxy,
selected from phenyl and naphthyl groups substituted with cyano, acetyl, benzoyl, phenyl, alkylphenyl, phenoxyphenyl, alkyl-substituted phenoxy, or alkoxyphenyl-substituted phenyl, and X is unsubstituted or halo, cyano, _C1 ～ _C6
a C2- _C17 alkylene group substituted with C1 _{- C6} alkyl, C1 _- C6 alkoxy, _C1 - _C6 alkoxyalkyl, or _C1 - _C6 alkoxyalkyleneoxy, Y is _C3 - _C12 acryloyl, _C3 to _C12 alkyl acryloyl, _C3 to _C12 acryloxyalkyl, _C3 to _C12 acryloxyhydroxyalkyl _, and _C3 to C12 alkylacryloxyhydroxyalkyl. a copolymerizable group or -RCR′=CHR″,
However, R is unsubstituted or substituted with a hydroxyl group
_C1 - _C10 phenylene group, _C1 - _C10 alkylene group, _C1 - _C10 oxyalkylene group or C1- _C10 oxyalkylene group
C ₁₀ alkyleneoxyalkylene group, R′ and R″ are hydrogen atoms or
1. A radiation-curable coating composition comprising a copolymerizable ultraviolet absorber compound represented by (representing a _C1 to _C6 alkyl group). 2. The coating composition according to claim 1, which contains a vinyl monomer copolymerizable with the oligomer. 3. The coating composition of claim 1, comprising an addition polymerization initiator present in an amount sufficient to prevent autopolymerization of the composition during storage. 4 Addition polymerization initiator is 100 to 100% by weight of the composition
A coating composition according to claim 3, present in an amount of 300 ppm. 5 The weight ratio of oligomer to vinyl monomer is 1:9 ~
The coating composition according to claim 3, wherein the ratio is 9:1. 6. The coating composition of claim 1 further comprising a photoinitiator present in an amount sufficient to initiate the desired polymerization under the influence of the amount of actinic energy absorbed. 7 Ultraviolet absorber is 0.5 to 0.5 to the weight of the composition
Coating composition according to claim 1, present in an amount of 5% by weight. 8. The coating composition according to claim 1, wherein (Ar) ₁ and (Ar) ₂ in the formula are phenyl groups. 9. The coating composition according to claim 1, wherein in the formula, X is a _C2 to _C6 alkylene group. 10 In the formula, Y is C ₃ to C ₁₂ acryloyl,
_C3 to _C12 methacryloyl, _C3 to _C12 3-acryloxy-2-hydroxypropyl, or _C3
The coating composition according to claim 1, which is a 3-methacryloxy-2-hydroxypropyl group of ~ _C12 . In formula 11, (Ar) ₁ and (Ar) ₂ are phenyl groups, X is a C ₂ to C ₆ alkylene group, and Y is a C ₃ to C 6 alkylene group.
_C12 acryloyl, _C3 ~ _C12 methacryloyl,
The coating composition according to claim 1, which is a C3 to _C12 3-acryloxy-2-hydroxypropyl group or a _C3 to _C12 3-methacryloxy-2 _- hydroxypropyl group. 12. The coating composition according to claim 1, wherein the formula is 2-(2-cyano-3,3-diphenylacryloxy)ethyl acrylate. 13. The coating composition according to claim 1, wherein the formula is 2-(2-cyano-3,3-diphenylacryloxy)ethyl methacrylate. 14. The coating composition according to claim 1, wherein the formula is 3-(2-cyano-3,3-diphenylacryloxy)propyl acrylate. 15. The coating composition according to claim 1, wherein the formula is 4-(2-cyano-3,3-diphenylacryloxy)butyl acrylate. 16. The coating composition according to claim 1, wherein the formula is 3-(2-cyano-3,3-diphenylacryloxy)-2-hydroxypropyl acrylate. 17. The coating composition according to claim 1, wherein the formula is 3-(2-cyano-3,3-diphenylacryloxy)-2-hydroxypropyl methacrylate. 18 A The following formula (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkylene group, R ³ is an aliphatic or alicyclic group, X is -O- or -NH-, and n is an integer from 2 to 50. ), B N-vinyl-2-pyrrolidone, C hexanediol diacrylate, D 2-(2-cyano-3,3) present in an amount of 0.5 to 5 weight percent relative to the weight of the composition.
- diphenyl acryloxyethyl acrylate, E a photoinitiator present in an amount of 0.01 to 5 percent by weight relative to the weight of the composition, F an addition polymerization initiator present in an amount of 100 to 300 ppm relative to the weight of the composition , G based on a silicone surfactant present in an amount of 0.1 to 5 percent by weight relative to the weight of the composition, with the proviso that A:B is 1:3 to 3:1;
A:C is 1:3 to 3:1, photopolymerized in the presence of ultraviolet light to produce weather-resistant, scratch-resistant, stain-resistant, abrasion-resistant, solvent-resistant, flexible A paint coating composition according to claim 1, which is capable of producing an adhesive film. 19 A The following formula (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkyl group, R ³ is an aliphatic or alicyclic group,
X is -O- or -NH-, n is an integer of 2 to 50), B N-vinyl-2-pyrrolidone, C hexanediol diacrylate D 0.5 to 3 based on the weight of the composition 2-(2-cyano-3,3
-diphenylacryloxy)ethyl acrylate, E. a photoinitiator present in an amount of 0.01 to 5 percent by weight relative to the weight of the composition, F. an addition polymerization initiator present in an amount of 100 to 300 ppm relative to the weight of the composition. G is based on a silicone surfactant present in an amount of 0.1 to 5 percent by weight relative to the weight of the composition, with the proviso that A:B is 1:3 to 3:1;
A:C is 1:3 to 3:1, photopolymerized in the presence of ultraviolet light to produce weather-resistant, scratch-resistant, stain-resistant, abrasion-resistant, solvent-resistant, flexible A coating composition according to claim 1, which is capable of producing an adhesive film. 20. The coating composition according to claim 1, wherein RCR'=CHR'' in the formula is allyl, crotyl, methylpropenyl, vinylbenzyl, vinyloxyether, allyloxy-2-hydroxypropyl or 2-hydroxy-3-butenyl. thing.