JP2008150508A - Active energy ray-curable coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition which can remarkably reduce the amount of an organic solvent contained while maintaining the performance of the conventional composition and enables spray coating. <P>SOLUTION: The active energy ray-curable coating material comprises 100 pts.mass polymerizable monomer mixture (A) containing 10-30 mass% (2-methyl-2-ethyl-1,3-dioxoran-4-yl)methyl acrylate (a), 70-90 mass% (meth)acryloyl monomer other than (a) or (meth)acryloyl oligomer, 5-15 pts.mass hydroxyphenylbenenzotriazole ultraviolet absorber or hydroxyphenyltriazine ultraviolet absorber (B), and 1-50 pts.mass organic solvent (C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention has an organic solvent content that is very low compared to conventional coating materials, and is an active energy ray curing that constitutes a top coat for polycarbonate molded products intended for outdoor use that can be cured by active energy rays such as ultraviolet rays. It relates to a mold coating material.

  In general, polycarbonate resin is widely used as an engineering plastic with excellent transparency, easy moldability, heat resistance, and impact resistance. Especially, taking advantage of the above performance, headlamp lens, tail lamp, side cover lamp and glazing. It is often used for automotive applications such as materials. Of these, polycarbonate is particularly used for the headlamp lens because of its light weight and improved design for improving the fuel efficiency of automobiles.

  However, since polycarbonate resin has insufficient wear resistance, it has the disadvantages that it is susceptible to damage such as scratches on the surface, and that weather resistance is insufficient compared to other engineering plastics. Especially for headlamp lenses that require high wear resistance and weather resistance because they are used in outdoor applications, such as scratches caused by dust or washing, reduced transparency due to ultraviolet rays contained in sunlight, cracks, crazing, etc. Deterioration of appearance such as occurrence and increase in yellowish color is likely to occur. For this reason, it is indispensable to form a coating film for improving wear resistance and weather resistance on the surface of the polycarbonate headlamp lens.

  As a method of forming a coating film that compensates for the disadvantages of such polycarbonate resins, a coating composition in which an ultraviolet absorber is blended with an acrylic, melamine, urethane, or silicone resin is applied to the surface of the molded polycarbonate product. However, a method of forming a coating film by curing using active energy rays such as heat, ultraviolet rays or electron beams has been developed (Patent Document 1). Among them, the active energy ray curing system using active energy rays has advantages such as superior productivity compared to other methods, so far it has provided excellent wear resistance and weather resistance to polycarbonate molded products. Many coating material compositions have been developed as possible methods (for example, Patent Documents 2 to 4).

When a conventional active energy ray-curable composition is applied to a three-dimensional molded body, spray coating is often used for film thickness control. In order to obtain a good appearance by spray coating, the viscosity of the paint must be lowered. Therefore, in order to control the viscosity, in many cases, it is often diluted with an organic solvent. Many organic solvents are released into the atmosphere after spray painting, polluting the environment. Therefore, the development of paints that reduce the content of organic solvents or do not use them at all has been progressing (Patent Document 5). However, in Patent Document 5, since many monofunctional (meth) acrylates used for viscosity reduction and bifunctional (meth) acrylate having a relatively low viscosity are used, conventional methods such as scratch resistance, weather resistance, and chemical resistance are used. There was a limit to maintaining performance.
JP 56-122840 A JP-A-5-275769 JP-A-9-286809 JP 2000-281935 A JP 2005-170890 A

  The present invention has been made to solve the above-mentioned problems that occur when reducing the amount of organic solvent used in an active energy ray-curable composition that imparts wear resistance and weather resistance to an outdoor polycarbonate molded body. Specifically, it is an object to provide an active energy ray-curable composition that can be spray-coated without impairing the performance of conventional products.

  The present invention relates to (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (a) in an amount of 10 to 30% by mass, and (meth) acryloyl monomer or (meth) acryloyl other than (a). 5 to 15 parts by mass of a hydroxyphenylbenzotriazole-based ultraviolet absorber or hydroxyphenyltriazine-based ultraviolet absorber (B) with respect to 100 parts by mass of the polymerizable monomer mixture (A) containing 70 to 90% by mass of the oligomer, and It is an active energy ray-curable coating material containing 1 to 50 parts by mass of an organic solvent (C).

  The coating material of the present invention can greatly reduce the amount of the organic solvent contained while maintaining the performance of the conventional composition. Moreover, the active energy ray-curable coating material of the present invention can be spray-painted as in the case of conventional compositions.

  The polymerizable monomer mixture (A) (hereinafter referred to as “component (A)”) constituting the coating material of the present invention is (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate ( 10-30 mass% of a) is contained.

  (2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (a) (hereinafter referred to as “component (a)”) has a very low viscosity and is contained in an active energy ray-curable coating material. It is used because it is excellent in compatibility with other monomer components and has strong dissolving power for hydroxyphenylbenzotriazole ultraviolet absorbers and hydroxyphenyltriazine ultraviolet absorbers. There are other UV curable monomers with low viscosity, but performances such as scratch resistance and weather resistance tend to deteriorate. (A) It is preferable to use 10-30 mass% in 100 mass% of components. A more preferred lower limit is 15% by mass, and a more preferred upper limit is 25% by mass. In the case of 10% by mass or more, the viscosity of the active energy ray-curable coating material is lowered and can be stored stably for a long time. When it is 30% by mass or less, the scratch resistance is improved.

  The (meth) acryloyl monomer or (meth) acryloyl oligomer other than the component (a) constituting the component (A) is not particularly limited as long as it can be cured by active energy rays. Usable monomers and oligomers include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloylalkoxysilane, etc. And monofunctional (meth) acrylate having a polymerizable unsaturated bond, polyfunctional (meth) acrylate, and the like, and may be selected as appropriate according to the required performance of the coating.

  Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth). Acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Cyclodecane (meth) acrylate, polyethylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) Mono (meth) acrylates such as acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, phthalic anhydride and 2-hydroxy And mono (meth) acrylate compounds such as adducts with ethyl (meth) acrylate. Since these monofunctional (meth) acrylates are low in viscosity, they are used for viscosity adjustment. However, if they are used in a large amount, they tend to cause deterioration in scratch resistance and weather resistance. Therefore, when using it, it is necessary to pay attention to the amount used so as not to reduce the performance.

  Specific examples of the polyfunctional (meth) acrylate include neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (number of repeating units (hereinafter referred to as “n”) = 2 to 15) di (Meth) acrylate, polypropylene glycol (n = 2-15) di (meth) acrylate, polybutylene glycol (n = 2-15) di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxy Phenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, trimethylolpropane diacrylate, bis (2- (meth) acryloxyethyl) -hydroxyethyl-isocyanurate Trimethylolpropane tri (meth) acrylate, tris (2- ( Ta) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, epoxy poly (meth) acrylate such as epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy and (meth) acrylic acid, 1,6-hexamethylene diisocyanate Urethane tri (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with trimer, urethane di (meth) acrylate obtained by reacting isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate Urethane hexa (meth) acrylate obtained by reacting isophorone diisocyanate and pentaerythritol tri (meth) acrylate, urethane di (meth) acrylate obtained by reacting dicyclomethane diisocyanate and 2-hydroxyethyl (meth) acrylate, dicyclomethane diisocyanate And urethane poly (meth) acrylate such as urethane di (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with a urethanization reaction product of poly (n = 6-15) tetramethylene glycol, and trimethylolethane Polyester (meth) acrylate reacted with succinic acid and (meth) acrylic acid, polyester reacted with trimethylolpropane and succinic acid, ethylene glycol, and (meth) acrylic acid ( Examples include polyester poly (meth) acrylates such as (meth) acrylate.

  An organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloylalkoxysilane is also used to increase the hardness of the coating film. Specifically, colloidal silica and vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 2 -Combinations of (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane And organic-inorganic hybrid vinyl compounds and organic-inorganic hybrid (meth) acrylate compounds.

  It is preferable to use a combination of a plurality of (meth) acryloyl monomers or (meth) acryloyl oligomers other than the component (a) constituting the component (A) as necessary. In particular, a combination of one or two types of polyfunctional acrylates and a urethane poly (meth) acrylate compound having at least two or more radically polymerizable unsaturated double bonds in one molecule is suitable for a headlamp. Among them, as the (meth) acryloyl monomer or (meth) acryloyl oligomer other than the component (a) constituting the component (A), a poly (meth) acrylate of mono- or polypentaerythritol, 5 to 35% by mass Urethane poly (meth) acrylate compound having at least two radically polymerizable unsaturated double bonds in one molecule, 5 to 35% by mass, and poly [(meth) acryloyloxyalkyl] (iso) cyanure G is a combination of 15 to 60% by mass, and the total of them is preferably 70 to 90% by mass in 100% by mass of component (A). If it is in this range, the coating film excellent in heat resistance, chemical resistance, durability, and adhesion to the substrate can be obtained. When the poly (meth) acrylate of mono- or polypentaerythritol is 5% by mass or more, a cured film having sufficient abrasion resistance is obtained, and when it is 35% by mass or less, sufficient abrasion resistance is obtained. . However, if it is added in an excessive amount, cracks are likely to occur in the cured film, cracks may occur in the cured film after the durability test or weather resistance test, and the heat resistance of the cured film also decreases. It becomes easy. When the urethane poly (meth) acrylate compound is 5% by mass or more, a cured film having sufficient toughness and weather resistance is obtained, and the curability in an air atmosphere is also good. If it is 35% by mass or less, sufficient wear resistance can be obtained. A poly [(meth) acryloyloxyalkyl] (iso) cyanurate with a content of 15% by mass or more provides a cured film having sufficient wear resistance and heat resistance, and a content of 60% by mass or less provides sufficient curability. It is done.

  The hydroxyphenylbenzotriazole-based ultraviolet absorber or the hydroxyphenyltriazine-based ultraviolet absorber (B) (hereinafter referred to as “component (B)”) is used to prevent the polycarbonate as a molding substrate from being colored. Among the components (B), 2-hydroxy-tert-butylphenylbenzotriazole, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis ( 2,4-Dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenyl) Phenyl) -1,3,5-triazine is preferred from the viewpoint of weather resistance. It is preferable to use 5-15 mass parts with respect to 100 mass parts of (A) component. A more preferred lower limit is 7 parts by mass, and a more preferred upper limit is 12 parts by mass. In the case of 5 parts by mass or more, not only can the coloring of the polycarbonate as the molding substrate be prevented, but also cracks and crazes generated in the cured product of the active energy ray-curable coating material can be prevented. In the case of 15 parts by mass or less, the scratch resistance is improved.

  The organic solvent (C) (hereinafter referred to as “component (C)”) is used to lower the viscosity. Among organic solvents, ketone-based, ester-based, and ethylene glycol-based solvents are used because they have excellent compatibility with the component (A) and the component (B). Examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and acetylacetone. Examples of the ester organic solvent include ethyl acetate, normal propyl acetate, isopropyl acetate, normal butyl acetate, and isobutyl acetate. Examples of the ethylene glycol organic solvent include phenoxyethanol and ethyl diglycol acetate. One or more of these solvents may be used. It is preferable to use 1-50 mass parts with respect to (A) component. A more preferred upper limit is 30 parts by mass. If it is 50 mass parts or less, the organic solvent discharge | release amount to air | atmosphere can be reduced significantly rather than the conventional active energy ray hardening-type composition.

  The coating material of the present invention can contain a radical polymerization initiator (D) and a light stabilizer (E).

  The radical polymerization initiator (D) (hereinafter referred to as “component (D)”) may be appropriately selected from the viewpoint of compatibility in the active energy ray-curable coating material, and is not particularly limited. Specific examples of the component (D) include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1- Carbonyl compounds such as hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide; 2,4 , 6-Trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethyl) Phosphoric acid compounds such as benzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide; 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butanone-1, camphorquinone and the like. These may be used individually by 1 type, or may be used in combination of 2 or more types, and can be combined arbitrarily according to the required coating film performance.

  The content of component (D) is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of component (A). In the case of 0.1 parts by mass or more, the effect of sufficiently accelerating the curing rate of the cured coating material tends to be exhibited, and the cured film obtained has excellent hardness (abrasion resistance). It tends to be able to impart adhesion and weather resistance. On the other hand, in the case of 10 parts by mass or less, it is possible to prevent coloring of the cured coating film and deterioration of weather resistance.

  Examples of the light stabilizer (E) (hereinafter referred to as “component (E)”) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, bis 1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc., among which bis (1-octoxy-2,2,6,6-tetramethyl-4 -Piperidyl) sebacate is particularly preferred.

  Moreover, the usage-amount of (E) component is 0.1-5 mass parts with respect to 100 mass parts of (A) component. When the amount of the component (E) is 0.1 parts by mass or more, the weather resistance of the cured coating film tends to be improved. On the other hand, when the amount is 10 parts by mass or less, the toughness, heat resistance, and resistance of the cured coating film are increased. Abrasion is improved.

  In addition, the active energy ray-curable coating material of the present invention includes an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickening agent, an anti-settling agent, an electrification as necessary. Components such as various additives such as an inhibitor and a surfactant may be contained.

  The active energy ray curable coating material of the present invention is particularly preferably used for an active energy curable coating material used outdoors. The active energy ray-curable coating material is mainly applied to the outside of the headlamp lens and vehicle sensor of an automobile. The base material outside the headlamp lens and the vehicle sensor is polycarbonate. Since the polycarbonate has high impact resistance, heat resistance, transparency and lightness, it is used for the headlamp lens and the vehicle sensor. However, since polycarbonate has insufficient performance such as chemical resistance, weather resistance, and scratch resistance, a coating material such as an active energy ray-curable coating material of the present invention is used.

  In addition, polycarbonate coated with the active energy ray-curable coating material of the present invention as a coating material has the same performance as glass, is lightweight, and has easy moldability, so in addition to automotive headlamp lenses and vehicle sensors, It can be suitably used in various fields. For example, it can be used for a wide variety of purposes, including outdoor signage, greenhouses and glass windows in outdoor buildings, terraces and garage roofs, balconies, and instrument covers.

<Method for adjusting coating film>
A coating material was air-sprayed onto a polycarbonate resin plate (trade name “Lexan LS-2”, manufactured by GE) having a thickness of 3 mm so that the cured film had a thickness of 8 μm. After the organic solvent is volatilized by heating in a heating furnace at 60 ° C. for 90 seconds, it is cured by irradiating energy of 3000 mJ / cm ² with an integrated light amount of 340 to 380 nm in air using a high-pressure mercury lamp. A test piece was obtained.

<Appearance determination of coating film>
The appearance of the test piece was visually evaluated. The test sample surface has good smoothness with no cracks or whitening, the test sample surface has no cracks or whitening but has poor smoothness, △, and cracks or whitening are observed x It was.

<Initial adhesion test of coating film>
Put a cross-cut reaching the base material at 1 mm intervals on the cured coating on the test piece, make 100 1 mm ² grids, paste Serotope (Registered Trademark) on it, peel it off, and peel off I counted my eyes. The case where there was no peeling was rated as ◯, the case where the number of peels was 1 or more and less than 50 was Δ, and the case where the number of peels was 50 or more was rated as x.

<Abrasion resistance test>
Using a Taber abrasion tester, the wear wheel CS-10F was worn 100 revolutions with a load of 500 g, and then the diffusion transmittance (haze value) was measured to determine the wear resistance. The criteria for judging wear resistance are as follows.
○ Increase haze value = 0% or more, less than 20% △ Increase haze value = 20% or more, less than 30% × Increase haze value = 30% or more <Thermal cycle test of coating film>
The thermal cycle test method for the cured coating is as follows. Using a constant temperature and humidity machine (KHW-40HP, manufactured by Satake Chemical Machinery Co., Ltd.), the test piece was subjected to 3 cycles of a thermal cycle test of -40 ° C. for 2 hours and 80 ° C. for 2 hours. The subsequent change of the cured coating film was confirmed as follows.

<Appearance after thermal cycle test>
The appearance of the test piece was visually evaluated. A sample having no cracks or spontaneous separation on the surface of the test sample was marked with ◯, and a sample where cracks or natural separation was observed was marked with ×.

<Adhesion after thermal cycle test>
Put a cross-cut reaching the base material at 1 mm intervals on the cured coating on the test piece, make 100 1 mm ² grids, paste Serotope (Registered Trademark) on it, peel it off, and peel off I counted my eyes. The case where there was no peeling was rated as ◯, the case where the number of peels was 1 or more and less than 50 was Δ, and the case where the number of peels was 50 or more was rated as x.

<Weather resistance test of coating film>
The weather resistance test method for the cured coating is as follows. Test specimens were tested using a sunshine bonbon weatherometer (Suga Test Instruments, WEL-SUN-HC-B type) weather resistance tester (black panel temperature 63 ± 3 ° C., rainfall 12 minutes, irradiation 48 minutes cycle) did. Changes in the cured coating after exposure for 2500 hours were confirmed as follows.

<Method for evaluating sample after weather resistance test>
(1) Appearance The appearance of the test piece was visually evaluated. A sample having no cracks or spontaneous separation on the surface of the test sample was marked with ◯, and a sample where cracks or natural separation was observed was marked with ×.

(2) Transparency The transparency of the test piece was measured according to JIS-K7105 using a haze meter HM-65W type manufactured by Murakami Color Research Laboratory.
A measurement haze value of 0 or more and less than 5% was evaluated as ◎, 5% or more and less than 10% as ○, and 10% or more as ×.

(3) Yellowing Yellowness (yellow index) of the test piece was measured according to JIS-K7105 using Otsuka Electronics instantaneous multi-photometry system MCPD-3000. When the measured yellow index value was 0 or more and less than 5, ◯ was set, and when it was 5 or more and less than 10, Δ was set.

<Total amount of VOC (volatile organic compound)>
All volatile organic compounds (VOC) were considered to be organic solvents, and the organic solvent was 0% or more and less than 40% in all paints, and 40% or more was rated as x.

(Examples and comparative examples)
[Example 1]
As shown in Table 1, 25 parts by mass of DPHA, 30 parts by mass of TAIC, 20 parts by mass of UA-1, 25 parts by mass of medol (a), 10 parts by mass of HBPB, and 28.7 parts by mass of n-butyl acetate 1 part by mass, 1 part by mass of BP, 1 part by mass of MPG, 2 parts by mass of APO and 0.5 part by mass of BOTS were mixed and stirred to obtain and evaluate an active energy ray-curable coating material. The abbreviations are described after the table.

[Examples 2 to 5, Comparative Examples 1 to 9]
An active energy ray-curable coating material was obtained and evaluated in the same manner as in Example 1 except that the raw materials and the composition ratio were changed as shown in Table 1 or Table 2.

In addition, the symbol of the compound in Tables 1-2 is as follows.

DPHA: dipentaerythritol hexaacrylate TAIC: tris (2-acryloyloxyethyl) isocyanurate UA-1: urethane acrylate MEDOL having a molecular weight of 2500 synthesized from 2 mol of dicyclohexylmethanediol, 1 mol of nonabutylene glycol and 2 mol of 2-hydroxyethyl acrylate: ( 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate DCPOEA: dicyclopentenyloxyethyl acrylate IBXA: isobornyl acrylate HBPB: 2- (2-hydroxy-5-tert-butylphenyl) Benzotriazole HPT1: 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2, -Dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Mixture of dimethylphenyl) -1,3,5-triazine and 1-methoxy-2-propanol (trade name Tinuvin 400, manufactured by Ciba Specialty Chemicals)
HPT2: 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (trade name Tinuvin 479, Ciba Specialty Chemicals) (Made by company)
HPT3: Tris [2,4,6- [2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl}]-1,3,5-triazine (trade name Tinuvin 777, Ciba Specialty Chemicals) (Made by company)
UVA1: ethanediamide-N- (2-ethoxy-phenyl) -N ′-(4-isododecylphenyl) -oxalic anilide (trade name: Sanduboa 3206 liq, manufactured by Clariant Japan)
MIBK: methyl isobutyl ketone BP: benzophenone MPG: methylphenylglyoxylate APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BOTS: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate And methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name SANOL LS-292, manufactured by Sankyo Lifetech Co., Ltd.)
Since the constituents of Examples 1 to 5 consisted of the composition and composition ratio shown in claim 1, the appearance, transparency and yellowness after the weather resistance test were good.

  Since the constituents of Comparative Examples 1 to 9 were not composed of the composition shown in claim 1, any of coating film appearance, scratch resistance, post-test adhesion after thermal cycle, weather resistance, and VOC was poor. It was.

Claims (1)

  10 to 30% by mass of (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (a) and 70 to (meth) acryloyl monomer or (meth) acryloyl oligomer other than (a) Hydroxyphenyl benzotriazole type ultraviolet absorber or hydroxyphenyl triazine type ultraviolet absorber (B) 5 to 15 parts by mass and organic solvent (C) with respect to 100 parts by mass of the polymerizable monomer mixture (A) 90% by mass ) Active energy ray-curable coating material containing 1 to 50 parts by mass.