JP5221159B2 - Active energy ray-curable coating composition and cured product thereof - Google Patents

Description

  The present invention provides a coating composition capable of forming a cured film on the surface of a substrate, which has excellent weather resistance, heat resistance, chemical resistance and adhesion to a substrate, and in particular excellent abrasion resistance, by irradiation with active energy rays. About.

  Synthetic resin molded products manufactured from polymethyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, polystyrene resin, AS resin, etc. are not only lightweight and excellent in impact resistance, but also have good transparency. As a plastic material for automobiles, it is widely used in various lamp lenses, glazing, instrument covers and the like. In particular, the use of plastic materials for headlamp lenses is increasing due to weight reduction and design diversification to improve automobile fuel efficiency. However, these synthetic resin molded products have insufficient surface wear resistance, so the surface is easily damaged by contact with other hard objects, friction, scratches, etc. It will reduce the value. In particular, in the case of polycarbonate resin or the like, the wear resistance is poor and the surface is easily damaged.

  Further, when used as a material for automobiles, the weather resistance is also an important performance. In particular, the polycarbonate resin has poor weather resistance and is deteriorated by active energy rays such as ultraviolet rays contained in sunlight, and the molded product is markedly yellowed or cracks are generated on the surface.

  Various methods for improving the drawbacks of such synthetic resin molded products have been studied in the past. For example, a coating material made of a silicon-based or melamine-based resin composition is applied to the surface of a synthetic resin molded product and heated. Proposed methods for improving wear resistance include a method of forming a crosslinked film by condensation and a method of forming a crosslinked film by irradiating active energy rays after applying a coating composition comprising a radical polymerizable monomer. (Patent Document 1).

  On the other hand, it is generally known that weather resistance is improved by using an ultraviolet absorber and a hindered amine light stabilizer in combination.

For example, as a hindered amine light stabilizer, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl A technique (Patent Document 2) in which a condensate with −3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol is used in combination with a benzotriazole-based ultraviolet absorber (hydroxyl triazine type) A technique (Patent Document 3) in which an ultraviolet absorber and a hindered amine light stabilizer are used in combination is known.
JP 56-122840 A JP 2002-155145 A JP 2006-63162 A

  However, when the ultraviolet absorber and the hindered amine light stabilizer are used in combination, the weather resistance of the coating material is improved, but the wear resistance tends to be lowered. In the market, in order to protect the headlamp lens for a long period from scratches caused by dust or a car wash, further improvement in wear resistance is required.

  The present invention has been made in the background described above, and the object thereof is a cured film having good weather resistance, heat resistance, chemical resistance and adhesion to a substrate, and particularly excellent wear resistance. It is providing the coating composition which can form.

  Thus, as a result of intensive studies to solve the above problems, the present inventors have found that weather resistance can be improved while maintaining wear resistance by using a specific compound and a hydroxyphenyltriazine type ultraviolet absorber in combination. .

In the present invention, (B) 0.1 to 5 parts by mass of a compound represented by the following formula (1), (C) 1 to 20 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber with respect to 100 parts by mass of the radically polymerizable compound (A). It is an active energy ray-curable coating composition in which parts are blended.

Moreover, (A) radically polymerizable compound in this invention is (a-1) 10-70 mass% of mono or polypentaerythritol poly (meth) acrylate shown to following formula (2), (a-2) 1 molecule inside 5 to 50% by mass of urethane poly (meth) acrylate having 2 or more (meth) acryloyloxy groups, and 0 to 85% by mass of a polymerizable compound other than the above (a-1) and (a-2) It is preferable that

[In the formula, at least three of α are (meth) acryloyloxy groups (CH ₂ ═CR—COO—) (R represents a hydrogen atom or a methyl group), (meth) acryloyl modified with caprolactone. An oxy group {CH ₂ ═CR—CO (O (CH ₂ ) ₅ C═O) _a —O—} (R represents a hydrogen atom or a methyl group, and a is an integer of 1 or more) or alkylene oxide. modified (meth) acryloyloxy group _{{CH 2 = CR-CO (} O (CH 2) b) c -O -} (R is a hydrogen atom or a methyl group, b is an integer in the range 2-4 , C is an integer of 1 or more). The remaining α is a hydroxyl group. n shows the integer of 0-4. ]
Moreover, (A) radically polymerizable compound in this invention is (a-1) 10-70 mass% of mono or polypentaerythritol poly (meth) acrylate shown to Formula (2), (a-2) in 1 molecule. 5 to 50% by mass of urethane poly (meth) acrylate having two or more (meth) acryloyloxy groups, (a-3) 10 to 50 mass of radically polymerizable group-containing inorganic fine particles, (a-4) (a-) It is more preferable from a viewpoint of abrasion resistance that it is a mixture containing 0-75 mass% of polymerizable compounds other than 1), (a-2), (a-3).

  Moreover, this invention is the hardened | cured material of the above-mentioned active energy ray hardening-type coating composition.

  By applying this coating composition to the surface of a synthetic resin molded article and irradiating with active energy rays, the weather resistance, heat resistance, chemical resistance and adhesion to the substrate are good, and particularly excellent in wear resistance. A synthetic resin molded article having a cured coating can be obtained.

  The present invention will be described in detail. First, each component of the coating composition of the present invention will be described.

<(A) Radical polymerizable compound>
As the radical polymerizable compound (hereinafter referred to as “component (A)”) constituting the active energy ray-curable coating composition of the present invention, a monofunctional or polyfunctional monomer or oligomer having a (meth) acryloyloxy group, radical polymerization And inorganic group-containing inorganic fine particles.

  Specifically, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, Tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, dipentaerythritol hexa (meth) acrylate in which α in formula (2) is modified with caprolactone, Α in 2) is dipentaerythritol hexaacrylate modified with ethylene oxide, α in formula (2) is propylene oxide -Modified dipentaerythritol hexaacrylate, urethane (meth) acrylates, polyester (meth) acrylates synthesized by condensation reaction of polyhydric alcohols with (meth) acrylic acid and polyfunctional carboxylic acids, bisphenol-type epoxy Examples thereof include epoxy (meth) acrylates synthesized by an addition reaction between a resin or a novolac type epoxy resin and (meth) acrylic acid. Moreover, you may use the radically polymerizable group containing inorganic fine particle synthesize | combined by processing inorganic fine particles, such as corosidal silica, with the silane coupling agent containing a (meth) acryloyl group. These are used in one or a mixture of two or more. As a specific mixed system, the following embodiments are preferable.

<About the compound represented by the formula (2)>
The mono- or polypentaerythritol poly (meth) acrylate represented by the formula (2) (hereinafter referred to as “component (a-1)”) exhibits a good polymerization activity upon irradiation with active energy rays and has a high crosslinking density. Forms a polymer with excellent wear resistance.

  Specific examples of the component (a-1) include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, Tripentaerythritol octa (meth) acrylate, dipentaerythritol hexa (medium) in which α in formula (2) is modified with caprolactone ) Acrylate, alpha in the formula (2) is dipentaerythritol hexaacrylate modified by ethylene oxide, alpha in the formula (2) is dipentaerythritol hexaacrylate modified by propylene oxide.

  (A-1) The usage-amount of a component has the preferable range of 10-70 mass% in 100 mass% of total amounts of (A) component. The lower limit is more preferably 20% by mass or more, and the upper limit is more preferably 50% by mass or less. (A-1) When the quantity of a component is 10 mass% or more, the abrasion resistance of the hardened | cured material of a coating composition becomes good. Moreover, when it is 70 mass% or less, the weather resistance and heat resistance of the hardened | cured material of a coating composition become good.

<About urethane poly (meth) acrylate having two or more (meth) acryloyl groups in one molecule>
Urethane poly (meth) acrylate having two or more (meth) acryloyl groups in one molecule (hereinafter referred to as “component (a-2)”) is a toughness, flexibility and heat resistance of the cured product of the coating composition. It is a component that improves the properties and weather resistance. A polyol compound is reacted with a urethanation reaction product of a (meth) acrylate containing a hydroxyl group and an isocyanate compound having two or more isocyanate groups in the molecule, and an isocyanate compound having two or more isocyanate groups in the molecule. After the synthesis of the adduct, a urethanization reaction product obtained by adding a (meth) acrylate containing a hydroxyl group to the remaining isocyanate group is exemplified. The latter urethane poly (meth) acrylate is preferred because it can further improve the toughness and flexibility of the cured product of the coating composition. Moreover, the weight average molecular weight by these GPC has a more preferable thing of 1,000-5,000 at the point that the adhesiveness to the base material of the film which hardened the coating composition is improved.

  Specific examples of the isocyanate compound having two or more isocyanate groups in the molecule include tolylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 4,4′-diphenylmethane. Diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine isocyanate, 4,4′-methylenebis (cyclohexyl) isocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, And polyisocyanate monomers such as imacic acid diisocyanate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, burettes and trimers thereof, and adducts of these with various polyols. it can.

  The polyol compound used for the synthesis of the adduct is not particularly limited, and specific examples thereof include alkyls such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, and glycerin. Examples include polyols, polyether polyols, polyester polyols, polycaprolactone polyols, and polycarbonate polyols.

  Specific examples of (meth) acrylates containing hydroxyl groups include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. In addition, addition reaction products of monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl methacrylate and (meth) acrylic acid, mono (meth) acrylic acid ester of polyethylene glycol, mono ( And (meth) acrylic acid ester, poly (butylene glycol) mono (meth) acrylic acid ester, polycaprolactone diol mono (meth) acrylic acid ester, and the like.

  The reaction between a hydroxyl group-containing (meth) acrylate and an isocyanate compound having two or more isocyanate groups in the molecule is such that the isocyanate groups and hydroxyl groups are almost equal in the presence of a tin-based catalyst such as dinormalbutyltin dilaurate. It is preferable to mix so that it may become quantity, and to heat at 60-70 degreeC for several hours. Since the reaction product generally has a high viscosity in general, it is preferable to dilute with an organic solvent or another dilution monomer during or after the reaction.

  The reaction between an isocyanate compound having two or more isocyanate groups in the molecule, a polyol compound and a (meth) acrylate containing a hydroxyl group is carried out in the presence of a tin-based catalyst such as dinormal butyltin dilaurate, Heating is performed at 60 to 70 ° C. for several hours using the hydroxyl groups so as to have approximately the same amount. Since the reaction product generally has a high viscosity in general, it is preferably diluted with an organic solvent or other dilution monomer during or after the reaction.

  (A-2) The usage rate of a component has the preferable range of 5-50 mass% in 100 mass% of total amounts of (A) component. The lower limit is more preferably 10% by mass or more, and the upper limit is more preferably 30% by mass or less. When the amount of the component (a-2) is 5% by mass or more, the weather resistance of the cured product of the coating composition and the curability in an air atmosphere are improved. Moreover, when it is 50 mass% or less, the abrasion resistance of the hardened | cured material of a coating composition becomes good.

<Polymerizable compounds other than (a-1) and (a-2)>
Examples of the polymerizable compound other than the above (a-1) and (a-2) include radical polymerizable group-containing inorganic fine particles, the component (a-4) exemplified later, and the like. The use ratio is preferably in the range of 0 to 85% by mass in 100% by mass of the total amount of component (A). The lower limit is more preferably 5% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 70% by mass or less, and further preferably 60% by mass or less.

<Regarding radically polymerizable group-containing inorganic fine particles>
The radical polymerizable group-containing inorganic fine particles (hereinafter referred to as “component (a-3)”) are preferably organic-coated silica having radical polymerizability, and can be synthesized by a known method. The component (a-3) is used for the purpose of imparting wear resistance. The use ratio of the component (a-3) is preferably in the range of 10 to 50% by mass in 100% by mass of the total amount of the component (A). The lower limit is more preferably 15% by mass or more, and the upper limit is more preferably 30% by mass or less. When the proportion of the component (a-3) used is 10% by mass or more, the wear resistance is improved. Moreover, when it is 50 mass% or less, the weather resistance of a coating film becomes good.

<Polymerizable compounds other than (a-1), (a-2), (a-3)>
As the polymerizable compound other than (a-1), (a-2), and (a-3) (hereinafter referred to as “component (a-4)”), among the compounds exemplified above as the component (A) And compounds other than the components (a-1), (a-2), and (a-3). (A-4) It is preferable that the usage-amount of a component is the range of 0-75 mass% in the total amount of 100 mass% of (A) component. The lower limit is more preferably 5% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 55% by mass or less, and further preferably 45% by mass or less.

  As the component (a-4), tetrahydrofurfuryl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, neopentylglycol di (meth) acrylate, bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, and the like are preferable. When these amounts are 5% by mass or more, the adhesion of the cured product of the coating composition to the substrate is improved. Moreover, when it is 70 mass% or less, the curability of the coating composition is improved.

<About the compound represented by Formula (1)>
The compound represented by the formula (1) constituting the active energy ray-curable coating composition of the present invention (hereinafter referred to as “component (B)”) is a hindered amine light stabilizer and is a radical generated by deterioration of the resin component. It is a component that enhances the weather resistance by trapping, and has the property of hardly bleeding out from the coating film, and imparts weather resistance to the cured product of the coating composition over a long period of time. 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4 , 8,10-tetraoxaspiro [5,5] undecane) diethanol is preferably obtained by condensation. As a commercial item, ADK STAB LA-63 (Corporation ADEKA) is mentioned.

  (B) The usage-amount of a component exists in the range of 0.1-5 mass parts with respect to 100 mass parts of (A) component. The lower limit is more preferably 0.3 parts by mass or more, and the upper limit is more preferably 1 part by mass or less. When the proportion of the component (B) used is 0.1 part by mass or more, the weather resistance is improved. Moreover, in the case of 5 mass parts or less, substrate adhesiveness becomes good.

<About hydroxyphenyltriazine UV absorber>
The hydroxyphenyltriazine-based ultraviolet absorber (hereinafter referred to as “component (C)”) constituting the active energy ray-curable coating composition of the present invention absorbs ultraviolet rays in sunlight, protects the substrate, and has weather resistance. It is a component that enhances. Compared to benzophenone type UV absorbers, benzotriazole type UV absorbers, etc., hydroxyphenyltriazine type UV absorbers have the property of being hard to bleed out from the cured product of the coating composition, and therefore provide weather resistance over a long period of time. To do.

  Specifically, 2- [4- (2-hydroxy-3-dodecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1,3,5- Triazine and a mixture of 2- [4- (2-hydroxy-3-tridecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1,3,5-triazine {Product name “Tinuvin 400” (Ciba Specialty Chemicals Co., Ltd.)}, 2- [4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl] -4,6- [bis (2, 4-dimethylphenyl)]-1,3,5-triazine {trade name: “Tinuvin 479” (Ciba Specialty Chemicals)}, Tris [2,4,6- [2- {4- ( Corruptible -2-methyl ethanoate ethylhexanoate) oxy-2-hydroxyphenyl}] - 1,3,5-triazine {trade name: such as "Tinuvin 777" (Ciba Specialty Chemicals Corp.)} and the like.

  (C) The usage-amount of a component exists in the range of 1-20 mass parts with respect to 100 mass parts of (A) component. The lower limit is more preferably 5 parts by mass or more, and the upper limit is more preferably 15 parts by mass or less. When the proportion of component (C) used is 1 part by mass or more, the weather resistance of the cured product of the coating composition is improved. Moreover, in the case of 20 mass parts or less, the base-material adhesiveness and abrasion resistance of the hardened | cured material of a coating composition become good.

  By using the component (B) and the component (C) in combination, the weather resistance can be improved without reducing the wear resistance of the cured product of the coating composition.

  The active energy ray-curable coating composition of the present invention comprises the above components (A), (B) and (C), and if necessary, a photopolymerization initiator, an organic solvent, an antioxidant, yellow Various additives such as anti-denaturing agents, bluing agents, pigments, leveling agents, antifoaming agents, thickeners, antisettling agents, antistatic agents, antifogging agents and the like may be contained. The organic solvent is preferably selected according to the type of substrate. For example, when polycarbonate is used as the base material, it is preferable to use one or two or more of alcohol solvents such as isobutanol and ester solvents such as normal butyl acetate.

  In order to apply the coating composition of the present invention to a substrate, brush coating, spray coating, dip coating, spin coating, flow coating, curtain coating, and the like are used. From the viewpoint of improving the smoothness, uniformity, and adhesion of the cured film to the substrate, it is preferable to add an appropriate organic solvent. Moreover, you may apply | coat, after heating a coating composition in order to adjust a viscosity.

The coating composition of the present invention is crosslinked by irradiation with active energy rays after being applied to a substrate to form a cured film. When curing by irradiation with active energy rays, the coating composition is preferably applied on the substrate so as to have a film thickness of 1 to 50 μm, more preferably 3 to 20 μm, and a high-pressure mercury lamp, a metal halide lamp or the like is used. Then, an ultraviolet ray having a wavelength of 340 nm to 380 nm is irradiated so as to be 1000 to 5000 mJ / cm ² . Moreover, you may irradiate with the acceleration voltage of 100-150 kV so that it may become 30-70 kGy. The atmosphere irradiated with ultraviolet rays may be air or an inert gas such as nitrogen or argon. On the other hand, the atmosphere in which the electron beam is irradiated preferably has an oxygen concentration of 300 ppm or less.

  The coating composition of the present invention can be used to modify the surface of various synthetic resin molded articles that are base materials. However, as this synthetic resin molded article, various types that have conventionally been requested to improve wear resistance, weather resistance, etc. A thermoplastic resin and a thermosetting resin are mentioned. Specific examples include polymethyl methacrylic resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin, and polyallyl diglycol carbonate resin. In particular, polymethyl methacrylic resin, polycarbonate resin, polystyrene resin, and polymethacrylimide resin are particularly effective to apply the coating composition of the present invention because they are excellent in transparency and have a strong demand for improving wear resistance. Synthetic resin molded products include sheet-shaped molded products, film-shaped molded products, and various injection molded products made of these resins.

  Therefore, a resin molded product in which a cured film is formed by applying the coating composition of the present invention to the surface of a polycarbonate resin molded product and irradiating active energy rays is suitable for a polycarbonate resin molded product for an automobile headlamp lens. is there.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The measurement evaluation in the examples was performed by the following method.

(1) Abrasion resistance of cured coating In accordance with JIS K7204 "Plastics-Wear test method using wear wheels", ROTARY ABRASION TESTER (manufactured by Toyo Seiki Co., Ltd.) and wear wheels CS-10F, 4.9N (500 gf) ) After wearing at 100 and 500 revolutions under load, the haze value was measured with a haze meter (HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.) to determine wear resistance. The criteria for judging wear resistance are as follows.
At 100 rotation wear ○ Increase haze value = 0 or more and less than 5.0 × Increase haze value = 5.0 or more At 500 rotation wear ◎ Increase haze value = 0 or more and less than 25.0 ○ Increase haze value = 25.0 or more 40. Less than 0 x increased haze value = 40.0 or more

(2) Scratch resistance Using a scratch tester (manufactured by KASAI. CO. LTD), steel wool: for Bonster business use, # 000 (extra fine), manufactured by Bonstar Sales Co., Ltd., load: 21.6 kPa, scratch speed: 4 cm / Second, scratch distance (one way): After 50 reciprocations under the condition of 6 cm, the haze value is measured with a haze meter (HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.), and scratch resistance is determined. Went. The criteria for determining scratch resistance are as follows.
○ Increase haze value = 0 or more and less than 1.0 × Increase haze value = 1.0 or more

(3) Weather resistance Sunshine carbon weatherometer (manufactured by Suga Test Instruments Co., Ltd., WEL-SUN-HC-B type) weather resistance tester, black panel temperature 63 ± 3 ° C, irradiation + rainfall 12 minutes, irradiation Only tested in a 48 minute cycle. The change in the cured film after 2000 hours exposure was observed and the adhesion was tested.

(A) Appearance For cracks, whitening, spiders, and peeling of the cured coating, those that did not occur were marked with ◯, and those that occurred were marked with x.

(B) Transparency Haze values before and after the test were measured using a haze meter (HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.).
◎ Increase haze value = 0 or more and less than 2.0 ○ Increase haze value = 2.0 or more and less than 5.0 × Increase haze value = 5.0 or more

(C) Yellowing degree The yellow index value was measured using an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.).
◎ Increase Yellow Index (YI) value = 0 or more and less than 1.0 ○ Increase Yellow Index (YI) value = 1.0 or more and less than 5.0 × Increase Yellow Index (YI) value = 5.0 or more

(D) Adhesion A cross-cut reaching the base material at intervals of 1 mm is put into the cured film, and 100 1 mm ² grids are made, on which cellophane tape (manufactured by Nichiban Co., Ltd., trade name “Selotape” (registered) Trademark))) was applied and peeled off rapidly and the peeled grids were counted. The case where there was no peeling was marked with ◯, the case where the peeled grids were in the range of 1-10, and the case where the peeled off grids were 11-100 were marked as x.

Synthesis example 1
Synthesis of radical polymerizable group-containing inorganic fine particles {component (a-3)} In a 3 liter four-necked flask equipped with a stirrer, thermometer and condenser, methanol silica sol (dispersion medium; methanol, SiO ₂ concentration; 30% by mass) Primary particle size: 12 nm, trade name: MT-ST, Nissan Chemical Industries, Ltd. (hereinafter abbreviated as “MT-ST”) 1200 g (360 g for SiO ₂ ), and γ-methacryloyloxy as the organosilane compound 230 g of propyltrimethoxysilane (trade name: SZ6030, manufactured by Toray Dow Corning Silicone Co., Ltd.) was added, the temperature was increased while stirring, and 100 g of pure water was gradually added dropwise at the same time as the reflux of the volatile components started. After completion, hydrolysis was performed with stirring for 2 hours under reflux.

  After the hydrolysis is completed, volatile components such as alcohol and water are distilled off under normal pressure. When the solid concentration reaches 60% by mass, 720 g of toluene is added, and alcohol, water and the like are azeotroped with toluene. Distilled.

  Next, 1000 g of toluene was added, and the solvent was completely replaced to obtain a toluene dispersion. The solid content concentration at this time was about 40% by mass.

  Further, the reaction was carried out at 110 ° C. for 4 hours while distilling toluene, so that the solid content concentration was about 60% by mass. Thereafter, 1000 g of 1-methoxy-2-propanol was further added, toluene was distilled off by evaporation, and the solvent was replaced to obtain a 1-methoxy-2-propanol dispersion. The obtained organic polymerized silica dispersion having radical polymerizability (hereinafter referred to as “MCS dispersion”) was a yellowish transparent liquid, and the solid content concentration was 50% by mass in the heating residue. The acid value of the MCS dispersion was 8 mgKOH / g, and it was 16 mgKOH / g when converted to the acid value of the organic-coated silica alone having radical polymerizability.

Example 1
A coating composition was prepared at a blending ratio shown in Table 1, and spray coating was performed on a polycarbonate resin plate having a thickness of 3 mm (manufactured by GE, trade name: “Lexan LS-2”) so that the film after curing was 8 μm. did. After volatilizing the organic solvent by heating at 80 ° C. for 3 minutes in an oven, the accumulated light quantity at a wavelength of 340 nm to 380 nm is 3000 mJ / cm ² {manufactured by Oak Manufacturing Co., Ltd. Irradiated with energy measured by an ultraviolet light meter UV-351 (SN type) to obtain a cured coating. The evaluation results of the obtained cured film are shown in Table 1.

Examples 2-12, Comparative Examples 1-11
A coating composition was prepared at a blending ratio shown in Tables 1 and 2, and a cured film was obtained under the same conditions as in Example 1. The evaluation results of the obtained cured coating are shown in Table 1, Table 2, and Table 3.

  In addition, the symbol of the compound in Table 1, Table 2, and Table 3 is as follows.

DPHA: dipentaerythritol hexaacrylate DPCA20: dipentaerythritol hexaacrylate modified with two caprolactones per molecule {trade name “Kayarad DPCA-20”, Nippon Kayaku Co., Ltd.}
UA1: urethane acrylate synthesized from 2 mol of dicyclohexylmethane diisocyanate, 1 mol of nonabutylene glycol (weight average molecular weight 850) and 2 mol of 2-hydroxyethyl acrylate.
UA2: urethane acrylate synthesized from 2 mol of dicyclohexylmethane diisocyanate, 1 mol of polycaprolactone diol (weight average molecular weight 530, trade name “Placcel-205”, Daicel Chemical Industries, Ltd.) and 2 mol of 2-hydroxyethyl acrylate.

MCS dispersion: Organic-coated silica dispersion having radical polymerizability synthesized in Synthesis Example 1 (solid content 50% by mass)
TAIC: tris (2-acryloyloxyethyl) isocyanurate TMPTA: trimethylolpropane triacrylate NDDA: 1,9-nonanediol diacrylate THFA: tetrahydrofurfuryl acrylate LA63: compound represented by the formula (1) {trade name “Adekastab LA-63P "(ADEKA Corporation)}
LS292: Mixture of 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 "Sankyo Lifetech Co., Ltd.}
LA68: 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2, 4,8,10-Tetraoxaspiro [5,5] undecane) condensate with diethanol {trade name “ADK STAB LA-68LD” (ADEKA)}
Tinuvin 123: reaction product of diester compound of decanedicarboxylic acid and 2,2,6,6-tetramethyl-1-octoxy-4-piperidinol, 1,1-dimethylethyl hydroperoxide and octane {trade name Tinuvin 123 "(Ciba Specialty Chemicals Co., Ltd.)}
LA52: Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate

HHBT: 2- [4- (2-hydroxy-3-dodecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1,3,5-triazine and 2 -[4- (2-hydroxy-3-tridecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1,3,5-triazine mixture {trade name “Chinubin 400” (Ciba Specialty Chemicals Co., Ltd.)}
OHBT: 2- [4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1,3,5-triazine {trade name “ Tinuvin 479 "(Ciba Specialty Chemicals Co., Ltd.)}
HBPB: 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole DHBP: 2,4-dihydroxybenzophenone {Brand name "Ubinal 3000" (BSF Japan Ltd.)}
BNP: benzophenone MPG: methylphenylglyoxylate TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BYK340: fluorine-based leveling agent {trade name “BYK-340”, Big Chemie Japan Co., Ltd.}
BYK333: Silicone leveling agent {Brand name "BYK-333", Big Chemie Japan Co., Ltd.}
PGM: Propylene glycol monomethyl ether MIBK: Methyl isobutyl ketone

  Examples 1-5 contain (a-1) component and (a-2) component, and content of each component exists in a more preferable range. Therefore, each physical property was favorable.

  Since Example 6 did not contain the component (a-2), transparency and yellowing after the weather resistance test were slightly deteriorated as compared with Examples 1-5.

  Example 7 contains the component (a-1) and the component (a-2), but the content of the component (B) is larger than the more preferable range. Therefore, the adhesion after the weather resistance test was slightly deteriorated as compared with Examples 1-5.

  Example 8 contains the component (a-1) and the component (a-2), but the content of the component (B) is less than the more preferable range. Therefore, the transparency after the weather resistance test was slightly deteriorated as compared with the coating compositions described in Examples 1 to 5.

  Example 9 contains the component (a-1) and the component (a-2), but the content of the component (C) is larger than the more preferable range. Therefore, the adhesion after the weather resistance test was slightly deteriorated as compared with Examples 1-5.

  Example 10 contains the component (a-1) and the component (a-2), but the content of the component (C) is less than the more preferable range. Therefore, the transparency and yellowing after the weather resistance test were slightly deteriorated as compared with Examples 1-5.

  Examples 11 and 12 contain the component (a-3) in addition to the component (a-1), the component (a-2), the component (B), and the component (C). Therefore, compared with Examples 1-10, abrasion resistance was still more favorable.

  Comparative Examples 1 to 4 do not contain the component (B) as a hindered amine light stabilizer, and contain a light stabilizer other than the component (B). Therefore, the wear resistance was poor.

  Comparative Examples 5 and 6 do not contain the component (C) as an ultraviolet absorber and contain an ultraviolet absorber other than the component (C). Therefore, the wear resistance was poor.

  Comparative Example 7 does not contain the component (B) as a hindered amine light stabilizer and contains a light stabilizer other than the component (B). Moreover, (C) component is not contained as a ultraviolet absorber, and ultraviolet absorbers other than (C) component are contained. Therefore, compared with Example 6, abrasion resistance deteriorated.

  The comparative example 8 has too much content of (B) component. Therefore, the adhesion after the abrasion resistance and weather resistance tests deteriorated.

  The comparative example 9 has too much content of (C) component. Therefore, the yellowing degree and adhesion after the abrasion resistance and weather resistance tests were deteriorated.

  Since Comparative Example 10 did not contain a hindered amine light stabilizer and an ultraviolet absorber, the weather resistance was poor.

  Since Comparative Example 11 did not contain the component (B), compared with Examples 11 and 12, the wear resistance and scratch resistance were deteriorated.

Claims (5)

(A) For 100 parts by mass of the radical polymerizable compound,
(B) 0.1 to 5 parts by mass of a compound represented by the following formula (1),
(C) 1 to 20 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber,
An active energy ray-curable coating composition containing

(A) the radical polymerizable compound is
(A-1) Mono- or polypentaerythritol poly (meth) acrylate represented by the following formula (2): 10 to 70% by mass,
(A-2) 5 to 50% by mass of urethane poly (meth) acrylate having two or more (meth) acryloyloxy groups in one molecule;
Polymerizable compounds other than (a-1) and (a-2) 0 to 85% by mass
The active energy ray-curable coating composition according to claim 1, which is a mixture comprising

[In the formula, at least three of α are (meth) acryloyloxy groups (CH ₂ ═CR—COO—) (R represents a hydrogen atom or a methyl group), (meth) acryloyl modified with caprolactone. An oxy group {CH ₂ ═CR—CO (O (CH ₂ ) ₅ C═O) _a —O—} (R represents a hydrogen atom or a methyl group, and a is an integer of 1 or more) or alkylene oxide. modified (meth) acryloyloxy group _{{CH 2 = CR-CO (} O (CH 2) b) c -O -} (R is a hydrogen atom or a methyl group, b is an integer in the range 2-4 , C is an integer of 1 or more. The remaining α is a hydroxyl group. n shows the integer of 0-4. ]   The active energy ray-curable coating composition according to claim 1, wherein (A) the radical polymerizable compound is a mixture containing 10 to 50 mass% of (a-3) radical polymerizable group-containing inorganic fine particles. (A) The radically polymerizable compound is (a-1) mono- or polypentaerythritol poly (meth) acrylate of 10 to 70% by mass represented by the following formula (2),
(A-2) 5 to 50% by mass of urethane poly (meth) acrylate having two or more (meth) acryloyloxy groups in one molecule;
(A-3) Radical polymerizable group-containing inorganic fine particles 10 to 50 mass,
(A-4) 0 to 75% by mass of a polymerizable compound other than the above (a-1), (a-2) and (a-3)
The active energy ray-curable coating composition according to claim 3, which is a mixture comprising

[In the formula, at least three of α are (meth) acryloyloxy groups (CH ₂ ═CR—COO—) (R represents a hydrogen atom or a methyl group), (meth) acryloyl modified with caprolactone. An oxy group {CH ₂ ═CR—CO (O (CH ₂ ) ₅ C═O) _a —O—} (R represents a hydrogen atom or a methyl group, and a is an integer of 1 or more) or alkylene oxide. modified (meth) acryloyloxy group _{{CH 2 = CR-CO (} O (CH 2) b) c -O -} (R is a hydrogen atom or a methyl group, b is an integer in the range 2-4 , C is an integer of 1 or more. The remaining α is a hydroxyl group. n shows the integer of 0-4. ] Hardened | cured material of the active energy ray hardening- type coating composition in any one of Claims 1-4.