Curable composition, cured product, and laminate having developability

Abstract

To provide an active energy ray-curable resin composition and a cured coating film which can achieve both excellent developability of an ultraviolet non-irradiation part and chemical resistance of the ultraviolet non-irradiation part, and a laminate having a cured coating film composed of the cured product on the surface of a base material.SOLUTION: An active energy ray-curable resin composition contains: a compound (A) having one carboxyl group and one (meth) acryloyl group in one molecule; an urethane (meth)acrylate compound (B) having at least two (meth)acryloyl groups in one molecule; a polyfunctional (meth)acrylate compound (C) having 4 or more (meth)acryloyl groups in the molecule; a photopolymerization initiator (D); and a silane coupling agent (E).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable resin composition, and more particularly to development after solvent drying and an active energy ray-curable resin composition excellent in developability, adhesion after curing, chemical resistance and hardness .

Background Art

[0002] On the cover window of display devices such as smartphones and tablet PCs , there is a bezel which is a non-display area. As one method for manufacturing a bezel, screen printing is known, but there have been problems in terms of film thickness uniformity and the like. Further, in photolithography methods there have been problems in terms of ease of development and strength of the film after curing.

[0003] For example, Patent Document 1 discloses a carboxyl group-containing (meth)acryloyl monomer and an acrylic resin composition made of an acrylic copolymer and excellent in alkali developability.

Prior Art Literature

Patent Literature

[0004]

Patent Document 1

Summary of the Invention

Problem to be Solved by the Invention

[0005] Although Patent Document 1 is excellent in alkali developability, it has a problem of being inferior in chemical resistance and scratch resistance .

[0006] An object of the present invention is to provide an active energy ray-curable resin composition that can achieve both developability after solvent drying, and adhesion after ultraviolet irradiation, chemical resistance and hardness .

[0007] The inventors of this invention have diligently studied to solve the above problems and have found that there is one CAL in one molecule. Compounds having a boxyl group and one (meth)acryloyl group, and at least one compound containing one (meth)acryloyl group in one molecule. A urethane (meth)acrylate compound having two or more (meth)acryloyl groups is incorporated. This has led to the discovery that the developability and alcohol resistance of the cured coating film are improved. It was the dawn of the Ming Dynasty. [Means for solving the problem]

[0008] In other words, the active energy ray curable resin composition of the present invention is [1] A molecule having one carboxyl group and one (meth)acryloyl group Compound (A) (hereinafter, component (A)) and at least two (meth)acryloys per molecule This contains a urethane (meth)acrylate compound (B) having a ru group (hereinafter referred to as component (B)). An active energy ray curable resin composition characterized by the following. [2] Component (A) is characterized by having at least one cyclic skeleton in one molecule. [1] The active energy ray curable resin composition described above. [3] In addition to components (A) and (B), the molecule contains four or more (meth)acryloyl groups It is characterized by containing a polyfunctional (meth)acrylate compound (C) (hereinafter referred to as component (C)). The active energy ray curable resin composition described in [1] or [2]. [4] Component (A) is 50-90% by mass of the total amount of components (A) to (C), and component (B) is The active energy described in [1]-[3], wherein component (C) is 1-30% by mass and component (C) is 1-20% by mass. A ghee wire-curing type resin composition. [5] Photopolymerization initiator (D) (hereinafter referred to as component (D)) relative to the total amount of components (A) to (C) The active energy ray-curable resin composition according to any one of [1] to [4], which comprises 1 to 30% by mass of . [6] The active energy ray-curable resin composition according to any one of [1] to [5], which comprises 1 to 20% by mass of a silane coupling agent (E) (hereinafter, component (E)) based on the total amount of component (A) to component (C). [7] A cured product obtained by irradiating the active energy ray-curable resin composition according to any one of [1] to [6] with an active energy ray and curing the same. [8] A laminate having the cured product according to [7] on the surface of a base material. Effects of the Invention

[0009] The present invention can provide an active energy ray-curable resin composition that can achieve both excellent developability after solvent drying, adhesion after ultraviolet irradiation, chemical resistance and hardness, a cured coating film, and a laminate having a cured coating film formed of the cured product on the surface of a base material. Mode for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail. In the present specification, "(meth)acrylate" means "acrylate" and / or "methacrylate"; "(meth)acryl" means "acryl " and / or "methacryl"; "(meth)acryloyl" means "acryloyl" and / or "methacryloyl"; "(meth)acrylonitrile" means "acrylonitrile " and / or "methacrylonitrile"; and "(co)polymerization" means "homopolymerization" and / or " copolymerization". Further, in the present specification, having developability means that the coating film in an uncured state after solvent drying can be removed from the base material when the coating film is immersed in an alkaline aqueous solution. . ​​​​

[0011] [Active energy ray-curable resin composition] The active energy ray-curable resin composition of the present invention (hereinafter referred to as the present composition) comprises, as described below a compound having one carboxyl group and one (meth)acryloyl group per molecule ( A) [referred to as component (A)], a urethane (meth)acrylate compound (B) having at least two or more (meth)acryloyl groups per molecule [referred to as component (B)], a polyfunctional (meth)acrylate compound (C) having four or more (meth)acryloyl groups in the molecule ( referred to as component (C)], a photopolymerization initiator (D) [referred to as component (D)], and a silane cou pling agent (E) [referred to as component (E)].

[0012] [Component (A)] Component (A) formulated in the present composition is a (meth)acrylate monomer having one carboxyl group and one ( meth)acryloyl group per molecule. It is used for imparting developability to a coating film and alcohol resistance to a cured coating film obtained by curing the present composition (hereinafter simply referred to as a cured coating film). It is used to impart the above properties.

[0013] The molecular weight of component (A) is preferably from 100 to 1000, more preferably from 110 to 500 , and even more preferably from 120 to 400. When the molecular weight is not lower than the lower limit, the toughness of the cured coating film is improved and alcohol resistance is enhanced; when the molecular weight is not higher than the upper limit, the developability of the coating film is improved.

[0014] Specific examples of component (A) include: (1) a monoester reaction product of an acid anhydride or a dibasic acid and a hydroxyl group-containing (meth)acryla te; and a reaction product of an organic lactone and a hydroxyl group-containing (meth)acryla ​(2) is a reaction product with T.

[0015] The dibasic acid or acid anhydride used to synthesize reaction product (1) is phthal Acids, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and these An anhydrous form is an example. In addition, hydroxyl group-containing (meth)acrylates include 2-hydroxy 2-Hyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-Hyethyl(meth)acrylate Droxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylates; 2-hydroxyethyl (meth)acrylate Additives of ethylene oxide to phosphate, and additives to 2-hydroxyethyl (meth)acrylate. Examples include propyl oxide adducts. Among these, those having an annular skeleton are preferred from the viewpoint of chemical resistance and scratch resistance, and further Since those having an aromatic ring are more preferable, phthalic acid, tetrahydrophthalic acid, and Xahydrophthalic acid is preferred, and phthalic acid is more preferred from the viewpoint of alkaline developability.

[0016] Furthermore, the lactone used to synthesize reaction product (2) is ε-caprolactone. Tons are mentioned, and as a hydroxyl group-containing (meth)acrylate, the above reaction product (1) Examples of compounds used in synthesis include those mentioned above. Among these, monophthalic acid is considered to have the developability of the coating film and the alcohol resistance of the cured coating film. Roxyethyl acrylate is preferred.

[0017] [Proportion of ingredient (A)] The proportion of component (A) is such that component (A) accounts for 50-90% of the total amount of components (A) to (C). A certain percentage is preferred, and 60-80% by mass is more preferred. The higher the amount of component (A), the better the developability. Furthermore, the less alcohol present, the better the alcohol resistance of the cured coating tends to be.

[0018] [Component (B)] Component (B) is a urea having at least two (meth)acryloyl groups in one molecule. It is a tan(meth)acrylate compound. Component (B) is selected according to the required performance of the cured coating film. You can choose as you see fit. For example, component (B) could be polyisocyanate (B1), polio (B2), and hydroxyl group-containing (meth)acrylate (B3) or polyisocyanate ( B1), and urethane obtained by reacting with hydroxyl group-containing (meth)acrylate (B3) Methacrylate is one example. Component (B) contributes to the toughness of the cured coating film.

[0019] [Polyisocyanate (B1)] Compound (B1) is an isocyanate compound having at least two isocyanate groups. It is a substance. Compound (B1) contributes to the flexibility of the cured coating film.

[0020] Examples of compound (B1) include tolylene diisocyanate and diphenylmethane. Socyanates, polyphenylmethane diisocyanates, modified diphenylmethane diisocyanates Nate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, phen Aromatic diisocyanates such as niren diisocyanate and naphthalene diisocyanate; Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysate Acyclic aliphatic diisocyanates such as lysine triisocyanate; Hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norborneol Diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl) Alicyclic diisocyanates such as (isocyanatomethyl)cyclohexane; polyhydric iso Using cyanates and the diisocyanates mentioned above, allophanate structures, nurate structures, and Examples include polymerized polyvalent isocyanate compounds having a uret structure, etc. One of these can be used alone, or two or more can be used in combination. For the synthesis of component (B), one compound alone or two or more compounds may be used as compound (B1). Compounds can be used in combination.

[0021] [Polyol (B2)] A specific example of a polyol (B2) used in the synthesis of component (B) is ethylene glyco Polypropylene glycol, butylene glycol, polyethylene glycol, polypropylene Polyethylene glycol, polybutylene glycol, polytetramethylene glycol, trimethyl Polypropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol Alcohols such as litol, sorbitol, mannitol, glycerin, and polyglycerin Polyether polyols are polyester polyols synthesized from polyhydric alcohols and polybasic acids. Examples include polyester polyols such as polycaprolactone polyol.

[0022] [Hydroxyl group-containing (meth)acrylate (B3)] As a specific example of a hydroxyl group-containing (meth)acrylate (B3) used in the synthesis of component (B): These are 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Relate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth ) Hydroxyalkyl (meth)acrylates such as acrylates; 2-hydroxyethyl (meth)acrylate and ethylene oxide adduct, 2-hydroxyethyl (meth)acrylate Adducts of relate and propylene oxide, 2-hydroxyethyl (meth)acrylate and Examples include adducts of organic lactones such as ε-caprolactone. (B) Composition For the synthesis of this compound, one compound (B3) is used alone or in combination of two or more compounds. can.

[0023] [Synthesis method for component (B)] The synthesis method for component (B) is, for example, the conventionally known urethane (meth)acrylate synthesis. The method can be used. A specific synthesis method is, for example, to put compound (B1) into a flask and add 2 ml After adding ol, a known catalyst such as dibutyltin dilaurate is mixed in, and the temperature inside the flask is raised. While maintaining a temperature of 40-80°C, add 1 mol of compound (B2) dropwise using a dropping funnel. A urethane prepolymer having isocyanate groups at its ends is obtained. Subsequently, the obtained urethane Compound (B3)2 having an equivalent amount of hydroxyl group on the isocyanate group remaining at the end of the prepolymer Add the mol dropwise and at 60-85°C, the isocyanate group of the urethane prepolymer and compound (B Component (B) can be synthesized by carrying out the addition reaction with the hydroxyl group in (3). The reaction rate at the endpoint can be determined by quantifying the remaining isocyanate group. The percentage is 97% or higher, more preferably 99% or higher.

[0024] The molecular weight of component (B) is preferably 500 to 50,000, and preferably 600 to 40,000. A molecular weight of 700 to 30000 is preferred, and more preferably 700 to 30000. If the molecular weight is above the lower limit, curing occurs. The toughness of the coating film is improved, and alcohol resistance is enhanced. The developability of the coating film is improved as long as it is below the upper limit. To improve.

[0025] [Proportion of ingredient (B)] The proportion of component (B) in this composition is 1 to 3 times the total amount of components (A) to (C). (B) The proportion of component (B) is preferably 0% by mass, and more preferably 5 to 25% by mass. The toughness of the hardened coating improves, and the less hardened the coating, the better the developability tends to be.

[0026] [Component (C)] Component (C) incorporated into this composition has four or more (meth)acryloyl groups in its molecule. It is a polyfunctional (meth)acrylate compound. Component (C) is the alcohol-resistant component of the cured coating film. It contributes to sexuality. A monomer having four or more (meth)acryloyl groups that can be used as component (C) For example, dipentaerythritol penta(meth)acrylate, dipentaerythritol Tall hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta (meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth) )Acrylate, pentaerythritol tetra(meth)acrylate, ethoxylate dopentaerythritol tetra(meth)acrylate and other pentaerythritol skeletons Poly(meth)acrylate; ditrimethylolpropanetetra(meth)acrylate Examples include poly(meth)acrylates having a trimethylolpropane skeleton.

[0027] The molecular weight of component (C) is preferably 200 to 800, and more preferably 250 to 700. If the molecular weight is above the lower limit, the toughness of the cured coating film improves, and alcohol resistance improves. If the value is below the upper limit, the developability of the coating film will improve.

[0028] [Component (D)] Component (D) is a photopolymerization initiator, which cures the composition by irradiation with active energy rays. It is a component. Component (D) includes, for example, benzophenone type, anthraquinone type, and ammonium compounds. Cylphenone type, thioxanthone type, acylphosphine oxide type, phenylglio Xylate-type photopolymerization initiators are one example.

[0029] Component (D) may include, for example, benzophenone, 4-methylbenzophenone, 2,4, 6-Trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenyl Benzophenones such as benzophenone; t-butylanthraquinone and 2-ethyl anthraquinone. Anthraquinone types such as raquinone; 2-hydroxy-2-methyl-1-phenylpropane 1-ONE, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phen [nyl]propanone, benzyldimethyl ketal, 1-hydroxycyclohexylphenic acid Luketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]- 2-Molfolino-1-propanone and 2-hydroxy-1-{4-[4-(2-hydroxy C-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, Alkylphenone types such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, di Thioxanthone types such as ethylthioxanthone and isopropylthioxanthone; 2,4, 6-Trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxy) Benzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4 Acylphosphines such as 6-trimethylbenzoyl)-phenylphosphine oxide Oxide type; phenylglyoxylic acid methyl esters and other phenylglyoxylic acid esters Examples include silate-type photopolymerization initiators. Among these, 2,4,6-trimethylbenzoyl is the most suitable in terms of the dryness of the cured coating film. Diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phen Luphosphine oxide is preferred. Component (D) can be one compound alone or two or more compounds in combination.

[0030] [Amount of ingredient (D)] The amount of ingredient (D) should preferably be 1 to 30% by mass relative to the total amount of ingredients (A) to (C). More preferably 5 to 25% by mass. The higher the amount of component (D), the better the air quality of this composition. The curing properties in an air atmosphere are improved, and the less of this component (D) there is, the less of the component (D) remaining in the cured coating film. There is a tendency for this to happen.

[0031] [Component (E)] Component (E) is a silane coupling agent, which is an ingredient that improves the adhesion of the cured coating film to the substrate. Yes. Component (E) is, for example, vinyltrimethoxysilane, vinyltriethoxysilane. Lan, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Toxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Ropiltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercapto Examples include propyltrimethoxysilane and 3-mercaptopropyltriethoxysilane. ru. Among these, 3-methacryloxypropyl is chosen for its substrate adhesion and storage stability of the paint. Trimethoxysilane is preferred.

[0032] [Amount of ingredient (E)] The amount of ingredient (E) should preferably be 1 to 20% by mass relative to the total amount of ingredients (A) to (C). Ideally, 3 to 10% by mass is preferred. The higher the amount of component (E), the better the adhesion to the substrate. The properties improve, and the lower the amount, the better the chemical resistance tends to be.

[0033] [Organic solvents] This composition may contain organic solvents as needed for purposes such as adjusting viscosity. Yes, it is possible. Examples of organic solvents include acetone, methyl ethyl ketone, and methyl isobutyl methyl ester. Ketone compounds such as ketones and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, Ester compounds such as ethyl lactate and methoxyethyl acetate; diethyl ether, ethylene glycol Dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol Ether compounds such as cellulose monobutyl ether and dioxane; toluene, xylene, etc. Aromatic compounds; aliphatic compounds such as pentane, hexane, and petroleum naphtha; isopropyl alcohols Alcohol compounds such as ethanol, isobutanol, and n-butanol; 1-methoxypropano Examples include propylene glycol compounds such as 1-methoxypropanol acetate. It is possible.

[0034] [Other ingredients] This composition contains leveling agents, defoaming agents, anti-settling agents, lubricants, abrasives, rust inhibitors, and antistatic agents. Additives such as stoppers, light stabilizers, UV absorbers, polymerization inhibitors, and pigments may be added.

[0035] [Cured product] The cured product of a curable composition is, for example, a coating film formed by applying the curable composition onto a substrate or the surface of an article. Formed by irradiating the coating film with active energy rays after drying as necessary. can.

[0036] Methods for applying this composition include, for example, brush application, spray coating, and dip coating. Examples include the t-coating method, spin coating method, flow coating method, and inkjet method. From the standpoint of properties, smoothness, and uniformity of the cured coating film, spray coating and inkjet methods are preferred. It seems so.

[0037] If this composition contains an organic solvent, the coated composition is irradiated with active energy rays. It is preferable to evaporate the organic solvent before curing. This can be done using an IR heater or hot air. It is preferable to heat the mixture to 30-70°C and allow the organic solvent to evaporate over 2-8 minutes.

[0038] Furthermore, the active energy rays used to cure this composition include ultraviolet light and electrons. Examples include lines, etc. For example, when irradiating with ultraviolet light using an LED-UV or high-pressure mercury lamp, The energy content is preferably 100-5000 mJ / cm2, and 500-2000 mJ / cm² is more preferable.

[0039] The thickness of the cured coating film is preferably in the range of 3 to 50 μm, more preferably in the range of 5 to 20 μm. If the thickness of the cured material is within the above range, it is easier to achieve the desired initial adhesion and hardness. The thickness of the cured material is determined by measurement using a film thickness gauge.

[0040] [Laminated structure] The laminate of the present invention is based on a cured coating film obtained by irradiating the composition with active energy rays and curing it. It is a laminate on the surface of the material. Glass or resin molded products are preferred as the base material. Examples of molded resins include ABS resin, AES resin, polycarbonate, and acrylic resin. Resins such as polystyrene and polypropylene; polyolefins such as polypropylene and polyethylene; Examples include molded articles of polyester such as PET and PBT. This composition is used with respect to glass. It is suitable as a material for cured coating films that have excellent developability and alcohol resistance. [Examples]

[0041] The present invention will be described in detail below with reference to examples, but unless the present invention exceeds its essence, The following examples are not the only ones. In the examples, "parts" and "%" refer to mass. do. The weight-average molecular weight of each component is calculated based on the weight-average molecular weight of standard polystyrene. This can be measured using high-performance liquid chromatography.

[0042] [Example 1] Ingredient (A) is M-5400 (manufactured by Toagosei, product name Aronics M-5400) 25 0.5 parts by mass, component (B) is UV-3000B (manufactured by Mitsubishi Chemical, product name: Shiko UV-3 000B) 3.4 parts by mass, component (C) is M600 (Made by Miwon, product name MIRA MER M600) 5.3 parts by mass, component (D) is TPO (manufactured by IGM Resins, Product name: Omnirad TPO) 7 parts by mass, component (D) as KBM-503 (Shin-Etsu Chemical) Product name KBM-503) 2 parts by mass, other ingredients include PM-21 (manufactured by Nippon Kayaku Co., Ltd., product name KAYARAD PM-21) 0.78 parts by mass, BYK-3440 (manufactured by BYK, product name) BYK-3400) 0.01 parts by mass, Titanium pigment (manufactured by Ishihara Sangyo, product name CR-90) 20 Mass part, TH-976C (manufactured by Mitsubishi Chemical, product name Diabeam TH-976C) 36 A composition curable by active energy rays was prepared by mixing and dissolving parts of the material.

[0043] The developability of this active energy ray curable composition was evaluated using the method described below. Furthermore, initial adhesion, alcohol resistance, and hardness were evaluated. The results are shown in Table 1.

[0044] [Evaluation of developability] The composition is applied to a glass substrate using a bar coater so that the cured film thickness is 10 μm. The mixture was then heated in an oven at 60°C for 2 minutes to evaporate the organic solvent. Then, it was immersed in a 1% sodium bicarbonate solution for 10 minutes, and the degree of paint peeling was determined. Image quality was evaluated. Developability was evaluated according to the following criteria. ◎...The coating peels off easily within 10 minutes. ○...When rubbed by hand after 10 minutes, the coating peels off easily. △...After 10 minutes, it peels off slightly when rubbed with your hand. ×...Does not peel off even when rubbed with a hand after 10 minutes.

[0045] [Evaluation of initial adhesion] After preparing the coating film using the same method as in the developability test, the following steps were performed using a Hamamatsu Photonics UV-LED irradiation device. (Wavelength: 395nm) was used, illuminance: 5000mW / cm2, integrated luminous intensity: 1500mJ The coating was cured by irradiation at 1 / cm². Then, it was annealed at 150°C for 30 minutes to obtain a cured coating. Then, a cross-shaped cut was made in the hardened coating with a utility knife, and Nichiban cellophane tape was placed on top of it. Apply the ープ(registered trademark) and then peel it off quickly to observe the state of delamination between the hardened coating and the substrate. Observations were made. Initial adhesion was evaluated according to the following criteria. ◎...No peeling in the peel test. ○...No peeling, but the cut grooves are slightly chipped. △...Slight peeling ×...Completely peeled off

[0046] [Evaluation of alcohol resistance] After preparing a cured coating film using the same method as for evaluating initial adhesion, 99.7% ethanol was used. A surface abrasion test was performed with a 500g load, consisting of 100 reciprocating cycles. Alcohol resistance was evaluated according to the following criteria. It was worth it. ◎...No change in appearance ○...Glossiness slightly decreases after alcohol resistance test. △...Slight peeling was observed after the alcohol resistance test. ×...to peel off completely

[0047] [Hardness evaluation] After preparing the cured coating film using the same method as for evaluating initial adhesion, the following steps were taken in accordance with JIS K-5600. The test was conducted and the pencil hardness was measured.

[0048] [Examples 2-8, Comparative Examples 1-2] Except for the formulation and composition shown in the composition column of Table 1, the activation energy is obtained in the same manner as in Example 1. Linear curing compositions were prepared and evaluated. The results are shown in Table 1.

[0049] [Table 1]

[0050] In Table 1, all numerical values ​​other than the mixing ratios are in parts by mass. The abbreviations in Table 1 refer to the following chemical combinations. To indicate an object. • M-5400: Toagosei Co., Ltd. Aronics M-5400 (product name, monohydroxyphthalate) Roxyethyl acrylate) • UV-3000B: Manufactured by Mitsubishi Chemical Corporation. (Product name: Urethane Acrylic) rate) • UV-7605B: Manufactured by Mitsubishi Chemical Corporation. (Product name: Urethane Acrylic) rate) • UV-1705B: Manufactured by Mitsubishi Chemical Corporation. (Product name: Urethane Acrylic) rate) • M600: Miwon MIRAMER M600 (product name, dipentaerythritol) (Hexaacrylate) • TPO: Made by IGM Resins, Omnirad TPO (product name, 2, 4, 6-T (methylbenzoyl diphenylphosphine oxide) • KBM-503: Manufactured by Shin-Etsu Chemical Co., Ltd. KBM-503 (product name, 3-methacryloxypro (Piltrimethoxysilane) • 4-HBA: Manufactured by Osaka Organic Chemical Industry Co., Ltd. 4-HBA (product name, 4-hydroxybutyl acrylate) rate) • BR-605: Manufactured by Mitsubishi Chemical Corporation. BR-605 (product name, methacrylic copolymer) • PM-21: KAYARAD PM-21 (product name, manufactured by Nippon Kayaku Co., Ltd., 2-methacryloyl Xyethyl caproate acid phosphate) • BYK-3440: BYK-made BYK-3440 (product name, acrylic copolymer type) Ring agent) • Titanium pigment: CR-90 (product name, titanium acid value) manufactured by Ishihara Sangyo Co., Ltd. ·TH-976C: Mitsubishi Chemical's Diabeam TH-976C (product name, dilution solvent) Naa)

[0051] From the above examples, the active energy ray curable resin composition of the present invention has improved the developability and curing properties of the coating film. The coating film exhibited excellent alcohol resistance. On the other hand, the activity of Comparative Example 1, which did not contain component (A), was excellent. The coating film and components formed from the energy-ray curable resin composition exhibited insufficient developability. , formed from the active energy ray curable resin composition of Comparative Example 2, which did not contain component (C). The coating and its components had insufficient hardness and alcohol resistance.

Claims

1. An active energy ray-curable resin composition characterized by comprising a compound (A) having one carboxyl group and one (meth)acryloyl group in one molecule (hereinafter referred to as component (A)), a urethane (meth)acrylate compound (B) having at least two or more (meth)acryloyl groups in one molecule (hereinafter referred to as component (B)), and a polyfunctional (meth)acrylate compound (C) having four or more (meth)acryloyl groups in one molecule (hereinafter referred to as component (C)), wherein component (A) accounts for 50 to 90% by mass, component (B) for 1 to 30% by mass, and component (C) for 1 to 20% by mass, based on the total amount of components (A) to (C), and used to form a cured coating film by applying it to a substrate, irradiating it with active energy rays to cure it, and then alkaline developing the cured coating film to remove the unirradiated portion of the coating film.

2. The active energy ray curable resin composition according to claim 1, characterized in that component (A) has at least one cyclic skeleton in one molecule.

3. The active energy ray curable resin composition according to claim 1 or 2, characterized in that component (C) comprises a poly(meth)acrylate having a pentaerythritol skeleton or a poly(meth)acrylate having a trimethylolpropane skeleton.

4. The active energy ray curable resin composition according to claims 1 to 3, wherein component (A) is 60 to 80% by mass, component (B) is 5 to 25% by mass, and component (C) is 1 to 20% by mass, based on the total amount of components (A) to (C).

5. The active energy ray curable resin composition according to any one of claims 1 to 4, characterized in that it contains 10 to 30% by mass of a photopolymerization initiator (D) (hereinafter referred to as component (D)) relative to the total amount of components (A) to (C).

6. The active energy ray curable resin composition according to any one of claims 1 to 5, characterized in that it contains 1 to 20% by mass of a silane coupling agent (E) (hereinafter referred to as component (E)) relative to the total amount of components (A) to (C).

7. A cured product obtained by curing an active energy ray-curable resin composition according to any one of claims 1 to 6 by irradiating it with active energy rays.

8. A laminate having the cured product described in claim 7 on the surface of a substrate.

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