Curable composition, cured product, and laminate

Abstract

To provide a curable composition which enables formation of a cured product that is excellent in scratch resistance and chemical resistance, and suppresses occurrence in cracking in molding and processing, a cured product of the curable composition, and a laminate having a layer composed of the cured product.SOLUTION: A curable composition contains a resin containing a curable group, and polyester-modified polydimyethylsiloxane having the curable group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a cured product of the curable composition, and a layer comprising the cured product. It relates to a laminate. [Background technology]

[0002] Surface protection and decoration of resin molding materials for automobile interior and exterior parts, electronic devices, miscellaneous goods, building materials, etc. To prevent this, methods such as hard coating the surface or attaching a film are known. Known decoration methods include insert method, thermal lamination method, and transfer method. In addition, the hard coat layer is generally made of a compound having a radical polymerizable group. and a photopolymerization initiator, and curing the curable composition by radical polymerization. However, when a hard coat layer is used to protect the surface, abrasion resistance and Although scratch resistance is improved, the elongation during molding processing is deteriorated, making it unsuitable for decorative applications. In addition, the hard coat layer is also required to have chemical resistance for surface protection.

[0003] Patent document 1 describes an insert film for in-mold labels, and patent document 2 describes an automobile Patent Document 3 describes a decorative sheet for interior use that is printed on hard paper by a thermal transfer printing method using a thermal transfer printer. A decorative hard coat film is described in which printing is performed directly on the hard coat layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-288720 [Patent Document 2] Japanese Patent Application Publication No. 2019-189043 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-110903 Summary of the Invention [Problem to be solved by the invention]

[0005] The hard coat layer described in Patent Document 1 has excellent scratch resistance, but it does not necessarily have good stretchability during molding. It does not satisfy the corrosion resistance, and it is difficult to follow the surface shape of the molding material, and the hard coat layer peels off. In the sheet described in Patent Document 2, The scratch resistance of the surface protective layer is not fully satisfied, and the hard coat film described in Patent Document 3 It is difficult to ensure elongation.

[0006] The present invention provides a material that has excellent scratch resistance and extensibility during molding (which suppresses the occurrence of cracks). a curable composition capable of forming a hard coat layer having excellent chemical resistance; and providing a laminate having a cured product of the curable composition and a layer made of the cured product. The purpose is to: [Means for solving the problem]

[0007] The present invention has the following aspects. [1] Resins containing curable groups and polyester-modified polysilicon containing curable groups A curable composition containing a methyl siloxane. [2] The curable resin according to [1], wherein the curable group of the resin is an active energy ray-curable group. composition. [3] The resin has an active energy ray-curable group equivalent of 0.01 to 10 mmol / g. The curable composition according to [1] or [2]. [4] The curable group of the polyester-modified polydimethylsiloxane is an active energy ray curable material. The curable composition according to any one of [1] to [3], wherein the group is a chemically reactive group. [5] An active enzyme different from the resin and the polyester-modified polydimethylsiloxane. The curable composition according to any one of [1] to [4], which contains an energy ray-curable compound. thing. [6] The curable composition according to any one of [1] to [5], which contains a photopolymerization initiator. . [7] Any of [1] to [6], wherein the photopolymerization initiator is an alkylphenone compound. 3. The curable composition according to claim 1. [8] The photopolymerization initiator according to any one of [1] to [7], wherein the photopolymerization initiator contains two or more photocleavable groups in the molecule. The curable composition according to any one of claims 1 to 10. [9] A cured product of the curable composition according to any one of [1] to [8].

[10] The cured product according to [9], wherein the elongation rate in a tensile test at 140°C is 5% or more. thing.

[11] A laminate in which the cured product according to [9] or

[10] is laminated on a substrate. [Effects of the Invention]

[0008] According to the present invention, a curable composition having excellent scratch resistance, chemical resistance and elongation properties is provided. This can be done. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" refers to the total of acrylates or methacrylates. Also, "(meth)acrylic" refers to acrylic or methacrylic, or (meth)acryloy. Acryloyl is a general term for acryloyl or methacryloyl. The "~" symbol indicates a range of values, and includes the values ​​before and after it as the lower and upper limits. The numerical ranges disclosed in this specification can be obtained by arbitrarily combining the lower and upper limits. The new numerical range can be created by combining the above.

[0010] <Curable composition> The curable composition of the present invention contains a resin containing a curable group.

[0011] The resin containing a curable group has a functional group that hardens in the resin, and is a conventionally known Examples of the curable group include an active energy ray curable group and a Examples include a thermosetting group, and from the viewpoint of performance and reactivity, an active energy ray-curable group is preferred. The types of resins include (meth)acrylic resin, urethane resin, and polyester resin. Various resins such as epoxy resins can be used. From this viewpoint, (meth)acrylic resins are preferred. The curable group is, for example, an active energy ray curable group, which is a group that can be cured by irradiating an active energy ray. This refers to all reactive groups that react by reacting with other groups, such as ethylenically unsaturated groups, (meth)acrylamide groups, etc. Examples of suitable thermosetting groups include carbon-carbon unsaturated bond groups such as aryl groups. This refers to all reactive groups that react with heat, such as hydroxyl groups and isocyanate groups.

[0012] Examples of resins containing active energy ray-curable groups include those containing carbon-carbon unsaturated bond groups. The carbon-carbon unsaturated bond is a carbon-carbon double bond or It means a carbon-carbon triple bond, and is preferably a carbon-carbon double bond, for example, (methyl) p) Acryloyl group, (meth)acrylamide group, vinyl group, allyl group, vinyl ether Among these, the following groups are preferred because of their excellent curability with active energy rays: A methacryloyl group is preferred, and an acryloyl group is particularly preferred. The resin containing the compound may contain only one of the functional groups, or may contain two or more of the functional groups. That's fine.

[0013] Examples of resins containing carbon-carbon unsaturated bond groups include resins containing (meth)acryloyl groups. A (meth)acrylic resin having the above structure is preferred. As a method for producing the vinyl resin, for example, a method for producing a vinyl resin by using (meth)acrylate containing an epoxy group and other The epoxy group portion of the polymer obtained by copolymerizing the (meth)acrylate monomer Examples of such methods include reacting with acids or bases containing carbon-carbon unsaturated bond groups. The method using sigil (meth)acrylate controls the amount of carbon-carbon unsaturated bonds. It is useful because it is easy to

[0014] Examples of (meth)acrylates containing an epoxy group include glycidyl (meth)acrylate. Acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxy Cyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. Among these, glycerol is the most popular, considering its good reactivity and ease of use. Glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred.

[0015] Introducing carbon-carbon unsaturated bond groups using (meth)acrylates containing epoxy groups In this case, the (meth)acrylate polymer contains an epoxy group. The proportion of acrylate is preferably 1 to 100% by mass, more preferably 2 to 80% by mass. % by mass, more preferably 3 to 50% by mass, particularly preferably 5 to 35% by mass, most preferably The range of use is generally 7 to 25% by mass. By using it in this range, the abrasion resistance of the cured product is improved. Scratch resistance, elongation and chemical resistance can be easily adjusted.

[0016] (Meth)acrylate polymers containing epoxy groups due to carbon-carbon unsaturated bond formation The compounds used for this purpose include acids and bases containing carbon-carbon unsaturated bond groups. p) Considering the stability of the acrylate polymer, acids are preferred, and among them, carboxylic acids are particularly preferred. It is preferable to use (meth)acrylic acid among the carboxylic acids. In this case, it is possible to introduce a double bond, which is a more preferred embodiment. Among acids, when considering the reactivity of the epoxy group with carboxylic acid and the reactivity of the introduced double bond, Acrylic acid is the best. In addition, two or more types of carbons can be used to form two or more types of structures. It is also possible to react carboxylic acids with epoxy groups.

[0017] The epoxy groups to be reacted are determined based on the total number of epoxy groups present in the (meth)acrylate polymer. Generally, the content is 1% by mass or more, preferably 20% by mass or more, and more preferably 50% by mass or more. More preferably, the range is 80% by mass or more, and the upper limit may be 100% by mass. By carrying out the reaction within this range, the amount of carbon-carbon unsaturated bonds in the resin can be made sufficient. This makes it easy to adjust the scratch resistance, elongation, and chemical resistance of the cured product. It becomes something.

[0018] When a (meth)acrylic resin is used as the resin containing a carbon-carbon unsaturated bond In addition to the above-mentioned compounds, various polymerizable compounds that are not involved in the introduction of carbon-carbon unsaturated bond groups can be used. For example, (meth)acrylic acid, methyl (Meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, Tearyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate ) acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate , dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth) Alkyl (meth)acrylate monomers such as acrylate; perfluorohexylethyl (Meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate fluoroacrylates such as 1H,1H,9H-hexadecafluorononyl (meth)acrylate (Meth)acrylate monomers having alkyl groups; N,N-diethylaminoethyl (meth)acrylate monomers having alkyl groups; ) acrylate, N,N-dimethylaminoethyl (meth)acrylate, etc. (Meth)acrylate monomers; 2-Hydroxypropyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate hydroxyl group-containing (meth)acrylates such as 1,6-hexanediol mono(meth)acrylate, Acrylate monomers; raw materials other than (meth)acrylic acid derivatives include styrene, p-acrylic acid, C12-12, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N- Vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol Taerythritol divinyl ether, 1,6-hexanediol divinyl ether, tri Methylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol Dipentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, ditrimethylol Examples of such hydrocarbon monomers include those having a vinyl group, such as diolpropane polyvinyl ether. .

[0019] The raw material used is not limited to one type, but two or more types may be used in combination to form (meth)acrylic resins. It is also possible to prepare a (meth)acrylic resin by using two or more kinds of the above in combination. I wish.

[0020] The above-mentioned (meth)acrylates that do not contribute to the introduction of carbon-carbon unsaturated bond groups are used. In this case, the ratio of (meth)acrylate in the (meth)acrylate polymer is The content is preferably 0 to 99% by mass, more preferably 20 to 98% by mass, and even more preferably is 50 to 97 mass%, particularly preferably 65 to 95 mass%, most preferably 75 to 93 mass% By using it in this range, the scratch resistance, elongation and This makes it easier to adjust the chemical resistance.

[0021] In addition, in consideration of adhesion to the substrate, it is preferable that the polymer contains a polar group. hydroxyl group, amino group, carboxyl group, sulfonic acid group, ether group, etc., Among these, hydroxyl, amino and carboxyl groups are preferred from the viewpoint of adhesion to the substrate, and water resistance In this sense, the epoxy group and the carboxyl group are more preferable. Resins containing carbon-carbon unsaturated bond groups formed by the reaction of carboxylic acids have hydroxyl groups. This is a preferred form because it also

[0022] The hydroxyl value is preferably 5 to 500 mgKOH / g, more preferably 10 to 100 mgKOH / g. 300 mgKOH / g, more preferably 15 to 250 mgKOH / g, particularly preferably 25 to 220 mg KOH / g, most preferably in the range of 40 to 150 mg KOH / g By using it in this range, the adhesion to the substrate is good. For example, the resin composition is reacted with excess acetic anhydride in pyridine, and the liberated acetic acid is converted into potassium hydroxide. It can be measured by titration with sodium.

[0023] The polymerization conditions for producing a (meth)acrylic resin containing a carbon-carbon unsaturated bond are There is no particular limitation, and a known method can be appropriately selected. The reaction to obtain the olefin is a radical polymerization reaction, and the raw materials are polymerized in an organic solvent in the presence of a radical polymerization initiator. By polymerizing the starting monomer, a (meth)acrylic resin can be obtained.

[0024] For example, the organic solvent may be acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like. ethanol, methanol, isopropyl alcohol, isobutanol, etc. Alcohol solvents; ethylene glycol dimethyl ether, propylene glycol monomethyl ether solvents such as diethyl ether; ethyl acetate, propylene glycol monomethyl ether Ester solvents such as acetate and 2-ethoxyethyl acetate; aromatic carbons such as toluene These organic solvents can be used alone or in combination of two or more. It may also be used in combination.

[0025] Radical polymerization initiators include benzoyl peroxide and di-t-butyl peroxide. Organic peroxides, 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethyl 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) These radical polymerization initiators are azo compounds such as benzotriazole and benzotriazole. Two or more of them may also be used in combination.

[0026] The polymerization temperature is usually 20 to 150°C, preferably 50 to 100°C. The incubation time is usually 1 to 72 hours, preferably 3 to 36 hours.

[0027] The reaction conditions for the above-mentioned epoxy group and carboxylic acid compound are not particularly limited, and may be any known reaction conditions. The reaction method can be appropriately selected. The reaction may be carried out in the absence or presence of a catalyst. The catalyst may be a tertiary amine such as triethylamine or benzyldimethylamine, or a tetramethylamine. Ammonium such as ethylammonium chloride and tetrabutylammonium bromide salts, phosphines such as triphenylphosphine and tributylphosphine, tetrabutylphosphine phosphonium salts such as phosphonium bromide and tetrabutylphosphonium iodide The amount of catalyst used is usually 0.5% by mass or more, preferably 0.5% by mass or more, based on the weight of the polymer. It is preferably 1.0 mass % or more, usually 5.0 mass % or less, and preferably 3.5 mass % or less. is.

[0028] The reaction temperature is usually 20 to 200°C, preferably 50 to 150°C. The incubation time is usually 1 to 72 hours, preferably 3 to 20 hours.

[0029] The weight average molecular weight (Mw) of the resin containing carbon-carbon unsaturated bonds is determined depending on the application of the laminate. It should be selected appropriately depending on the situation, but it is preferably 5,000 to 200,000, more preferably Preferably 7,000 to 100,000, more preferably 9,000 to 70,000, and even more preferably Preferably, it is in the range of 10,000 to 60,000. By using it in the above range, scratch resistance is improved. It also has improved adhesiveness to the substrate and good extensibility during molding. The weight average molecular weight (Mw) of the (meth)acrylic polymer is determined by the gel permeation The values ​​were determined using gel permeation chromatography (GPC) and converted to polystyrene standards. The specific measurement conditions are as described below.

[0030] From the viewpoint of curability, the resin containing the carbon-carbon unsaturated bond group is Group equivalent (active energy ray curable group equivalent, for example, acryloyl group concentration (acryloyl group The amount of introduction) is preferably 0.01 to 10 mmol / g, more preferably 0.3 to 10 mmol / g. 6.0 mmol / g, more preferably 0.5 to 4.0 mmol / g, particularly preferably 0 The range is preferably 0.8 to 3.0 mmol / g, and most preferably 1.0 to 2.0 mmol / g. By setting the content within the above range, the balance of scratch resistance, elongation and chemical resistance when the cured product is obtained is maintained. will be a good thing.

[0031] The curable composition contains a curable compound, particularly a compound that improves scratch resistance and chemical resistance when cured. A curable compound other than the resin containing the above-mentioned curable group for increasing or adjusting the viscosity. It is also a preferred embodiment to use an active energy ray curable compound. Examples include active energy ray curable compounds and thermosetting compounds, but from the viewpoint of reactivity, active energy ray curable compounds are preferred. Things are preferred.

[0032] As the active energy ray curable compound other than the resin containing a curable group, conventionally known materials A suitable material may be used, for example, (meth)acrylate. The (meth)acrylate is not particularly limited, and may be a monofunctional (meth)acrylate, a bifunctional ( It may be either a (meth)acrylate or a trifunctional or higher polyfunctional (meth)acrylate. (Meth)acrylates that are commercially available as curable resin materials can also be used. p) The acrylate may contain other components within the scope of the present invention. Among these, bifunctional or trifunctional or more multifunctional compounds are preferred because they have particularly excellent scratch resistance. (Meth)acrylates are preferred, and tri- or higher functional (meth)acrylates are particularly preferred. preferable.

[0033] The monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n- Butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate Acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl (meth)acrylate meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (Meth)acrylate, Tricyclodecane (meth)acrylate, Polyethylene Glyco- Mono(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofuran Furyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyl Thenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, Mono(meth)acrylates such as phenoxyethyl (meth)acrylate and phenyl (meth)acrylate ) acrylate, adduct of phthalic anhydride and 2-hydroxyethyl (meth)acrylate and the like mono(meth)acrylate compounds.

[0034] Examples of bifunctional polyfunctional (meth)acrylates include 1,4-butanediol di( meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexa Nonanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, Alkanediol di(meth)acrylate such as tricyclodecanedimethylol di(meth)acrylate Acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bis Phenol F ethylene oxide modified di(meth)acrylate and other bisphenol modified di(meth)acrylates (Meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene ethylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di( methacrylates, etc.

[0035] Examples of trifunctional or higher polyfunctional (meth)acrylates include dipentaerythritol. Hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, Prolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol Pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate Trimethylolpropane tri(meth)acrylate, ethylene oxide Iodo-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified Ethylene oxide modified (meth)acrylate such as pentaerythritol tetra(meth)acrylate Acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ε- Isocyanuric acid modified such as caprolactone-modified tris(acryloxyethyl) isocyanurate Tri(meth)acrylate, Pentaerythritol triacrylate hexamethylene diacrylate Isocyanate urethane prepolymer, pentaerythritol triacrylate toluene Diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate Urethane (meth)acrylates such as hexamethylene diisocyanate urethane prepolymer etc. Among these, (meth)acrylates with four or more functional groups are particularly preferred because they have excellent scratch resistance. Further, (meth)acrylates having 6 or more functional groups are more preferred. Considering compatibility with elongation during processing, polyfunctional (meth)acrylate with extended alkyl chains is In particular, tetrafunctional or more (meth)acrylates with an extended alkyl chain are preferred. More preferred are (meth)acrylates with six or more functional groups. For example, caprolactone Dipentaerythritol hexa(meth)acrylate modified with ethylenediamine is the most suitable material. It is preferable for extensibility that the ratio of caprolactone to one molecule of methacrylate is 2 or more. In particular, for applications where elongation is important, it is more preferable that the elongation be 6 or more.

[0036] The curable composition may contain an active energy ray-curable compound other than (meth)acrylate. For example, styrene, vinyl halide, vinyl acetate, etc. Vinyl compounds, vinylidene halides, 1,3-butadiene, isoprene, chloroprene and other diene compounds.

[0037] When the curable composition is to be a thermosetting composition, a resin having a crosslinking group and a crosslinking agent are thermally reacted. There are ways to do this. For example, (meth)acrylic polyol, polyester polyol, polyvinyl Examples of such methods include a method of combining a resin having a polyol structure, such as methyl methyl acrylate, with an isocyanate. do.

[0038] The curable composition contains a resin other than the resin containing a curable group, i.e., a resin not having a curable group. For example, (meth)acrylic resin, polyester resin, Among them, (meth)acrylic resins are preferred. This makes it possible to improve the coating properties when applying the coating to form a film, and to adjust the elongation. This becomes:

[0039] The curable composition further contains a polyester-modified polydimethylsiloxane having a curable group. The polyester-modified polydimethylsiloxane containing a curable group is It works as a leveling agent to improve the appearance of the finished product. Many types of curing agents are known, but polyester derivatives having a curable group are The use of a water-soluble polydimethylsiloxane gives the cured product high slip properties. This allows the resin to react with other compounds having a curable group, improving scratch resistance. This allows the resin to be incorporated into the cured product, providing long-term slip properties and scratch resistance. In addition, in the course of our investigation, we discovered that polyester-modified polymers with curable groups It was found that didimethylsiloxane is particularly good in terms of chemical resistance. When compared with polyether-modified polydimethylsiloxane, which has a curable group as a compound It was speculated that the polyester modification could improve the hardening resin. By forming stronger hydrogen bonds with other resins and compounds in the composition, A dense hardened structure is formed, making it difficult for chemicals to penetrate into the hardened material, resulting in high chemical resistance. We believe that this is what is being expressed.

[0040] The curable group of the polyester-modified polydimethylsiloxane containing the curable group may be an active It is preferable that the group is a reactive energy ray curable group, and in consideration of ease of synthesis and reactivity, It is more preferably a (meth)acryloyl group, and even more preferably an acryloyl group. I wish.

[0041] Polyester modification of polyester-modified polydimethylsiloxane with curable groups has been conventionally Known modified polyesters may be used, and the main components may include, for example, the following polyvalent carbo Examples of the polycarboxylic acid include those made of polycarboxylic acids and polyhydroxy compounds. Examples include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyl Nyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4- Cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalate, 5-sodium sulfoyl Sophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, Phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid monopotassium salt and their derivatives Ester-forming derivatives and the like can be used. As the polyvalent hydroxy compound, ethylene propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 -Propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl -1,5-Pentanediol, Neopentyl glycol, 1,4-Cyclohexane dimethicone p-xylylene glycol, bisphenol A-ethylene glycol adduct, di Ethylene glycol, triethylene glycol, polyethylene glycol, polypropylene Glycol, polytetramethylene glycol, polytetramethylene oxide glycol , dimethylolpropionic acid, glycerin, trimethylolpropane, dimethylolethyl sodium dimethylolsulfonate, potassium dimethylolpropionate, etc. can be used. In addition, lactone-modified types are preferred from the viewpoint of compatibility with other compounds in the curable composition. Among these compounds, the ε-caprolactone-modified type is particularly preferred. One or more of these may be appropriately selected and a modified polyester may be synthesized by a conventional polycondensation reaction. .

[0042] Polydimethylsiloxane, a polyester-modified polydimethylsiloxane with curable groups Conventionally known polydimethylsiloxanes can be used.

[0043] In order to improve the weather resistance of the cured product, the curable composition contains an ultraviolet absorber. From the viewpoint of heat resistance, those with a molecular weight of 500 or more are preferred. From the viewpoint of good solubility in the composition and improvement of weather resistance, triazine-based and benzophenone-based benzotriazoles, cyclic imino esters, salicylic acid esters, or Derived from cyanoacrylate compounds, with a maximum absorption wavelength of 240-3 Among these, ultraviolet absorbers with particularly good ultraviolet absorption properties are preferred. In terms of excellent appearance when cured, triazine-based and benzotriazine-based The sol-based solvents are more preferred, and the triazine-based solvents are even more preferred.

[0044] The triazine-based ultraviolet absorber includes, but is not limited to, the following: 2- [4-([2-hydroxy-3-dodecyloxypropyl]oxy)-2-hydroxypropyl phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2- [4-([2-hydroxy-3-tridecyloxypropyl]oxy)-2-hydroxy phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (T inuvin (registered trademark) 400 (BASF), 2-[4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyl) 2-(2,4-dihydroxypropyl)-2-hydroxypropoxy]phenol), phenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product (Tinuvin® ) 405, manufactured by BASF), 2,4-bis "2-hydroxy-4-butoxyphenyl" - 6-(2,4-dibutoxyphenyl)-1,3-5-triazine (Tinuvin (registered trademark) BASF 460, 2-(4,6-diphenyl-1,3,5-triazine- 2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin® 1 577, BASF), 2-(4,6-diphenyl-1,3,5-triazine-2-yl) 2-(2-ethylhexanoyloxy)ethoxy]-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol (ADK STAB LA46, manufactured by ADEKA), 2-(2-hydroxy-4-[1-octyl [oxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3 ,5-triazine (Tinuvin (registered trademark) 479, manufactured by BASF), etc. .

[0045] Benzophenone-based UV absorbers (benzophenone-based compounds), oxybenzophenone-based Examples of ultraviolet absorbers (oxybenzophenone compounds) include 2,4-dihydroxybenzophenone. Dibenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4- Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methylbenzophenone Toxicbenzophenone (trade name "KEMISORB111", manufactured by Chemipro Chemical Co., Ltd.) , 2,2',4,4'-tetrahydroxybenzophenone (trade name "SEESORB10 6", manufactured by Shipro Chemical Co., Ltd.), 2,2'-dihydroxy-4,4-dimethoxybenzofuran Examples include phenon.

[0046] Benzotriazole-based ultraviolet absorbers include, but are not limited to, the following: For example, 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H -Benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl )phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacrylamide (2'-hydroxypropyl)phenyl]-2H-benzotriazole, [5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl) phenyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert -butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazol 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5- Chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyl 2-[2'-hydroxyethyl)phenyl]-5-methoxy-2H-benzotriazole hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzo[b] 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]phenyl Nyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy- 5'-(Methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazo Examples include ru.

[0047] The cyclic iminoester-based ultraviolet absorber is not limited to the following, but examples thereof include: For example, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, Xazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)- 3,1-Benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2- p-Benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl 2-o-Methoxyphenyl-3,1-benzoxazin-4-one, 2-o-Methoxyphenyl-3,1-benzoxazin-4-one benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, N -phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N -benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, N- Benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline Phosphorus, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazine-4 -one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-ethylene Bis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis(3,1 -benzoxazin-4-one), 2,2'-decamethylenebis(3,1-benzoxazin-4-one), Zin-4-one, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) ), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2' -(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2' -(2,6- or 1,5-naphthylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one) ), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4- ion), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine- 4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazine) -4-one), 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)benzyl Benzene, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis(1,3)- Oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d;4 ,5-d') Bis(1,3)-oxazine-4,9-dione, 2,8-diphenyl-4H ,8H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine-4,6-di ion, 2,7-diphenyl-4H,9H-benzo(1,2-d;4,5-d')bis(1 ,3)-Oxazine-4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzyl) benzoxazin-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzoxazin-4-one) sazin-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazine -4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxazine -4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazolidinone), 6,6'-ethylenebis(2-methyl-4H,3,1-benzoxazol-1-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzoxa- din-4-one), 6,6'-butylenebis(2-methyl-4H,3,1-benzoxa din-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-benzoxyl) sazin-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzoxa din-4-one), 6,6'-oxybis(2-phenyl-4H,3,1-benzoxa 6,6'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), sazin-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,1-benzo oxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one) zooxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H,3,1- benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H,3,1- benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4H,3,1 -benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), oxazin-4-one), 7,7'-ethylenebis(2-methyl-4H,3,1-benzoxazin-4-one) oxazin-4-one), 7,7'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one) oxazin-4-one), 7,7'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one) oxazin-4-one), 7,7'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one) benzoxazin-4-one), 6,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one) 6,7'-bis(2-phenyl-4H,3,1-benzoxazine- 4-one, 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazine-4 -one), 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxazine- 4-one) and the like.

[0048] Examples of salicylate ester-based ultraviolet absorbers (salicylate ester-based compounds) include , phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy -3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate , phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate phenyl-2-hydroxybenzoate, Phenyl-2-hydroxy-3-methylbenzoate, Phenyl-2-hydroxy-4-methylbenzoate phenyl 2-hydroxy-5-methylbenzoate, phenyl 2- Hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate (Tinuvin®) 120, manufactured by BASF).

[0049] Cyanoacrylate-based ultraviolet absorbers (cyanoacrylate-based compounds) include, for example: , alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxy Alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkoxyalkyl ... quinyl-2-cyanoacrylate, etc. In addition, these compounds may be used alone. One or more of these may be used in combination.

[0050] To further improve the weather resistance of the cured product, the curable composition may contain a light stabilizer. The light stabilizer is not particularly limited as long as it is a hindered amine light stabilizer. Specific examples include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis(1-methyl 2,2,6,6-tetramethyl-4-piperidyl sebacate, bis(1-ethoxy) Oxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-propionyl) 2,2,6,6-tetramethyl-4-piperidyl sebacate, bis(1-butoxy) bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-pentyl) bis(1-hexyl)-2,2,6,6-tetramethyl-4-piperidyl) sebacate 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-heptyl) Thyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-octyl) 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-octyl) Nitrile-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-demethyl) Caniloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1- Dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methoxy-benzylidene tetrakis(2,2,6,6-pentamethyl-4-piperidyl) 1,2 ,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentane) Aminomethyl (4-piperidyl) 1,2,3,4-butanetetracarboxylate, etc. The carboxylic acid-containing compounds, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentanetetracarboxylic acid, β,β,β,β-tetramethyl-3,9-(2,4,8 ,10-tetraoxaspiro[5,5]undecane) condensation product with diethanol, 1,2 ,3,4-Butanetetracarboxylic acid and 2,2,6,6-pentamethyl-4-piperidino β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro) [5,5]) undecane) condensation product of diethanol, decanedicarboxylic acid and 2,2,6, Diester compound with 6-tetramethyl-1-octoxy-4-piperidinol and 1,1 -Reaction product of dimethyl ethyl hydroperoxide and octane (BASF, trade name) Tinuvin 123), bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[ [3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]methyl](BA Examples include amino ether group-containing compounds such as Tinuvin 144 (trade name, manufactured by SF Co., Ltd.). Among these, amino ether group-containing compounds are preferred from the viewpoint of weather resistance of the cured product, and bis(1 ,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,di Particularly preferred are methylethyl-4-hydroxyphenylmethyl. The compounds may be used alone or in combination of two or more.

[0051] In the case of a product cured by active energy ray curing, photopolymerization is used to promote the curing of the curable composition. It is preferable that the photopolymerization initiator contains an initiator. The photopolymerization initiator is preferably a compound having a molecular weight of less than 1,000. The lower limit is not particularly limited, but it is preferably 200 or more. It is preferable that the number is 300 or more.

[0052] Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, a photocatalytic polymerization initiator, and a photopolymerization initiator. Among these, photo-radical polymerization initiators are preferred. The dicarboxylic polymerization initiators are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl {2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one Pan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy 2-methyl-[4-(methylthio)phenyl]-2-morpholino -1-Propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1 -propanone and other alkylphenone compounds, 2,2-dimethoxy-2-phenylacetone, Benzyl ketal compounds such as phenone, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-fluoro Benzophenone-type compounds such as phenylbenzophenone; t-butylanthraquinone, 2-ethoxybenzophenone, Anthraquinone compounds such as thiathraquinone; 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropyl Thioxanthone-type compounds such as thioxanthone; 2,4,6-trimethylbenzoyldifluoro Phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-triphenylphosphine oxide Trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- Acylphosphine oxide compounds such as phenylphosphine oxide; Examples of such compounds include phenylglyoxylate compounds such as phenylglyoxylic acid methyl ester. Among these, Acetone is the most popular because it cures even with a small amount of active energy ray irradiation. Alkylphenone type compounds or benzil ketal type compounds are preferred, and alkylphenone Among alkylphenone type compounds, α-hydroxyapatite type compounds are more preferred. Alkyl alkylphenone type compounds and α-amino alkylphenone type compounds are preferred, and α-hydro An alkoxyalkylphenone type compound is more preferable. A photopolymerization initiator containing a functional group that generates radicals by cleavage upon irradiation with reactive energy rays is used. These polymerization initiators are preferred from the viewpoint of chemical resistance. may be used in combination.

[0053] The curable composition contains particles from the viewpoint of preventing blocking and providing easy lubrication when cured. The particles may be organic particles or inorganic particles, and two or more types may be used in combination. The inorganic particles are coated with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The particles may be surface-modified.

[0054] The curable composition may also contain a polymerization accelerator, an antistatic agent, or the like, within a range that does not impair the effects of the present invention. The composition may contain additives such as a binder, a plasticizer, an antioxidant, and an infrared absorbing agent.

[0055] Furthermore, when forming a cured product, if the coating solution is prepared and applied, workability is improved. For this purpose, it is preferable to use a solvent as needed. Aromatic solvents such as silane; methyl ethyl ketone, acetone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran Dioxane, ethylene glycol dimethyl ether, ethylene glycol di Ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole, etc. Ether solvents: ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate Ester solvents such as acetate; dimethylformamide, diethylformamide, N-methyl Amide solvents such as methylpyrrolidone; methyl cellosolve, ethyl cellosolve, butyl cellosol Cellosolve solvents such as ethanol, propanol, isopropanol, Alcohol-based solvents such as butanol; halogen-based solvents such as dichloromethane and chloroform; These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents are preferred because they tend to improve workability during application. Preferred are solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents.

[0056] The solid content of the curable composition can be appropriately changed depending on the application. When forming a cured film using a non-volatile component, from the viewpoint of improving operability in the coating operation, is preferably 1 to 100%, more preferably 5 to 90%, and further preferably 10 to 80%, and particularly preferably in the range of 20 to 70%.

[0057] The content of the resin containing the curable group in the curable composition depends on the application and the required properties of the cured product. Although it is difficult to generalize because it changes depending on the amount of non-volatile matter, it is preferable to use a range of 5 to 99.9%. % by mass, more preferably 10 to 98% by mass, even more preferably 20 to 95% by mass, and particularly preferably The range is preferably 30 to 90% by mass, and most preferably 50 to 85% by mass. By using this material, it is possible to ensure scratch resistance while also achieving good extensibility and chemical resistance during molding. It can be said that. The non-volatile content is the total mass of components other than the solvent, such as the organic solvent. can be measured by a conventionally known method, for example, by spreading 1 g of the composition and measuring It can be calculated from the change in weight when the organic solvent is evaporated by heating for one hour.

[0058] The content of the curable compound other than the resin containing the curable group in the curable composition may vary depending on the application and requirements. It is difficult to generalize because it depends on the properties of the cured product required, but it is preferable to use a non-volatile component. Preferably it is 90% by mass or less, more preferably 1 to 80% by mass, and even more preferably 3 to 50% by mass. %, particularly preferably 5 to 40 mass %, and most preferably 7 to 20 mass %. By using it within this range, it is possible to ensure elongation during molding processing while improving scratch resistance and chemical resistance. It can be done.

[0059] The content of polyester-modified polydimethylsiloxane containing curable groups in the curable composition The content is preferably 0.001 to 20 mass% of the nonvolatile content, more preferably 0. 0.1 to 10 mass%, more preferably 0.1 to 5 mass%, particularly preferably 0.2 to 4 mass% %, and most preferably in the range of 0.3 to 3 mass %. By using it in this range, This not only improves the appearance of the product, but also improves scratch resistance. It has also been found to contribute to improved quality.

[0060] The content of the ultraviolet absorber in the curable composition is preferably 20 mass % based on the nonvolatile content. % by mass or less, more preferably 0.01 to 15% by mass, and even more preferably 0.1 to 10% by mass The range is particularly preferably 0.5 to 8 mass %, and most preferably 1 to 5 mass %. By using it in this environment, a cured product can be formed effectively and the weather resistance of the cured product can be improved.

[0061] The content of the light stabilizer in the curable composition is preferably 20% by mass based on the nonvolatile content. The content is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, particularly The range is preferably 0.5 to 8 mass %, and most preferably 1 to 5 mass %. By using this compound, a cured product can be formed effectively and the weather resistance of the cured product can be improved.

[0062] The content of the photopolymerization initiator in the curable composition is preferably 20 mass % based on the nonvolatile content. % by mass or less, more preferably 0.1 to 15% by mass, and even more preferably 0.3 to 10% by mass, The range is particularly preferably 0.5 to 8 mass %, and most preferably 1 to 7 mass %. By using the composition in this range, a cured product can be effectively formed.

[0063] <Cured product (cured film)> The cured product of the curable composition can be prepared by applying the curable composition to a substrate or an article to form a coating film. After drying as necessary, in the case of an active energy ray curable composition, the composition is irradiated with active energy rays. In the case of a thermosetting composition, the coating can be formed by applying radiation or by heating. There is no particular limitation on the coating method. For example, a dip coating method, an air knife coating method, a curtain coating method, coating method, spin coating method, roller coating method, bar coating method, wire bar coating method, graphite coating method The coating can be carried out by a known method such as via coating or spray coating.

[0064] When the curable composition contains an organic solvent, it is preferable to heat-dry it before the curing reaction. By pre-heating and drying, the organic solvent in the coating film can be effectively removed. The drying temperature for the heat drying is preferably 30 to 200°C, more preferably 40 to 150°C. The drying temperature is preferably 50 to 120°C. The drying time is preferably 0.01 to 30 minutes. 0.1 to 10 minutes is more preferable.

[0065] In the case of an active energy ray-curable composition, the active energy ray may be ultraviolet light, an electron beam, Visible light, infrared light, X-rays, etc. are examples. Among these, from the viewpoint of hardening property and prevention of resin deterioration, From this viewpoint, ultraviolet rays and electron beams are preferred, and ultraviolet rays are more preferred. can be appropriately selected depending on the active energy rays to be irradiated.

[0066] For example, when ultraviolet light is used, the cumulative light intensity is 20 to 5,000 mJ / cm 2 is preferred 100 to 3,000 mJ / cm 2 More preferably, 200 to 2,000 mJ / cm 2 The illuminance is more preferably 10 to 600 mW / cm. 2 is preferred, and 20 ~450mW / cm 2 More preferably, 40 to 300 mW / cm 2 is more preferable. The sources are medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halide lamps Electron beams from a lamp, scanning type, or curtain type electron beam acceleration path, etc. High pressure mercury lamp, ultra-high pressure mercury lamp, etc. , a low-pressure mercury lamp, etc. can be used.

[0067] When curing is performed by electron beam irradiation, various electron beam irradiation devices can be used. The irradiation dose (Mrad) of the electron beam is usually 0.5 to 20 Mrad. It is preferred from the viewpoints of curability of the energy ray-curable composition, flexibility of the cured product, prevention of damage to the substrate, etc. Typically 1 to 15 Mrad.

[0068] The thickness of the cured product (cured film) is preferably 0.1 to 20 μm, more preferably 0.2 to 1 When the thickness of the cured product is within the above range, the thickness is preferably in the range of 0.0 μm, and more preferably in the range of 0.3 to 7 μm. If the thickness is less than 100 μm, it is easy to achieve desired properties such as scratch resistance. The thickness of the cured product can be determined by observing the cross section using an electron microscope or the like.

[0069] The haze of the cured product is measured by the method described in the examples below. The optimum value varies depending on the application, but it is preferable to keep it at 5% or less, and more preferably 3% or less. % or less, more preferably 1% or less, particularly preferably 0.5% or less, and most preferably 0. The range is 2% or less. There is no particular lower limit, but the lower limit is preferably 0.0%. By setting the range, it becomes possible to use it for various purposes.

[0070] The elongation of the cured product is preferably measured as an elongation percentage in a tensile test at 140°C as described below. The elongation is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. When used in applications where corrosion resistance is important, the content is preferably 40% or more, more preferably 50% or more. More preferably, 70% or more, particularly preferably 100% or more, and most preferably 120% or more. % or more. There is no particular upper limit, but it is preferably 300%. This can prevent defects such as cracks during molding.

[0071] <Laminate> The laminate of the present invention (hereinafter also referred to as "the present laminate") comprises a substrate layer and a curable composition. The laminate further comprises a layer made of the substrate layer and a layer made of a material (cured film, hard coat layer). a primer layer provided between the cured product and the substrate layer, and a side of the substrate layer opposite to the cured product side; and a back surface functional layer provided on the surface of the substrate. In addition, as long as the effect of the present invention is not impaired, the surface of the cured product opposite to the substrate layer side may be It may have a surface functional layer disposed thereon.

[0072] As the substrate layer, known substrates can be used, for example, resin substrates, metal substrates, and paper substrates. Among these, resin substrates are preferred from the viewpoint of processability. The resin substrate has a single layer structure. The resin substrate may be a single layer or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable to have a multi-layer structure of two or more layers, each layer having its own characteristics, and to achieve multi-function. stomach.

[0073] As the resin substrate, various resin films (sheets) can be used, for example, polyester films. Film, poly(meth)acrylate film, polyurethane film, polyolefin film Film, polycarbonate film, polyimide film, triacetyl cellulose film Film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film , nylon film, etc.

[0074] This laminate is used for surface protection and decoration of resin molding materials for interior and exterior automotive parts and electronic devices. When using polyester film, poly(meth)acrylate film, polyurethane Polyethylene film and polyolefin film are preferable, and polyester film is also preferable in consideration of formability. Preferred are vinyl films, poly(meth)acrylate films and polyurethane films, particularly Polyester film and poly(meth)acrylate film are preferred. For applications where performance is important, poly(meth)acrylate films are preferred.

[0075] The polyester film may be a non-stretched film or a stretched film. A stretched film is preferred. Among them, a uniaxially stretched film or a biaxially stretched film is preferred. A biaxially stretched film is preferred, from the viewpoint of excellent balance of mechanical properties and flatness. Therefore, biaxially stretched films are more preferable. Also, easily moldable types with improved moldability are preferable. For example, copolymerization of an isophthalic acid structure or the like into the structure of polyethylene terephthalate is Examples include polyester.

[0076] The base layer is designed to provide slipperiness, prevent scratches during each process, and improve blocking resistance. It is possible to include particles as a coating, and to improve weather resistance, it is possible to include an ultraviolet absorber. If necessary, additives other than the above-mentioned particles and ultraviolet absorbers can be added. The additives may include antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, etc. Known additives such as colorants, dyes, and pigments can be used.

[0077] The thickness of the substrate layer is not particularly limited, but is preferably in the form of a film. Preferably 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 150 μm. μm range.

[0078] In addition, the base layer is subjected to corona treatment or printing in order to improve adhesion to the cured product of the curable composition. Plasma treatment may be applied.

[0079] The primer layer is formed between the substrate layer and the cured product of the curable composition in order to provide various functions. For example, an adhesion improving layer, an antistatic layer, etc. may be provided. The primer layer is an adhesion improving layer. If the adhesion between the substrate layer and the cured product is insufficient, In some cases, the laminate cannot be used. By having an adhesion improving layer, the laminate can be easily cured with the base layer. The adhesiveness to the surface is improved, and the laminate can be used for various purposes. Examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin ( polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.

[0080] The surface functional layer can be provided on the surface of the cured product to impart various functions. Examples of functional layers include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low reflection layer, etc.), ), an infrared absorbing layer, an ultraviolet absorbing layer, a color correction layer, etc. The surface functional layer can be formed by a known method. It can be formed by

[0081] The back functional layer is provided on the surface of the substrate opposite to the cured product to impart various functions. The backside functional layer includes an adhesive layer, an antistatic layer, a refractive index adjustment layer, an anti-blocking layer, etc. The adhesive layer is provided to bond the laminate to various adherends. The outermost surface of the laminate, especially the outermost surface of the base material layer opposite the cured layer, is subject to peeling electrification and friction. This is provided to prevent the adhesion of dust and other foreign matter due to triboelectric charging and the resulting defects. The refractive index adjusting layer is provided, for example, to improve the total light transmittance of the laminate. The back functional layer is provided to reduce blocking of the laminate. It can be formed by the following method.

[0082] The haze of a laminate consisting of a substrate and a cured material layer is measured by the method described in the examples below. The optimum value varies depending on the application, so it is difficult to generalize, but it is preferably 10% or less, and more preferably Preferably it is 5% or less, more preferably 2% or less, particularly preferably 1% or less, most preferably The range is 0.5% or less. There is no particular lower limit, but the lower limit is preferably 0.0%. By setting the content within the above range, it becomes possible to use the material for various purposes.

[0083] The total light ray of a laminate consisting of a substrate and a cured material layer measured by the method described in the Examples below. The optimum transmittance varies depending on the application, but it is preferable to set it at 80% or more. More preferably, it is in the range of 85% or more, and even more preferably, 90% or more, with no particular upper limit. Although it is not necessary to set the content within this range, it is preferably 100%. By setting the content within this range, the transparency is excellent and it is suitable for various applications. It will be suitable for.

[0084] <Application> The cured product obtained from the curable composition of the present invention has excellent scratch resistance, chemical resistance and stretchability. Therefore, it can be suitably used as a curable composition for decorative films. It can be effectively applied to exterior building materials, automobiles, home appliances, information and electronic materials, etc. It is Noh. [Example]

[0085] The present invention will be described in more detail below with reference to examples, but the present invention will not be limited to the gist of the present invention. However, the present invention is not limited to the following examples. The measurement and evaluation methods used in the present invention are as follows.

[0086] (1) Weight average molecular weight The weight average molecular weight of the copolymer was measured by GPC under the following conditions. Equipment: Waters "e2695" Column: TSKgel Super H3000+H4000+H manufactured by Tosoh Corporation 6000", Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0087] (2) Measurement method for total light transmittance and haze The measurement object was a laminate consisting of a substrate / cured product layer. Total light transmittance and haze were measured according to JIS Z 8722 (Geometric conditions for irradiating and receiving light through a transparent object), JIS K 7361-1 (Pro JIS K 7136 (Plastic - Test method for total light transmittance of transparent materials) and JIS K 7136 (Plastic The haze meter manufactured by Nippon Denshoku Industries Co., Ltd. conforms to the method for determining the haze of transparent materials. The value was measured at a wavelength of 550 nm using SH7000. The haze of the laminate is determined by the incident light from the outermost surface of the substrate layer on the side where the cured layer is present. Of the transmitted light that passes through, forward scattering occurs at a distance of 0.044 rad (2.5°) or more from the incident light. It is the percentage of transmitted light that deviates (the ratio of diffuse transmittance to total light transmittance). The haze of the cured product was calculated by subtracting the haze value of the substrate from the haze value of the laminate. The absolute value was calculated.

[0088] (3) Evaluation of elongation (cured product) The laminated body having the cured product of the curable composition was cut into a width of 10 mm and subjected to tensile testing using a Tensilon tensile tester. (Imada Co., Ltd. "MX2-500N"), temperature 140℃, tensile speed 40m The specimen was stretched at a rate of 1000 m / min with a chuck distance of 40 mm, and the breaking elongation (cracks were visually observed) was measured. The elongation rate was evaluated by measuring the elongation until the sample was broken. The elongation rate was calculated by dividing the length at which a crack appeared in the cured product by the length before the tensile test. In addition, when the value exceeds 300%, it is written as >300 in Table 2.

[0089] (4) Evaluation method for scratch resistance (cured product) Fold one Kimwipe (registered trademark) Wiper S200 sheet into a 5 x 1 cm piece and fold it. A 1cm square flat surface was created and the surface of the cured product was rubbed hard five times. After that, the surface of the cured product was observed to see if there were any marks. A: No marks, B: Light marks, and C: Clear marks. A rating of C was given to cases where an A or B rating was given to a favorable situation and the scope of application was An A rating is more preferable in that it can be used more widely.

[0090] (5) Evaluation method for chemical resistance (cured product) A 3cm cross cut is made on the surface of the cured material, and a metal washer (2.5mm thick) is inserted. Place a washer (21mm inner diameter) at the center of the cross cut on the surface of the cured material, and insert 0 Add 0.35 mL of 1% sodium hydroxide solution, then cover with a lid and let the water evaporate. The mixture was heated at 90°C for 30 minutes, with the sodium hydroxide solution in a Kimtowel. The surface of the cured product was then wiped off and the appearance of the surface was visually inspected and evaluated immediately afterwards. A: Thin whitening is observed on the underside of the washer. B: Whitening is observed in the center of the washer. For wider application, an A rating is preferable.

[0091] Examples of compounds that may constitute the curable composition are as follows: (Compound example) (Meth)acrylic resin containing active energy ray-curable groups: A-1 A (meth)acrylic resin produced by the method shown below. In a flask equipped with a thermometer, stirrer and reflux condenser, add propylene glycol monomethyl ether. Ether (178 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate Acrylate (79 parts by weight), ethyl acrylate (1.0 part by weight), and 2,2'-azobis( ... (2,4-dimethylvaleronitrile) (0.6 parts by mass) was added and the mixture was reacted at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 After adding propylene glycol monomethyl ether (48 parts by mass) and reacting for 3 hours, parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added. By adding the active energy ray curable group (acryloyl The acryloyl group concentration (amount of acryloyl group introduced) was 1.6 mmol / g of (meth)acrylic resin (A -1) was obtained. The weight average molecular weight was 48,800. The hydroxyl value was 91 mg KOH / m It was g. (Meth)acrylic resin containing active energy ray-curable groups: A-2 A (meth)acrylic resin produced by the method shown below. In a flask equipped with a thermometer, stirrer and reflux condenser, add propylene glycol monomethyl ether. Ether (178 parts by mass), glycidyl methacrylate (10 parts by mass), methyl methacrylate Acrylate (89 parts by weight), ethyl acrylate (1.0 part by weight), and 2,2'-azobis( ... (2,4-dimethylvaleronitrile) (0.6 parts by mass) was added and the mixture was reacted at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 After adding propylene glycol monomethyl ether (48 parts by mass) and reacting for 3 hours, parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C. Next, acrylic acid (5 parts by mass) and triphenylphosphine (1.2 parts by mass) were added. Then, by reacting at 110°C for 12 hours, the amount of active energy ray-curable groups (acryloyl The acryloyl group concentration (amount of acryloyl group introduced) was 0.9 mmol / g of (meth)acrylic resin (A -2) was obtained. The weight average molecular weight was 53,700. The hydroxyl value was 50 mgKOH / m It was g.

[0092] (Meth)acrylate: B-1 Dipentaerythritol hexahydrate modified with 12 caprolactones per molecule Acrylate (hexafunctional) (Kayarad (registered trademark) DPCA-12 manufactured by Nippon Kayaku Co., Ltd.) 0) (Meth)acrylate: B-2 Dipentaerythritol hexaester modified with two caprolactone units per molecule Acrylate (hexafunctional) (Kayarad (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) (Meth)acrylate: B-3 Dipentaerythritol hexaacrylate (hexafunctional) (Kayala, manufactured by Nippon Kayaku Co., Ltd.) (registered trademark DPHA)

[0093] Leveling agent: C-1 Polyester modified polydimethylsiloxane containing active energy ray curable groups (acryloyl groups) Siloxane (BYK BYK-UV3570) Leveling agent: C-2 Polyether-modified polydimethylsiloxane containing active energy ray-curable groups (acryloyl groups) Siloxane (BYK BYK-UV3500) Leveling agent: C-3 Polyester-modified silicone without active energy ray-curable groups (BYK) K-370)

[0094] UV absorber: D 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)- 4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF Ti nuvin 479) Light stabilizer: E Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis( 1,1,dimethylethyl)-4-hydroxyphenyl]methyl] (BASF Tin uvin 144)

[0095] Photopolymerization initiators containing two or more photocleavable groups in the molecule: F-1 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzoyl] {[[(2-methyl-2-phenyl)phenyl]}-2-methylpropan-1-one (IGM Resins BV) (Omnirad 127) Photopolymerization initiator: F-2 1-Hydroxycyclohexyl phenyl ketone (IGM Resins BV) Omnirad 184)

[0096] (Meth)acrylic resin that does not contain active energy ray-curable groups: G Mitsubishi Chemical Corporation BR83 (100% by mass of structural units derived from MMA) Weight average molecular weight (Mw) 40,000 (meth)acrylic polymer

[0097] The curable composition contains the materials shown in Table 1 in the proportions (parts by mass) shown in Table 1, calculated as nonvolatile content. Methyl ethyl ketone was also mixed so that the solid content concentration was 25% by mass. The mixture was stirred until homogenized to obtain each coating liquid (curable composition).

[0098] [Example 1] The coating liquid (active energy ray curable composition) shown in Table 1 below was applied to a (meth)acrylic resin substrate. Film (Mitsubishi Chemical Corporation, Acriplene (registered trademark) HBA010P, 7 5μm thick) using a bar coater so that the coating thickness after drying is 5μm, Heat-dried at 80°C for 2 minutes. After that, it was irradiated with a high-pressure mercury lamp in an air atmosphere with an integrated light intensity of 240 m J / cm 2 , illuminance 50mW / cm 2 UV rays are irradiated to form a hardened material (hardened film) and laminated. I got a body.

[0099] The obtained laminate had good elongation, scratch resistance, and chemical resistance. Shown in Table 2 below.

[0100] [Examples 2 to 10] The same procedure as in Example 1 was carried out except that the coating solution composition was changed to the coating solution composition shown in Table 1. The properties of the resulting laminate are shown in Table 2 below. .

[0101] [Examples 11 and 12] The coating liquid (active energy ray curable composition) shown in Table 1 below was used as a substrate and subjected to corona treatment. The corona treated surface of the easily molded polyester film (thickness: 100 μm) was coated with a bar coater. The coating was applied using a coating solution so that the coating thickness after drying would be 5 μm, and then heated and dried at 80° C. for 2 minutes. After that, a high-pressure mercury lamp was used in an air atmosphere with an integrated light intensity of 240 mJ / cm 2 , illuminance 50mW / c m 2 The laminate was then irradiated with ultraviolet light at 100° C. to form a cured product (cured film), thereby obtaining a laminate. The properties are shown in Table 2 below.

[0102] [Comparative Examples 1 to 6] The same procedure as in Example 1 was carried out except that the coating solution composition was changed to the coating solution composition shown in Table 1. The properties of the resulting laminate are shown in Table 2 below. As shown in the table, the results showed poor scratch resistance and chemical resistance. Since modified polydimethylsiloxane is not used, chemical resistance is poor. In Comparative Examples 5 and 6, the resin containing a curing group was used, and the scratch resistance was poor because no blocking agent was used. Since no adhesive was used, scratch resistance was poor.

[0103] [Table 1]

[0104] [Table 2]

Claims

1. Resins containing curable groups and polyesters different from said resins containing curable groups. A curable composition comprising a silyl-modified polydimethylsiloxane.

2. The curable composition according to claim 1, wherein the curable group of the resin is an active energy ray-curable group. thing.

3. the resin has an active energy ray-curable group equivalent of 0.01 to 10 mmol / g; Item 3. The curable composition according to item 2.

4. The curable group of the polyester-modified polydimethylsiloxane is an active energy ray-curable group.

2. The curable composition of claim 1, wherein

5. The resin and the polyester-modified polydimethylsiloxane have different activation energies. The curable composition of claim 1 further comprising a radiation-curable compound.

6. The curable composition according to claim 1, which contains a photopolymerization initiator.

7. The curable composition according to claim 6, wherein the photopolymerization initiator is an alkylphenone type compound.

8. The curable composition according to claim 6, wherein the photopolymerization initiator contains two or more photocleavable groups in the molecule. Finished product.

9. A cured product of the curable composition according to any one of claims 1 to 8.

10. The cured product according to claim 9, which has an elongation of 5% or more in a tensile test at 140°C.

11. A laminate comprising a substrate and the cured product according to claim 9 laminated thereon.

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