Composition, cured product, laminate, and method for producing the cured product

Abstract

To provide a curable composition for improving adhesion between an inorganic coat material and a resin substrate, a cured product which is excellent in appearance, adhesion and durability and a method for manufacturing the same, and a laminate having a cured product layer which is excellent in appearance, adhesion and durability.SOLUTION: A curable composition contains a copolymer (A) having a monomer (X) having one or more kinds selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom and a silicon atom, and a monomer (Y) having a functional group represented by chemical formula (1): -R1-M(R2)r(OR3)m-r. In the chemical formula (1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, R1 represents a hydrocarbon group having 1 to 5 carbon atoms, R2 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an aryl group, R3 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group or an acyl group, or hydrogen, m represents an integer of 3 to 4 according to M, r represents an integer of 0 to 3, when r is 2 or more, r pieces of R2 may be different, when m-r is 2 or more, (m-r) pieces of R3 may be different.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a composition, a cured product, a laminate, and a method for producing a cured product. [Background technology]

[0002] Resin materials such as polycarbonate have a lower specific gravity and are lighter than inorganic glass, and are easy to process. Taking advantage of its ease of processing and impact resistance, it is used as a material for a wide variety of components, including those for vehicles. It is used in this way. On the other hand, resin materials are prone to surface scratches and easily lose their gloss and transparency. It is susceptible to damage from organic solvents, and lacks weather resistance (e.g., photostability to ultraviolet rays) and heat resistance. It has drawbacks such as inferior quality. Automotive windows, for example, are exposed to sunlight for long periods of time. This is often the case. Therefore, when using resin materials in automotive components, a protective layer is applied to the surface. It is necessary to impart abrasion resistance and weather resistance to the resin material by coating it with a special material. Coating agents primarily made from inorganic materials have a silicon dioxide-based structure, providing weather resistance and scratch resistance. A coating with good properties can be obtained. On the other hand, cracks may occur due to temperature changes, and the painted surface and tree may be affected. The problem was that it had poor adhesion to organic materials such as lipid substrates.

[0003] Conventional techniques for applying inorganic coating agents to resin materials include a resin substrate and the resin base A compound having an intermediate layer placed on the surface of the material and a silicon oxide layer placed on the surface of the intermediate layer. A layered structure is known. Patent Document 1 describes a Si non-crystalline intermediate layer containing (meth)acrylic groups. A composition containing the compound and a siloxane compound containing a (meth)acrylic group is cured. The Si concentration on the silicon oxide layer side of the intermediate layer is higher than that on the resin substrate side. It has been proposed that increasing the viscosity will improve adhesion. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] (Japanese) Patent Application Laid-Open No. 2019-18449 [Summary of the Invention] [Problems to be Solved by the Invention]

[0005] The intermediate layer described in Patent Document 1 contains a siloxane compound in the intermediate layer, thereby achieving both adhesion to the resin substrate and adhesion to the outermost inorganic layer. However, according to the study by the present inventors, when a siloxane compound is used alone, the surface orientation is not sufficient, and a large amount of the siloxane compound must be added, and there are cases where the performance of the intermediate layer itself is insufficient.

[0006] The present invention aims to provide a curable composition for improving adhesion to an inorganic coating material and a resin substrate, a cured product excellent in appearance, adhesion, and durability, and a method for producing the same, and a laminate having a cured product layer excellent in appearance, adhesion, and durability.

[0007] [Means for Solving the Problems] The present invention has the following aspects. [1] A curable composition containing a copolymer (A) having at least one monomer (X) selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom, and a monomer (Y) having a functional group represented by the following chemical formula (1). -R -M(R 2 ) r (OR 3 ) m-r ···(1) (However, M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta represents, R 1 represents a hydrocarbon group having 1 to 5 carbon atoms, R 2 represents an alkyl group having 1 to 5 carbon atoms, carbon number represents an alkenyl group having 2 to 5 carbon atoms, or an aryl group, R 3 represents an alkyl group having 1 to 5 carbon atoms, carbon number represents an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group or hydrogen, m represents an integer of 3 to 4 according to M represents, r represents an integer of 0 to 3, and when r is 2 or more, r R 2 may be different from each other When m - r is 2 or more, (m - r) R 3 may be different from each other .) [2] In the copolymer (A), at least one or more types selected from an aromatic ketone group, a vinyl ether group, an epoxy group, and a ( (meth)acryloyl group, a hydroxyl group, and an isocyanate group The curable composition according to [1], which contains a monomer (Z) having a crosslinkable functional group. [3] The curable composition according to [1 to [2], wherein the (X) component contained in the copolymer (A) is an alkyl group having 4 or more carbon atoms. [4] The curable composition according to any one of [1] to [3], wherein the (Z) component contained in the copolymer (A) is an aromatic ketone group or a (meth)ac ryloyl group. [5] The proportion of the (X) component contained in the copolymer (A) is 10 to 70% by mass, the (Y) component is 10 to 90% by mass, and the (Z) component is in the range of 0 to 80% by mass. The curable composition according to any one of [1] to [4] . [6] A cured film hardened product of the curable composition according to any one of [1] to [5]. [7] A method for producing a cured product, which irradiates or heats the curable composition according to any one of [1] to [5] with active energy rays to cure the curable composition. [8] A substrate, a primer layer provided on the substrate, and a primer layer provided on the primer layer The primer layer has a top coat layer and contains alkyl groups with 4 or more carbon atoms, fluorine A monomer (X) having one or more types selected from the group consisting of elementary atoms and silicon atoms, It contains a copolymer (A) comprising a monomer (Y) having a functional group represented by the following chemical formula (1), A laminate in which the top coat layer is an inorganic coating layer. -R 1 -M(R 2 ) r (OR 3 ) m-r ...(1) (However, M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta) And, R 1 R represents a hydrocarbon group with 1 to 5 carbon atoms. 2 These are alkyl groups with 1 to 5 carbon atoms, and 2 carbon atoms. ~5 represents an alkenyl group or aryl group, R 3 C1-C5 alkyl groups, C4 2-5 represent alkenyl groups, aryl groups, acyl groups, or hydrogen atoms, and m corresponds to M. R represents an integer between 3 and 4, r represents an integer between 0 and 3, and if r is 2 or greater, there are r R 2 they They may be different, and if mr is 2 or more, there are (mr) R's. 3 They are different from each other. That's good too. [9] The inorganic coating layer is a compound consisting of an alkoxysilane or a hydrolysis condensate thereof. The laminate described in [8], comprising 40% or more by mass. [Effects of the Invention]

[0008] According to the present invention, a curable composition is available that can form a cured product with excellent appearance, adhesion, and durability. A cured product with excellent appearance, adhesion, and durability, and a method for producing the same, with excellent appearance, adhesion, and durability. A laminate having a cured layer can be provided. [Modes for carrying out the invention]

[0009] The embodiments of the present invention will be described in detail below, but the following description is based on the embodiments of the present invention. This is just one example, and the present invention is not limited to the following description unless it exceeds the gist of the invention. stomach. In this specification, when the expression "~" is used, the numbers or physical properties before and after it are... It shall be used as an inclusive expression. Also, in this invention, the term "(meth)acrylic" When used, the terms "acrylic" and "methacrylic" are intended to mean either or both. The same applies to "(meth)acrylate," "(meth)acryloyl," etc.

[0010] [Composition] A curable composition according to one aspect of the present invention (hereinafter also referred to as "this composition") has 4 or more carbon atoms. It has one or more elements selected from the group consisting of alkyl groups, fluorine atoms, and silicon atoms. A copolymer containing monomer (X) and monomer (Y) having a functional group represented by the following chemical formula (1) Includes combination (A). This composition may further contain resin components as needed. This composition may further contain ultraviolet absorbers and light stabilizers, if necessary. This composition may further contain a diluent, if necessary. This composition may, if necessary, contain other components not listed above, to the extent that it does not impair the effects of the present invention. It may also be included in the following.

[0011] <Copolymer A> Copolymer (A) has units based on monomer (X) and units based on monomer (Y), Furthermore, it may have units based on monomers (Z) and monomers (V).

[0012] <Monomer X> Monomer (X) is a group consisting of alkyl groups having 4 or more carbon atoms, fluorine atoms, and silicon atoms. It is a compound having one or more selected from the above and a radical polymerizable group. Monomer (X) is a monomer with low surface tension, and copolymer (A) is based on monomer (X). If it has a position, when a coating film of the curable polymer composition is formed, the copolymer (A) will form a coating film It tends to segregate towards the surface side. Copolymer (A) having reactive functional groups with the inorganic coating layer If segregation occurs on the surface side of the coating film, the number of reaction sites with the inorganic coating layer applied on top increases, improving adhesion. This increases the efficiency of segregating functional groups to the surface, which is particularly beneficial for curable polymerization. It is possible to suppress the amount of compound added that has poor compatibility with components throughout the body, and furthermore, the physical properties of the entire composition are not affected. Suppress loss.

[0013] The monomer (X) consists of an alkyl group having 4 or more carbon atoms, a fluorine atom, or a silicon atom. Examples include compounds having one or more elements selected from the group and a radical polymerizable group.

[0014] Alkyl alkyl groups having 4 or more carbon atoms may be linear, branched, or cyclic. The alkyl group may be monocyclic or polycyclic. Copolymer (A) is more effectively applied to the surface of the coating film. From the viewpoint of segregation, the alkyl group is preferably linear. The number of carbon atoms in alkyl groups with 4 or more carbon atoms allows copolymer (A) to be more effectively distributed across the surface of the coating film. From the viewpoint of analysis, preferably in the range of 4 to 30, more preferably in the range of 6 to 20, and further Preferably, the range is 12 to 18.

[0015] Monomers having alkyl groups with 4 or more carbon atoms are easier to synthesize and have 4 or more carbon atoms. From the viewpoint of ease of adjusting the amount of alkyl group introduced, having an alkyl group with 4 or more carbon atoms Alkyl methacrylate is preferred. Examples of monomers having an alkyl group with 4 or more carbon atoms include butyl(meth)acrylate. Pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate Isodecyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate ) Acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, iso Stearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyl Oxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dichloromethyl Lopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl Examples include (meth)acrylates. Among these, (meth)acrylates having a linear alkyl group with 4 or more carbon atoms are particularly important. It is preferable to include a kill ester. (Meta) having a linear alkyl group with 4 or more carbon atoms. )As alkyl acrylates, the number of carbon atoms of the alkyl group is within the preferred range described above. It is preferable to use 2-ethylhexyl(meth)acrylate, and considering ease of manufacture, etc. Rate, Octyl(meth)acrylate, Dodecyl(meth)acrylate, Stearyl( Meth)acrylate is more preferred, and stearyl (meth)acrylate is particularly preferred. These (meth)acrylic acid esters may be used individually or in combination of two or more. That's fine.

[0016] Examples of monomers containing a fluorine atom include monomers containing a fluoroalkyl group. It can be given. A specific example of a fluoroalkyl group is perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is preferably 4 or more. Examples of monomers containing silicon atoms include monomers having polydimethylsiloxane chains. Examples include methacrylates with a molecular weight of 500 to 50,000. Examples include royl group-substituted polydimethylsiloxanes. The molecular weight is 1000 to 3000. A value of 0 is preferred, and a value between 1,500 and 20,000 is more preferred.

[0017] As for the monomer (X), from the viewpoint of wettability and adhesion of the inorganic coating layer, it has 4 or more carbon atoms. It is preferable that the monomer has an alkyl group.

[0018] <Monomer Y> Monomer (Y) has a group represented by the following formula (1) (hereinafter also referred to as "group (1)"). When group (1) is introduced into copolymer (A) by monomer (Y), The group (1) reacts with the functional group components contained in the inorganic coating, improving adhesion and durability. . -R 1 -M(R 2 ) r (OR 3 ) m-r ...(1) However, M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta. And, R 1 R represents a hydrocarbon group with 1 to 5 carbon atoms. 2 These are alkyl groups with 1 to 5 carbon atoms, and groups with 2 to 5 carbon atoms. 5 represents an alkenyl group or an aryl group, R 3 These are alkyl groups with 1 to 5 carbon atoms, and 2 carbon atoms. ~5 represents an alkenyl group, aryl group, acyl group, or hydrogen, and m is 3 corresponding to M. R represents an integer between 0 and 4, r represents an integer between 0 and 3, and if r is 2 or greater, there are r R 2 They are different from each other It may be the case that if mr is 2 or more, there are (mr) R 3 Even if they are different from each other good. In formula (1), M is Al (aluminum), Fe (iron), In (indium), Ge (Germanium), Hf (Hafnium), Si (Silicon), Ti (Titanium), Sn ( It may be any of tin, zirconium (Zr), or tantalum (Ta), but the reactivity and Al, Si, Ti, or Zr are preferred due to their availability, and they are inexpensive and easy to use. Si is particularly preferred.

[0019] R 2 and R 3 Examples of aryl groups include phenyl, toluyl, and naphthyl groups. It can be done. R 2 and R 3 Even if the alkyl, alkenyl, and aryl groups have substituents Good. Substituents include, for example, halogen atoms such as chlorine atoms, methoxy groups, and ethoxy groups. Examples include lucoxy groups. R 3 Examples of acyl groups include (meth)acrylic groups, acetyl groups, and acetimidoyl groups. Group, aldehyde group, thioacetyl group, propionyl group, benzenesulfonyl group, benzoyl Examples include the 'L' group.

[0020] Ure 3 These include alkoxy groups, alkenyloxy groups, aryloxy groups, acyloxy groups, It can be subdivided into ketoximate groups and hydroxyl groups. Among these, the one with the highest reactivity... Furthermore, alkoxy groups, alkenyloxy groups, acyloxy groups, and hydroxyl groups are preferred, and Because their water-degradability is easily controlled and they are easy to handle, alkoxy groups such as methoxy and ethoxy groups are used. A group or a hydroxyl group is particularly preferred.

[0021] When M in formula (1) is Si, the group (1) (also called a hydrolyzable silyl group) is as follows: For example, trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group , dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl tris(2-propenyloxy)silyl group, (chloromethyl)dimethoxysilyl group , (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, ( An example is the ethoxymethyl dimethoxysilyl group. Of the above, trimethoxysilyl is the most versatile, highly active, and provides good curing properties. The group, triethoxysilyl group, and dimethoxymethylsilyl group are preferred, and dimethoxymethylsilyl A lyl group is more preferable. From the standpoint of storage stability, a dimethoxymethylsilyl group and a triethoxymethyl group are preferable. A sisilyl group is preferred. In particular, (chloromethyl)dimethoxycyan is preferred because it exhibits high curability. Lyl groups and (methoxymethyl)dimethoxysilyl groups are preferred. This improves the resilience of the cured product. One trend is the use of trifunctional silyl groups such as trimethoxysilyl and triethoxysilyl groups. It is preferable.

[0022] The monomer (Y) consists of the group (1) and a polymerizable functional group or an addition to the polymer (polymer). Examples include compounds having reactive groups that can react. Examples of polymerizable functional groups are the same as those described above, and the preferred embodiments are also the same. Examples of reactive groups include vinyl groups, (meth)acryloyl groups, and (meth)acryloyl groups. Mido group, epoxy group, cyclic epoxy group, mercapto group, amino group, diamino group, acid anhydride Examples include isocyanate groups and so on. Group (1) and the polymerizable functional group or reactive group may be bonded via a linking group. Examples of such groups include hydrocarbon groups such as alkylene groups having 1 to 6 carbon atoms.

[0023] Examples of monomers (Y) include vinyltrimethoxysilane and vinyltriethoxylan. Vinyl tris(β-methoxyethoxy)silane, (meth)acrylic acid (3-trimeth Xysilyl)propyl, (meth)acrylate (3-dimethoxymethylsilyl)propyl, (meth)acrylate (2-trimethoxysilyl)ethyl, (meth)acrylate (2-dimethyl Toxymethylsilyl)ethyl, (meth) trimethoxysilylmethyl acrylate, (meth) Vinyl silane compounds such as (dimethoxymethylsilyl)methyl acrylate, γ-aminobutyric acid Ropiltrimethoxylan, N-β-(aminoethyl)γ-aminopropyltrimethoxysyl Lan, N-β-(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-ure Amino silane compounds such as Idopropyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxylane , epoxy silane compounds such as γ-glycidoxypropylmethyldiethoxysilane, γ- Mercapto-silane compounds such as mercaptopropyltrimethoxysilane, N-phenyl- Silanes such as γ-aminopropyltrimethoxysilane and other phenylamino silane compounds Examples include silane coupling agents. These silane coupling agents are available commercially. It is preferable from a handling perspective. However, monomers (Y) are not limited to these. For example, they can co-weight with other monomers. Titanium having a polymerizable functional group that can be combined or a reactive group other than (1) that can be added to the polymer A nate-based, aluminate-based, or zirconate-based coupling agent may also be used. Monomer (Y) may be used alone or in combination of two or more types.

[0024] When monomer (X) and monomer (Y) copolymerize, the copolymerization of monomer (X) and monomer (Y) The better the polymerization properties, the more unreacted monomers can be reduced, and the cured resin composition of this composition... The adhesion and durability tend to improve. From this perspective, the polymerizability of monomer (X) When the functional group is a (meth)acryloyl group, monomer (Y) is a (meth)acryloyl group Vinyl silane compounds having the following properties are particularly preferred.

[0025] <Monomer Z> Copolymer (A) contains monomers (X) and monomer (Y), to the extent that it does not impair performance. (meth)acryloyl group, aromatic ketone group, epoxy group, vinyl ether group, hydroxyl group, i It contains a monomer (Z) having at least one functional group selected from the socianate group. Alternatively, the copolymer (A) may consist of a (meth)acryloyl group, an aromatic ketone group, and an epoxy. At least one selected from the group consisting of xy group, vinyl ether group, hydroxyl group, and isocyanate group It also has one type of functional group. When active energy rays are used to cure this composition, the copolymer ( A) has a (meth)acryloyl group, an aromatic ketone group, an epoxy group or a vinyl ether group By including it, stronger bonds can be formed in the cured film. This composition does not require heat for curing. If present, the copolymer (A) contains hydroxyl groups or isocyanate groups, which further enhances the cured film. It can form a strong bond.

[0026] One method for introducing monomer-derived structural units into copolymer (A) is, for example, monomer A monomer (Z) having polymerizable functional groups that can copolymerize with monomer (X) and monomer (Y), and monomer One method involves copolymerizing the compound (X) and the monomer (Y).

[0027] Examples of monomers containing aromatic ketone groups include 4-(meth)acryloyloxybenzo Phenone, 4-(meth)acryloyloxyethoxybenzophenone, 4-(meth)ac Liloyloxy-4'-methoxybenzophenone, 4-(meth)acryloyloxyethone Xy-4'-methoxybenzophenone, 4-(meth)acryloyloxy-4'-bromo Benzophenone, 4-(meth)acryloyloxyethoxy-4'-bromobenzophenone , 2-[4'-(2-hydroxy-2-methylpropanoyl)phenoxy]ethylmeth Crilate is one example.

[0028] Examples of monomers containing epoxy groups include glycidyl (meth)acrylate and 3,4-epoxy Cyclohexylmethyl methacrylate, 4-hydroxybutyl (meth)acrylate Examples include glycidyl ether.

[0029] Examples of monomers containing a vinyl ether group include (meth)acrylic acid 2-(2-vinyloxy Ethoxyethyl is one example. These can be used individually or in combination of two or more.

[0030] Among the above, aromatic ketone groups are used from the viewpoint of surface hardening properties due to ultraviolet energy. It is preferable to use 4-(meth)acryloyloxybenzophenone. That is particularly preferable.

[0031] Furthermore, when the active energy ray used to cure this composition is ultraviolet light, copolymer (A) A (meth)acryloyl group may be introduced into the side chain. One method for introducing (meth)acryloyl groups into copolymer (A) is, for example, epoxy groups A method of reacting an acrylic polymer having a double bond and a carboxyl group with a compound having a double bond and a carboxyl group. Method (Method 1): An acrylic polymer having a carboxyl group has a double bond and an epoxy group. A method of reacting compounds (Method 2), a double bond in an acrylic polymer having a hydroxyl group A method for reacting compounds having a carboxyl group (Method 3), A method for reacting an acrylic polymer with a compound having a double bond and a hydroxyl group (Method 4), A compound having a double bond and a hydroxyl group is reacted with an acrylic polymer having a socianate group. Method (Method 5), adding a double bond and isocyanate group to an acrylic polymer having a hydroxyl group A method for reacting compounds having (Method 6) is mentioned. Furthermore, the above methods can be combined. It can be used in combination.

[0032] In the above method 1, the epoxy group used to obtain an acrylic polymer having epoxy groups Examples of monomers having a poxy group include glycidyl (meth)acrylate, 3,4- Epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl Examples include (meth)acrylates. Among these, those with particularly good reactivity and usability of the material are desirable. Considering ease of use, glycidyl (meth)acrylate is preferred. These are one type You may use only one type, or you may combine two or more types. Furthermore, as a compound having a double bond and a carboxyl group in Method 1, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, glycerin di(meth) ) Additives of acrylate and succinic anhydride, pentaerythritol tri(meth)acrylate Adductors of t and succinic anhydride, pentaerythritol tri(meth)acrylate and anhydrous ptamine Examples include adducts of acrylic acid. Among these, (meth)acrylic acid and pentaerythritol are notable. Adducts of ethyl tri(meth)acrylate and succinic anhydride are preferred, and (meth)acrylic acid This is particularly preferable. Furthermore, using only one compound having a double bond and a carboxyl group is preferable. You can use one type, or you can combine two or more types.

[0033] In the above method 2, used to obtain an acrylic polymer having a carboxyl group. Examples of monomers having a carboxyl group include (meth)acrylic acid, carboxyl Examples include chill (meth)acrylate and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred. These may be used individually or in combination of two or more. You may combine them. Furthermore, in method 2, examples of compounds having a double bond and an epoxy group include , glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl Examples include zyl ethers. Among these, glycidyl (meth)acrylate is preferred. These may be used individually or in combination of two or more types.

[0034] In the above method 3, the hydroxyl group used to obtain an acrylic polymer having a hydroxyl group Examples of monomers having this include 2-hydroxyethyl (meth)acrylate and 4-hydroxyethyl (meth)acrylate. Examples include hydroxybutyl (meth)acrylate and hydroxypropyl (meth)acrylate. These can be used individually or in combination of two or more types. Furthermore, in method 3, the compound having a double bond and a carboxyl group is the previous The same compounds as those used in Method 1 can be used.

[0035] In the above method 4, the acrylic polymer having a carboxyl group is the same as in the above method 2. Similar materials can be used. Furthermore, in method 4, the compound having a double bond and a hydroxyl group is, for example, 2 -Hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Examples include hydroxypropyl (meth)acrylate, etc. These can be used by using only one type. You can use one type, or you can combine two or more types.

[0036] In the above method 5, used to obtain an acrylic polymer having an isocyanate group Examples of monomers having an isocyanate group include isocyanate ethyl (meth) Examples include acrylates. Furthermore, in method 5 described above, the compound having a double bond and a hydroxyl group is, for example, the previous Compounds similar to those listed in Method 4 can be used.

[0037] In method 6, the acrylic polymer having a hydroxyl group is the same as in method 3. Similar compounds can be used. Furthermore, in method 6, the compounds having a double bond and an isocyanate group are: Examples include isocyanate ethyl (meth)acrylate. There is only one type of these. You may use one type, or you may combine two or more types.

[0038] Among the above methods, from the viewpoint of improving the storage stability of copolymer (A) and curable composition... Method 6 is preferred. In Method 6, the double bond is double bonded to the acrylic polymer having a hydroxyl group. It is introduced by reacting compounds having a nucleotide and isocyanate group.

[0039] In the above method 6, the compound having a double bond and an isocyanate group is an acrylic compound It is preferable to add 10 to 150 mol% to the hydroxyl groups during bonding, and 30 to 130 It is more preferable to add mol% and even more preferable to add 50-110 mol%. By using it within this range, the reaction will proceed without excess or deficiency, and the residue of the raw materials will be reduced. From that perspective, it is preferable.

[0040] <Other monomers V> Other monomers (V) can copolymerize with monomers (X), (Y), and (Z). If possible, for example, a compound having the polymerizable functional group described above (however, monomer (X Examples include (excluding monomers (Y) and monomer (Z)). Other specific examples of monomers (V) include the following: Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate Pill, isopropyl (meth)acrylate, 2-aminoethyl (meth)acrylate, (meth (Meth)acrylic acid monomers such as ethylene oxide adducts of acrylic acid; (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide (T) Acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth) Acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth) Acrylamide, N-dimethylaminoethyl (meth)acrylamide, N-dimethylamino Propyl(meth)acrylamide, diacetone(meth)acrylamide, N-(meth) Cryloylpiperidine, (meth)acroylmorpholine, and other (meth)acrylamide compounds Quantity; Styrene, vinyltoluene, alpha-methylstyrene, chlorostyrene, chloromethylstyrene Styrene monomers such as styrene, styrene sulfonic acid, and its salts; Maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid Fumaric acid, monoalkyl and dialkyl esters of fumaric acid; Maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide Imide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylma Maleimide monomers such as reimide, phenylmaleimide, and cyclohexylmaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amylamide, methacrylamide, and other amide-containing vinyl monomers; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate vinyl esters such as; Alkenes such as ethylene and propylene; Conjugated dienes such as butadiene and isoprene; Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. Other monomers (V) may be used individually or in combination of two or more.

[0041] A site for copolymerizing monomer (X), monomer (Y), and monomer (Z) with other monomers (V). In addition, the better the copolymerization of each monomer, the more unreacted monomers can be reduced, and the composition The appearance and durability of the cured product tend to improve. From this perspective, monomer (X), monomer When the polymerizable functional group of (Y) and monomer (Z) is a (meth)acryloyl group, Merger (Z) consists of at least one styrene monomer and a (meth)acrylic acid monomer. Seeds are preferred, and (meth)acrylic acid monomers are particularly preferred.

[0042] <Percentage of each constituent unit in copolymer (A)> The proportion of monomer (X) in the constituent components of copolymer (A) is 10 to 70% by mass. Preferably, it is 20-70% by mass, and more preferably 25-70% by mass. It is even more preferable that it be 25 to 65% by mass, and particularly preferable that it be 30 to 60% by mass. It is particularly preferable that the proportion of monomer (X) is equal to or greater than the lower limit of the curable polymer composition. When the coating film is formed, copolymer (A) tends to segregate to the surface side of the coating film, and beyond the upper limit The lower value improves compatibility with the curable polymer composition and results in a better appearance.

[0043] The proportion of monomer (Y) in the constituent components of copolymer (A) is 10 to 90% by mass. Preferably, 10 to 80% by mass is more preferred, and 10 to 70% by mass is even more preferred. It is particularly preferable that the amount be 10-60% by mass, and most preferably 10-50% by mass. If the proportion of constituent units (Y) is above the lower limit, the reactivity with the inorganic coating layer will improve. Adhesion is improved, and if it is below the upper limit, the ratio of monomer (X) to monomer (Z) is sufficiently high. Therefore, segregation towards the surface and crosslinking with the resin components of this composition are promoted, improving adhesion.

[0044] The proportion of monomer (Z) in the constituent components of copolymer (A) should be between 0 and 80% by mass. Preferably, 0 to 50% by mass, and more preferably 0 to 40% by mass. More preferably, 5 to 40% by mass is preferred, and 10 to 40% is most preferred. Preferred. If the proportion of monomer (Z) is above the lower limit, the reactivity with the resin component in this composition is To improve adhesion, if the ratio of monomer (X) to monomer (Z) is below the upper limit, Because the surface segregation can be made sufficiently high, the reactivity with the inorganic coating layer is improved.

[0045] The proportion of monomer (V) in the constituent components of copolymer (A) should be between 0 and 50% by mass. Preferably, 0 to 40% by mass, and more preferably 0 to 30% by mass. More preferably, it is 0 to 20% by mass, and particularly preferably 0 to 10% by mass. Particularly preferable. If the proportion of monomer (V) is above the lower limit, the compatibility during polymerization improves, and the upper limit If the value is below this level, the composition ratio of other monomers will improve, affecting surface segregation, resin components and inorganic compounds in the composition. The reactivity with the court layer is improved.

[0046] <Mw of copolymer (A)> The Mw of copolymer (A) is preferably 1,000 to 400,000, and 3,000 to 200. 000 is more preferable, and 5000 to 150,000 is particularly preferable. Furthermore, 8000 to 1 20,000 is more preferable. Copolymerization occurs if the Mw of copolymer (A) is equal to or greater than the above lower limit. Since body (A) is firmly fixed within the hardened material, adhesion tends to improve, and the above upper limit If the following conditions are met, the compatibility with other components in this resin composition will improve, and the appearance of the cured product will be There is a tendency for improvement. The Mw of copolymer (A) is determined by gel permeation chromatography (GPC) as described below. This is a value equivalent to standard polystyrene, measured by [the specified method].

[0047] <Method for producing copolymer (A)> Copolymer (A) is formed by polymerizing monomer components, for example, monomer (X) and monomer (Y). It is obtained by doing so. The monomer components are monomer (Z) and monomer (V) as needed. It may further contain one or more of the other monomers. Furthermore, polymerization is typically carried out in the presence of a radical polymerization initiator. Furthermore, a chain transfer agent may be used in combination. Polymerization methods include solution polymerization, suspension polymerization, and bulk polymerization. Known methods such as emulsion polymerization are mentioned, and among them, solution polymerization is the most convenient and productive method. Polymerization is preferred.

[0048] <Content of copolymer (A)> The content of copolymer (A) is 0.01 to 30% of the mass of the cured product of this composition. A certain percentage is preferred, 0.01 to 20% by mass is more preferred, and 0.01 to 10% by mass is even more preferred. Preferably, 0.05 to 10% by mass is particularly preferred, and 0.05 to 5% by mass is most preferred. If the content of copolymer (A) is above the lower limit, adhesion improves; if it is below the upper limit, The appearance and strength of the cured material are superior.

[0049] <Resin components> Examples of resin components in this composition include acrylic resin, polyester resin, and urethane resin. Examples include oils and vinyl resins. Among these, the ability to improve adhesion is particularly important. From the viewpoint of improvement, acrylic resin or urethane resin is preferred. The components may be used individually or in combination of two or more. Furthermore, the resin component may be monomer Alternatively, it is preferable that the composition is a curable composition that hardens the oligomer on a substrate.

[0050] Examples of curable layers include those curable by active energy rays and those that are thermosetting. Curable composition If the resin substrate is coated with this and then cured by heat, there is a risk that the resin substrate will deform due to the heat. However, if cured with activated energy rays, thermal deformation of the resin substrate can be suppressed. Therefore, it can be applied to resin substrates with low heat resistance. Also, curing by active energy rays is generally possible. Compared to other curing methods such as heat curing and moisture curing, this method has a shorter curing time and is expected to improve productivity. .

[0051] Copolymer (A) contains monomers (Z) such as aromatic ketone groups, vinyl ether groups, and epoxy groups. Or, if it contains at least one selected from (meth)acryloyl groups, the curing of the composition By using activated energy rays, stronger bonds can be formed within the cured film. In the case of active energy ray curable resin components, conventionally known active energy ray curable compounds It is also possible to use any known type that has a radical polymerizable group. Compounds can be used, for example, (meth)acrylate, and (meth)acrylate and Other polymerizable monomers and the like are also examples. Examples of compounds having radical polymerizable groups include monofunctional and difunctional compounds. Examples include compounds and polyfunctional compounds with three or more functions, among which those that improve adhesion to the hardened layer are particularly effective. To create a primer layer with a higher degree of curing, using a polyfunctional compound is more effective. preferable.

[0052] While there are no particular limitations on the type of methacrylate used for three or more functional groups, For example, pentaerythritol triacrylate, dipentaerythritol triacrylate Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate Dipentaerythritol hexaacrylate, trimethylolpropane triacrylate Rate, neopentyl glycol-modified trimethylolpropanedi(meth)acrylate, etc. (Meth)acrylate, ditrimethylol, having a skeleton derived from trimethylolpropane. Propanetetraacrylate, bis(2-acryloyloxyethyl)-2-hydroxy (Meth)acrylates having an isocyanurate skeleton, such as ethyl isocyanurate; anhydrous Pentaerythritol triacrylate adduct to succinic acid, dipenta Polyfunctional acrylates such as erythritol pentaacrylate adducts; side chains or side chains and ends Polyester oligomer having an acryloyl group at the end (specifically, M80 manufactured by Toagosei) Polyester (meth)acrylates such as 30, M7100, etc.; isophorone diisocyane Isocyanurate of phosphate (IPDI), polytetramethylene glycol (PTMG) and Reaction product of hydroxyethyl acrylate (HEA), hexamethylene diisocyanate (HDI) and the reaction products of pentaerythritol triacrylate to PTMG, etc. Functional urethane (meth)acrylate; oligoester using polycarbonate diol and a polyethylene having a carbonate bond, such as a reaction product of pentaerythritol triacrylate Ster(meth)acrylate; reaction products of diisocyanates and polyols with three or more functionalities, Polyurethane (meth)acrylate, such as reaction products of hydroxyl group-containing (meth)acrylate; Triethoxyisocyanurate triacrylate and other triethoxyisocyanurate rings cy(meth)acrylate; these alkylene oxide modified products; these polycaprol Examples include chthonic altered materials. Among these, pentaerythritol was chosen from the viewpoint of viscosity, curability, and hardness of the cured film. Dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Dipentaacrylate, dipentaerythritol hexaacrylate, trimethylol Propane triacrylate, ditrimethylolpropanetetraacrylate, dipentae Lithritol triacrylate; its alkylene oxide variants; its capro It is preferable to include a lactone-modified material from the viewpoint of curability and coating hardness. (Meth)acrylate can be used alone or in combination of two or more types. good.

[0053] While there are no particular limitations on difunctional or polyfunctional (meth)acrylates, for example... 1,4-Butanediol di(meth)acrylate, neopentyl glycol di(meth) Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi All di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate Alkanediolic di(meth)acrylates such as bisphenol A ethylene oxide Di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acrylate Bisphenol-modified di(meth)acrylates such as phosphates, polyethylene glycol di(meth)acrylates (Meth)acrylate, polypropylene glycol, (meth)acrylate, urethane (meth)acrylate Acrylates, epoxy di(meth)acrylates, and these alkylene oxide-modified acrylates. Examples include these polycaprolactone-modified products.

[0054] Examples of monofunctional compounds include monofunctional (meth)acrylates and (meth)acrylic acid. It can be. As a monofunctional (meth)acrylate, it is not particularly limited, but for example, Butyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate )acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, Alkyl cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and other alkyl groups. (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl ( meth)acrylate, hydroxybutyl (meth)acrylate and other hydroxyalkyl ( Methacrylate, Methoxyethyl (meth)acrylate, Ethoxyethyl (meth)acrylate Relate, Methoxypropyl (meth)acrylate, Ethoxypropyl (meth)acrylate Alkoxyalkyl (meth)acrylates such as phosphates, benzyl (meth)acrylates, and other phosphates. Aromatic (meth)acrylates such as phenoxyethyl (meth)acrylate, diaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and other amino group-containing ( Meth)acrylate, methoxyethylene glycol (meth)acrylate, phenoxypropyl Reethyleneglyceryl (meth)acrylate, phenylphenol ethylene oxide modified (meth)acrylate and other ethylene oxide-modified (meth)acrylates, glycidyl ( Examples include meth)acrylate and tetrahydrofurfuryl(meth)acrylate.

[0055] The copolymer (A) has a monomer (Z) selected from a hydroxyl group or an isocyanate group. If even one of these is included, using thermocuring to cure the composition will result in a stronger bond in the cured film. It is possible to form this. In the case of thermosetting resin components, conventionally known thermosetting compounds can be used. For example, thermosetting can be performed using various polyols and various polyisocyanates.

[0056] Examples of polyols include those that are conventionally known, such as polycarbonate poly Polyol, polyester polyol, acrylic polyol, polyurethane polyol, poly Polymers such as olefin polyols, polyether polyols, and polyvinyl alcohol , possessing a dendritic branched structure with hydroxyl groups at its ends, such as dendrimers and hyperbranched polymers. Polymers such as ethylene glycol, 1,2-propylene glycol, and 1,3-propylene Lenglycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol ol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexa 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, neopentin Glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane Trimethylolethane, trimethylolpropane, glycerol, polycaprolactone Triol, erythritol, pentaerythritol, polycaprolactone tetraol Examples include polyhydric alcohols such as diglycerin. Among these, polymer ties have a high crosslinking density and excellent curability and durability. Polyols having a branched structure are preferred, and among them, those that form a highly branched structure are preferred. Furthermore, from the perspective of effectively increasing crosslink density and improving durability, dendrimers and hyperbrakes are used. Ranch polymers are more preferred. These polyols can be used individually or in combination. It may be used.

[0057] Examples of polyisocyanates include those that are already known, such as toluene Socyanates, xylylene diisocyanates, methylenediphenyl diisocyanates, f Ethylene diisocyanate, naphthalene diisocyanate, toridine diisocyanate, etc. Aromatic diisocyanates, α,α,α',α'-tetramethylxylylene diisocyanates Aliphatic diisocyanates, methylene diisocyanates, and propylene compounds having aromatic rings such as phosphates. Lysine diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate aliphatic diisocyanates such as hexamethylene diisocyanate, cyclohexane di Isocyanates, methylcyclohexane diisocyanate, isophorone diisocyanate , dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl diiso Examples include alicyclic diisocyanates such as cyanates. Also, these bifunctional polyiso... Trimethylolpropane adduct, a biuret compound synthesized using cyanate as a starting material. Other examples include polyisocyanates with three or more functionalities, such as isocyanurates and allophanates. These can be used individually or in combination. Among these, those with a high crosslinking density and superior curability and durability have three or more functional properties. It is preferable that it contains a polyisocyanate, and more preferably that it is an isocyanurate. Furthermore, from the viewpoint of durability of the hardened layer, those having an aromatic ring structure or an alicyclic structure are preferred. From the viewpoint of being less prone to yellowing, it is preferable that the material has an aliphatic or alicyclic structure. .

[0058] <UV absorbers, light stabilizers> This composition contains an ultraviolet absorber or light stabilizer, which protects the coating film itself from ultraviolet light, etc. This is a desirable shape because it suppresses the deterioration of the resin substrate that forms the base of the coating, improving weather resistance and durability. To become.

[0059] Examples of UV absorbers include organic UV absorbers and inorganic UV absorbers, From the viewpoint of brightness, organic UV absorbers are preferred. As for organic UV absorbers, there are no particular limitations. It is not defined, but for example, hydroxyphenyltriazine derivatives, benzotriazole derivatives, cyclic derivatives Iminoester derivatives, benzophenone derivatives, salicylate derivatives, cyanoacrylate derivatives, etc. Among these, hydroxyphenyl triglycerides is considered to have the most weather resistance and durability. Zin-based, benzotriazole-based, and cyclic iminoester-based hydroxyphosphate-based esters are more preferred. Nyltriazine-based materials are even more preferred. Furthermore, UV absorbers may be used individually or in pairs. It is also possible to use more than one of these compounds in combination. Furthermore, these compounds can be incorporated into polymers. It is also possible to use the one that was made.

[0060] Hydroxyphenyltriazine-based UV absorbers are not limited to the following: However, for example, 2-[4-([2-hydroxy-3-dodecyloxypropyl]oxy) -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5 -Triazine and 2-[4-([2-hydroxy-3-tridecyloxypropyl]oxy )-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3, 5-Triadin (Tinuvin® 400, manufactured by BASF), 2 -[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl] -5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), 2-(2 ,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3 Reaction product of 5-triazine and (2-ethylhexyl)-glycidic acid ester (Tin uvin(registered trademark) 405 (manufactured by BASF), 2,4-bis"2-hydroxy-4-bu" Toxyphenyl-6-(2,4-dibutoxyphenyl)-1,3-5-triazine(T inuvin(registered trademark) 460 (manufactured by BASF), 2-(4,6-diphenyl-1,3) ,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol(Tinuv (in (registered trademark) 1577, manufactured by BASF), 2-(4,6-diphenyl-1,3,5- Triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-f Enol (ADK STAB LA46, manufactured by ADEKA), 2-(2-hydroxy-4 -[1-Octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenyl Phenyl)-1,3,5-triazine (Tinuvin® 479, BASF) Examples include (manufactured by...).

[0061] Benzotriazole-based UV absorbers are not limited to the following, but for example... , 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H -benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl )phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacrylate [Royloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy C-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl [2H-benzotriazole, 2-[2'-hydroxy-5'-tert] -butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole Lu, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5- Chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyl Oxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-H Droxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-ben Zotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl) phen [Nyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy- 5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazo Examples include [mention specific examples].

[0062] Examples of cyclic iminoester-based UV absorbers include, but are not limited to, the following: For example, 2-methyl-3,1-benzoxazine-4-one, 2-butyl-3,1-benzo Xazazine-4-one, 2-phenyl-3,1-benzoxazine-4-one, 2-(1- Or 2-naphthyl)-3,1-benzoxazine-4-one, 2-(4-biphenyl) -3,1-benzoxazine-4-one, 2-p-nitrophenyl-3,1-benzox Sazin-4-one, 2-m-nitrophenyl-3,1-benzoxazine-4-one, 2 -p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyf phenyl-3,1-benzoxazine-4-one, 2-o-methoxyphenyl-3,1-be Benzooxazine-4-one, 2-cyclohexyl-3,1-benzoxazine-4-one , 2-p-(or m-)phthalimidophenyl-3,1-benzoxazine-4-one N-phenyl-4-(3,1-benzoxazine-4-on-2-yl)phthalimide N-benzoyl-4-(3,1-benzoxazine-4-on-2-yl)aniline, N-benzoyl-N-methyl-4-(3,1-benzoxazine-4-on-2-yl) Aniline, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazine -4-one, 2,2'-bis(3,1-benzoxazine-4-one), 2,2'-eth Lenbis(3,1-benzoxazine-4-one), 2,2'-tetramethylenebis(3 ,1-benzoxazine-4-one), 2,2'-decamethylenebis(3,1-benzo Xazazine-4-one, 2,2'-p-phenylenebis(3,1-benzoxazine-4) -on), 2,2'-m-phenylenebis(3,1-benzoxazine-4-on), 2 ,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), 2 ,2'-(2,6- or 1,5-naphthylene)bis(3,1-benzoxazine-4- ON), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine- 4-ONE), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazi n-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzooxy (Sadin-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzo) Xazazine-4-one), 1,3,5-tri(3,1-benzoxazine-4-one-2- Il)benzene, 1,3,5-tri(3,1-benzoxazine-4-one-2-yl) Naphthalene, 2,4,6-tri(3,1-benzoxazine-4-on-2-yl)naph Talene, 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-diphen Nyl-4H,8H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine- 4,6-dione, 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-Benzoxazine-4-one), 6,6'-Bis(2-ethyl-4H,3,1- Benzoxazine-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzo Oxazin-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzo Oxazine-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-ben) Zooxazine-4-one), 6,6'-ethylenebis(2-methyl-4H,3,1-ben Zooxazine-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-be (6,6'-butylenebis(2-methyl-4H,3,1 (6,6'-butylenebis(2-phenyl-4H,3,1-) Benzoxazine-4-one), 6,6'-oxybis(2-methyl-4H,3,1-be (Xinooxazine-4-one), 6,6'-oxybis(2-phenyl-4H,3,1-be) (Nzooxazine-4-one), 6,6'-sulfonylbis(2-methyl-4H,3,1- Benzoxazine-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3, 1-Benzoxazine-4-one), 6,6'-Carbonylbis(2-methyl-4H,3 ,1-benzoxazine-4-one), 6,6'-carbonylbis(2-phenyl-4H ,3,1-benzoxazine-4-one),7,7'-methylenebis(2-methyl-4H ,3,1-benzoxazine-4-one), 7,7'-methylenebis(2-phenyl-4 H,3,1-benzoxazine-4-one), 7,7'-bis(2-methyl-4H,3, 1-Benzoxazine-4-one), 7,7'-ethylenebis(2-methyl-4H,3, 1-Benzoxazine-4-one), 7,7'-Oxybis(2-methyl-4H,3,1 -Benzoxazine-4-one), 7,7'-Sulfonylbis(2-methyl-4H,3, 1-Benzoxazine-4-one), 7,7'-Carbonylbis(2-methyl-4H,3 ,1-benzoxazine-4-one), 6,7'-bis(2-methyl-4H,3,1-be (Nzooxazine-4-one), 6,7'-bis(2-phenyl-4H,3,1-benzo) Xazazine-4-one, 6,7'-methylenebis(2-methyl-4H,3,1-benzo Xazazine-4-one), 6,7'-methylenebis(2-phenyl-4H,3,1-benzo Examples include oxazine-4-one.

[0063] Benzophenone-based UV absorbers (benzophenone compounds), oxybenzophenone-based Examples of UV absorbers (oxybenzophenone compounds) include 2,4-dihydrox Cibenzophenone, 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 Toxybenzophenone (product name "KEMISORB111", manufactured by Chemipro Chemical Co., Ltd.) , 2,2',4,4'-tetrahydroxybenzophenone (product name "SEESORB10") 6"), manufactured by Cipro Chemical Co., Ltd., 2,2'-dihydroxy-4,4-dimethoxybenzof Enon, among others, is one example.

[0064] Examples of salicylate ester-based UV absorbers (salicylate ester compounds) include, for example, , 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-acryloyloxy-5-methylbenzoate Liloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, Phenyl-2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4methylbenzoate Tylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl-2- Hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate (Tinuvin®) Examples include the 120 (manufactured by BASF).

[0065] Examples of cyanoacrylate-based UV absorbers (cyanoacrylate compounds) include, for example, , alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, aldehyde Coxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, al Examples include quinyl-2-cyanoacrylate.

[0066] The light stabilizers are not particularly limited, but examples include amine-based light stabilizers and phenol-based light stabilizers. Examples include stabilizers, phosphorus-based light stabilizers, and thioether-based light stabilizers, and among these, ami Phosphorus-based light stabilizers, phenol-based light stabilizers, and phosphorus-based light stabilizers are preferred, and those that cause less yellowing are particularly preferred. Considering these factors, amine-based light stabilizers are more preferable. These light stabilizers can be used individually. They can be used individually, and it is also possible to use two or more types in combination. Furthermore, these compounds can be polymerized. It is also possible to use the version incorporated into the MA system.

[0067] Examples of amine-based light stabilizers include dimethyl succinate and 4-hydroxy-2,2 ,6,6-tetramethyl-1-piperidineethanol polymer (Tinuvin (Registered Trademark) (Standard) 622, manufactured by BASF, dimethyl succinate and 4-hydroxy-2,2,6,6 -Tetramethyl-1-piperidineethanol polymer and N,N',N'',N'''-Te Trachth-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylbutyl Peridine-4-yl)amino)triazine-2-yl)-4,7-diazadecane-1, 1:1 reaction product with 10-diamine (Tinuvin® 119, BASF) (Manufactured by [company name]), dibutylamine·1,3-triazine·N,N'-bis(2,2,6,6-tetra Lamethyl-4-piperidiyl-1,6-hexamethylenediamine and N-(2,2,6,6- Tetramethyl-4-piperidyl)butylamine polycondensate (Tinuvin®) (Manufactured by BASF in 2020), poly[{6-(1,1,3,3-tetramethylbutyl)amine No-1,3,5-triazine-2-4-diyl}{2,2,6,6-tetramethyl-4-p [Peridylimino]Hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) IMINO}) (Tinuvin(registered trademark) 944, manufactured by BASF), screws (1,2,2, 6,6-Pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6- Pentamethyl-4-piperidyl sebacate mixture (Tinuvin® 765 Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (manufactured by BASF) (Tinuvin® 770, manufactured by BASF), bis(2,2,6, decanediate) 6-Tetramethyl-1-(octyloxy)-4-piperidinyl) ester, 1,1-di Reaction product of methyl ethyl hydroperoxide and octane (Tinuvin®) 123 (BASF), bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]buty Lumalonate (Tinuvin® 144, manufactured by BASF), cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4 Reaction product of 6-trichloro-1,3,5-triazine with 2-aminoethanol Product (Tinuvin® 152, manufactured by BASF), screws (1, 2, 2, 6, 6) Pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamyl Chil-4-piperidyl sebacate mixture (Tinuvin® 292, BAS (Manufactured by Company F), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentameth Ru-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl) Mixed esterified product with )-2,4,8,10-tetraoxaspiro[5.5]undecane Examples include (ADK STAB LA63P, manufactured by ADEKA). These amine-based light Among stabilizers, hindered amine-based stabilizers are particularly preferred due to their superior performance.

[0068] Examples of phenolic light stabilizers include 2,6-di-tertiary butyl-4-methylphenyl Nol, 4-hydroxymethyl-2,6-di-tertiary butylphenol, 2,6-di- Tertiary butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl -3-(4-hydroxy-3,5-di-tertiary butylphenyl)propionate, diste Allyl-(4-hydroxy-3-methyl-5-tertiary butyl)benzylmalonate, Toco Ferrol, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2 ,2'-methylenebis(4-ethyl-6-tertiary butylphenol), 4,4'-methylene 2,6-di-tertiary butylphenol, 4,4'-butylidenebis(6-tertiary) 6-tertiary butyl-m-cresol), 4,4'-thiobis(6-tertiary butyl-m-cresol) ), styrene-modified phenol, N,N'-hexamethylenebis(3,5-di-tertiary butyl -4-Hydroxyhydrocinnamide, bis(3,5-di-tertiary-butyl-4-hydroxy Ethyl benzylphosphonate calcium, 1,1,3-tris(2-methyl-4 -hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetraki s[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxime thyl]methane, 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4 -hydroxyphenyl)propionate], 2,2´-methylenebis(4-methyl-6- cyclohexylphenol), 2,2´-methylenebis[6-(1-methylcyclohex yl)-p-cresol], 1,3,5-tris(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl)isocyanuric acid, 1,3,5-tris(3,5-di-tert-but yl-4-hydroxybenzyl)isocyanuric acid, triethylene glycol-bis[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 2,2´ -oxamidobis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6-(4-hydroxy-3,5-di-tert-butylanilino)-2, 4-dioctylthio-1,3,5-triazine, bis[2-tert-butyl-4-methyl- 6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephtha late, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphen yl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxa spiro[5.5]undecane, 3,9-bis{2-[3-(3,5-di-tert-but yl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl}-2, Examples include 4,8,10-tetraoxaspiro[5.5]undecane.

[0069] Examples of phosphorus-based light stabilizers include trisnonylphenyl phosphite, tris(2, 4-di-tertiary butylphenyl) phosphite, Tris[2-tertiary butyl-4-(3- Tertiary butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phos Phyto, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)mo Nophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, dis Tearylpentaerythritol diphosphite, di(nonylphenyl)pentaerythritol Diphosphate, bis(2,4-di-tertiary butylphenyl)pentaerythritol Diphosphite, bis(2,6-di-tertiary butyl-4-methylphenyl)pentaerythritol Litol diphosphite, bis(2,4,6-tri-tertiary butylphenyl)pentaeri Slithol diphosphite, tetra(tridecyl)isopropylidene diphenol diphosphite Phyto, Tetra(tridecyl)-4,4'-n-butylidenebis(2-tertiary butyl- 5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris( 2-Methyl-4-hydroxy-5-tertiary butylphenyl)butane triphosphite, te Trachis(2,4-ditertiary butylphenyl)biphenylenediphosphonite, 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Tris( 2-[(2,4,8,10-tetrakis-tertiary butyldibenzo[d,f][1,3,2 Examples include dioxaphosphine-6-yl(oxy)ethyl(amine).

[0070] Examples of thioether-based light stabilizers include dilauryl thiodipropionate and dimyris. Dialkylthiodipropionate compounds such as tyl and distearyl; tetrakis[methylene] (3-dodecylthio)propionate] β-alkyl mercapto of polyols such as methane Examples include propionic acid ester compounds.

[0071] Regarding the total content of UV absorbers and light stabilizers, for example, the total mass of the cured film of the composition. Preferably 30% by mass or less, more preferably 0.01 to 20% by mass, and even more preferably The amount is in the range of 0.1 to 15% by mass, and particularly preferably 0.3 to 15% by mass. By using it in a controlled environment, the weather resistance of the base material and components can be improved while maintaining other properties. This makes it possible to prevent deterioration.

[0072] <Diluent> This composition may contain a diluent as needed. The diluent may be water or an organic solvent. These are some examples. Examples of organic solvents include alcohol-based solvents, glycol-based solvents, hydrocarbon solvents, and esters. Examples include ketone solvents, ether solvents, etc. Alcohol-based solvents include... Butanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, oc Examples include tanol, n-propyl alcohol, acetylacetone alcohol, etc. Examples of glycol-based solvents include ethylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, propylene glycol monomethyl ether Ru, propylene glycol monoethyl ether, propylene glycol monobutyl ether Ru, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene Glycol monomethyl ether acetate and the like can be mentioned. Examples of hydrocarbon solvents include benzene, kerosene, toluene, xylene and the like. Examples of ester solvents include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like Benzene, kerosene, toluene, xylene, etc. are mentioned. As ester solvents, acetic acid Methyl, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, etc. are mentioned . Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, a Cetyl acetone and the like can be mentioned. Examples of ether solvents include ethyl ether, butyl ether Ter, methyl cellosolve, ethyl cellosolve, dioxane, furan, tetrahydrofuran Etc. The organic solvent may be used alone or in combination of two or more

[0073] <Other components> This composition may contain, as other components, for example, a leveling agent, a silane coupling agent, an antifoaming agent , a thickener, an antistatic agent, an infrared absorber, a foaming agent, inorganic fine particles, organic fine particles, dyes, pigments, An antioxidant, a yellowing inhibitor, a bluing agent, an antifogging agent, a sedimentation inhibitor, etc. may be included The content of other components is not particularly limited, but for example, it can be about 0 to 30% by mass with respect to 100% by mass of the cured product. However, in order not to impair the performance of this composition The ratio of other components is preferably low

[0074] [Cured product] The cured product according to one aspect of the present invention (hereinafter, also referred to as "this cured product") is the cured product of this composition It is This cured product is obtained by curing this composition. The curing method involves irradiating the composition with active energy rays or curing it by heating. Methods include curing using moisture in the air, and the temperature applied to the substrate and productivity are important. From this viewpoint, a method of irradiating the composition with active energy rays is preferred.

[0075] Examples of active energy rays include ultraviolet rays and electron beams. They are easily available and heavy Ultraviolet light is preferred due to its superior compatibility. When curing this resin composition by ultraviolet irradiation, the light source may be a high-pressure mercury lamp or an ultraviolet lamp. High-pressure mercury lamps, metal halide lamps, UV-LEDs, low-pressure mercury lamps, xenon excimer lamps Lamps and the like can be used. From a productivity standpoint, maximum irradiation is performed at wavelengths of 150-420 nm. It is preferable to use a light source that indicates intensity. Furthermore, the cumulative irradiation dose of ultraviolet light should be 50 to 3000. mJ / cm 2 Preferably, 100-2000 mJ / cm² 2 This is preferable.

[0076] The active energy rays may be irradiated in an air atmosphere, or in an inert gas such as nitrogen or argon. It may be irradiated in a humid atmosphere.

[0077] The duration for irradiating with active energy rays is preferable in relation to the appearance and strength of the cured product. The duration is in the range of 1 minute or less, more preferably 30 seconds or less, and even more preferably 15 seconds or less. There is no specific lower limit, but for example, it is 0.1 seconds. Hardening is achieved by irradiating with active energy rays. This method allows for curing in a shorter time than the heat curing method, thus improving productivity and cost This is a favorable configuration considering the strike.

[0078] If this resin composition contains a diluent, before irradiating this resin composition with active energy rays, The resin composition may be subjected to heat treatment to remove the diluent. This heat treatment is performed near This can be done by irradiation with an infrared lamp, circulation of warm air, etc.

[0079] Furthermore, the resin composition may be subjected to heat treatment after being irradiated with active energy rays. The heat treatment can be carried out by irradiation with a near-infrared lamp, circulation of hot air, etc. The cured product obtained by heating after curing by irradiation with ion energy rays has an increased condensation reaction rate. Because the heat treatment process results in a higher temperature compared to materials that have not undergone heat treatment, the resulting materials tend to have superior hardness and durability.

[0080] The cured product described above is a cured product of a resin composition containing copolymer (A). Therefore, it exhibits excellent adhesion to resin components and inorganic coating layers.

[0081] This cured product is suitable as a primer layer to improve the adhesion between the inorganic coating layer and the resin substrate. It can be used appropriately.

[0082] [Laminated structure] A laminate according to one aspect of the present invention (hereinafter also referred to as "this laminate") comprises a base material and the composition A primer layer consisting of a cured product and an inorganic coating layer provided on the primer layer (hereinafter, It also has a "top coat layer."

[0083] <Base material> The base materials include polymethyl methacrylate resin, polycarbonate resin, and polyester resin. Fat, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, Polyurethane resin, polyvinyl resin, triacetylcellulose, polymethacrylimide resin Examples include resin substrates such as lipids and polyallyl diglycol carbonate resin. Considering that the laminate will be used for various components, the resin to be used should have transparency and mechanical strength. From the perspective of degree, polycarbonate resin, polyester resin, triacetylcellulose, Polyurethane resin or polyvinyl resin is preferred, and polycarbonate resin or polyester is also acceptable. Resin is preferred. In addition to the resin, the resin substrate may contain an ultraviolet absorber, a light stabilizer, a plasticizer, and an antistatic agent. Contains additives such as agents, flame retardants, reinforcing materials, fillers, colorants, lubricants, foaming agents, lubrication agents, and curing catalysts. You can stay like that. If necessary, an adhesive layer, anti-fogging layer, and anti-reflective layer may be applied to the side of the substrate opposite to the side where the cured material layer is located. It is also possible to have functional layers such as those mentioned above.

[0084] <Top coat layer> The top coat layer of this laminate is an inorganic coating layer, and is produced by vacuum deposition, sputtering, It may also be formed by so-called dry coating methods such as chemical vapor deposition, where the solution is applied and then cured. It may be formed by the so-called wet coat method. In the case of the dry coat method, conventionally known methods It is possible to use the method. For example, organosilicon compounds, titanium dioxide, titanium and lanthanum Examples of coatings include composite oxides of zinc, zinc oxide, zirconium oxide, and magnesium fluoride. In the case of the wet method, conventionally known thermosetting, room-temperature curing, moisture curing, or activated energy curing methods are used. It is possible to use coating materials such as wire-hardening type. From the standpoint of productivity and handling, It is preferable to use the wet method, for example, silazane film, polysiloxane film, mesoporous Examples include silica films. When using inorganic coating materials by the wet method, the quality of the cured film is 40%. From the perspective of curability and hardness, alkoxysilane or its hydrolysis condensate should account for % or more of the total composition. Therefore, it is preferable.

[0085] The laminate of the present invention comprises a primer layer disposed on the surface of a resin substrate, and the surface of the said layer Because it has a top coat layer arranged on the surface, these layers act as a protective layer for the resin substrate. Deterioration can be effectively prevented. The laminate of the present invention is suitable for window glass and sensing members (millimeter-wave radar - Suitable for use as a material for vehicle components such as the surface of components through which electromagnetic waves (LiDAR, etc.) pass. It can be used. The vehicle component of the present invention comprises the laminate of the present invention. As a vehicle component, Automobile vehicles, industrial vehicles, personal vehicles, self-propelled vehicle bodies, interior and exterior components and exterior panels for railways, etc. Examples include resin windows, etc. Exterior components include door moldings, door mirror frames, wheel caps, and spoilers. L-shaped bumper, turn signal lens, pillar garnish, rear finisher, headlights Examples include lamp lens covers for lamps, sensing component covers, and the like.

[0086] Interior components include the instrument panel, console box, meter cover, Door lock bezel, steering wheel, power window switch base, center Examples include the cluster, dashboard, and hood.

[0087] Exterior panels include the front fenders, door panels, roof panel, hood panel, and trunnion. Examples include the lintel and back door panel.

[0088] Examples of resin windows include the sunroof, windshield, side windows, and rear window. Examples include rear quarter glass and rear door quarter glass.

[0089] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Various modifications and improvements that can be made by those skilled in the art can be implemented in various forms without departing from the gist of the present invention.

Examples

[0090] Examples and comparative examples are given below to explain the present invention in more detail. However, the present invention is not limited to these. "Parts" in the description represent "parts by mass". The measurements and evaluations were performed by the following methods.

[0091] [Measurement and Evaluation Methods] [Measurement of Mw] The Mw of the copolymer and the partially hydrolyzed condensate of the silane compound produced in this example was measured by gel permeation chromatography (GPC) under the following conditions. Equipment: "e2695" manufactured by Waters, Column: "TSKgel Super H3000 + H4000 + H6000" manufactured by Tosoh ", Detector: Differential refractive index detector (RI detector / built-in), Solvent: Tetrahydrofuran, Temperature: 40 °C, Flow rate: 0.5 mL / min, Injection volume: 10 μL, Concentration: 0.2 mass%, Calibration sample: Monodisperse polystyrene, Calibration method: Polystyrene conversion.

[0092] [Appearance] The appearance of the paint and the coating film was evaluated visually for the presence or absence of abnormalities such as precipitation, whitening, separation, and peeling. .

[0093] [Adhesion] The adhesion of the laminate was evaluated by cellophane tape peeling. Specifically, at 23 °C and 50% RH Under environmental conditions, a cutter knife was used to make a grid pattern on the surface of the evaluation sample at 1 mm intervals, reaching the substrate. Insert the net, 1mm 2 Make 100 squares, press cellophane tape with your fingers, and quickly It was peeled off at a 45° angle forward. The area of ​​the peeled hardened layer (peeling area) was visually confirmed. The adhesion properties were assessed. The criteria for evaluating adhesion are as follows: A: Number of peeled-off squares is 0 B: Number of peeled-off squares is between 1 and 20 C: Number of peeled-off squares is between 21 and 60 D: Number of peeled-off squares: 61-100

[0094] <Durability (wet resistance)> For the cured film of the evaluation sample, a wet testing machine (device name: wet testing machine, model CT-3H, Using a test machine (manufactured by Suga Test Instruments Co., Ltd.), under conditions of a chamber temperature of 50°C and a chamber humidity of 99%RH or higher, 1 A 00-hour durability test (moisture resistance test) was conducted. After durability testing, the above-mentioned appearance and adhesion properties were evaluated.

[0095] <Abbreviation> The meanings of the abbreviations used below are as follows: SMA: Stearyl methacrylate (Mitsubishi Chemical's Acryester S) EHMA: 2-Ethylhexyl methacrylate (manufactured by Mitsubishi Chemical Corporation) Acryester EH ) KBM-503: "KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd. (3-(trimethoxysilicone) (Propyl methacrylate) HPA: 2-Hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) HEMA: 2-Hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation) Acryester H O) MBP: 4-Methacryloylbenzophenone (Shinryo MBP) HHMPMA:2-[4'-(2-hydroxy-2-methylpropanoyl)phenoxy Ethyl methacrylate (manufactured by Mitsubishi Chemical) AOI: 2-Isocyanatoethyl acrylate (manufactured by Showa Denko) nDM: Dodecyl mercaptan KBM-803:3-mercaptopropyltrimethoxysilane MMA: Methyl methacrylate (Mitsubishi Chemical Corporation, Acryester M) AMBN: 2,2'-Azobis(2-methylbutyronitrile) (Manufactured by Otsuka Chemical Co., Ltd.) ) DBTDL: Dibutyltin dilaurate KBM-5103: "KBM-5103" (3-acryloxy) manufactured by Shin-Etsu Chemical Co., Ltd. Propyltrimethoxysilane, 100% non-volatile component. FM-0721: JNC Corporation's "Sylaplane FM-0721" (with metal at one end) Polydimethylsiloxane containing a crylyl group, Mw4200, 100% non-volatile components. MS51: "MS51" manufactured by Mitsubishi Chemical Corporation (tetramethoxysilane partial hydrolysis condensate) Mw800~1100, Non-volatile content (100% non-volatile components) Photoacid generator: "CPI-200K" (p-phenylthiophenyl) manufactured by Sunapro Co., Ltd. Diphenylsulfonium hexafluorophosphate, non-volatile components (50%). PGM: Propylene glycol monomethyl ether. Perocta-O: Manufactured by NOF Corporation, "Perocta-O" (2-ethylhexanoperoxy acid 1) ,1,3,3-tetramethylbutyl). BYK-356: "BYK-356" (Polyacrylic) manufactured by Big Chemie Japan Co., Ltd. (Rate-based surface conditioning agent)

[0096] [Method for preparing polymers] Preparation method for partially hydrolyzed condensates of copolymers and silane compounds used in the examples and comparative examples. Let me explain the law. Note that copolymers (A-1) to (A-7) fall under copolymer (A). Therefore, comparative copolymers (B-1) to (B-4) do not correspond to copolymer (A). It is a comparable product.

[0097] <Synthesis Example 1: Method for preparing copolymer (A-1)> In a flask equipped with a stirrer, condenser, and thermometer, methyl isobutyl ketone (hereinafter, M 69.7 parts of IBK were added and stirring was started. Next, the flask was purged with nitrogen and 80 Heat to °C, then add 20.0 parts by mass of SMA, 40 parts by mass of EHMA, and 20 parts by mass of KBM-503. Parts of 100 parts by mass of HPA, 0.3 parts by mass of nDM as a chain transfer agent, and AM as a polymerization initiator. A mixed solution of 0.75 parts by mass of BN and 29.9 parts by mass of MIBK was added dropwise over 3 hours. Every 30 minutes after the end of the dropping process, 0.25 parts by mass of AMBN and MIB are added to increase the polymerization rate. The process of adding a mixture of 1.0 parts by mass of K was repeated three times and held for 1.5 hours. After that, the internal temperature was turned up. The temperature is raised to 105°C, held for 2 hours, then 50.8 parts by mass of MIBK are added, and 40 It was cooled to below °C. In this way, a MIBK solution (A-1) of the copolymer was obtained. Below, The solid content in liquid (A-1) is called copolymer (A-1). The solid content (non-volatile content) of solution (A-1) was 40% by mass. Also, copolymer (A-1 The weight-average molecular weight (Mw) of ) was 118,000.

[0098] <Synthesis Example 2: Method for preparing copolymer (A-6)> In a flask equipped with a stirrer, condenser, and thermometer, methyl isobutyl ketone (hereinafter, M 69.4 parts of IBK were added and stirring was started. Next, the flask was purged with nitrogen and 80 Heat to °C, then add 20.0 parts by mass of SMA, 30.0 parts by mass of EHMA, and 30 parts by mass of KBM-503. 0.0 parts by mass, 20.0 parts by mass of HEMA, 0.60 parts by mass of AMBN as a polymerization initiator, and A mixed solution of 29.7 parts by mass of MIBK was added dropwise over 3 hours. Every 30 minutes after the end of the dropwise addition... To increase the polymerization rate, a mixture of 0.25 parts by mass of AMBN and 1.0 part by mass of MIBK was added. The process of adding the contents was repeated three times and held for 1.5 hours. After that, the temperature was raised until the internal temperature reached 105°C. After holding for 2 hours, a mass portion of MIBK82.0 was added and cooled to below 40°C. Next, while continuing to stir, a gas consisting of air and nitrogen in a volume ratio of 1:4 is flowed, and p- Methoxyphenol 0.030 parts by mass, DBTDL 0.061 parts by mass, AOI 21 Add 0.7 parts by mass and 2.6 parts by mass of MIBK3, and raise the internal temperature to 80°C while monitoring for heat generation. The temperature was increased, the reaction was carried out for 8 hours, and the isocyanate group (2270 cm) was measured using FT-IR. -1 ) After confirming that the mark had disappeared, the device was cooled to below 40°C. In this way, a MIBK solution (A-6) of the copolymer was obtained. Below, the solids in solution (A-6) The form is called a copolymer (A-6). The solid content (non-volatile content) of solution (A-6) was 40% by mass. Also, copolymer (A-1 The weight-average molecular weight (Mw) of ) was 49,600.

[0099] <Synthesis examples 3 to 10: Copolymers (A-2) to (A-5), (A-7), comparative copolymers (B -1) to (B-3) adjustment method > Copolymer (A-2) was synthesized in the same manner as in Synthesis Example 1, except that the monomers were changed to those listed in Table 1 or 2. (A-7) and comparative copolymers (B-1) to (B-3) were obtained. The weight-average molecular weight (Mw) of copolymer (A-2) was 40,100. The weight-average molecular weight (Mw) of copolymer (A-3) was 49,300. The weight-average molecular weight (Mw) of copolymer (A-4) was 44,100. The weight-average molecular weight (Mw) of copolymer (A-5) was 40,400. The weight-average molecular weight (Mw) of copolymer (A-7) was 18,200. The weight-average molecular weight (Mw) of copolymer (B-1) was 48,900. The weight-average molecular weight (Mw) of copolymer (B-2) was 16,500. The weight-average molecular weight (Mw) of copolymer (B-3) was 18,800.

[0100] [Table 1]

[0101] [Table 2]

[0102] <Adjustment of primer resin components> Dipentaerythritol hexaacrylate (DPHA) is a modified form of caprolactone (Japanese A resin made by mixing 22 parts of "DPCA-20" (manufactured by Honka Pharmaceutical Co., Ltd.) and 16 parts of urethane acrylate. The mixture contains 0.9 parts of benzophenone as a photopolymerization initiator and tinuvin 40 as an ultraviolet absorber. 3 parts of 0 (BASF), and 0.15 parts of Chinuvin 123 (BASF) as a light stabilizer. A portion was added to prepare an active energy ray-curable primer resin component. Furthermore, the urethane acrylate was prepared as follows. Flask equipped with a dropper funnel with heat retention function, reflux condenser, stirring blade, and temperature sensor. Inside, 530g (2mol) of dicyclohexylmethane diisocyanate, dilaurate 300 ppm of n-butyltin was charged and heated to 40°C. Afterward, the polyol compound was prepared. Polycarbonate diol (product name: Kuraray Polyol C-770, manufactured by Kuraray Co., Ltd.) 800g (weight-average molecular weight 800) and 650g (1 mol) were added dropwise over 4 hours. 40 After stirring at °C for 2 hours, the temperature was raised to 70°C over 1 hour. Then, 2-hydroxy Add 232g (2mol) of ethyl acrylate (HEA) dropwise over 2 hours, and then for another 2 hours... The mixture was stirred to obtain urethane acrylate. The resulting product had a non-volatile content of 75%. It was a polymer with a molecular weight of 1500.

[0103] <Adjusting Top Coat 1> 308g of methyl silicate oligomer MS51 (manufactured by Mitsubishi Chemical Corporation) It contains 624g of alcohol, 65g of water, and 3g of aluminum(III) acetylacetone, and is suitable for use in rooms. The mixture was stirred at warm temperature for 3 days to obtain a colorless, transparent, and uniform liquid topcoat 1.

[0104] <Adjusting Top Coat 2> 1000 mL five-neck separator with stirrer, dropping funnel, cooling condenser, and thermometer In a Bull flask, add 73.0g of KBM-5103, 41.7g of FM-0721, and PGM. 264.9g of and 0.52g of Perocta O were added. Also, KBM- 5103: 73.0g, FM-0721: 20.9g, PGM: 225.3g, per octane 0.52g of TA-O was added. Next, the flask was placed in the oil bath under a nitrogen atmosphere. Stirring was started below, and the temperature was raised until the internal temperature reached 85°C. After the internal temperature reached 85°C, 30 After minutes, the monomer mixture is added dropwise from the dropping funnel over 2 hours and held for 1 hour, then per octa Add 0.21g of O, and one hour later add another 0.21g of perocta O, 5 The reaction was carried out over time and then cooled. The resulting product consisted of 30% non-volatile components and a weight-average molecular weight ( The polymer had a Mw of 16,200. The obtained composition and topcoat 1 were calculated on a solids basis. Mixing them in a 5:5 ratio yielded Top Coat 2.

[0105] [Example 1] <Preparation of Primer Composition> Mix 0.5 parts of copolymer (A-1) with 100 parts of the primer resin composition described above. A primer composition was prepared by diluting it with PGM so that the non-volatile components amounted to 30% by mass.

[0106] <Creation of evaluation samples> 3mm thick polycarbonate resin sheet (PC sheet) (Mitsubishi Engineering Plastics) (Manufactured by S Company, product name: "IUPILON ML-300"), with a cured thickness of 10 μm. The curing composition is spray-painted in such a manner, and then dried in a hot air dryer preheated to 70°C for 12 minutes. The coating was heated for 0 seconds to dry (the solvent evaporated). Then, the dried coating was subjected to an air atmosphere. In an open atmosphere, using a high-pressure mercury lamp (I-Graphic, USX5-0902), 2000m J / cm 2 (The cumulative irradiation dose at wavelengths of 340-380 nm was measured using a UV-351 ultraviolet light meter.) (Measured using a device manufactured by Oak Manufacturing Co.) The coating film is hardened by irradiating it with ultraviolet light, and then plastic is placed on the PC board. An imer layer was formed.

[0107] Next, spray coat Topcoat 1 so that the thickness after curing is 0.7 μm. The coating is then dried (the solvent is evaporated) by heating it for 120 seconds in a hot air dryer preheated to 60°C. Next, the dried coating film was subjected to a high-pressure mercury lamp (made by iGraphic) in an air atmosphere. Using USX5-0902, 1000 mJ / cm² 2 (At wavelengths of 340-380 nm) The cumulative irradiation dose is measured using an ultraviolet light meter UV-351 (manufactured by Oak Manufacturing Co., Ltd.). The coating film is cured by irradiation, and a laminate is obtained in which a topcoat layer is laminated on top of a primer layer. Ta.

[0108] <Rating> The obtained evaluation samples were assessed based on their initial appearance and adhesion (before durability testing), and durability testing. The subsequent appearance and adhesion were evaluated.

[0109] [Examples 2-7, Comparative Examples 1-5] The procedure was the same as in Example 1, except that the type and amount (in parts) of the primer layer were as shown in Table 3. Evaluation samples were then prepared. The evaluation results of the evaluation samples are shown in Table 3. However, the comparative example is... In case 4, the ingredients separated, so no evaluation was performed.

[0110] [Examples 8-17, Comparative Examples 6-9] The type and amount (parts) of the primer layer are as shown in Table 4, and the topcoat layer is topcoat An evaluation sample was prepared in the same manner as in Example 1, except that part 2 was used. The evaluation results are shown in Table 4.

[0111] [Table 3]

[0112] [Table 4]

[0113] As shown in Tables 3-4, the laminates of Examples 1-17 exhibited good appearance both initially and after durability testing. It had excellent adhesion. On the other hand, since the cured film of Comparative Example 1 used a copolymer that does not contain monomer (X), the copolymer It did not segregate on the surface and exhibited low adhesion. The cured film of Comparative Example 2 used a copolymer that did not contain monomer (Y), therefore in the primer layer The material lacked adhesion-enhancing components, resulting in low adhesion. The cured film of Comparative Example 3 had poor compatibility because it used a copolymer with an excess of monomer (X) and the formulation It separated. The cured film in Comparative Example 4 had low adhesion because monomer (Y) was used alone. Comparative Example 5 did not contain copolymer (A), and therefore exhibited low adhesion. Since the cured film of Comparative Example 6 used a copolymer that did not contain monomer (X), the copolymer formed on the surface. It did not segregate and exhibited low adhesion. The cured film of Comparative Example 7 used a copolymer that did not contain monomer (Y), therefore in the primer layer The material lacked adhesion-enhancing components, resulting in low adhesion. The cured film in Comparative Example 8 had low adhesion because monomer (Y) was used alone. Comparative Example 9 did not contain copolymer (A), and therefore exhibited low adhesion.

Claims

1. A curable composition comprising a monomer (X) having one or more selected from the group consisting of alkyl groups having 4 or more carbon atoms, fluorine atoms, and polydimethylsiloxane chains; a monomer (Y) having a functional group represented by the following chemical formula (1); and a monomer (Z) having at least one crosslinkable functional group selected from aromatic ketone groups or (meth)acryloyl groups, wherein the proportion of monomer (X) in the constituent components of copolymer (A) is 10% by mass or more and 70% by mass or less, and the proportion of monomer (Z) is 25% by mass or more and 80% by mass or less. -R １ -M(R ２ ) ｒ (OR ３ ) ｍ－ｒ ・・・(1) (However, M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta, and R １ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ２ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group. R ３ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, an acyl group or hydrogen. m represents an integer of 3 to 4 corresponding to M, r represents an integer of 0 to 3. When r is 2 or more, r R ２ may be different from each other. When m - r is 2 or more, (m - r) R ３ may be different from each other.)

2. The curable composition according to claim 1, comprising a monomer (Z) having at least one crosslinkable functional group selected from aromatic ketone groups in the copolymer (A).

3. The curable composition according to any one of claims 1 to 2, wherein the (X) component contained in the copolymer (A) is an alkyl group having 6 or more carbon atoms.

4. The curable composition according to any one of claims 1 to 3, wherein the (Z) component contained in the copolymer (A) is 4-(meth)acryloyloxybenzophenone, 4-(meth)acryloyloxyethoxybenzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, 4-(meth)acryloyloxyethoxy-4'-methoxybenzophenone, 4-(meth)acryloyloxy-4'-bromobenzophenone, 4-(meth)acryloyloxyethoxy-4'-bromobenzophenone, 2-[4'-(2-hydroxy-2-methylpropanoyl)phenoxy]ethyl methacrylate, or 4-methacryloylbenzophenone.

5. The curable composition according to any one of claims 1 to 4, wherein the proportion of component (X) contained in the copolymer (A) is in the range of 10 to 65% by mass, component (Y) is in the range of 10 to 60% by mass, and component (Z) is in the range of 25 to 80% by mass.

6. A cured film product of a curable composition according to any one of claims 1 to 5.

7. A method for producing a cured product, comprising curing the curable composition according to any one of claims 1 to 5 by irradiating or heating the curable composition with an active energy ray.

8. A laminate comprising a base material, a primer layer provided on the base material, and a topcoat layer provided on the primer layer, wherein the primer layer contains a copolymer (A) having monomer (X) having one or more selected from the group consisting of alkyl groups having 4 or more carbon atoms, fluorine atoms, and polydimethylsiloxane chains, monomer (Y) having a functional group represented by the following chemical formula (1), and monomer (Z) having at least one crosslinkable functional group selected from aromatic ketone groups or (meth)acryloyl groups, wherein the proportion of monomer (X) in the constituent components of copolymer (A) is 10% by mass or more and 70% by mass or less, and the proportion of monomer (Z) is 25% by mass or more and 80% by mass or less, and the topcoat layer is an inorganic coating layer. -R １ -M(R ２ ) ｒ (OR ３ ) ｍ－ｒ ・・・(1) (However, M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta, and R １ R represents a hydrocarbon group with 1 to 5 carbon atoms. ２ R represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group. ３ R represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, an acyl group, or hydrogen; m represents an integer from 3 to 4 corresponding to M; r represents an integer from 0 to 3; if r is 2 or more, r numbers of R ２ The R values ​​may be different from each other, and if m-r is 2 or more, there are (m-r) R values. ３ They may be different from each other.

9. The laminate according to claim 8, wherein the inorganic coating layer comprises 40% by mass or more of a compound consisting of an alkoxysilane or a hydrolysis condensate thereof.

Images