JP2023140772A - Composition, cured product, laminate, and method for manufacturing cured product - Google Patents

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

The present invention relates to a composition, a cured product, a laminate, and a method for producing a cured product.

Resin materials such as polycarbonate have a lower specific gravity and are lighter than inorganic glass, are easy to process, and are resistant to impact, and are used as materials for a wide variety of components, including vehicle components. On the other hand, resin materials have drawbacks such as the surface being easily damaged and losing gloss and transparency, being easily attacked by organic solvents, and having poor weather resistance (for example, photostability against ultraviolet light) and heat resistance. Automobile window glass and the like are often exposed to sunlight for long periods of time. Therefore, when a resin material is used for an automobile member, it is necessary to provide the resin material with wear resistance and weather resistance, such as by coating the surface with a protective layer.
Coating agents mainly made from inorganic raw materials have a skeleton of silicon oxide or the like and can provide coating films with good weather resistance and scratch resistance. On the other hand, there have been problems with cracks occurring due to temperature changes and poor adhesion to organic materials such as painted surfaces and resin substrates.

A conventional technique for applying an inorganic coating agent to a resin material is a laminate including a resin base material, an intermediate layer disposed on the surface of the resin base material, and a silicon oxide layer disposed on the surface of the intermediate layer. The body is known. Patent Document 1 discloses that the intermediate layer is obtained by curing a composition containing a Si-free compound containing a (meth)acrylic group and a siloxane compound containing a (meth)acrylic group, and It has been proposed that the adhesion is improved by making the Si concentration on the silicon oxide layer side higher than on the resin base material side.

JP 2019-18449 Publication

The intermediate layer described in Patent Document 1 achieves both adhesion to the resin base material and adhesion to the outermost inorganic layer by containing a siloxane compound in the intermediate layer. However, according to the studies of the present inventors, when a siloxane compound is used alone, the surface orientation is insufficient and a large amount of the siloxane compound must be added, and the performance of the intermediate layer itself is insufficient. There is.

The present invention provides a curable composition for improving the adhesion of inorganic coating materials to resin substrates, appearance,
The object of the present invention is to provide a cured product with excellent adhesion and durability, a method for producing the same, and a laminate having a cured product layer with excellent appearance, adhesion, and durability.

The present invention has the following aspects.
[1] A monomer (X) having one or more types 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 having a functional group represented by the following chemical formula (1). A curable composition comprising a copolymer (A) having a polymer (Y).
-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, R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. represents an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or an aryl group, and 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 according to M, r represents an integer of 0 to 3, and when r is 2 or more, r R ² may be different from each other, and m−r is 2. In the above case, (m−r) R ³ may be different from each other.)
[2] The copolymer (A) contains an aromatic ketone group, a vinyl ether group, an epoxy group, and (
The curable composition according to [1], which contains a monomer (Z) having at least one type of crosslinkable functional group selected from a meth)acryloyl group, a hydroxyl group, and an isocyanate group.
[3] Component (X) contained in the copolymer (A) is an alkyl group having 4 or more carbon atoms [1
] to [2].
[4] The curable composition according to any one of [1] to [3], wherein the component (Z) contained in the copolymer (A) is an aromatic ketone group or a (meth)acryloyl group. .
[5] The proportion of component (X) contained in the copolymer (A) is in the range of 10 to 70% by mass, component (Y) in the range of 10 to 90% by mass, and component (Z) in the range of 0 to 80% by mass. The curable composition according to any one of [1] to [4].
[6] A cured film of the curable composition according to any one of [1] to [5].
[7] A method for producing a cured product, comprising curing the curable composition according to any one of [1] to [5] by irradiating or heating the curable composition with active energy rays.
[8] having a base material, a primer layer provided on the base material, and a top coat layer provided on the primer layer, an alkyl group having 4 or more carbon atoms in the primer layer, A monomer (X) having one or more types selected from the group consisting of fluorine atoms and silicon atoms, and
Contains a copolymer (A) containing a monomer (Y) having a functional group represented by the following chemical formula (1),
A laminate, wherein the top coat layer is an inorganic coat 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, R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. Alkyl group, carbon number 2
~5 alkenyl group or 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, or an acyl group, or hydrogen, and m corresponds to M. represents an integer from 3 to 4, r represents an integer from 0 to 3, when r is 2 or more, r R ² may be different from each other, and when m−r is 2 or more, (m− r) R ³ may be different from each other. )
[9] The laminate according to [8], wherein the inorganic coat layer contains 40% by mass or more of a compound consisting of an alkoxysilane or a hydrolyzed condensate thereof.

According to the present invention, a curable composition that can form a cured product with excellent appearance, adhesion, and durability;
It is possible to provide a cured product with excellent appearance, adhesion and durability, a method for producing the same, and a laminate having a cured product layer with excellent appearance, adhesion and durability.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist thereof. isn't it.
Note that when the expression "~" is used in this specification, it is used as an expression that includes numerical values or physical property values before and after it. Furthermore, in the present invention, when the expression "(meth)acrylic" is used, it means one or both of "acrylic" and "methacrylic". The same applies to "(meth)acrylate", "(meth)acryloyl", etc.

[Composition]
The curable composition according to one embodiment of the present invention (hereinafter also referred to as "the present composition") has one or more types selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. It contains a copolymer (A) containing a monomer (X) and a monomer (Y) having a functional group represented by the following chemical formula (1).
The composition may further contain a resin component, if necessary.
The composition may further contain an ultraviolet absorber and a light stabilizer, if necessary.
The composition may further contain a diluent, if necessary.
The present composition may further contain other components other than those mentioned above, as necessary, to the extent that the effects of the present invention are not impaired.

<Copolymer A>
The copolymer (A) has a unit based on the monomer (X), a unit based on the monomer (Y), and further has a unit based on the monomer (Z) and the monomer (V). You may.

<Monomer X>
Monomer (X) is a compound having one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom, and a radically polymerizable group.
Monomer (X) is a monomer with low surface tension, and if copolymer (A) has units based on monomer (X), the coating film of the curable polymer composition can be formed. When formed, the copolymer (A) tends to segregate on the surface side of the coating film. If the copolymer (A) having a functional group reactive with the inorganic coat layer is segregated on the surface side of the coating film, the number of reactive sites with the overlying inorganic coat layer will increase, and the adhesion will increase. In addition, since functional groups can be efficiently segregated on the surface side, the amount of addition can be suppressed, especially for compounds that are poorly compatible with components in the curable polymer, and furthermore, loss of physical properties of the entire composition can be suppressed.

Examples of the monomer (X) include compounds having one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, or a silicon atom, and a radically polymerizable group.

The alkyl group having 4 or more carbon atoms may be linear, branched, or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregation of the copolymer (A) on the surface of the coating film, the alkyl group is preferably linear.
The number of carbon atoms in the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, from the viewpoint of more effectively segregation of the copolymer (A) on the surface of the coating film. More preferably, the number is in the range of 12 to 18.

A monomer having an alkyl group having 4 or more carbon atoms has an alkyl group having 4 or more carbon atoms, from the viewpoint of ease of compound synthesis and ease of adjusting the amount of the alkyl group having 4 or more carbon atoms. (Meth)acrylic acid alkyl esters are preferred.
Examples of monomers having an alkyl group having 4 or more carbon atoms include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl. (meth)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, isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentanyl Examples include (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and the like.
Among these, it is preferable to include a (meth)acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms. The (meth)acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms is preferably one in which the number of carbon atoms in the alkyl group is within the above-mentioned preferred range, and considering ease of production, etc. - Ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (
Meth)acrylate is more preferred, and stearyl (meth)acrylate is particularly preferred.
These (meth)acrylic esters may be used alone or in combination of two or more.

Examples of the monomer having a fluorine atom include a monomer having a fluoroalkyl group. Specific examples of the fluoroalkyl group include perfluoroalkyl groups. The number of carbon atoms in the perfluoroalkyl group is preferably 4 or more.
Examples of the monomer having a silicon atom include a monomer having a polydimethylsiloxane chain. A specific example is a polydimethylsiloxane substituted with a (meth)acryloyl group at one end and having a molecular weight of 500 to 50,000. The molecular weight is 1000 to 30,00
0 is preferred, and 1500 to 20,000 is more preferred.

The monomer (X) is preferably a monomer having an alkyl group having 4 or more carbon atoms from the viewpoint of wettability and adhesion of the inorganic coat layer.

<Monomer Y>
Monomer (Y) has a group represented by the following formula (1) (hereinafter also referred to as "group (1)"). When the group (1) is introduced into the copolymer (A) by the monomer (Y), the group (1) in the copolymer (A) reacts with the functional group component contained in the inorganic coat. , adhesion and durability are improved.
-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, R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. Alkyl group, carbon number 2~
5 alkenyl group or aryl group, R ³ is an alkyl group having 1 to 5 carbon atoms, or 2 carbon atoms.
~5 alkenyl group, aryl group, or acyl group or hydrogen, m is 3 according to M
represents an integer of ~4, r represents an integer of 0 ~ 3, when r is 2 or more, r R ² may be different from each other, and when m−r is 2 or more, ) R ³ may be different from each other.
In formula (1), M is Al (aluminum), Fe (iron), In (indium),
Ge (germanium), Hf (hafnium), Si (silicon), Ti (titanium), Sn (
(tin), Zr (zirconium), Ta (tantalum), but Al, Si, Ti, or Zr is preferable from the viewpoint of reactivity and availability, and Si is preferable because it is cheap and easy to use. is particularly preferred.

Examples of the aryl group for R ² and R ³ include a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, alkenyl group, and aryl group of R ² and R ³ may each have a substituent. Examples of the substituent include halogen atoms such as chlorine atoms, alkoxy groups such as methoxy groups and ethoxy groups.
Examples of the acyl group for R ³ include (meth)acrylic group, acetyl group, acetimidoyl group, aldehyde group, thioacetyl group, propionyl group, benzenesulfonyl group, and benzoyl group.

OR ³ is an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group,
It can be subdivided into ketoximate group and hydroxy group. Among these, alkoxy groups, alkenyloxy groups, acyloxy groups, and hydroxy groups are preferred because of their high reactivity; Particularly preferred are groups.

When M in formula (1) is Si, examples of the group (1) (also called a hydrolyzable silyl group) include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a dimethoxymethylsilyl group. group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, tris(2-propenyloxy)silyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (
ethoxymethyl)dimethoxysilyl group.
Among the above, trimethoxysilyl group, triethoxysilyl group, and dimethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group is more preferred, from the viewpoint of being versatile, having high activity, and providing good curability. From the viewpoint of storage stability, dimethoxymethylsilyl group and triethoxysilyl group are preferred. From the viewpoint of particularly high curability, (chloromethyl)dimethoxysilyl group and (methoxymethyl)dimethoxysilyl group are preferred. Trifunctional silyl groups such as trimethoxysilyl group and triethoxysilyl group are preferred in that the restorability of the cured product tends to be high.

Examples of the monomer (Y) include compounds having the group (1) and a polymerizable functional group or a reactive group capable of addition (polymer reaction) to a polymer.
Examples of the polymerizable functional group include those mentioned above, and preferred embodiments are also the same.
Examples of the reactive group include a vinyl group, (meth)acryloyl group, (meth)acrylamide group, epoxy group, cyclic epoxy group, mercapto group, amino group, diamino group, acid anhydride group, isocyanate group, etc. .
The group (1) and the polymerizable functional group or reactive group may be bonded via a linking group. Examples of the linking group include hydrocarbon groups such as alkylene groups having 1 to 6 carbon atoms.

Examples of the monomer (Y) include vinyltrimethoxysilane, vinyltriethoxylane, vinyl tris(β-methoxyethoxy)silane, (meth)acrylic acid (3-trimethoxysilyl)propyl, and (meth)acrylic acid. (3-dimethoxymethylsilyl)propyl acid,
(meth)acrylic acid (2-trimethoxysilyl)ethyl, (meth)acrylic acid (2-dimethoxymethylsilyl)ethyl, (meth)acrylic acid trimethoxysilylmethyl, (meth)
Vinyl silane compounds such as (dimethoxymethylsilyl)methyl acrylate, γ-aminopropyltrimethoxylane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-amino Amino silane compounds such as propylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxylane, γ-glycidoxypropyl Epoxy-based silane compounds such as methyldiethoxysilane, γ-
Mercapto-based silane compounds such as mercaptopropyltrimethoxysilane, N-phenyl-
Examples include silane coupling agents such as phenylamino silane compounds such as γ-aminopropyltrimethoxysilane. These silane coupling agents are commercially available,
Preferable from the viewpoint of handling.
However, the monomer (Y) is not limited to these. For example, a titanate-based, aluminate-based, or zirconate-based coupling agent having a polymerizable functional group that can be copolymerized with other monomers or a reactive group other than the group (1) that can be added to a polymer may be used. good.
Monomer (Y) may be used alone or in combination of two or more.

When copolymerizing monomer (X) and monomer (Y), the better the copolymerizability of monomer (X) and monomer (Y), the more unreacted monomer can be reduced. This tends to improve the adhesion and durability of the cured product of the resin composition. From this viewpoint, when the polymerizable functional group of the monomer (X) is a (meth)acryloyl group, the monomer (Y) is particularly preferably a vinyl-based silane compound having a (meth)acryloyl group.

<Monomer Z>
Copolymer (A) contains, in addition to monomer (X) and monomer (Y), as long as the performance is not impaired.
It may contain a monomer (Z) having at least one functional group selected from a (meth)acryloyl group, an aromatic ketone group, an epoxy group, a vinyl ether group, a hydroxyl group, and an isocyanate group. In this case, the copolymer (A) has at least one functional group selected from the group consisting of (meth)acryloyl group, aromatic ketone group, epoxy group, vinyl ether group, hydroxyl group, and isocyanate group. When using active energy rays to cure this composition, copolymer (
When A) contains a (meth)acryloyl group, an aromatic ketone group, an epoxy group, or a vinyl ether group, stronger bonds can be formed in the cured film. When the present composition uses heat for curing, the copolymer (A) containing a hydroxyl group or an isocyanate group can form stronger bonds in the cured film.

As a method for introducing a structural unit derived from the monomer (Z) into the copolymer (A), for example, a method for introducing a structural unit derived from the monomer (Z) is to use a copolymer having a polymerizable functional group copolymerizable with the monomer (X) and the monomer (Y). Examples include a method of copolymerizing monomer (Z), monomer (X), and monomer (Y).

Examples of monomers having an aromatic ketone group include 4-(meth)acryloyloxybenzophenone, 4-(meth)acryloyloxyethoxybenzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, and 4-(meth)acryloyloxybenzophenone. ) Acryloyloxyethoxy-4'-methoxybenzophenone, 4-(meth)acryloyloxy-4'-bromobenzophenone, 4-(meth)acryloyloxyethoxy-4'-bromobenzophenone, 2-[4'-(2-hydroxy) -2-methylpropanoyl)phenoxy]ethyl methacrylate.

Examples of the monomer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

Examples of the monomer having a vinyl ether group include 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. These may be used alone or in combination of two or more.

Among the above, it is preferable to use an aromatic ketone group from the viewpoint of surface curability due to ultraviolet energy. Among them, it is particularly preferable to use 4-(meth)acryloyloxybenzophenone.

Further, when the active energy ray used for curing the present composition is ultraviolet rays, a (meth)acryloyl group may be introduced into the side chain of the copolymer (A).
Examples of methods for introducing a (meth)acryloyl group into the copolymer (A) include a method in which an acrylic polymer having an epoxy group is reacted with a compound having a double bond and a carboxyl group (method 1); A method of reacting an acrylic polymer with a compound having a double bond and an epoxy group (Method 2), a method of reacting an acrylic polymer having a hydroxyl group with a compound having a double bond and a carboxyl group (Method 3), A method of reacting an acrylic polymer having a carboxyl group with a compound having a double bond and a hydroxyl group (method 4), a method of reacting an acrylic polymer having an isocyanate group with a compound having a double bond and a hydroxyl group (method 5) ), a method (method 6) in which an acrylic polymer having a hydroxyl group is reacted with a compound having a double bond and an isocyanate group. Moreover, the above methods may be used in combination.

In method 1, the monomer having an epoxy group used to obtain the acrylic polymer having an epoxy group includes, for example, glycidyl (meth)acrylate, 3,4-
Examples include epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and the like. Among these, glycidyl (meth)acrylate is particularly preferred in view of good reactivity and ease of use of the material. These may be used alone or in combination of two or more.
In addition, examples of the compound having a double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerin di(meth)acrylate and succinic anhydride, and pentaerythritol trifluoride. Examples include adducts of (meth)acrylate and succinic anhydride, and adducts of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid, an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, and (meth)acrylic acid is particularly preferred. In addition, only one type of compound having a double bond and a carboxyl group may be used, or two or more types may be used in combination.

In method 2, the monomer having a carboxyl group used to obtain the acrylic polymer having a carboxyl group includes, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, polybasic acid-modified (meth) ) acrylate, etc. Among these, (meth)acrylic acid is preferred. These may be used alone or in combination of two or more.
In Method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and the like. Among these, glycidyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.

In method 3, the monomer having a hydroxyl group used to obtain the acrylic polymer having a hydroxyl group includes, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl ( Examples include meth)acrylate. These may be used alone or in combination of two or more.
Furthermore, in Method 3, the same compound as in Method 1 can be used as the compound having a double bond and a carboxyl group.

In method 4, the acrylic polymer having a carboxyl group is
Something similar to can be used.
In addition, in method 4, the compound having a double bond and a hydroxyl group is, for example, 2
-Hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.

In method 5, the isocyanate group-containing monomer used to obtain the isocyanate group-containing acrylic polymer is, for example, isocyanate ethyl (meth)
Examples include acrylate.
Further, in the method 5, as the compound having a double bond and a hydroxyl group, for example, compounds similar to those listed in the method 4 can be used.

In Method 6, the same compound as in Method 3 can be used as the acrylic polymer having a hydroxyl group.
In addition, in the method 6, the compound having a double bond and an isocyanate group is:
For example, isocyanate ethyl (meth)acrylate and the like. These may be used alone or in combination of two or more.

Among the above methods, method 6 is preferred from the viewpoint of improving the storage stability of the copolymer (A) and the curable composition. In Method 6, a double bond is introduced by reacting an acrylic polymer having a hydroxyl group with a compound having a double bond and an isocyanate group.

In method 6, the compound having a double bond and an isocyanate group is preferably added in an amount of 10 to 150 mol%, and 30 to 130 mol%, based on the hydroxyl group in the acrylic polymer.
It is more preferable to add mol%, and even more preferably 50 to 110 mol%. Use within this range is preferable from the viewpoint of allowing the reaction to proceed in just the right amount and reducing the amount of residue of the raw material.

<Other monomer V>
Other monomers (V) may be used as long as they are copolymerizable with monomers (X), monomers (Y), and monomers (Z), such as compounds having the above-mentioned polymerizable functional groups. (However, monomer (X
), excluding monomer (Y) and monomer (Z). ).
Specific examples of other monomers (V) include the following.
Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-aminoethyl (meth)acrylate, ethylene oxide adduct of (meth)acrylate (meth)acrylic acid monomers such as;
(meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, Nn-propyl (meth)acrylamide , N-isopropyl (meth)acrylamide, N-dimethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, N-(meth)acryloylpiperidine, (meth)acryloylmorpholine, etc. (meth)acrylamide monomer;
Styrenic monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, chloromethylstyrene, styrene sulfonic acid and its salts;
Maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid;
Maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;
Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;
Vinyl monomers containing amide groups such as acrylamide and methacrylamide;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate;
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 alone or in combination of two or more.

When copolymerizing monomers (X), monomers (Y), and monomers (Z) with other monomers (V), the better the copolymerizability of each monomer, the more unreacted The amount of monomer can be reduced, and the appearance and durability of the cured product of the present composition tend to improve. From this point of view, when the polymerizable functional group possessed by monomer (X), monomer (Y), and monomer (Z) is a (meth)acryloyl group, monomer (Z) is a styrene-based At least one consisting of a monomer and a (meth)acrylic acid monomer
Species are preferred, and (meth)acrylic acid monomers are particularly preferred.

<Ratio of each structural unit in copolymer (A)>
The proportion of monomer (X) in the constituent components of copolymer (A) is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, and 25 to 70% by mass. It is more preferably 25 to 65% by weight, particularly preferably 30 to 60% by weight. If the proportion of the monomer (X) is more than the lower limit, when a coating film of the curable polymer composition is formed, the copolymer (A) tends to segregate on the surface side of the coating film, and the upper limit value If it is below, the compatibility with the curable polymer composition will improve and the appearance will be good.

The proportion of the monomer (Y) in the constituent components of the copolymer (A) is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, even more preferably 10 to 70% by mass,
Particularly preferably from 10 to 60% by weight, most preferably from 10 to 50% by weight. If the ratio of the structural unit (Y) is more than the lower limit, the reactivity with the inorganic coating layer will improve, so the adhesion will be improved, and if it is less than the upper limit, the ratio of the monomer (X) and the monomer (Z ) can be made sufficiently high, so segregation to the surface side and crosslinking with the resin component of the composition progresses, improving adhesion.

The proportion of the monomer (Z) in the constituent components of the copolymer (A) is preferably 0 to 80% by mass, more preferably 0 to 50% by mass, and 0 to 40% by mass. It is more preferably 5 to 40% by weight, most preferably 10 to 40% by weight. If the ratio of monomer (Z) is above the lower limit, the reactivity with the resin component in the composition will improve, and the adhesion will be improved; if it is below the upper limit, monomer (X) and monomer Since the proportion of polymer (Z) can be made sufficiently high, surface segregation properties and reactivity with the inorganic coating layer are improved.

The proportion of monomer (V) in the constituent components of copolymer (A) is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and 0 to 30% by mass. It is more preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight. If the proportion of monomer (V) is above the lower limit value, the compatibility during polymerization will improve, and if it is below the upper limit value, the composition ratio of other monomers will improve, and the surface segregation property and the resin in the composition will be improved. The reactivity with the components and the inorganic coating layer is improved.

<Mw of copolymer (A)>
The Mw of the copolymer (A) is preferably 1000 to 400,000, 3000 to 200,
000 is more preferable, and 5000 to 150,000 is particularly preferable. Another 8000~1
20,000 is more preferred. If the Mw of the copolymer (A) is more than the above lower limit, the copolymer (A) will be firmly fixed in the cured product, so the adhesion will tend to improve; For example, since the compatibility with other components in the present resin composition is improved, the appearance of the cured product tends to be improved.
The Mw of the copolymer (A) can be determined by gel permeation chromatography (GPC) described below.
This is a standard polystyrene equivalent value measured by

<Method for producing copolymer (A)>
Copolymer (A) can be obtained, for example, by polymerizing monomer components containing monomer (X) and monomer (Y). Monomer components include monomer (Z) and monomer (V) as necessary.
and any one or more of other monomers may be further included.
Moreover, polymerization is typically performed in the presence of a radical polymerization initiator. During polymerization, a chain transfer agent may be used in combination, if necessary. Examples of the polymerization method include known methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization, among which solution polymerization is preferred because it is easy to operate and has high productivity.

<Content of copolymer (A)>
The content of the copolymer (A) is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, and 0.01 to 10% by mass based on 100% by mass of the cured product of the present composition. %, particularly preferably 0.05 to 10% by weight, most preferably 0.05 to 5% by weight.
If the content of the copolymer (A) is more than the lower limit, the adhesion will improve, and if it is less than the upper limit,
The appearance and strength of the cured product are better.

<Resin component>
Examples of the resin component in the present composition include acrylic resin, polyester resin, urethane resin, vinyl resin, and the like. Among these, acrylic resins or urethane resins are particularly preferred from the viewpoint of improving adhesion. These resin components may be used alone or in combination of two or more. Furthermore, the resin component is preferably a curable composition that cures a monomer or oligomer on a substrate.

Examples of the curable layer include active energy ray curable and thermosetting layers. If a curable composition is applied to a resin base material and then cured by heat, there is a risk that the resin base material will be deformed by heat, but if it is cured by active energy rays, the deformation of the resin base material due to heat will be prevented. Since it can be suppressed, it can also be applied to resin base materials with low heat resistance. Furthermore, in general, curing using active energy rays takes a shorter curing time than other curing methods such as heat curing and moisture curing, and can be expected to improve productivity.

When the copolymer (A) contains at least one selected from an aromatic ketone group, a vinyl ether group, an epoxy group, or a (meth)acryloyl group as a monomer (Z), active energy rays are used to cure the composition. This allows a stronger bond to be formed in the cured film.
In the case of the active energy ray curable resin component, it is possible to use conventionally known active energy ray curable compounds. Any compound having a radically polymerizable group can be used, and various known compounds can be used, such as (meth)acrylate and other monomers copolymerizable with (meth)acrylate.
Examples of compounds having a radically polymerizable group include monofunctional compounds, bifunctional compounds, and polyfunctional compounds having a radically polymerizable group of trifunctionality or more. It is more preferred to use polyfunctional compounds in order to obtain an enhanced primer layer.

Although trifunctional or higher functional (meth)acrylates are not particularly limited,
For example, pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, etc. (Meth)acrylates having an isocyanurate skeleton such as (meth)acrylates having a skeleton derived from methylolpropane, ditrimethylolpropane tetraacrylate, and bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate; Multifunctional acrylates such as pentaerythritol triacrylate adducts and dipentaerythritol pentaacrylate adducts to succinic anhydride; polyester oligomers having acryloyl groups at side chains or side chains and terminals (specifically, M80 manufactured by Toagosei Co., Ltd.);
Polyester (meth)acrylates such as 30, M7100, etc.; isocyanurate derivatives of isophorone diisocyanate (IPDI), reaction products of polytetramethylene glycol (PTMG) and hydroxyethyl acrylate (HEA), and PTMG reaction with hexamethylene diisocyanate (HDI). Polyfunctional urethane (meth)acrylates, such as reaction products of pentaerythritol triacrylate to products; Polyester (meth)acrylates having carbonate bonds, such as reaction products of oligoesters using polycarbonate diol and pentaerythritol triacrylate; Diisocyanates and 3 A reactant of a polyol with more than a functional level,
Polyurethane (meth)acrylates such as reactants of hydroxyl group-containing (meth)acrylates; triethoxy(meth)acrylates having an isocyanurate ring such as triethoxyisocyanuric triacrylate; alkylene oxide modified products of these; polycaprolactone modified products of these, etc. can be mentioned.
Among these, from the viewpoint of viscosity, curability, and hardness of cured film, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, It is preferable to include acrylate, dipentaerythritol triacrylate; alkylene oxide modified products thereof; and caprolactone modified products thereof from the viewpoint of curability and coating hardness.
One type of (meth)acrylate may be used, or two or more types may be used in combination.

Examples of difunctional polyfunctional (meth)acrylates include, but are not limited to, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc.
Acrylate, alkanediol di(meth)acrylate such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethyloldi(meth)acrylate, bisphenol A ethylene oxide Modified di(meth)acrylate, bisphenol-modified di(meth)acrylate such as bisphenol F ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate Examples include (meth)acrylates, alkylene oxide-modified products of these; and polycaprolactone-modified products of these.

Examples of the monofunctional compound include monofunctional (meth)acrylate, (meth)acrylic acid, and the like. Monofunctional (meth)acrylates include, but are not particularly limited to, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. ) acrylate,
Alkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (
hydroxyalkyl(meth)acrylate, hydroxybutyl(meth)acrylate, etc.
Alkoxyalkyl (meth)acrylates such as meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. ) acrylate and other aromatic (meth)acrylates, diaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and other amino group-containing (
Ethylene oxide-modified (meth)acrylates such as meth)acrylate, methoxyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenylphenol ethylene oxide-modified (meth)acrylate, glycidyl (
Examples include meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like.

When the copolymer (A) contains at least one selected from hydroxyl groups and isocyanate groups as the monomer (Z), stronger bonds are formed in the cured film by using heat curing to cure the composition. be able to.
In the case of the thermosetting resin component, conventionally known thermosetting compounds can be used.
For example, heat curing using various polyols and various polyisocyanates can be mentioned.

Examples of the polyol include conventionally known polyols, including polymers such as polycarbonate polyols, polyester polyols, acrylic polyols, polyurethane polyols, polyolefin polyols, polyether polyols, and polyvinyl alcohol, as well as polymers with terminal ends such as dendrimers and hyperbranched polymers. Polymers with a dendritic branched structure consisting of hydroxyl groups, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8
-Octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, trimethylolethane, trimethylolpropane, glycerol , polyhydric alcohols such as polycaprolactone triol, erythritol, pentaerythritol, polycaprolactone tetraol, and diglycerin.
Among these, polymer-type polyols or polyols with a branched structure are preferred because they have a high crosslink density and are excellent in curability and durability.Among them, polyols that form a highly branched structure and can effectively increase the crosslink density Dendrimers and hyperbranched polymers are more preferred from the viewpoint of improved durability. Note that these polyols may be used alone or in combination.

Examples of the polyisocyanate include conventionally known ones, such as aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, α, α, α', α '-Aliphatic diisocyanates with aromatic rings such as tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, Examples include alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isopropylidene dicyclohexyl diisocyanate. Also included are trifunctional or higher functional polyisocyanates such as burettes, trimethylolpropane adducts, isocyanurates, and allophanates synthesized using these bifunctional polyisocyanates as starting materials. These may be used alone or in combination.
Among these, it is preferable to include a trifunctional or higher functional polyisocyanate, and isocyanurates are more preferable because they have a high crosslinking density and are excellent in curability and durability. In addition, from the viewpoint of durability of the cured layer, those having an aromatic ring structure or an alicyclic structure are preferable.
From the viewpoint of resistance to yellowing, it is preferable to have an aliphatic structure or an alicyclic structure.

<Ultraviolet absorber, light stabilizer>
This composition contains an ultraviolet absorber or a light stabilizer, so that the coating film itself is protected against ultraviolet rays, etc.
This is a preferred form because it suppresses deterioration of the resin base material that forms the base of the coating film and improves weather resistance and durability.

Examples of the ultraviolet absorber include organic ultraviolet absorbers and inorganic ultraviolet absorbers, and organic ultraviolet absorbers are preferred from the viewpoint of transparency. Examples of organic ultraviolet absorbers include, but are not limited to, hydroxyphenyltriazine-based, benzotriazole-based, cyclic iminoester-based, benzophenone-based, salicylic acid ester-based, cyanoacrylate-based, and the like. Among these, from the viewpoint of weather resistance and durability, hydroxyphenyltriazine, benzotriazole, and cyclic iminoester are more preferred, and hydroxyphenyltriazine is even more preferred. Moreover, one type of ultraviolet absorber may be used alone or two or more types may be used in combination. Furthermore, it is also possible to use these compounds incorporated into polymers.

Hydroxyphenyltriazine-based ultraviolet absorbers include, but are not limited to, 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-triazine (Tinuvin® 400 manufactured by BASF), 2
-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]
-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), 2-(2
,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3
, 5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product (Tin
uvin (registered trademark) 405, manufactured by BASF), 2,4-bis “2-hydroxy-4-butoxyphenyl”-6-(2,4-dibutoxyphenyl)-1,3-5-triazine (T
inuvin (registered trademark) 460, manufactured by BASF), 2-(4,6-diphenyl-1,3
,5-triazin-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]-phenol (ADK STAB LA46, manufactured by ADEKA), 2-(2-hydroxy-4
-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (Tinuvin (registered trademark) 479, manufactured by BASF) and the like.

Examples of benzotriazole-based ultraviolet absorbers include, but are not limited to, 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H
-Benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzo Triazole, 2-[2'-hydroxy-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole,
2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert
-Butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-
Chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl) ) phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy -
Examples include 5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole.

Cyclic iminoester ultraviolet absorbers include, but are not limited to, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4- one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1-
or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)
-3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2
-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4 -one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, N-phenyl-4-(3, 1-Benzoxazin-4-one-2-yl)phthalimide, N-benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline,
N-benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)
Aniline, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazin-4-one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2' -ethylenebis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis(3
, 1-benzoxazin-4-one), 2,2'-decamethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4
-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2
,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one),2
,2'-(2,6- or 1,5-naphthylene)bis(3,1-benzoxazine-4-
), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-
4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-chloro-p-phenylene)bis(3 , 1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one), 1,3,5-tri(3,1- Benzoxazin-4-one-2-
yl)benzene, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)
Naphthalene, 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d ') screw (1
,3)-oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2
-d;4,5-d') bis(1,3)-oxazine-4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2-d;5,4-d') Bis(1,3)-oxazine-
4,6-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-benzoxazin-4-one), 6,6'-bis(2-ethyl-4H,3,1-
benzoxazin-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-methylenebis(2-methyl-4H,3,1- benzoxazin-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-ethylenebis(2-methyl-4H,3,1 -benzoxazin-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-butylenebis(2-methyl-4H,3, 1-benzoxazin-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-
benzoxazin-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-oxybis(2-phenyl-4H,3,1- benzoxazin-4-one), 6,6'-sulfonylbis(2-methyl-4H,3,1-
benzoxazin-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,
1-benzoxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,3
, 1-benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H
, 3,1-benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H
, 3,1-benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4-one),
H,3,1-benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,
1-benzoxazin-4-one), 7,7'-ethylenebis(2-methyl-4H,3,
1-benzoxazin-4-one), 7,7'-oxybis(2-methyl-4H,3,1
-benzoxazin-4-one), 7,7'-sulfonylbis(2-methyl-4H,3,
1-benzoxazin-4-one), 7,7'-carbonylbis(2-methyl-4H,3
, 1-benzoxazin-4-one), 6,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-phenyl-4H,3 , 1-benzoxazin-4-one, 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-methylenebis(2-phenyl-4H,3, 1-benzoxazin-4-one) and the like.

Examples of benzophenone ultraviolet absorbers (benzophenone compounds) and oxybenzophenone ultraviolet absorbers (oxybenzophenone compounds) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4
-Methoxybenzophenone-5-sulfonic acid (anhydride and trihydrate), 2-hydroxy-4-
Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone,
4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone (trade name "KEMISORB111", manufactured by Chemipro Kasei Co., Ltd.)
, 2,2',4,4'-tetrahydroxybenzophenone (trade name: SEESORB10
6'', manufactured by Cipro Kasei Co., Ltd.), 2,2'-dihydroxy-4,4-dimethoxybenzophenone, and the like.

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

Examples of cyanoacrylate ultraviolet absorbers (cyanoacrylate compounds) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, and alkynyl-2-cyanoacrylate. - Examples include cyanoacrylate.

Examples of the light stabilizer include, but are not limited to, amine light stabilizers, phenol light stabilizers, phosphorus light stabilizers, thioether light stabilizers, etc. Among these, amine light stabilizers, Phenol-based light stabilizers and phosphorus-based light stabilizers are preferred, and amine-based light stabilizers are particularly preferred in view of less yellowing. These light stabilizers may be used alone or in combination of two or more. It is also possible to use these compounds incorporated into polymers.

Examples of amine light stabilizers include dimethyl succinate and 4-hydroxy-2,2
, 6,6-tetramethyl-1-piperidine ethanol polymer (Tinuvin (registered trademark) 622, manufactured by BASF), dimethyl succinate and 4-hydroxy-2,2,6,6
- Tetramethyl-1-piperidine ethanol polymer and N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6 -tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,
1:1 reaction product with 10-diamine (Tinuvin® 119, BASF
), dibutylamine/1,3-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6 ,6-
Polycondensate of tetramethyl-4-piperidyl)butylamine (Tinuvin®
2020, manufactured by BASF), poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazin-2-4-diyl}{2,2,6,6- Tetramethyl-4-piperidyl}imino]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-
Mixture of pentamethyl-4-piperidyl sebacate (Tinuvin® 765
, manufactured by BASF), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin (registered trademark) 770, manufactured by BASF), bis(2,2,6,
6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (Tinuvin®)
123, manufactured by BASF), bis(1,2,2,6,6-pentamethyl-4-piperidyl)
[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate (Tinuvin® 144, manufactured by BASF), cyclohexane and N-butyl peroxide 2,2, 6,6-tetramethyl-4-piperidinamine-2,4,
The reaction product of 6-trichloro1,3,5-triazine and 2-aminoethanol (Tinuvin (registered trademark) 152, manufactured by BASF), bis(1,2,2,6,6
Pentamethyl-4-piperidyl) sebacate and a mixture of methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (Tinuvin® 292, BAS
F), 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl) )-2,4,8,10-tetraoxaspiro[5.5]undecane mixed ester (ADK STAB LA63P, manufactured by ADEKA). Among these amine light stabilizers, hindered amine stabilizers are particularly preferred because of their excellent performance.

Examples of phenolic light stabilizers include 2,6-di-tertiary-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tertiary-butylphenol, and 2,6-di-tertiary-butylphenol. butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl-3-(4-hydroxy-3,5-di-tertiary-butylphenyl)propionate, distearyl-(4-hydroxy-3-methyl- 5-tertiary butyl) benzyl malonate, tocopherol, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2
, 2'-methylenebis (4-ethyl-6-tertiary butylphenol), 4,4'-methylenebis (2,6-di-tertiary butylphenol), 4,4'-butylidenebis (6-tertiary butylphenol),
butyl-m-cresol), 4,4'-thiobis(6-tert-butyl-m-cresol), styrenated phenol, N,N'-hexamethylenebis(3,5-di-tert-butyl) -4-hydroxyhydrocinnamide, bis(3,5-di-tertiary-butyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris(2-methyl-4
-Hydroxy-5-tertiary butylphenyl)butane, 1,3,5-trimethyl-2,4,
6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]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-methylcyclohexyl)-p-cresol], 1,3,5-tris(4-tert-butyl-3-hydroxy-2,
6-dimethylbenzyl)isocyanuric acid, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, triethylene glycol-bis[3-(
3-tertiary 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] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) ) propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis{2-[3-(3,5-di-th) tertiary butyl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl}-2,
Examples include 4,8,10-tetraoxaspiro[5.5]undecane.

Examples of phosphorus light stabilizers include trisnonylphenyl phosphite, tris(2,
4-di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-(3-
Tertiary-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol di Phosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di- tertiary-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tertiary-butylphenyl) pentaerythritol diphosphite, tetra(tridecyl)isopropylidene diphenol diphosphite, Tetra(tridecyl)-4,4'-n-butylidenebis(2-tertiary butyl-
5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(
2-Methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Tris(
2-[(2,4,8,10-tetrakis-tertiary butyldibenzo[d,f][1,3,2
]dioxaphosphepin-6-yl)oxy]ethyl)amine, and the like.

Examples of thioether light stabilizers include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl; β-alkylmercaptopropionic acids of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane; Examples include ester compounds.

Regarding the total content of the ultraviolet absorber and the light stabilizer, for example, the total content of the cured film of the composition is preferably 30% by mass or less, more preferably 0.01 to 20% by mass, and even more preferably 0. The range is from .1 to 15% by weight, particularly preferably from 0.3 to 15% by weight. By using it within the above range, it is possible to improve the weather resistance of the base material and members while maintaining other properties, and it is possible to prevent deterioration.

<Diluent>
The present composition can contain a diluent if necessary. Examples of the diluent include water, organic solvents, and the like.
Examples of the organic solvent include alcohol solvents, glycol solvents, hydrocarbon solvents, ester solvents, ketone solvents, and ether solvents. Examples of alcoholic solvents include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, octanol, n-propyl alcohol, and acetylacetone alcohol. Glycol 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, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl Examples include ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. Examples of the hydrocarbon solvent include benzene, kerosene, toluene, xylene, and the like. Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and the like. Examples of the ether solvent include ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan, and tetrahydrofuran. The organic solvents may be used alone or in combination of two or more.

<Other ingredients>
This composition includes other components such as a leveling agent, a silane coupling agent, an antifoaming agent, a thickener, an antistatic agent, an infrared absorber, a foaming agent, an inorganic fine particle, an organic fine particle, a dye, a pigment,
It may contain an antioxidant, an anti-yellowing agent, a bluing agent, an antifogging agent, an antisettling agent, and the like.
The content of other components is not particularly limited, but for example, 0 to 100% by mass based on 100% by mass of the cured product.
It can be about 30% by mass. However, it is preferred that the proportions of other components be low so as not to impair the performance of the composition.

[Cured product]
The cured product according to one embodiment of the present invention (hereinafter also referred to as "main cured product") is a cured product of the present composition.
The cured product is obtained by curing the composition.
Examples of curing methods include irradiating the composition with active energy rays, curing by heating, and curing using moisture in the air. , a method of irradiating the present composition with active energy rays is preferred.

Examples of active energy rays include ultraviolet rays and electron beams. Ultraviolet light is preferred because it is easily available and has excellent polymerizability.
When curing the resin composition by ultraviolet irradiation, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a UV-LED, a low pressure mercury lamp, a xenon excimer lamp, etc. can be used as the light source. From the viewpoint of productivity, it is preferable to use a light source that exhibits maximum irradiation intensity at a wavelength of 150 to 420 nm. In addition, the cumulative irradiation amount of ultraviolet rays is 50 to 3000
mJ/cm ² is preferable, and 100 to 2000 mJ/cm ² is more preferable.

The active energy rays may be irradiated in an air atmosphere or in an inert gas atmosphere such as nitrogen or argon.

The time for irradiating the active energy rays is preferably 1 minute or less, more preferably 30 seconds or less, and still more preferably 15 seconds or less, in view of the appearance and strength of the cured product.
Although there is no particular lower limit, it is, for example, 0.1 second. The method of curing by irradiating active energy rays is a preferable method in consideration of productivity and cost, since it can be cured in a shorter time than the method of thermosetting.

When the present resin composition contains a diluent, before irradiating the present resin composition with active energy rays,
In order to remove the diluent, the resin composition may be subjected to heat treatment. This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.

Furthermore, heat treatment may be performed after irradiating the resin composition with active energy rays. This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like. A cured product obtained by heat treatment after curing by irradiation with active energy rays has a higher condensation reaction rate than one without heat treatment, and thus tends to have excellent hardness and durability.

Since the cured product described above is a cured product of a resin composition containing the copolymer (A), it has excellent adhesion to the resin member and the inorganic coat layer.

This cured product can be suitably used as a primer layer for improving the adhesion between the inorganic coat layer and the resin base material.

[Laminated body]
A laminate according to one embodiment of the present invention (hereinafter also referred to as "this laminate") includes a base material, a primer layer made of a cured product of the present composition, and an inorganic coat layer provided on the primer layer. (below,
Also referred to as "top coat layer." ).

<Base material>
As a base material, polymethyl methacrylate resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin,
Examples include resin base materials such as polyurethane resin, polyvinyl resin, triacetylcellulose, polymethacrylimide resin, and polyallyl diglycol carbonate resin. As the resin constituting the resin base material, polycarbonate resin, polyester resin, triacetyl cellulose, polyurethane resin, or polyvinyl resin is preferable from the viewpoint of transparency and mechanical strength, considering that the laminate is used for various members. , polycarbonate resin or polyester resin are preferred. In addition to resin, the resin base material contains additives such as ultraviolet absorbers, light stabilizers, plasticizers, antistatic agents, flame retardants, reinforcing materials, fillers, colorants, lubricants, foaming agents, lubricants, curing catalysts, etc. It may also contain an agent.
If necessary, it is also possible to provide a functional layer such as an adhesive layer, an anti-fog layer, an anti-reflection layer, etc. on the side of the base material opposite to the side where the cured product layer is present.

<Top coat layer>
The top coat layer of this laminate is an inorganic coat layer, which can be formed by vacuum evaporation method, sputtering method,
It may be formed by a so-called dry coating method such as a chemical vapor deposition method, or it may be formed by a so-called wet coating method in which a solution is applied and then cured. In the case of the dry coating method, conventionally known methods can be used. Examples include coatings of organosilicon compounds, titanium oxide, composite oxides of titanium and lanthanum, zinc oxide, zirconium oxide, and magnesium fluoride. In the case of the wet method, it is possible to use a conventionally known coating material such as a thermosetting type, a room temperature curing type, a moisture curing type, or an active energy ray curing type. From the viewpoint of productivity and handling, it is preferable to use a wet method, and examples thereof include a silazane film, a polysiloxane film, a mesoporous silica film, and the like. When using an inorganic coating material formed by a wet method, it is preferable from the viewpoint of curability and hardness that alkoxysilane or a hydrolyzed condensate thereof accounts for 40% by mass or more of the cured film.

Since the laminate of the present invention has a primer layer disposed on the surface of the resin base material and a top coat layer disposed on the surface of the primer layer, these layers serve as a protective layer and prevent deterioration of the resin base material. can be suitably prevented. The laminate of the present invention can be suitably used as a material for vehicle members such as window glass and surfaces of members through which electromagnetic waves such as sensing members (millimeter wave radar, LiDAR, etc.) pass. The vehicle member of the present invention includes the laminate of the present invention. Examples of vehicle components include interior and exterior components, outer panels, and resin windows for automobiles, industrial vehicles, personal vehicles, self-propelled vehicle bodies, railroads, and the like.
Exterior members include door moldings, frame frames of door mirrors, wheel caps, spoilers, bumpers, turn signal lenses, pillar garnishes, rear finishers, various lamp lens covers such as headlamps, sensing member covers, and the like.

Interior components include instrument panels, console boxes, meter covers,
Examples include door lock bezels, steering wheels, power window switch bases, center clusters, dashboards, and bonnets.

External panels include front fenders, door panels, roof panels, hood panels, trunk lids, back door panels, and the like.

Plastic windows include sunroofs, windshields, side windows, rear windows,
Examples include rear quarter glass and rear door quarter glass.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. Without departing from the gist of the present invention, the present invention can be implemented in various forms with modifications and improvements that can be made by those skilled in the art.

EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited thereto. "Parts" in the description represent "parts by mass." Measurement and evaluation were performed using the following methods.

[Measurement and evaluation method]
<Measurement of Mw>
The Mw of the partially hydrolyzed condensate of the copolymer and silane compound produced in this example is:
It was measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: Waters “e2695”,
Column: Tosoh “TSKgel Super H3000+H4000+H6000
”,
Detector: differential refractive index detector (RI detector/built-in),
Solvent: tetrahydrofuran,
Temperature: 40℃,
Flow rate: 0.5mL/min,
Injection volume: 10μL,
Concentration: 0.2% by mass,
Calibration sample: monodisperse polystyrene,
Calibration method: Polystyrene conversion.

<Exterior>
The appearance of the paint and coating film was visually evaluated for the presence of abnormalities such as precipitation, whitening, separation, and peeling.

<Adhesion>
The adhesion of the laminate was evaluated by peeling off cellophane tape. Specifically, under an environment of 23°C and 50% RH, cut the surface of the evaluation sample in a grid pattern with a cutter knife at 1 mm intervals to reach the base material, make 100 squares of 1 ^mm square, and then attach cellophane tape to the surface. I crimped it with a button and quickly peeled it off in a 45° diagonal direction. The area of the peeled cured layer (peeled area) was visually confirmed to evaluate the adhesion. The evaluation criteria for adhesion are as follows.
A: The number of peeled squares is 0.
B: The number of peeled squares is 1 to 20.
C: Number of peeled squares is 21 to 60
D: Number of peeled squares is 61 to 100

<Durability (wet resistance)>
The cured film of the evaluation sample was tested using a wet tester (equipment name: wet tester, model CT-3H,
(manufactured by Suga Test Instruments Co., Ltd.) under conditions of an internal temperature of 50°C and an internal humidity of 99% RH or higher.
A 00 hour durability test (wet resistance test) was conducted.
After the durability test, the above appearance and adhesion were evaluated.

<Abbreviation>
The meanings of the abbreviations used below are as follows.
SMA: Stearyl methacrylate (Mitsubishi Chemical Acryester S)
EHMA: 2-ethylhexyl methacrylate (acryester EH manufactured by Mitsubishi Chemical)
)
KBM-503: Shin-Etsu Chemical Co., Ltd. "KBM-503" (3-(trimethoxysilyl)propyl methacrylate)
HPA: 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry)
HEMA: 2-Hydroxyethyl methacrylate (Mitsubishi Chemical Acryester H
O)
MBP: 4-methacryloylbenzophenone (MBP manufactured by Shinryo)
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 (Acryester M manufactured by Mitsubishi Chemical)
AMBN: 2,2'-azobis(2-methylbutyronitrile) (manufactured by Otsuka Chemical AMBN)
)
DBTDL: Dibutyltin dilaurate KBM-5103: "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd. (3-acryloxypropyltrimethoxysilane, 100% nonvolatile components).
FM-0721: "Siraplane FM-0721" manufactured by JNC Corporation (polydimethylsiloxane having a methacryloyl group at one end, Mw 4200, non-volatile components 100%).
MS51: "MS51" manufactured by Mitsubishi Chemical Corporation (tetramethoxysilane partial hydrolysis condensate, Mw 800-1100, non-volatile component 100%)
Photoacid generator: "CPI-200K" manufactured by San-Apro Co., Ltd. (p-phenylthiophenyldiphenylsulfonium hexafluorophosphate, non-volatile component: 50%).
PGM: Propylene glycol monomethyl ether.
Perocta O: "Perocta O" manufactured by NOF Corporation (2-ethylhexane peroxy acid 1
, 1,3,3-tetramethylbutyl).
BYK-356: "BYK-356" manufactured by BYK Chemie Japan Co., Ltd. (polyacrylate surface conditioner)

[Polymer preparation method]
A method for preparing a partially hydrolyzed condensate of a copolymer and a silane compound used in Examples and Comparative Examples will be described. Copolymers (A-1) to (A-7) correspond to copolymer (A), and comparative copolymers (B-1) to (B-4) correspond to copolymer (A). This is a comparative product that does not fall under Polymer (A).

<Synthesis Example 1: Method for preparing copolymer (A-1)>
Methyl isobutyl ketone (hereinafter referred to as M
69.7 parts of IBK) were added and stirring was started. Next, the inside of the flask was replaced with nitrogen and
The temperature was raised to ℃, and 20.0 parts by mass of SMA, 40 parts by mass of EHMA, 20 parts by mass of KBM-503, 20 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, add 0.25 parts by mass of AMBN and MIB to increase the polymerization rate.
The operation of adding a mixed solution of 1.0 parts by mass of K was performed three times, and the mixture was maintained for 1.5 hours. After that, the temperature was raised until the internal temperature reached 105°C, and after holding for 2 hours, 50.8 parts by mass of MIBK was added, and 40.
Cooled to below ℃. In this way, a copolymer MIBK solution (A-1) was obtained. Hereinafter, the solid content in solution (A-1) will be referred to as copolymer (A-1).
The solid content (nonvolatile content) of solution (A-1) was 40% by mass. In addition, copolymer (A-1
) had a weight average molecular weight (Mw) of 118,000.

<Synthesis Example 2: Method for preparing copolymer (A-6)>
Methyl isobutyl ketone (hereinafter referred to as M
69.4 parts of IBK) were added and stirring was started. Next, the inside of the flask was replaced with nitrogen and
℃, 20.0 parts by mass of SMA, 30.0 parts by mass of EHMA, 30 parts by mass of KBM-503.
．． A mixed solution of 0 parts by mass, 20.0 parts by mass of HEMA, 0.60 parts by mass of AMBN as a polymerization initiator, and 29.7 parts by mass of MIBK was added dropwise over 3 hours. Every 30 minutes after the completion of dropping, a mixed solution of 0.25 parts by mass of AMBN and 1.0 parts by mass of MIBK was added three times to increase the polymerization rate, and the mixture was maintained for 1.5 hours. Thereafter, the temperature was raised until the internal temperature reached 105°C and held for 2 hours, after which 82.0 parts by mass of MIBK was added and the mixture was cooled to 40°C or lower.
Next, while stirring was continued, a gas consisting of air:nitrogen at a volume ratio of 1:4 was flowed into the p-
0.030 parts by mass of methoxyphenol, 0.061 parts by mass of DBTDL, AOI 21
．． 7 parts by mass and 32.6 parts by mass of MIBK were added, the internal temperature was raised to 80°C while checking for heat generation, and the reaction was carried out for 8 hours, and the peak of the isocyanate group (2270 cm ^-1 ) disappeared in FT-IR After confirming that the temperature was high, the temperature was cooled to below 40°C.
In this way, a copolymer MIBK solution (A-6) was obtained. Hereinafter, the solid content in solution (A-6) will be referred to as copolymer (A-6).
The solid content (nonvolatile content) of solution (A-6) was 40% by mass. In addition, copolymer (A-1
) had a weight average molecular weight (Mw) of 49,600.

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

<Adjustment of primer resin components>
0.9 parts of benzophenone as a photopolymerization initiator was added to a resin mixed with 22 parts of a caprolactone modified product of dipentaerythritol hexaacrylate (DPHA) ("DPCA-20" manufactured by Nippon Kayaku Co., Ltd.) and 16 parts of urethane acrylate. Tinuvin 40 as a UV absorber
3 parts of Tinuvin 123 (manufactured by BASF) as a light stabilizer and 0.15 parts of Tinuvin 123 (manufactured by BASF) as a light stabilizer.
An active energy ray-curable primer resin component was prepared.
The urethane acrylate was prepared as follows.
530 g (2 mol) of dicyclohexylmethane diisocyanate and 300 ppm of di-n-butyltin dilaurate were placed in a flask equipped with a dropping funnel with a heat-retaining function, a reflux condenser, a stirring blade, and a temperature sensor, and the mixture was heated to 40°C. Thereafter, polycarbonate diol (trade name: Kuraray Polyol C-770, manufactured by Kuraray Co., Ltd.) was used as a polyol compound.
650 g (1 mol) of 800 g (weight average molecular weight 800) was added dropwise over 4 hours. 40
After stirring at ℃ for 2 hours, the temperature was raised to 70 ℃ over 1 hour. Thereafter, 232 g (2 mol) of 2-hydroxyethyl acrylate (HEA) was added dropwise over 2 hours, and the mixture was further stirred for 2 hours to obtain urethane acrylate. The obtained product has a non-volatile content of 75%,
It was a polymer with a molecular weight of 1,500.

<Adjustment of top coat 1>
624 g of methanol, 65 g of water, and 3 g of acetylacetonaluminum (III) were blended with 308 g of methyl silicate oligomer MS51 (manufactured by Mitsubishi Chemical Corporation), and the mixture was stirred at room temperature for 3 days to obtain a colorless, transparent, and uniform liquid top coat 1.

<Adjustment of top coat 2>
In a 1000 mL 5-neck separable flask equipped with a stirrer, dropping funnel, cooling condenser, and thermometer, 73.0 g of KBM-5103, 41.7 g of FM-0721, and PGM.
264.9 g of Perocta O and 0.52 g of Perocta O were added. Also, to the dropping funnel, KBM-
73.0 g of 5103, 20.9 g of FM-0721, 225.3 g of PGM, and 0.52 g of Perocta O were added. Next, the flask was set in an oil bath, stirring was started under a nitrogen atmosphere, and the temperature was raised until the internal temperature reached 85°C. 30 minutes after the internal temperature reaches 85℃
After 1 hour, the monomer mixture was added dropwise from the dropping funnel over 2 hours and held for 1 hour, then 0.21 g of Perocta O was added, and 1 hour later, 0.21 g of Perocta O was added.
After reacting for an hour, the mixture was cooled. The obtained product had a non-volatile content of 30% and a weight average molecular weight (
It was a polymer with a Mw) of 16,200. The obtained composition and top coat 1 in terms of solid content
Top coat 2 was obtained by mixing at a ratio of 5:5.

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

<Preparation of evaluation sample>
On top of a 3 mm thick polycarbonate resin plate (PC board) (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: "IUPILON ML-300"), the thickness after curing is 10 μm.
The curable composition was spray-painted so that
The coating film was dried (volatilized the solvent) by heating for 0 seconds. Next, the dried coating film was heated for 2000 m in an air atmosphere using a high-pressure mercury lamp (manufactured by Eye Graphic, USX5-0902).
J/cm ² (The cumulative irradiation amount at wavelengths 340 to 380 nm was measured using an ultraviolet light meter UV-351.
The coating film was cured by irradiation with ultraviolet rays (measured using a PC board manufactured by Oak Seisakusho) to form a primer layer on the PC board.

Next, Top Coat 1 was spray-coated to a thickness of 0.7 μm after curing, and then heated for 120 seconds in a hot air dryer preheated to 60°C to dry the coating (volatize the solvent). I let it happen. Next, the dried coating film was measured in an air atmosphere using a high-pressure mercury lamp (manufactured by Eye Graphic, USX5-0902) to measure the cumulative irradiation amount at 1000 mJ/cm ² (wavelength: 340 to 380 nm) using an ultraviolet light meter UV-351. The coating film was cured by irradiating it with ultraviolet rays (measured using a product manufactured by Oak Seisakusho) to obtain a laminate in which a top coat layer was laminated on the primer layer.

<Evaluation>
The obtained evaluation samples were evaluated for initial appearance and adhesion (before the durability test) and appearance and adhesion after the durability test.

[Examples 2 to 7, Comparative Examples 1 to 5]
Evaluation samples were prepared in the same manner as in Example 1, except that the type and amount (parts) of the primer layer were as shown in Table 3. Table 3 shows the evaluation results of the evaluation samples. However, comparative example
4, the formulation separated and was not evaluated.

[Examples 8 to 17, Comparative Examples 6 to 9]
An evaluation sample was prepared in the same manner as in Example 1, except that the type and amount (parts) of the primer layer were as shown in Table 4, and Top Coat 2 was used for the top coat layer. Table 4 shows the evaluation results of the evaluation samples.

As shown in Tables 3 and 4, the laminates of Examples 1 to 17 had excellent appearance and adhesion both initially and after the durability test.
On the other hand, since the cured film of Comparative Example 1 used a copolymer that did not contain monomer (X), the copolymer did not segregate on the surface and its adhesion was low.
Since the cured film of Comparative Example 2 used a copolymer that did not contain the monomer (Y), no adhesion-imparting component was present in the primer layer, and the adhesion was low.
The cured film of Comparative Example 3 used a copolymer containing an excess of monomer (X), so the compatibility was poor and the mixture separated.
The cured film of Comparative Example 4 had low adhesion because the monomer (Y) was used alone.
Comparative Example 5 did not contain the copolymer (A), so its adhesion was low.
Since the cured film of Comparative Example 6 used a copolymer that did not contain monomer (X), the copolymer did not segregate on the surface and had low adhesion.
Since the cured film of Comparative Example 7 used a copolymer that did not contain the monomer (Y), no adhesion-imparting component was present in the primer layer, and the adhesion was low.
The cured film of Comparative Example 8 had low adhesion because the monomer (Y) was used alone.
Comparative Example 9 did not contain the copolymer (A), so its adhesion was low.

Claims (9)

A monomer (X) having one or more types 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 (X) having a functional group represented by the following chemical formula (1). Y
) A curable composition comprising a copolymer (A) having:
-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, R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. Alkyl group, carbon number 2
~5 alkenyl group or 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, or an acyl group, or hydrogen, and m corresponds to M. represents an integer from 3 to 4, r represents an integer from 0 to 3, when r is 2 or more, r R ² may be different from each other, and when m−r is 2 or more, (m− r) R ³ may be different from each other. ) In the copolymer (A), a monomer (Z ) The curable composition according to claim 1. The curable composition according to claim 1, wherein the component (X) contained in the copolymer (A) is an alkyl group having 4 or more carbon atoms. The curable composition according to any one of claims 1 to 3, wherein the component (Z) contained in the copolymer (A) is an aromatic ketone group or a (meth)acryloyl group. The proportion of component (X) contained in the copolymer (A) is 10 to 70% by mass, and the proportion of component (Y) is 1% by mass.
The curable composition according to any one of claims 1 to 4, wherein the content of the (Z) component is 0 to 90% by mass and 0 to 80% by mass. A cured film of the curable composition according to any one of claims 1 to 5. A method for producing a cured product, comprising curing the curable composition according to any one of claims 1 to 5 by irradiating the curable composition with active energy rays or heating the curable composition. It has a base material, a primer layer provided on the base material, and a top coat layer provided on the primer layer, and the primer layer includes an alkyl group having 4 or more carbon atoms, a fluorine atom, and a copolymer (A) containing a monomer (X) having one or more types selected from the group consisting of silicon atoms and a monomer (Y) having a functional group represented by the following chemical formula (1). , wherein the top coat layer is an inorganic coat 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, R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. Alkyl group, carbon number 2~
5 alkenyl group or aryl group, R ³ is an alkyl group having 1 to 5 carbon atoms, or 2 carbon atoms
~5 alkenyl group, aryl group, or acyl group or hydrogen, m is 3 according to M
represents an integer from 0 to 4, r represents an integer from 0 to 3, when r is 2 or more, r R ² may be different from each other, and when m−r is 2 or more, (m−r ) R ³ may be different from each other. ) The inorganic coat layer contains a compound consisting of an alkoxysilane or a hydrolyzed condensate thereof.
The laminate according to claim 8, which accounts for % or more by mass.