JP2001114841A - Ultravoilet light-absorbing copolymer and thin film comprising the copolymer, and multi-layered laminate containing the thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer which has improved weather resistance without generating coloration and deterioration due to ultraviolet light and gives thin films having excellent bending whitening resistance and excellent solvent resistance, to provide a thin film which has the above characteristics and is used for protecting surfaces by using the copolymer, and further to provide a multilayer laminate. SOLUTION: A copolyme obtained by polymerizing monomer components comprising 3 to 60 wt.% of a reactive silyl group-having monomer and 15 to 70 wt.% of a UV light-absorbing group-having monomer is disclosed. Further, a thin film containing the copolymer as a main component and used for protecting surface is disclosed, and a multilayer laminate in which the copolymer is formed as a protecting layer of the resin substrate is also disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a copolymer which suppresses coloring and deterioration by ultraviolet rays and provides an ultraviolet absorbing thin film having excellent weather resistance, bending whitening resistance and solvent resistance, and a copolymer comprising the same. The present invention relates to an ultraviolet-absorbing thin film containing a main component, and further to an ultraviolet-absorbing multilayer laminate containing the thin film as a lamination component.

[0002]

2. Description of the Related Art Resin members such as resin films, resin sheets, and resin plates, such as polycarbonate, are excellent in transparency, impact resistance, heat resistance, flame retardancy, and the like. It is widely used for such applications, and it is expected that its use will be further expanded in the future. However, these resins generally have insufficient weather resistance, and in particular, have a problem that the surface is deteriorated or colored when exposed to ultraviolet rays.

In order to prevent the ultraviolet rays that degrade the base resin from reaching the surface of the resin member, for example, Japanese Patent Publication Nos. 60-53701, 2-37938, 10-245521 and Kaihei 11-
No. 58654 proposes a method in which an ultraviolet absorber is contained in a surface layer such as a primer layer or a surface hardened layer, and the surface layer absorbs ultraviolet light. Also prevents the solvent resistance etc. of the surface layer from deteriorating due to the contained ultraviolet absorber,
Further, many methods have been proposed for improving the composition of the surface-hardened layer and the primer layer in order to further improve the adhesiveness (for example, Japanese Patent Publication No. 1-7582, Japanese Patent Publication No. 1-32246, Japanese Patent Publication No. 1-18944). , Tokuhei 2-3793
No. 8). By these methods, deterioration of the base resin surface due to ultraviolet rays can be suppressed to some extent.

[0004] However, in order to completely block ultraviolet rays with the surface-hardened layer and the primer layer, it is necessary to add a large amount of an ultraviolet absorber to these layers, so that the surface-hardened layer and the primer layer are not colored or turbid. As a result, when viewed as a whole resin member, the transparency which is a characteristic of the resin is impaired, or further, the ultraviolet absorbent bleeds out to cause a problem such as deterioration of appearance and deterioration of scratch resistance. .

In order to solve such a problem, for example, JP-A-7-26155, JP-A-7-286013, and JP-A-10-265712 disclose a monomer having a reactive silyl group and a UV-absorbing monomer. It has been proposed to use an ultraviolet absorbing copolymer obtained by copolymerizing a monomer having a functional group as a surface protective layer.

However, in these known methods, a large amount of UV-absorbing monomer cannot be copolymerized due to the necessity of securing the properties of the coating film, and the copolymerization amount accounts for all monomers. The ratio is suppressed to about 10% by mass or less.
Therefore, in order to effectively exert a satisfactory ultraviolet ray deterioration preventing action, the thickness of the base material protective layer must be considerably thick, and the mechanical and inherent properties of the base material resin are accordingly accompanied. A problem arises in that optical characteristics are impaired. In addition, when the thickness of the surface protective layer is increased, for example, when the surface protective layer formed on the sheet-shaped base resin is bent, the surface protective layer is whitened or cracked, and the appearance is significantly deteriorated. cause.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve weather resistance without causing problems such as coloring and deterioration due to ultraviolet rays, and to achieve an excellent weather resistance. A UV-absorbing copolymer that can provide a thin-film surface protective layer having bending whitening property and solvent resistance is provided, and an UV-absorbing thin film using the copolymer is further provided. An object of the present invention is to provide a multi-layer laminate including a laminate component.

[0008]

The ultraviolet-absorbing copolymer according to the present invention, which has solved the above-mentioned problems, comprises (1) a monomer having a reactive silyl group: 3 to 60% by mass,
(2) A monomer having an ultraviolet absorbing group: an ultraviolet absorbing copolymer obtained by polymerizing a monomer component containing 15 to 70% by mass.

The copolymer of the present invention may further comprise (3) a monomer having an ultraviolet light-stable group: 0.1
Copolymerization of up to 15% by mass is preferable because it results in a copolymer having excellent ultraviolet stability.

Among the above-mentioned monomers having an ultraviolet absorbing group used in the present invention, particularly preferred are the following formulas:
These are monomers represented by (1) or (2), which can be used alone or in combination of two or more if necessary.

[0011]

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(Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
8 represents a hydrocarbon group, R ² represents a lower alkylene group, R ³ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group, A nitro group or any of R ¹ and X above represents a hydrogen atom)

[0013]

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(Wherein R ⁴ represents a lower alkylene group;
R ⁵ represents a hydrogen atom or a methyl group. ).

As the monomer having an ultraviolet light-stable group, which is used as a copolymerization component, if necessary, monomers represented by the following general formulas (3) and (4) are exemplified as preferred ones, and these may be used alone. In addition to being able to use, it is possible to use 2 or more types together as needed.

[0016]

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(Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, R ⁹ represents a hydrogen atom or a hydrocarbon group,
Y represents an oxygen atom or an imino group. )

[0018]

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(Wherein R ⁶ represents a hydrogen atom or a cyano group, R ⁷ , R ⁸ , R ^{7 ′} and R ^{8 ′} each independently represent a hydrogen atom or a methyl group, and Y represents an oxygen atom or an imino group. Represents a group).

Further, the type of the monomer having a reactive silyl group is not particularly limited, but those having a hydrolyzable silyl group are preferably used in the present invention. 5) to (7). These monomers having a reactive silyl group can be used alone or in combination of two or more if necessary.

[0021]

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(Wherein, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents a hydrocarbon group having 1 to 6 carbon atoms, and a
Represents an integer of 1 to 3, and b represents 0 or 1.)

[0023]

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(Wherein, R ¹² has the same meaning as R ¹¹ or an alkyloxyalkyl group, and c represents 0 or 1)
Represents)

[0025]

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(Wherein, R ¹³ has the same meaning as R ^11, and d represents 0 or 1).

The copolymer of the present invention contains a specific amount of a monomer having a reactive silyl group and a monomer having an ultraviolet-absorbing group, and if necessary, an ultraviolet-stable monomer and the like, together with a copolymerization component. 10 when cured
Even in the case of a thin film with a thickness of about μm or less, it is possible to effectively suppress the deterioration of the base resin by ultraviolet rays (decrease in mechanical properties and transparency, yellowing, etc.), and the base resin is inherently present even after the weather resistance test. This can maintain the mechanical and optical properties of the film, and can provide a thin film having excellent resistance to bending whitening and solvent. Therefore, a multilayer laminate including the thin film as a laminate component is also included in the scope of the present invention. The resin composition in which the resin component containing the copolymer: 3 to 95% by mass is dissolved in the non-aqueous solvent: 5 to 97% by mass is useful as a UV-absorbing film forming material.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have been able to maintain, for example, the excellent transparency and impact resistance inherent to polycarbonate resins and the like, while at the same time lacking weather resistance and ultraviolet light, which have been regarded as problems. As a result of intensive studies to improve deterioration and poor bending whitening resistance, a curable UV-absorbing polymer containing a monomer having a reactive silyl group and a monomer having a UV-absorbing group in a specific ratio as monomer components When a thin film containing is formed on the protective surface side of the resin substrate, the resulting multilayer laminated resin member has excellent resistance to ultraviolet light degradation, resistance to bending whitening, and even solvent resistance, as well as resin resistance. Obtained the knowledge that the excellent mechanical and optical properties originally possessed can be maintained even after the weather resistance test,
The present invention has been accomplished.

Therefore, the characteristics of the copolymer according to the present invention are as follows:
As a monomer component, a monomer having a reactive silyl group and a monomer having an ultraviolet absorbing group are contained at a specific ratio, and by specifying the type of these monomers and the content ratio, the copolymer is used as a main component. Provides excellent mechanical properties (including flexibility and whitening resistance to bending) and chemical properties (including weather resistance, UV degradation resistance, solvent resistance, etc.) and a high level of UV shielding It has succeeded in giving action.

In the present invention, a monomer having a reactive silyl group, which is preferably used as a monomer component of the ultraviolet absorbing copolymer, has a polymerizable double bond and a hydrolyzable silyl group in the molecule. More specifically, at least one kind of the monomers represented by the general formulas (5) to (7) is used alone or in combination of two or more kinds. Here, the hydrolyzable silyl group generates a silanol group by a hydrolysis reaction.

The monomer represented by the general formula (5) is an acrylic monomer having an alkoxysilyl group,
In the general formula (5), R ¹⁰ is a hydrogen atom or a methyl group, and R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms (methyl group,
An alkyl group such as an ethyl group and a propyl group; an alkenyl group such as a vinyl group, an isopropenyl group and an allyl group; and an aryl group such as a phenyl group);
Represents 0 or 1.

Specific examples of the acrylic monomer having an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltributoxysilane, and 3-methacryloxypropyl. Triisopropenoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltributoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl Tributoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethyltributoxysilane, 3-methacryloxypropylmethyl Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldibutoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxymethylmethyldibutoxysilane, 3-acryloxy Examples include propylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldibutoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethylmethyldiethoxysilane, and acryloxymethylmethyldibutoxysilane. Is done. Among these, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane are particularly preferable in consideration of ease of handling, reactivity, crosslink density and the like.

The monomer represented by the general formula (6) is a vinyl-functional compound having an alkoxysilyl group,
The monomer represented by the general formula (7) is a vinyl-functional alkoxysilane compound, and in these general formulas (6) and (7), R ¹² and R ¹³ have the same meanings as the above R ¹¹ or alkyl. Means an oxyalkyl group, c and d are vinyl-functional monomers representing 0 or 1;

Specific examples of these vinyl-functional monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyl Diethoxysilane, vinylmethyldibutoxysilane, vinylmethylbis (2-methoxyethoxy), 3-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane, 3-vinyloxypropylmethyldimethoxysilane, 3-vinyl Oxypropylmethyldiethoxysilane and the like are exemplified, and among these, particularly preferable in consideration of ease of handling and reactivity, vinyltrimethoxysilane, vinyltriethoxysilane, 3-vinyloxy Shi trimethoxysilane and the like.

By using such a monomer having a hydrolyzable silyl group as a copolymer component, silanol groups generated by the hydrolysis reaction are cross-linked to the copolymer constituting the surface protective layer by a condensation reaction. This gives thermosetting properties, mechanical properties and weather resistance when formed into a thin film,
Solvent resistance is increased.

The monomer having an ultraviolet absorbing group which is copolymerized with the monomer having a hydrolyzable silyl group includes:
Although any monomer having a polymerizable double bond and an ultraviolet absorbing group in the molecule at the same time can be used, particularly preferably used in the present invention is an ultraviolet absorbing compound represented by the general formula (1) or (2). It is a monomer having a functional group, and by using these monomers as a copolymer component, the obtained copolymer is provided with an ultraviolet absorbing ability.

Accordingly, the thin film containing the copolymer as a main component has excellent ultraviolet shielding properties and ultraviolet stability by itself, exhibits excellent weather resistance, and has flexibility and bending whitening resistance. It also has excellent mechanical properties. Therefore, when a thin film made of this polymer is formed on the surface of the resin base material as a protective film forming material by coating or laminating, ultraviolet rays are absorbed by the surface protective layer before reaching the resin base material, and the resin base by the ultraviolet rays is formed. Deterioration and discoloration of the material can be suppressed. Moreover, since the ultraviolet absorber does not bleed out as in the conventional material containing the additive type ultraviolet absorber, the durability of the ultraviolet protection performance is enhanced, and this is laminated and formed as a surface protective layer of the resin base material. Those exhibit excellent bending whitening resistance and solvent resistance.

The above-mentioned copolymer may be obtained by copolymerizing one or more monomers having a UV-stable group as another monomer component, thereby further improving the weather resistance of the copolymer. Is preferred.

As the monomer having an ultraviolet light-stable group used herein, any type may be used as long as it has a polymerizable double bond and an ultraviolet light-stable group in the molecule at the same time. It is a monomer having an ultraviolet light-stable group represented by the general formulas (3) and (4).

In the present invention, the monomer having an ultraviolet absorbing group represented by the general formula (1) is preferably a compound represented by the formula: wherein R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ² is a lower alkylene group. , R ³ is a hydrogen atom or a methyl group, X is hydrogen,
Benzotriazoles which are halogen, hydrocarbon groups having 1 to 8 carbon atoms, lower alkoxy groups, cyano groups or nitro groups.

In the above formula, examples of the substituent represented by R ¹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary group.
t-butyl group, pentyl group, hexyl group, heptyl group,
A chain hydrocarbon group such as an octyl group; a cyclopropyl group,
A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an alicyclic hydrocarbon group such as cyclooctyl group; a phenyl group, a tolyl group, a xylyl group, a benzyl group, an aromatic hydrocarbon group such as a phenethyl group, Table by R ² The substituent is specifically an alkylene group having 1 to 6 carbon atoms, such as a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; a propylene group; and 2-methyltrimethylene. And a branched alkylene group such as a 2-methyltetramethylene group, and the substituent represented by X is hydrogen; a halogen such as fluorine, chlorine, iodine, or iodine; a methyl group, an ethyl group, or a propyl group. , Isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl and other chain hydrocarbons An alicyclic hydrocarbon group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a cyclooctyl group; an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a xylyl group, a benzyl group, or a phenethyl group; A lower alkoxy group having 1 to 6 carbon atoms such as a group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a heptoxy group; a cyano group; a nitro group.

More specific examples of the monomer represented by the general formula (1) include, for example, 2- [2'-hydroxy-
5 '-(methacryloyloxymethyl) phenyl] -2
H-benzotriazole, 2- [2'-hydroxy-5 '
-(Methacryloyloxyethyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxypropyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyhexyl) phenyl] -2H-
Benzotriazole, 2- [2′-hydroxy-3′-t
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'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5- Nitro-2
Examples include H-benzotriazole, but are not particularly limited thereto. These monomers represented by the general formula (1) may be used alone or in combination of two or more.

In the monomer having an ultraviolet absorbing group represented by the general formula (2), the substituent represented by R ⁴ is a lower alkylene group, and the substituent represented by R ⁵ is a hydrogen atom. Or benzotriazoles which are methyl groups. R
Particularly preferred among the substituents represented by ⁴ are alkylene groups having 2 or 3 carbon atoms, such as an ethylene group, a trimethylene group, and a propylene group.

More specific examples of the monomer represented by the general formula (2) include, for example, 2- [2'-hydroxy-
5 ′-(β-methacryloyloxyethoxy) -3′-t
tert-butylphenyl] -5-tert-butyl-2
Examples include H-benzotriazole, but are not particularly limited thereto. The monomer represented by the general formula (2) may be used alone, or two or more kinds may be used in combination as needed.

Further, in the monomers represented by the above general formulas (3) and (4) which can be copolymerized as required in the present invention, the substituent represented by R ⁶ is a hydrogen atom or a cyano group; ^The substituents represented by ⁷ , R ⁸ , R ^{7 ′} and R ^{8 ′} are each independently a hydrogen atom or a methyl group, the substituent represented by R ⁹ is a hydrogen atom or a hydrocarbon group, and the substituent represented by Y is These are piperidines which are oxygen atoms or imino groups.

Specific examples of the substituent represented by R ⁹ include a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. Chain hydrocarbon group; alicyclic hydrocarbon group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; aromatic group such as phenyl group, tolyl group, xylyl group, benzyl group and phenethyl group Non-limiting examples include hydrocarbon groups.

A more specific example of the monomer having an ultraviolet light-stable group represented by the general formula (3) is, for example, 4
-(Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2 , 2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-
1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6
6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine and the like, without limitation. These can be used alone or in combination of two or more as needed.

More specific examples of the monomer represented by the general formula (4) include, for example, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-
Tetramethylpiperidine, 1- (meth) acryloyl-
4-cyano-4- (meth) acryloylamino-2,
Examples include, but are not limited to, 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, which can be used alone or required. May be used in appropriate combination of two or more.

In the present invention, the ratio of the monomer having a reactive silyl group in the copolymer to the total monomers is such that the mechanical and chemical properties as a thin film constituting material by the monomers are improved. If necessary, the copolymerization ratio must be in the range of 3 to 60% by mass. A more preferred lower limit is 5% by mass and a more preferred upper limit is 50% by mass.

If the copolymerization ratio of the monomer having a reactive silyl group is less than 3% by mass, the weather resistance and the solvent resistance of the thin film constituting material are reduced. Conversely, when the copolymerization ratio is 50
If the amount is more than 10% by mass, the copolymer becomes too hard, causing whitening or cracking when bent, and the storage stability of the copolymer tends to deteriorate.

When the copolymer is obtained, the amount of the monomer having an ultraviolet-absorbing group used is preferably 15% by mass or more and 70% by mass or less based on the total amount of the monomer components constituting the copolymer. More preferably, the lower limit is 20% by mass, the upper limit is 60% by mass, and still more preferably 50% by mass. If the copolymerization ratio of the monomer having a UV-absorbing group is less than 15% by mass, the UV-shielding effect when formed into a thin film or when laminated on a resin substrate becomes insufficient, so that the film thickness must be increased. And the mechanical and optical properties inherent to the resin base material are reduced, and the resin base material is liable to be whitened or cracked when bent. Conversely, if the content exceeds 70% by mass, the coating film may be whitened or cracked during the weather resistance test, or the adhesion to the base resin may be reduced.

The amount of the monomer components represented by the general formulas (3) and (4) is not particularly limited, but may be 0.1 to 15 in the copolymer constituting the surface protective layer. It is desired that the content be set to mass%. More preferably, the lower limit is 0.5% by mass, more preferably 1% by mass, and the upper limit is 5% by mass, more preferably 3% by mass. If the total amount of the monomer component having a UV-stable group is less than 0.1% by mass, a thin film (surface protective layer)
Tends to deteriorate, and when it exceeds 15% by mass, the thin film may cause deterioration in physical properties.

In the above-mentioned copolymer of the present invention, one or more copolymerizable reactive monomers other than the above-mentioned monomer components may be used as long as they do not impair the ultraviolet absorbing ability required as a thin film. Can be used in combination as another monomer component. As those other monomer components,
From the viewpoint of the weather resistance of the copolymer and the like, a monomer component represented by the following general formula (8) is exemplified as a preferable one.

[0054]

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(Wherein, R ¹⁴ represents a hydrogen atom or a methyl group, and Z represents a hydrocarbon group having 4 or more carbon atoms).

In the above formula, the substituent represented by Z is an alicyclic hydrocarbon group having 4 or more carbon atoms such as a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group; a butyl group, an isobutyl group, a tert-butyl group; Linear or branched alkyl group having 4 or more carbon atoms such as 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, octadecyl group; bornyl group, isobornyl A polycyclic hydrocarbon group having 4 or more carbon atoms, such as an alicyclic hydrocarbon group,
A branched alkyl group and a linear alkyl group having 6 or more carbon atoms are preferred.

More specific examples of the monomer component represented by the general formula (8) include, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, te
rt-butylcyclohexyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, and the like are included without limitation, and one or more of these can be used.

The amount of the monomer component represented by the general formula (8) is not particularly limited, but is preferably 1 to 50% by mass, more preferably 3 to 30% by mass in the copolymer. %, Particularly preferably in the range of 5 to 20% by weight. When the amount is less than 1% by mass, the effect of improving the weather resistance is significantly less likely to be exerted. On the other hand, when the amount exceeds 50% by mass, the physical properties of the thin film are reduced, or the adhesiveness between layers with the resin substrate is adversely affected. There is a fear of it.

Still other copolymerizable monomer components include monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic acid, and maleic anhydride;
-Acidic phosphoric ester monomers such as (meth) acryloyloxyethyl acid phosphate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) ) Monomers having a group having an active hydrogen such as acrylate (for example, manufactured by Daicel Chemical Industries, Ltd .; trade name “Placel FM”); methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (Meth) such as (meth) acrylate
Acrylic acid lower alkyl esters; Nitrogen-containing monomers such as (meth) acrylamide, N, N'-dimethylaminomethyl (meth) acrylate, imide (meth) acrylate, N-methylol (meth) acrylamide; ethylene glycol di (meth) acrylate Monomers having two polymerizable double bonds; halogen-containing monomers such as vinyl chloride and vinylidene chloride; aromatic monomers such as styrene, α-methylstyrene, and vinyltoluene; and vinyl ethers. However, the present invention is not limited to this. These other monomer components can be used alone or in combination of two or more if necessary.

The polymerization method for producing the above copolymer is not particularly limited, and conventionally known polymerization methods such as a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used. As the solvent, a non-aqueous solvent is preferable from the viewpoint of the solubility of the monomer having an ultraviolet absorbing group. In this case, the preferable amount of the non-aqueous solvent is in the range of 5 to 97% by mass in the total composition. preferable. As a solvent used when polymerizing the monomer component using a solution polymerization method,
Toluene, xylene, and other aromatic solvents;
Alcohol solvents such as propyl alcohol and n-butyl alcohol; ether solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellosolve and butyl cellosolve; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; acetone; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; dimethylformamide and the like can be used. Of course, the type of solvent used is not limited to these. One of these solvents may be used alone, or two or more thereof may be used as a mixed solvent. The amount of the solvent used may be appropriately determined in consideration of the concentration of the obtained copolymer and the like.

When the monomer components are copolymerized, a polymerization initiator is usually used. Examples of the polymerization initiator include 2,2'-azobis- (2-methylbutyronitrile) and tert- Examples include ordinary radical polymerization initiators such as butylperoxy-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, benzoyl peroxide, and di-tert-butyl peroxide. The amount of the polymerization initiator to be used is not particularly limited as it should be appropriately determined according to the required characteristics of the copolymer and the like, but is preferably in the range of 0.01 to 50% by mass based on the total amount of the monomer components. Preferably 0.05 to 20% by mass
Range.

If necessary, for example, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, _{(CH 3 O) 3 Si-} S-S-Si (OCH 3) 3,
It is also effective to add one or more chain transfer agents such as (CH ₃ O) ₃ Si—S ₄ —Si (OCH ₃ ) ₃ to adjust the molecular weight of the copolymer. If a chain transfer agent having a hydrolyzable silyl group in the molecule, such as 3-mercaptopropyltrimethoxysilane, is continuously added to the monomer mixture, the hydrolyzable silyl group can be added to the terminal of the vinyl monomer simultaneously with the molecular weight control. It is preferable because it can be introduced.

The reaction temperature is not particularly limited either.
The range of 00 ° C is preferable, and 40 to 140 ° C is more preferable. The reaction time may be appropriately set according to the composition of the monomer component used, the type of the polymerization initiator, and the like so that the polymerization reaction can be completed efficiently.

The weight average molecular weight (Mw) of the copolymer is not particularly limited, but is preferably from 2,000 to 500,000, more preferably from 4,000 to 300,000, and still more preferably from 5,000 to 5,000. It is in the range of 250,000. Here, the mass average molecular weight means a value measured by polystyrene standard GPC.

Next, formation of a thin film (surface protective layer) using the copolymer will be described. The copolymer obtained as described above is mixed with another polymer used in combination as necessary, and diluted with an appropriate solvent to obtain a composition for forming a thin film. Then, this is applied to the release sheet surface so as to have an arbitrary dry thickness, dried and formed into a thin film, and then heat-laminated to a resin substrate, or through a primer layer or the like as necessary on the resin substrate surface. It may be applied and dried to form a surface protective layer. The application of the composition is dipping, spraying, brushing,
It can be performed by a method such as curtain flow coating, gravure coating, roll coating, spin coating, bar coating, and electrostatic coating.

When the present invention is used as a constituent material for a surface protective layer of a resin substrate, examples of the resin substrate include polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, ABS resin, and polystyrene resin. Examples thereof include vinyl chloride resins. The shape and production method of the resin base material may be of any shape and are not particularly limited, but those having high versatility include plate-shaped, curved-plate, corrugated and other plate-like or film-like ones. Further, it is also possible to use a resin base material having a design and subjected to wood grain printing or the like.

The copolymer constituting the thin film exhibits curing reactivity due to the presence of the reactive silyl group introduced into the molecule, but it is effective to use a curing catalyst to promote further curing. As the curing catalyst to be used, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, tin octylate; phosphoric acid, monomethyl phosphate,
Phosphoric acid or phosphate such as monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; alkyl titanate; tris (ethyl acetoacetate) ) Organic aluminum compounds such as aluminum; organic zirconium compounds such as tetrabutyl zirconate, tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium; maleic acid, adipic acid, azelaic acid , Sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid and their anhydrides, Acidic compounds such as rat toluenesulfonic acid; amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; Non-limiting examples include alkaline compounds such as sodium and potassium hydroxide.

Among these curing catalysts, particularly preferred are organotin compounds having particularly high catalytic activity, acidic phosphoric acid esters, mixtures or reactants of acidic phosphoric acid esters and amines, saturated or unsaturated polycarboxylic acids or their acids. Examples include an anhydride, a reactive silicon compound, an organic titanate compound, an organic aluminum compound, or a mixture thereof.

The curing catalyst is preferably used in an amount of 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the monomer unit having a reactive silyl group in the copolymer. % Range.

The composition containing the copolymer of the present invention into which a reactive silyl group has been introduced may optionally contain a dehydrating agent in order to suppress hydrolysis during storage and the resulting decrease in storage stability. It is also effective to let them do so. Examples of such a dehydrating agent include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methylsilicate, and ethyl silicate. Non-limiting examples include decomposable ester compounds, and these can be used alone or in combination of two or more. When these hydrolyzable ester compounds include a vinyl monomer having a reactive silyl group as a copolymerization component, they may be added at any stage before, during or after copolymerization.

The copolymer of the present invention is as described above.
When using the copolymer as a thin film forming composition,
It is also possible to use another polymer together with the copolymer into which at least a reactive silyl group and an ultraviolet absorbing group have been introduced by a copolymerization reaction. Such other polymers include:
Examples thereof include a thermoplastic polymer and a thermosetting polymer which is crosslinked and cured alone or by a crosslinking agent. The type and amount of these other polymers may be appropriately determined according to the use and required characteristics of the copolymer according to the present invention. Examples of the other polymer include thermoplastic polymers such as vinyl chloride resin, polyester resin, acrylic resin, and silicone resin;
Examples thereof include thermosetting polymers that cure alone, such as urethane resins, aminoplast resins, silicone resins, and epoxy resins; and thermosetting polymers that cure with a curing agent such as polyester resins, acrylic resins, and epoxy resins.

When a thin film containing the copolymer is cured,
The curing temperature varies depending on the type of the crosslinkable functional group, the amount used, and the type of the curing catalyst used, but it is preferable to cure at a temperature of, for example, room temperature to 250 ° C.

The thickness of the thin film is determined by Lambert-Beer
Is not particularly limited as long as it satisfies the desired weather resistance and ultraviolet shielding performance, but the preferred thickness when forming as a surface protective layer is 10 μm. Hereinafter, it is more preferably 0.5 to 8 μm, and still more preferably 2 to 6 μm. When the thickness exceeds 10 μm, not only the coating speed is reduced, but also the mechanical and optical properties inherent to the resin base material are reduced, and whitening or cracking is likely to occur when the resin base material is bent. On the other hand, when the thickness is less than 0.5 μm, it is difficult to uniformly coat the substrate, and the ultraviolet absorbing ability may be insufficient.

It is also effective to add colloidally dispersed silica sol, alumina or the like in order to enhance the scratch resistance and stain resistance. These commercial products include:
For example, “Nalcoag 1034A” (manufactured by Nalco Chemical Co., USA), “Cataloid-OSCAL-1”
432 "(manufactured by Catalyst Kasei Kogyo)," Snowtex C "
(Manufactured by Nissan Chemical Industries, Ltd.). In addition,
Composite inorganic fine particles having an organic polymer fixed on the surface of inorganic fine particles as described in JP-A-7-178335 and JP-A-9-302257 can also be used.

Further, in order to increase the scratch resistance and the surface hardness, it is effective to laminate a silicone-based curable resin or an organic-based curable resin. The silicone-based curable resin used here is a resin having a siloxane bond,
For example, a partially hydrolyzed product of trialkoxysilane and tetraalkoxysilane or an alkylated product thereof, a product obtained by hydrolyzing a mixture of methyltrialkoxysilane and phenyltrialkoxysilane, a partially hydrolyzed condensate of organotrialkoxysilane filled with colloidal silica And the like. Commercially available products include, for example, “Si coat 2” (manufactured by Daihachi Chemical Co., Ltd.); “Tosgard 510”, “UV
HC8553 "," UVHC8556 "," UVHC8 "
558 "(from Toshiba Silicone Co., Ltd.);" KP-85
1 "," KP-854 "," X-12-2206 ",
"X-12-2400", "X-12-2450" (all manufactured by Shin-Etsu Silicone Co., Ltd.); "Solgard NP72
0 "," Solgard NP730 "," Solgard RF0
831 "(both manufactured by Nippon Dacro Shamrock Co., Ltd.) and the like.

The organic curable resin includes, for example, melamine resin, urethane resin, alkyd resin, acrylic resin, polyfunctional acrylic resin and the like. Examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, and epoxy acrylate.

The multilayer laminate comprising the ultraviolet-absorbing copolymer of the present invention can have a heat ray shielding function, for example, an organic heat ray shielding substance such as phthalocyanine or a metal oxide. It can be provided by an inorganic heat ray shielding material such as an object.

In putting the copolymer of the present invention into practical use as a composition for forming a thin film (surface protective layer), it may contain various other additives in addition to the above-mentioned constituent components. Examples of the additives include silane, titanate, and aluminate-based coupling agents. Examples of the silane coupling agent include, for example, "A-187" manufactured by Nippon Unicar,
"A-189", "A-1100", "A-1120"
And the like. In addition, a leveling agent, an antioxidant, a filler, a rust inhibitor, a fluorescent brightener, an antioxidant, an antistatic agent, a pigment, a dye, a thickener generally used in a composition for forming a layer such as a paint. And the like, and may further contain an ultraviolet stabilizer such as a hindered amine-based or benzoate-based or an ultraviolet absorber such as a benzotriazole-based, benzophenone-based, or triazine-based.

[0079]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these, and may be appropriately modified within a range that can conform to the above and subsequent points. It is also possible to implement, and all of them are included in the technical scope of the present invention. In the following Examples and Comparative Examples, “parts” and “%” indicate parts by mass or% by mass.

(Synthesis of UV-Absorbing Copolymer Having Reactive Silyl Group) (Synthesis Example 1) A 500-ml flask equipped with a stirrer, a dropping port, a thermometer, a cooling pipe, and a nitrogen gas inlet was charged with 2- [2'-Hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole 1
5 g, 3-methacryloxypropyltrimethoxysilane ("KBM503" manufactured by Shin-Etsu Chemical Co., Ltd.) 60 g, methyl methacrylate 15 g, butyl acrylate 20 g, and propylene glycol monomethyl ether 200 g were charged, and nitrogen gas was introduced. Kept.
As an initiator, a mixture of 4.0 g of t-butyl peroxy-2-ethylhexanoate and 33 g of propylene glycol monomethyl ether was added dropwise to the charge over 2 hours. After the addition, the mixture was heated for another 4 hours to obtain 30% of the acrylic resin.
A solution was obtained. The weight average molecular weight of this copolymer was 3
It was 3,000.

The ultraviolet absorbing copolymer having a reactive silyl group is referred to as a copolymer (1). Table 1 shows the types and amounts of the monomers and the characteristic values of the obtained copolymer (1).

(Synthesis Examples 2 to 10) UV-absorbing copolymers having a reactive silyl group were produced in the same manner as in Synthesis Example 1 with the monomer compositions and compounding amounts shown in Table 1. The produced copolymers are referred to as copolymers (2) to (10), respectively.

[0083]

[Table 1]

UVA1: 2- [2'-hydroxy-5'-
(Methacryloyloxyethyl) phenyl] -2H-benzotriazole UVA2: 2- [2'-hydroxy-5 '-(β-methacryloyloxyethoxy) -3'-tert-butylphenyl] -5-tert-butyl-2H- Benzotriazole HALS1: 4-methacryloyloxy-1,2,2,2
6,6-pentamethylpiperidine HALS2: 1-methacryloyl-4-methacryloylamino-2,2,6,6-tetramethylpiperidine KBM503: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) CHMA: cyclohexyl methacrylate MMA: methyl methacrylate BA: butyl acrylate Initiator: tert-butyl peroxy-2-ethylhexanoate Reaction solvent: propylene glycol monomethyl ether.

Example 1 To 100 parts of the UV-absorbing copolymer (1) having a reactive silyl group obtained in Synthesis Example 1, 0.03 parts of a leveling agent (trade name “BYK331” manufactured by Big Chemie) was added. The resulting mixture was adjusted to a predetermined viscosity with toluene to prepare an acrylic resin solution. Next, the acrylic resin solution was applied to a corona discharge treated surface of a 50 μm-thick polyethylene terephthalate film (product number “E5101” manufactured by Toyobo Co., Ltd.) so that the thickness in a final cured state became 10 μm, and room temperature was applied. , And cured by heating at 120 ° C for 20 minutes. The obtained polyethylene terephthalate film was evaluated for the following evaluation items.

[Solvent resistance] 2 cc of toluene was dropped at room temperature on the thin film on the surface protective layer side of the laminate obtained in each example.
After a lapse of time, the surface of the thin film was visually observed after wiping with absorbent cotton. ：: No abnormality, ×: Whitening occurred.

[Weather Resistance Test] Using a super energy irradiation tester manufactured by Suga Test Instruments Co., Ltd., [temperature 70 ° C. × humidity 70%,
Each test piece was exposed under the condition that light intensity: irradiation at 100 m / w for 6 hours] → [temperature 80 ° C. × humidity 90% for 6 hours] was repeated for 8 cycles, and the following tensile test was performed before and after the weather resistance test. The retention of strength and elongation and the degree of yellowing were measured.

[Bending Whitening Property] The laminate obtained in each example was bent at 180 ° before and after the weather resistance test, and the whitening state of the bent portion was visually observed. ：: no whitening, ×: whitening.

[Method of Measuring Retention of Tensile Strength and Elongation]
Using a temperature variable material tester (Shimadzu Autograph “AGS-100D”) manufactured by Shimadzu Corporation, the test piece was 40 m in length.
Cut to size of mx 10mm, chuck distance 40
mm, the test speed was 200 mm / min, and the tensile strength and elongation were measured at a test temperature of 23 ° C. And uncoated thickness 5
The tensile strength of a polyethylene terephthalate film of 0 μm (product number “E5101” manufactured by Toyobo Co., Ltd.) [1820 (kg /
cm ² )] and the elongation [168 (%)] as a reference, the retention was determined by the following equation. In addition, the same test piece was measured five times and evaluated by the average value.

Tensile strength retention rate before weather resistance test (%) = (tensile strength before weather resistance test) / 1820 (kg / cm ² ) × 100 Tensile strength retention rate after weather resistance test (%) = (weather resistance Tensile strength after weathering test) / 1820 (kg / cm ² ) × 100 Elongation retention before weathering test (%) = (Elongation before weathering test) / 168 (%) × 100 After weathering test Elongation retention (%) = (elongation after weather resistance test) / 168 (%) × 100

[Measurement of Yellowing Degree] The degree of yellowing (Δb) was determined before and after the test by using a Hunter's color difference equation in accordance with JIS K5400. The larger the value, the greater the yellowing degree.

Examples 2 to 6, Comparative Examples 1 to 4, Reference Example 1 In the same manner as in Example 1, a resin solution containing a predetermined polymer shown in Table 2 was coated on a polyethylene terephthalate film (the same as above). After heat curing, the same evaluation test as in Example 1 was performed. Table 2 shows the results.

[0093]

[Table 2]

* 1) The substrate was whitened after the test, and measurement was impossible. * 2) The base material was broken after the test, and measurement was not possible.

[0095]

The present invention is constructed as described above, and contains at least a monomer having a reactive silyl group and a monomer having an ultraviolet absorbing group in a specific ratio as copolymer components, thereby providing weather resistance and resistance to weathering. It is possible to provide a UV shielding thin film having excellent solvent properties and excellent bending whitening resistance,
By forming the thin film as a protective layer on the surface of the resin substrate, coloring, discoloration, and the like of the resin substrate due to ultraviolet rays can be suppressed as much as possible. In addition, it is possible to provide a multilayer laminate that does not cause whitening even when bent and maintains the mechanical and optical characteristics inherent to the base resin even after the weather resistance test.

The ultraviolet absorbing copolymer of the present invention, the thin film comprising the copolymer, and the multilayer laminate containing the thin film have excellent properties as described above. Food, packaging materials for solar cells, polymer cells, etc.), electrical terminals, optics (such as lenses), building materials (such as soundproof walls), antifouling sheets and tents, marking films, outdoor expansion ( It can be applied to a wide range of applications such as agricultural houses), indoor and outdoor overlays (display materials, illuminated signs, etc.), windows (vehicles, architecture, daylighting materials, etc.). This thin film is not limited to resin substrates, but can be glass, metal, wood, paper,
It can be formed as a protective layer on the surface of cloth, inorganic material, etc., and this thin film or multilayer laminate can be applied to any member, for example, wood-grain-printed base material by painting or heat laminating, or adhesive or It is also possible to stick together using an adhesive.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takahiro Aoyama 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4F071 AA30 AA30X AA33 AA33X AF29 AG05 AG12 AG28 BA02 BB02 BC01 BC02 BC12 4F100 AK25A AK25J AK42 AK52A AK52J AL01A AT00B BA01 BA02 EH46 GB04 GB07 GB15 GB31 GB90 JB07 JD09 JD09A JD14A JK02 JK08 JL09 JN28 YY00A 4J002 BE041 BG071 BG081 BG121 BQ001 FD050 FD200 GF00 HA05 4J100 AE09Q AL08P AL08Q AM21R AM23R AP16Q BA02P BA03P BA40R BA77Q BB01P BC43P BC65R BC73P CA05 CA06 FA03 JA03 JA33 JA58 JA64 JA67

Claims (9)

[Claims] (1) (1) Monomer having a reactive silyl group: 3
(2) a monomer having an ultraviolet absorbing group: (15) a monomer component containing 15 to 70% by weight; 2. The ultraviolet-absorbing copolymer according to claim 1, wherein the monomer component further comprises (3) a monomer having an ultraviolet-stable group: 0.1 to 15% by mass. 3. The ultraviolet absorbent according to claim 1, wherein the monomer having an ultraviolet absorbent group is at least one monomer represented by the following general formula (1) or (2). Polymer. Embedded image (Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a lower alkylene group, R ³ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a halogen, a carbon atom, Represents a hydrocarbon group, lower alkoxy group, cyano group or nitro group of the formulas ^{1 to 8,} and any one of R ¹ and X represents a hydrogen atom. (In the formula, R ⁴ represents a lower alkylene group, and R ⁵ represents a hydrogen atom or a methyl group.) 4. The ultraviolet-absorbing copolymer according to claim 2, wherein the monomer having an ultraviolet-stable group is at least one monomer represented by the following general formula (3) or (4). Embedded image (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7, R
⁸ each independently represents a hydrogen atom or a methyl group,
R ⁹ represents a hydrogen atom or a hydrocarbon group, and Y represents an oxygen atom or an imino group. ) (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7, R
⁸ , R ^{7 ′} and R ^{8 ′} each independently represent a hydrogen atom or a methyl group, and Y represents an oxygen atom or an imino group. ) 5. The method according to claim 1, wherein the monomer having a reactive silyl group has a hydrolyzable silyl group.
5. The copolymer according to any one of 4. 6. The copolymer according to claim 5, wherein the monomer having a reactive silyl group is at least one monomer represented by the following general formulas (5) to (7). Embedded image (Wherein, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹
Represents a hydrocarbon group having 1 to 6 carbon atoms, a represents an integer of 1 to 3, and b represents 0 or 1. (Wherein, R ¹² has the same meaning as R ¹¹ or an alkyloxyalkyl group, and c represents 0 or 1). (Wherein, R ¹³ has the same meaning as R ^11, and d represents 0 or 1) 7. A resin component containing the ultraviolet-absorbing copolymer according to claim 1: 3 to 95% by mass.
And a non-aqueous solvent: 5 to 97% by mass, wherein the resin component is dissolved in the non-aqueous solvent. 8. An ultraviolet-absorbing thin film comprising the ultraviolet-absorbing copolymer according to claim 1 as a main component and having a thickness in a cured state of 10 μm or less. 9. An ultraviolet absorbing multilayer laminate comprising the ultraviolet absorbing thin film according to claim 8.