JP2001047574A - Ultraviolet absorbable resin member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin member for improving weather resistance without inviting coloring or deteriorating due to an ultraviolet ray, a decrease in a surface hardness and a decrease in interlayer adhesive properties and having high surface hardness and marring resistance. SOLUTION: The resin member of a laminated type is obtained by forming a base material protective layer containing a copolymer including a monomer having a reactive silyl group and a monomer having an ultraviolet absorbable group as monomer components, and forming a hard coating layer constituted of at least one type of resin preferably selected from a silicone curable resin and a curable resin having organic polymer composite inorganic fine particles on the protective layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated ultraviolet-absorbing resin member which suppresses coloring and deterioration by ultraviolet rays, has good interlayer adhesion, and has excellent scratch resistance and weather resistance.

[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 are inferior in various surface properties such as surface hardness, scratch resistance, solvent resistance and the like as compared with metals, glass, etc., so their use is limited, and improvement of the surface properties of the base resin is strongly demanded. I have. As a method of improving the surface characteristics, a method of coating the surface of a base resin with a surface treating agent is known. For example, there is a method of forming a cured layer on the surface with an ultraviolet curable acrylic compound, a thermosetting melamine resin, or a thermosetting organopolysiloxane resin.

Among these proposals, particularly excellent surface hardness and chemical resistance can be obtained by a method of forming a surface hardened layer on the surface of a base resin with a thermosetting organopolysiloxane resin. Apply and cure a partial hydrolysis condensate of organotrialkoxysilane alone, a partial hydrolysis condensate of tetraalkoxysilane and organotrialkoxysilane or a partial hydrolysis condensate of colloidal silica-filled organotrialkoxysilane Thereby, a laminated resin having excellent surface hardness can be obtained. Paints that form these surface hardened layers show good adhesion when the base resin is polymethyl methacrylate resin,
There is a problem in adhesion to polycarbonate resin,
The surface hardened layer may peel off.

Therefore, as a method for improving the adhesion of the surface hardened layer, for example, JP-B-63-5155 and JP-B-6-155
In JP-A-3-52668 and the like, a method of pretreating the surface of a polycarbonate resin to form a primer layer has been proposed. According to this method, the adhesion of the surface hardened layer is certainly improved.

[0005] On the other hand, the resin plate generally has insufficient weather resistance, and has another problem that the surface is deteriorated or colored especially when exposed to ultraviolet rays. Although the initial adhesion of the surface hardened layer is improved by the above method, neither the surface hardened layer nor the primer layer has a function of blocking ultraviolet rays, so that the transmitted ultraviolet rays deteriorate the surface of the base resin, Adhesion, which should have been improved, is deteriorated, and problems with weatherability such as coloring and strength reduction are caused.

Therefore, as a method for preventing ultraviolet rays that degrade the base resin from reaching the surface of the resin member, for example, Japanese Patent Publication No. 60-53701, Japanese Patent Publication No. 2-37938, Japanese Patent Application Laid-Open No. 10-245521, 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, the deterioration of the base resin surface due to ultraviolet rays was prevented to some extent, and the adhesiveness became satisfactory.

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 of the resin member, there is a problem that transparency, which is a characteristic of the resin, is impaired, or further, the ultraviolet absorber bleeds out to cause a deterioration in appearance and a deterioration in abrasion resistance. Bleed-out of the ultraviolet absorber also causes a problem that the interlayer adhesion between the surface hardened layer and the primer layer or between the primer layer and the base resin is deteriorated. Furthermore, since the ultraviolet absorber itself is not high in hardness, there arises a problem that the addition of a large amount of the ultraviolet absorber lowers the excellent surface hardness of the surface hardened layer. That is, if a large amount of the ultraviolet absorber is not added, the resin member surface is deteriorated by ultraviolet rays and the adhesion of the surface hardened layer is deteriorated. Conversely, if a large amount of the ultraviolet absorber is added, coloring or surface hardness is reduced. There was a problem.

In order to solve these problems, for example, Japanese Patent Application Laid-Open Nos. 9-3135 and 10-34840 propose that an acrylic resin copolymerized with a reactive ultraviolet absorber be used for the surface layer. . According to this proposal,
Although a large amount of an ultraviolet absorbing component can be used, it cannot be said that surface hardness, scratch resistance and the like are still satisfactory.

Further, Japanese Patent Application Laid-Open No. 4-106161 discloses that
A copolymer obtained by copolymerizing a monomer having an ultraviolet absorbing group is formed on a substrate surface as a primer, and an organopolysiloxane hard coat layer is formed thereon,
Methods for improving heat resistance, scratch resistance, surface hardness, surface gloss, and the like are disclosed. The publication also describes that it is preferable to copolymerize a UV-stable monomer with a UV-absorbing monomer. However, in these techniques, since the ultraviolet absorbing copolymer is thermoplastic, even if its surface is coated with a hard coat layer, the weather resistance and scratch resistance of the primer layer itself are insufficient, so that the hard coat layer Has insufficient weather resistance and abrasion resistance, and furthermore, the adhesion between the primer layer and the hard coat layer cannot be said to be good, and satisfactory interlayer adhesion cannot always be obtained.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to cause problems such as coloring and deterioration by ultraviolet rays, a decrease in surface hardness, and a decrease in interlayer adhesion. It is an object of the present invention to provide a laminated resin member having improved weather resistance, high surface hardness and excellent abrasion resistance without any problem.

[0011]

The resin member according to the present invention, which has solved the above-mentioned problems, has a base material protective layer formed on the protective surface side of a resin base material, and a hard coat on the protective layer. A laminated resin member having a layer formed thereon, wherein the base material protective layer contains a monomer having a monomer having a reactive silyl group and a monomer having a UV absorbing group as a monomer component. However, it has a gist.

The copolymer constituting the base material protective layer may contain a monomer having an ultraviolet light-stable group as another monomer component. The monomer having a reactive silyl group is most preferably a monomer having a hydrolyzable silyl group.

As the monomer having an ultraviolet absorbing group, any monomer having a polymerizable double bond and an ultraviolet absorbing group in a molecule can be used. Among them, particularly preferred is a compound represented by the following general formula ( Monomers represented by (I) or (II), which can be used alone or
More than one species can be used in combination.

[0014]

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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, Represents a nitro group or a nitro group. )

[0016]

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(In the formula, R ⁴ represents a lower alkylene group, and R ⁵ represents a hydrogen atom or a methyl group.)

As the monomer having an ultraviolet light-stable group, any monomer having a polymerizable double bond and an ultraviolet light-stable group in a molecule can be used, and particularly preferred is a compound represented by the following general formula (III) ) Or (IV), which may be used alone or in combination of two or more if necessary.

[0019]

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(In the formula, 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, and Y represents Represents an oxygen atom or an imino group.)

[0021]

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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.)

As the monomer having a reactive silyl group, a monomer having a hydrolyzable silyl group is preferable. Specifically, the monomers represented by the following general formulas (V) to (VII) may be used alone or when necessary. Can be used in combination of two or more.

[0024]

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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,
Represents an integer of 1 to 3, and b represents 0 or 1.)

[0026]

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(Wherein, R ¹² has the same meaning as R ¹¹ described above, and c represents 0 or 1)

[0028]

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

Further, the hard coat layer formed on the base material protective layer is preferably composed of at least one resin selected from a silicone-based curable resin and a curable resin containing organic polymer composite inorganic fine particles. In the case of a hard coat layer made of such a material, the base resin and the hard coat layer can be firmly laminated and integrated under high adhesion through the base material protective layer characterized by the present invention. it can.

When a curing catalyst is added to the composition constituting the base material protective layer, not only can the hardening of the base material protective layer itself be promoted, but also the hardening of the surface protective layer can be promoted. The curing time of the protective layer can be shortened, and it is also preferable from the viewpoint of improving weather resistance and abrasion resistance.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have made an effort to improve the surface hardness and weather resistance, which have been conventionally regarded as problems, while maintaining the excellent properties such as transparency and impact resistance inherent to resins. As a result of intensive studies, a substrate protective layer containing a monomer having a reactive silyl group and a curable UV-absorbing polymer containing a monomer having an ultraviolet-absorbing group as a monomer component is provided on the protective surface side of the resin substrate. If formed and covered with a hard coat layer, the resulting laminated resin member will be
The inventors have found that they have excellent resistance to deterioration by ultraviolet rays and also have excellent interlayer adhesion, surface hardness, and weather resistance, and have accomplished the present invention.

Accordingly, a feature of the present invention is that a substrate protective layer containing a curable copolymer containing a monomer having a reactive silyl group and a monomer having an ultraviolet absorbing group as monomer components is used for protecting a resin substrate. A hard coat layer formed of at least one resin selected from the group consisting of a silicone-based curable resin and a curable resin containing organic polymer composite inorganic fine particles is preferably formed on the protective surface on the protective surface. By specifying the constituent material of the base material protective layer in this way, the base material protective layer is provided with a high level of ultraviolet shielding action, and the lamination integrity with the base material resin and the hard coat layer is improved. It was successful in raising it.

As the resin substrate used in the present invention, for example, polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, A
Examples of the resin include a BS resin, a polystyrene resin, and a vinyl chloride resin. 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.

In the present invention, a monomer having a reactive silyl group used as a monomer component of the copolymer constituting the base material protective layer preferably 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 (V) to (VII) 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 (V) is an acrylic monomer having an alkoxysilyl group,
In the general formula (V), in the formula, 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-methacryloxypropylmethyldiethoxysilane are particularly preferable in consideration of ease of handling, reactivity, crosslink density and the like.

The monomer represented by the above general formula (VI)
Is a vinyl functional compound having an alkoxysilyl group,
The monomer represented by the general formula (VII) has a vinyl functionality
Alkoxysilane compounds having the general formulas (VI) and (VI
In I), wherein R is¹², R ¹³Is R¹¹The same meaning as
Or an alkyloxyalkyl group, and c and d are 0
Or a vinyl-functional monomer representing 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 these monomers having a hydrolyzable silyl group as a copolymerization component, the silanol groups generated by the hydrolysis reaction are cross-linked to the copolymer constituting the base material protective layer by a condensation reaction. Thereby, thermosetting properties are imparted, and the surface hardness and weather resistance of the base material protective layer are enhanced. Furthermore, due to the presence of the silanol group, the adhesion of the base material protective layer to the resin base material is enhanced, and the base material contains a silicone-based curable resin and organic polymer composite inorganic fine particles coated on the base material protective layer. Adhesion with the hard coat layer composed of curable resin etc.
It becomes possible to remarkably improve interlayer adhesion as a laminated resin member.

The monomer having an ultraviolet absorbing group copolymerized with the monomer having a hydrolyzable silyl group includes:
Although all monomers 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 (I) or (II). It is a monomer having a functional group, and by using these monomers as a copolymer component, the obtained copolymer has an ultraviolet absorbing function. Therefore, by using this copolymer as a main component of the substrate protective layer, the substrate protective layer can be provided with an ultraviolet shielding function.

Therefore, when this base material protective layer is formed on the surface of the resin base material, ultraviolet rays are absorbed by the base material protective layer before reaching the resin base material, so that deterioration and discoloration of the resin base material due to the ultraviolet rays are suppressed. . Furthermore, unlike the conventional additive UV absorber, the UV absorbing component does not bleed out, so that it does not adversely affect the interlayer adhesion between the resin base material and the hard coat layer, and maintains the UV protection performance. Is also enhanced.

The above-mentioned copolymer constituting the base material protective layer may be obtained by copolymerizing at least one kind of a monomer having a UV-stable group as another monomer component. It is preferable because the weather resistance of the layer can be further enhanced.

The type of the monomer having an ultraviolet light-stable group used herein is not particularly limited as long as it has a polymerization-reactive double bond and an ultraviolet light-stable group in the molecule at the same time. And the general formula (III)
And a monomer having an ultraviolet light-stable group represented by (IV).

In the present invention, the monomer having an ultraviolet absorbing group represented by the above general formula (I) 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, and X is hydrogen, halogen, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group or a nitro group.

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 (I) include, for example, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl]-
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(methacryloyloxyethyl) phenyl] -2
H-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 (I) may be used alone or in combination of two or more.

Further, in the monomer having an ultraviolet absorbing group represented by the general formula (II), 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.

In the above formula, the substituent represented by R ⁴ is specifically an alkylene group having 2 or 3 carbon atoms, such as an ethylene group, a trimethylene group or a propylene group.

More specific examples of the monomer represented by the general formula (II) include, for example, 2- [2'-hydroxy-
5 ′-(β-methacryloyloxyethoxy) -3′-t
tert-butylphenyl] -4-tert-butyl-2
Examples include H-benzotriazole, but are not particularly limited thereto. The monomer represented by the general formula (II) may be used alone, or may be used in combination of two or more as necessary.

Further, in the monomers represented by the above general formulas (III) and (IV) 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. Groups, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 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.

More specific examples of the monomer having an ultraviolet light-stable group represented by the general formula (III) include, for example,
(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 (IV) 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 which is the main component of the base material protective layer in all the monomers is not particularly limited.
In order to increase the hardness of the base material protective layer by the monomer and to enhance the interlayer adhesion with the hard coat layer formed thereon, the copolymerization ratio is preferably in the range of 2 to 70% by weight, A more preferred lower limit is 5% by weight and a more preferred upper limit is 50% by weight.

When the copolymerization ratio of the monomer having a reactive silyl group is less than 2% by weight, the adhesion to the hard coat layer after the weather resistance test and the hot water resistance test is reduced.
Conversely, if the copolymerization ratio exceeds 70% by weight, the copolymer becomes too hard, and the adhesion to the hard coat layer after the weather resistance test is reduced, and the storage stability of the copolymer is reduced.

The amount of the monomer components represented by the above general formulas (I) and (II) in obtaining the copolymer is not particularly limited, either, but it accounts for all the monomer components constituting the copolymer. The ratio is preferably 1% by weight or more and 90% by weight or less, more preferably 5% by weight on the lower limit side, and further preferably 10% by weight. On the other hand, the upper limit is preferably 70% by weight, more preferably 50% by weight.
When the amount of the monomer having an ultraviolet absorbing group is less than 1% by weight, it is necessary to increase the thickness of the base material protective layer in order to prevent deterioration of the resin base material due to ultraviolet rays, and the hard coat layer is cured thereon. Occasionally, cracks are likely to occur, and cracks may occur even after long-term use. Conversely, if the content exceeds 90% by weight, the physical properties of the base material protective layer may be adversely affected.

The amount of the monomer components represented by the above general formulas (III) and (IV) is not particularly limited either, but is preferably 0.1 to 15 in the copolymer occupying the base material protective layer.
It is desired that the content be% by weight. More preferably, the lower limit is 0.5% by weight, more preferably 1% by weight, and the upper limit is 5% by weight, more preferably 3% by weight. If the total amount of the monomer component having a UV-stable group is less than 0.1% by weight, the base material protective layer tends to be easily deteriorated, while if it exceeds 15% by weight, the physical property of the base material protective layer is deteriorated. May occur.

In the present invention, the copolymer which is a main constituent material of the base material protective layer includes a copolymerizable reactive monomer other than the above-mentioned monomer components, as well as the ultraviolet absorbing ability and interlayer resistance required for the base material protective layer. One type or two or more types can be used in combination as another monomer component as long as the effect of improving the adhesion is not impaired. As those other monomer components,
From the viewpoint of improving the weather resistance of the base material protective layer, the following general formula (VII)
The monomer component represented by I) is exemplified as preferred.

[0060]

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(In the formula, 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 and 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 (VIII) include, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth)
Acrylate, cyclododecyl (meth) acrylate,
tert-butylcyclohexyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Non-limiting examples include one or more of these.

The amount of the monomer component represented by the general formula (VIII) is not particularly limited, but is preferably in the range of 3 to 70% by weight in the copolymer constituting the base material protective layer. More preferably, it is in the range of 5 to 50% by weight. If the amount is less than 3% by weight, the effect of improving the weather resistance is not significantly exhibited, while if it exceeds 70% by weight, the adhesiveness between layers with the hard coat layer may be adversely affected.

When a monomer having an epoxy group or vinyl acetate is used as a monomer component, the interlayer adhesion of the obtained base material protective layer containing the copolymer to the base resin and the hard coat layer is more effectively improved. Along with
It is preferable because the weather resistance is further improved. Preferred monomers having an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, and alicyclic epoxy group-containing (meth) acrylate (“CYCLOMER M-100”, “C
YCLOMER A-200 "), and the preferred content in these copolymers is 1 to 10% by weight.
Range.

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 acid ester monomers such as-(meth) acryloyloxyethyl acid phosphate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate (for example, (Manufactured by Daicel Chemical Industries, Ltd .; brand name having an active hydrogen such as "Placcel FM"); methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate (Meth) acrylic acid lower alkyl esters such as; (meth) acrylamide,
Nitrogen-containing monomers such as N, N'-dimethylaminomethyl (meth) acrylate, imide (meth) acrylate and N-methylol (meth) acrylamide; and two polymerizable double bonds such as ethylene glycol di (meth) acrylate Monomers having: halogen-containing monomers such as vinyl chloride and vinylidene chloride; aromatic monomers such as styrene, α-methylstyrene and vinyltoluene; vinyl ethers, but are not particularly limited thereto. These other monomer components can be used alone or in combination of two or more if necessary.

There are no particular restrictions on the polymerization method used to produce the above-mentioned copolymer constituting the base material protective layer, and conventionally known polymerization methods such as solution polymerization, dispersion polymerization, suspension polymerization, and emulsion polymerization can be used. A polymerization method or the like can be used. Solvents used for polymerizing the monomer components using the solution polymerization method include toluene, xylene, and other aromatic solvents; alcohol solvents such as iso-propyl alcohol and n-butyl alcohol; propylene glycol methyl ether; Ether solvents such as dipropylene glycol methyl ether, ethyl cellosolve and butyl cellosolve; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as acetone, 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, but a solvent that erodes the resin substrate is not preferred. 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 weight based on the total amount of the monomer components. Preferably 0.05 to 20% by weight
Range.

If necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane,
3-mercaptopropylmethyldiethoxysilane, (C
_{H 3 O) 3 Si-S} -S-Si (OCH 3) 3, (CH
It is also effective to adjust the molecular weight of the copolymer by adding one or more chain transfer agents such as ₃ O) ₃ Si—S ₄ —Si (OCH ₃ ) ₃ . 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, but is
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 as the main component of the base material protective layer is not particularly limited.
~ 500,000, more preferably 4,000.
0 to 300,000, more preferably 5,000.
~ 250,000. Here, the weight average molecular weight means a value measured by polystyrene standard GPC.

Next, the formation of the base material protective layer will be described.
The copolymer obtained as described above is mixed with another polymer, if necessary, to be used as a composition for forming a base material protective layer, which is applied on a resin base material. At this time, the base material protective layer may be formed directly on the surface of the resin base material, or may be formed thereon after forming a primer layer on the surface of the resin base material.
The application of the composition to a resin substrate can be performed by a method such as dipping, spraying, brushing, curtain flow coating, gravure coating, roll coating, spin coating, bar coating, electrostatic coating, or the like.

The copolymer constituting the base material protective layer exhibits curing reactivity due to the presence of the reactive silyl group introduced into the molecule. However, it is necessary to use a curing catalyst to promote further curing. Are effective as curing catalysts, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl Phosphoric acid or phosphoric acid ester such as 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, Acidic compounds such as sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid and their anhydrides, paratoluenesulfonic acid; hexylamine, di-2-ethylhexylamine, N, Examples include, but are not limited to, amines such as N-dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; and alkaline compounds such as sodium hydroxide 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 weight, more preferably 0.05 to 5% by weight, based on the monomer unit having a reactive silyl group in the copolymer. % Range.

In the composition for forming a base material protective layer containing the copolymer of the present invention into which a reactive silyl group has been introduced, hydrolysis during storage and a reduction in storage stability due to the hydrolysis are described. It is also effective to include a dehydrating agent if necessary. 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 which is the main component of the base material protective layer in the present invention is as described above. In the present invention, at least a reactive silyl group and an ultraviolet absorbing group are introduced by a copolymerization reaction. It is also possible to use other polymers together with the copolymer. Examples of such another polymer include a thermoplastic polymer and a thermosetting polymer which is crosslinked and cured by itself 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 resin member 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; and thermosetting polymers such as urethane resin, aminoplast resin, silicone resin, and epoxy resin that cure alone. A thermosetting polymer that is cured by a curing agent such as a polyester resin, an acrylic resin, and an epoxy resin.

When the substrate protective layer 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 room temperature to 250 ° C., for example.

The thickness of the base material protective layer is Lambert-B
Since it depends on the amount of the ultraviolet absorber to be copolymerized according to the Eer's law, there is no particular limitation as long as the weather resistance of the resin base material and the performance of the base material protective layer are satisfied. The range is preferably from 5 to 200 μm, more preferably from 1 to 100 μm, and still more preferably from 2 to 30 μm. When the thickness exceeds 200 μm, the coating speed becomes slow,
In addition, the original performance of the resin substrate may be impaired. On the other hand, when the thickness is less than 0.5 μm, it is difficult to uniformly coat the resin base material, and the ultraviolet absorbing ability may be insufficient.

Another feature of the present invention resides in that a hard coat layer is provided on the surface of the base material protective layer. That is, in the present invention, the hardness, heat resistance, weather resistance, etc. can be increased by setting the UV-absorbing copolymer having a reactive silyl group constituting the base material protective layer as a curing type as described above,
Further, by forming a hard coat layer having a high surface hardness thereon, the surface hardness, abrasion resistance and weather resistance can be drastically improved in combination with the excellent hardness, heat resistance and weather resistance of the underlayer. is there.

The resin forming the hard coat layer is not particularly limited, but is preferably a silicone-based curable resin or a curable resin containing organic polymer composite inorganic fine particles from the viewpoints of surface hardness, scratch resistance, interlayer adhesion and the like.

The silicone-based curable resin is a resin having a siloxane bond. For example, trialkoxysilane and tetraalkoxysilane or a partial hydrolyzate of an alkylated product thereof, and a mixture of methyltrialkoxysilane and phenyltrialkoxysilane are used. Examples thereof include hydrolyzed products and partially hydrolyzed condensates of colloidal silica-filled organotrialkoxysilanes. Commercially available products include, for example, “Si Coat 2” (manufactured by Daihachi Chemical Co., Ltd.); “Tosgard 510”, “UVHC8553”, “UVHC8”.
556 "," UVHC8558 "(all manufactured by Toshiba Silicone Co.);" KP-851 "," KP-854 "," X
-12-2206 "," X-12-2400 "," X-
12-2450 "(all manufactured by Shin-Etsu Silicone Co., Ltd.);" Solgard NP720 "," Solgard NP730 ",
"Solgard RF0831" (both manufactured by Nippon Dacro Shamrock Co., Ltd.) and the like. These include alcohols and the like generated during the condensation reaction, but may be further dissolved or dispersed in any organic solvent, water, or a mixture thereof as necessary. Examples thereof include lower fatty acid alcohols, polyhydric alcohols and ethers and esters thereof.

The organic polymer composite inorganic fine particles mean composite inorganic fine particles in which the organic polymer is fixed on the surface of the inorganic fine particles, and the surface hardness is improved by forming a surface protective layer with a curable resin containing the fine particles. And so on. Details of the composite inorganic fine particles and a method for producing the same are described in, for example,
JP-A-178335, JP-A-9-302257, JP-A-11-124467, and the like.

The curable resin containing the composite inorganic fine particles is not particularly limited, and examples thereof include a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, and a polyfunctional acrylic resin. As a polyfunctional acrylic resin,
Polyol acrylate, polyester acrylate,
Resins such as urethane acrylate and epoxy acrylate can be mentioned.

As a commercially available curable resin containing the above-mentioned composite inorganic fine particles, for example, “Udable C-330”
0 "and" U-double C-3600 "(all manufactured by Nippon Shokubai Co., Ltd.).

The method for forming the hard coat layer includes a thermosetting method in which the composition for forming a hard coat layer is applied to the surface of a base material protective layer and cured by heating, or an active energy such as ultraviolet ray, electron beam, or radiation. An active energy ray curing method of curing by irradiating a ray is included. Of these, thermosetting methods are mainly used for silicone-based curable resins, and thermosetting methods and active energy ray curing methods using ultraviolet rays or electron beams are mainly used for curable resins containing organic polymer composite inorganic fine particles. Can be

The method for applying the composition for forming a layer constituting the hard coat layer on a base material protective layer formed on a resin member includes a dipping method, a spray coating method, a flow coating method, and a roll coating method. And a spin coating method.

The thickness of the hard coat layer is from 0.1 to 200
μm, preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the thickness of the hard coat layer is less than 0.1 μm, the surface hardness is low and the surface protection effect as the hard coat layer becomes insufficient.
If it exceeds μm, the physical properties of the resin member, particularly, mechanical strength such as bending strength may be adversely affected.

The substrate protective layer and the hard coat layer may contain various other additives in addition to the above-mentioned constituents.
Examples of the additive include silane, titanate, and aluminate-based coupling agents. Examples of the silane coupling agent include "A-18" manufactured by Nippon Unicar Co., Ltd.
7 "," A-189 "," A-1100 "," A-11 "
20 "and the like. Also, a leveling agent, an antioxidant, a light stabilizer, a filler, a rust inhibitor, a fluorescent brightener, an antioxidant, an antistatic agent, a pigment, a dye generally used in a composition for forming a layer such as a paint. , A thickener and the like.

[0090]

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 weight or% by weight.

(Synthesis of Ultraviolet Absorbing Polymer) (Synthesis Example 1) 2- [2'-hydroxy-5 was placed in a 500-ml flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube, and a nitrogen gas inlet. '-(Methacryloyloxyethyl) phenyl] -2H-benzotriazole 1
0 g, 3-methacryloxypropyltrimethoxysilane ("KBM503" manufactured by Shin-Etsu Chemical Co., Ltd.), 5 g, methyl methacrylate, 80 g, butyl acrylate, 5 g, and dipropylene glycol methyl ether, 120 g, were charged, and nitrogen gas was introduced. Heated. A mixture of 0.5 g of t-butyl peroxy-2-ethylhexanoate as an initiator and 30 parts of dipropylene glycol methyl ether was added dropwise to the charge over 2 hours, and after the addition, the mixture was heated for 2 hours. Then, the temperature was raised to 120 ° C.
Heating for 40 hours gave a 40% solution of acrylic resin. In addition,
The weight average molecular weight of this copolymer was 210,000.

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

(Synthesis Examples 2 to 6) UV-absorbing copolymers having a reactive silyl group were produced in the same manner as in Synthesis Example 1 using the monomer compositions and compounding amounts shown in Table 1. However, Synthesis Example 5 does not have ultraviolet absorption performance, and Synthesis Example 6 does not have a reactive silyl group. The produced copolymers are referred to as copolymers 2 to 6, respectively.

[0094]

[Table 1]

UVA1: 2- [2'-hydroxy-5'-
(Methacryloyloxyethyl) phenyl] -2H-benzotriazole UVA2: 2- [2'-hydroxy-5 '-(β-methacryloyloxyethoxy) -3'-tert-butylphenyl] -4-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 VAc: vinyl acetate GMA: glycidyl methacrylate Initiator: tert-butyl peroxy-2-ethylhexanoate Reaction solvent: dipropylene glycol methyl ether

Example 1 To 100 parts of the UV-absorbing copolymer having a reactive silyl group obtained in Synthesis Example 1, 0.04 part of a leveling agent (trade name “BYK331” manufactured by Big Chemie) was added, and propylene glycol was added. An acrylic resin solution was prepared by adjusting the viscosity to a predetermined value with monomethyl ether. Next, after washing the surface of the polycarbonate resin plate having a thickness of 3 mm with ethyl alcohol, the acrylic resin solution is applied to the surface of the polycarbonate resin plate so that the coating film thickness becomes 10 μm, and left at room temperature for 10 minutes. Then, it was cured by heating at 60 ° C. for 10 minutes. Next, a silicone-based hard coating agent A ("Tosgard 510" manufactured by Toshiba Silicone Co., Ltd.) is applied to the surface of the polycarbonate resin plate provided with the base material protective layer so that the coating film thickness becomes 5 μm, and the coating is performed at room temperature for 10 minutes. After leaving, 120
The composition was cured by heating at ℃ for 1 hour. The obtained polycarbonate resin plate was evaluated for the following evaluation items.

[Weather Resistance Test] Using a sunshine weather meter manufactured by Suga Test Instruments Co., Ltd., using a sunshine super long life carbon, at a constant temperature of 63 ° C., a test piece was repeatedly cycled for 2 hours without rainfall and 18 minutes for rainfall. Were exposed for 2,000 and 8,000 hours. As the evaluation after the weather resistance test, the following interlayer adhesion, surface hardness,
The degree of yellowing was measured.

[Interlayer Adhesion] A 100-piece square (1 mm ² ) is applied to the coating film, a cellophane tape is adhered to the portion of the square, and the adhered cellophane tape is peeled off at right angles and sharply. At this time, the number of stitches remaining without peeling was counted, and the following judgment was made based on the number of remaining stitches with respect to a total of 100 stitches. A (good coating film adhesion): 100 remaining stitches (all remaining) B (weak adhesion): 99-70 remaining stitches (partially peeled) C (not adhered): remaining 70 or less (almost peeled)

[Yellowness (Y1)] JIS K-7103
The yellowness (Y1) indicating coloring (especially yellowishness) of the test piece at an ambient temperature of 23 ° C. was measured in accordance with the above.

[Yellowness (△ Y1)] Indicates the change from the initial yellowness, and is calculated from the following equation. Yellowing degree (△ Y1) = (yellowness after test)-(initial yellowness) If the value of yellowing degree (△ Y1) is large, it is colored compared to the initial value (yellowish color becomes deeper) When the degree of yellowing (ΔY1) exceeds 4, it is clearly visible by visual observation that coloring has occurred.

[Surface Hardness] According to ASTM D 1044, a test piece is worn using a wear wheel CS-10F by a Taber abrasion tester. At this time, the test load is 500 g
f, the number of tests was 500. The change in haze (haze value) of the worn portion of the test piece before and after the test was determined according to JISK-710.
5, and the surface hardness was evaluated according to the following judgment. A (has sufficient surface hardness): Haze change 10% or less B (Slightly scratches easily): Haze change 10 to 20% C (Scratches): Haze change 20% or more

[Hot water resistance] After immersion in boiling water for 2 hours, the same test as the interlayer adhesion was performed. The evaluation criteria are the same as in the case of interlayer adhesion.

Examples 2 to 4, Comparative Examples 1 and 2 and Reference Example In the same manner as in Example 1, a substrate protective layer containing a predetermined polymer was formed on the resin substrate shown in Table 2, and An ultraviolet-absorbing laminated resin plate was formed by forming a predetermined hard coat layer thereon, and the same evaluation test as in Example 1 was performed for each resin plate. Table 2 shows the results.

[0104]

[Table 2]

PC: Polycarbonate addition type ultraviolet absorber: "MARK LA31" (manufactured by Adeka Argus Chemical Co.) Curing catalyst A: dibutyltin dilaurate Silicone hard coat agent A: Tosgard 510 (Toshiba Silicone Co.) Silicone hard coat agent B: Solgard NP730
(Nippon Dacro Shamrock Co.) Organic Hard Coating Agent C: NK Oligo U4H (Shin-Nakamura Chemical Co., Ltd.) / Light Ester 1.6HX-A (Kyoeisha Chemical Co., Ltd.) = 7/3 (weight ratio) * 1) Radical After one part of an initiator ("Darocur 1173" manufactured by Ciba Geigy) is added and an organic hard coat C adjusted to a predetermined viscosity is applied, it is dried with hot air at 80 ° C. for 30 minutes and moved at a speed of 5 m / min. It was placed on a conveyor and irradiated with ultraviolet light twice from a height of 20 cm using a high-pressure mercury lamp (120 W / cm). * 2) The test was stopped because the coating film was whitened and cracked after 3500 hours.

As is apparent from Table 2, the resin plates of Examples 1 to 5 in which the base material protective layer containing the UV-absorbing polymer having a reactive silyl group and the hard coat layer formed on the surface thereof were used, The interlayer adhesion, one of the indicators of weather resistance,
It is excellent in A or B rank, and yellowing degree is in the range of 1 to 3, showing good weather resistance. In addition, the surface hardness of the resin plates of Examples 1 to 5 are all A rank, and
Rank has been obtained.

On the other hand, in Comparative Example 1 in which the additive type ultraviolet absorber was added to the base material protective layer, the surface hardness was C rank, and the interlayer adhesion and the hot water resistance were C rank or less, which is unsuitable for practical use. And the degree of yellowing was also poor. In Comparative Example 2 using a copolymer not using a monomer having a reactive silyl group, the weather resistance after 2,000 hours passed was good, but the surface hardness and interlayer adhesion after 8,000 hours passed. Shortage. The reference example in which the organic hard coat was provided on the outermost layer also had good weather resistance after 2,000 hours, but it was found that the interlayer adhesion and the yellowing degree after 8000 hours were slightly insufficient. .

[0108]

According to the present invention, the protective surface of the resin substrate is formed by a copolymer comprising at least a monomer having a reactive silyl group and a monomer having an ultraviolet absorbing group as a copolymerization component. By protecting with a base material protective layer mainly composed of and covering the surface with a hard coat layer, coloring or discoloration of the resin base material due to ultraviolet rays can be suppressed as much as possible. It can enhance surface properties such as interlayer adhesion, surface hardness, abrasion resistance, and weather resistance as a resin member, and can be used for windows and skylights in automobiles, trains, aircraft, ships, and other transportation and buildings, lighting materials, and highways. To provide an ultraviolet-absorbing resin member that can be widely and effectively used for a portion where metal or glass is conventionally used, such as a sound insulation wall, or a surface protective material for a solar cell or a polymer battery. It became. In addition, the present resin material can be bonded to any other member, for example, a wood-grain-printed building material using an adhesive or an adhesive.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takahiro Aoyama 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4F100 AA01C AK01A AK01C AK25 AK45 AK52C AL01B BA03 BA10A BA10C CA07B CA23C DE01C EG002 EH462 EJ082 EJ422 GB07 GB31 GB32 JB12C JB14B JD09 JD09B JK06 JK12 JK14 JL08B JN01 4J002 BG071 EC076 EE046 EF066 EN026 EV236 EW046 EZ046 FD156 FD200 GH00 4J100 AL03S AL04S AL05S AL08P AL08Q AL08R AL08S AL66Q AM21Q AM23Q AP16R BA02P BA03P BA05P BA40P BA40Q BA41P BA75R BA77R BB01P BB03P BB05P BB07P BC02P BC02S BC03P BC04P BC04S BC08S BC43P BC65Q BC73P CA03 CA06 JA43 JA67

Claims (8)

[Claims] 1. A resin member having a base material protective layer formed on the protective surface side of a resin base material and a hard coat layer formed thereon, wherein the base material protective layer comprises a reactive silyl group. And a copolymer containing, as a monomer component, a monomer having an ultraviolet-absorbing group. 2. The copolymer constituting the base material protective layer,
2. The ultraviolet absorbing resin member according to claim 1, comprising a monomer having an ultraviolet light stable group as another monomer component. 3. The ultraviolet absorbent resin member according to claim 1, wherein the reactive silyl group is a hydrolyzable silyl group. 4. The method according to claim 1, wherein the monomer having an ultraviolet absorbing group comprises at least one monomer represented by the following general formula (I) or (II).
The ultraviolet absorbent resin member according to any one of claims 1 to 3, which is a kind of monomer. 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.) (In the formula, R ⁴ represents a lower alkylene group, and R ⁵ represents a hydrogen atom or a methyl group.) 5. The ultraviolet-absorbing resin according to claim 2, wherein the monomer having an ultraviolet-stable group is at least one monomer represented by the following general formula (III) or (IV). Element. 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. ) 6. The ultraviolet absorbing resin according to claim 1, wherein the monomer having a reactive silyl group is at least one monomer represented by the following general formulas (V) to (VII). Element. 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. The ultraviolet absorbing resin member according to claim 1, wherein the composition for forming the base material protective layer contains a curing catalyst. 8. The hard coat layer according to claim 1, wherein the hard coat layer is composed of at least one selected from a silicone-based curable resin and a curable resin containing organic polymer composite inorganic fine particles. UV absorbing resin member.