JP2003128730A - Ultraviolet light-absorbing polymer, laminated material and glass-substituting member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new ultraviolet light-absorbing polymer, capable of forming a cured layer effective for the protection of a synthetic resin substrate layer for a glass-substituting member, a laminated layer formed with the substrate protection layer containing the polymer and a glass-substituting member consisting of the laminated material. SOLUTION: This ultraviolet light-absorbing polymer consists of 5-50 wt.% ultraviolet light-absorbing monomer, 5-60 wt.% (meth)acrylate monomer containing a branched alkyl, and the rest of methyl methacrylate, and has >=150,000 weight-average molecular weight and >=90 deg.C glass transition point. The laminated material is obtained by forming the base substrate protection layer containing 1 kind or >=2 kinds of the ultraviolet light-absorbing polymer, or 1 kind or >=2 kinds of the ultraviolet light-absorbing polymer and a synthetic resin on the protecting surface side of the resin substrate. The glass-substituting member consists of the laminated material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet absorbing polymer, a laminated material and a glass substitute member.

[0002]

2. Description of the Prior Art Window glass for automobiles has a temperature of -30 ° C.
In a fairly wide temperature range of about ℃, it is constantly exposed to sunlight, rain, snow, etc., it receives extremely strong wind pressure while driving, and it is further affected by scratches due to the operation of the wiper and flying of pebbles, etc. Very high mechanical strength, weather resistance, wear resistance,
Scratch resistance, cold-heat cycle resistance, etc. are required. Therefore, as window glass for automobiles, air-cooled tempered glass containing soda lime as a main component, laminated glass obtained by laminating two or more kinds of glass having different characteristics, and the like are widely used.

However, since the air-cooled tempered glass and the laminated glass have insufficient moldability and are difficult to be molded into an arbitrary shape, the design of the vehicle body structure is restricted. In addition, the weight of these glasses becomes a problem from the viewpoint of reducing fuel consumption due to weight reduction of automobiles due to global warming.

Considering the molding processability and lightness, synthetic resins are strong candidates for glass substitute members. Among them, polycarbonate has high transparency and mechanical strength, and is excellent in heat resistance, impact resistance and the like, and has properties suitable as a glass substitute member. However, since polycarbonate has insufficient weather resistance, abrasion resistance, scratch resistance, etc., when used as a glass substitute member, the surface of the base material layer made of polycarbonate (hereinafter referred to as “polycarbonate base material layer”) To organopolysiloxane,
It is essential to stack a cured layer made of another resin such as an acrylic resin.

[0005]

Among the resins forming the cured layer, organopolysiloxane shows a certain degree of good surface hardness (impact resistance, abrasion resistance), but insufficient adhesion to the polycarbonate substrate layer. However, it has a fatal defect that peeling easily occurs. On the other hand, acrylic resin has high surface hardness and good adhesion, and is useful as a hardened layer for protecting the polycarbonate base material layer with respect to physical factors applied from the outside. However,
Although the acrylic resin itself has a weather resistance that does not hinder practical use, it cannot easily protect the polycarbonate base layer from sunlight because it easily transmits light.

In order to improve the properties of such acrylic resin, various (meth) acrylic esters and reactive (polymerizable)
An ultraviolet absorbing acrylic resin formed by copolymerizing with an ultraviolet absorber has been proposed. Specific examples of the ultraviolet absorbing acrylic resin include, for example, a copolymer of cycloalkyl (meth) acrylate and benzotriazole (meth) acrylate (JP-A-9-3135), alkyl (meth) acrylate and benzophenone methacrylate. And a copolymer (JP-A-10-34840). These ultraviolet absorbing acrylic resins are useful to some extent in protecting the polycarbonate base layer from sunlight and improving its weather resistance.
However, this ultraviolet-absorbing acrylic resin has lower surface hardness and thus lower scratch resistance than general acrylic resins, and cannot be said to have satisfactory heat resistance, thermal cycle resistance, etc. It is unsuitable as a material for a protective cured layer of polycarbonate.

Further, in Japanese Patent Laid-Open No. 2000-177070, UV-absorbing property, which is a copolymer of (meth) acrylic ester and benzotriazole (meth) acrylate, is formed on a protective surface of a substrate made of synthetic resin such as polycarbonate. A laminated body is described in which a base material protective layer containing an acrylic resin and a surface protective layer made of various curable resins are sequentially formed. However, all of the ultraviolet absorbing acrylic resins specifically disclosed in this publication have a weight average molecular weight of 150,000 and a glass transition temperature of lower than 90 ° C. Such UV-absorbing acrylic resin is particularly poor in thermal cycle resistance, and when left outdoors in seasons or areas with large daily differences, microcracks (cracks) are likely to occur on the cured surface, resulting in automobile window glass. Is not preferable as a substitute member.

An object of the present invention is to provide a novel ultraviolet absorbing polymer capable of forming a cured layer effective for protecting a synthetic resin substrate layer for a glass substitute member, and a substrate protective layer containing the polymer. An object is to provide a formed laminated material and a glass substitute member made of the laminated material.

[0009]

According to the present invention, 5 to 50% by weight of an ultraviolet absorbing monomer, 5 to 60% by weight of a (meth) acrylate monomer containing a branched alkyl group, and the balance methylmethacrylate are used. Consisting of 15,000 weight average molecular weight
An ultraviolet absorbing polymer having a glass transition temperature of 0 ° C. or higher and a glass transition temperature of 90 ° C. or higher, one or more of the ultraviolet absorbing polymers or one of the ultraviolet absorbing polymers on the protective surface side of the resin substrate.
TECHNICAL FIELD The present invention relates to a laminated material on which a base material protective layer made of an ultraviolet absorbing resin composition containing one kind or two or more kinds and a synthetic resin is formed, and a glass substitute member made of the laminated material.

According to the research conducted by the present inventor, when a UV-absorbing monomer, a (meth) acrylate monomer containing a branched alkyl group and methyl methacrylate are copolymerized at a specific ratio, A UV-absorbing acrylic resin having a weight average molecular weight of 150,000 or more and a glass transition temperature of 90 ° C. or more is obtained, and the UV-absorbing acrylic resin can be used for molding processability, lightness, surface hardness, transparency, heat resistance, polycarbonate, etc. In terms of adhesion with other synthetic resins, it shows performance equivalent to or better than conventional acrylic resin, not only efficiently shields ultraviolet rays, but also has excellent resistance to cold and heat cycles, and causes sudden temperature changes. It was found that even in the case of the above, fine cracks and the like did not occur.

Therefore, the laminated material of the present invention in which the base material protective layer containing the above-mentioned ultraviolet absorbing polymer is provided on the protective surface of the resin base material can be molded into any shape, and is lightweight, transparent and impact resistant. Excellent in heat resistance, scratch resistance, heat resistance, heat and cold cycle resistance, adhesion to other synthetic resins, etc., and these characteristics do not decrease significantly even after a long period of time. It can be used preferably.

The glass replacement member of the present invention can be used similarly to glass. Among them, it can be preferably used as transportation equipment for automobiles, trains, aircrafts, ships, etc., daylights for windows of buildings, skylights, sound insulation walls for highways, surface protection materials for solar cells, polymer batteries, etc. It can be used particularly preferably as a substitute for window glass of transportation equipment.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The ultraviolet absorbing polymer of the present invention is
UV absorbing monomer 5 to 50% by weight, preferably 10
20% by weight and 5 to 60% by weight of a (meth) acrylate monomer containing a branched chain alkyl group, preferably 10 to 50% by weight and the balance methyl methacrylate, and a weight average molecular weight of 150,000 or more, preferably 150,000 to
300,000 or more and a glass transition temperature of 90 ° C or more, preferably 95 to 150 ° C, more preferably 100 to 130.
It is an acrylic resin that absorbs UV light at ℃. The weight average molecular weight is a value measured by polystyrene standard GPC.

When the contents of the UV absorbing monomer and the (meth) acrylate monomer containing a branched chain alkyl group are out of the above specified ranges, either one or both of the weight average molecular weight and the glass transition temperature are in the above range. If it is below the specified range, an ultraviolet absorbing acrylic resin having desired physical properties cannot be obtained. More specifically, if the weight average molecular weight is less than 150,000, the film-forming strength and thus the surface hardness of the ultraviolet-absorbing acrylic resin may decrease, and microcracks may occur during molding or over time. The glass transition point is 90
When the temperature is lower than ℃, resistance to cold and heat cycle, adhesion with other synthetic resins, transparency, strength, etc. are deteriorated.

The UV absorbing monomer is not particularly limited, and any known UV absorbing compound having a polymerizable double bond can be used, but a (meth) acrylate monomer containing a branched chain alkyl group is used. In consideration of copolymerization with, for example, a benzotriazole compound represented by the formula (1) (hereinafter referred to as “benzotriazole compound (1)”), a benzophenone compound represented by the formula (2) (hereinafter referred to as “ A benzophenone compound (2) "), a triazine compound represented by the formula (3) (hereinafter referred to as" triazine compound (3) ") and the like can be preferably used. The ultraviolet absorbing monomers may be used alone or in combination of two or more.

[0016]

[Chemical 5]

[Wherein R ₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an aralkyl group, or 1 to 4 carbon atoms]
Represents an alkoxy group or a halogen atom. R ₂ represents an alkylene group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a cumyl group or an alkoxy group having 1 to 4 carbon atoms. R ₄ represents a hydrogen atom or a methyl group. ]

[0018]

[Chemical 6]

[Wherein R ₂ and R ₄ are the same as above. R ₅ represents a hydrogen atom or a hydroxyl group. R ₆ represents a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. ]

[0020]

[Chemical 7]

[Wherein R ₂ and R ₄ are the same as above. R ₇ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. ]

In the above formulas (1) to (3), each group is specifically as follows. As the alkyl group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Can be mentioned. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-
Examples thereof include linear or branched C1-C4 alkoxy groups such as butoxy group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamerylene group, 2-methyltrimethylene group, 2 Examples thereof include linear or branched alkylene groups having 1 to 8 carbon atoms such as a methyltetramethylene group and a 2-methylhexamethylene group.

Examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group,
Butyl group, pentyl group, hexyl group, heptyl group, octyl group and other linear alkyl groups having 1 to 8 carbon atoms, isopropyl group, isobutyl group, tert-butyl group, tert.
A branched chain alkyl group having 2 to 8 carbon atoms such as an octyl group,
3 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group
The cycloalkyl group of 8 can be mentioned. Examples of the lower alkoxy group having 1 to 4 carbon atoms are the same as those of R ₁ .

Examples of the alkoxy group having 1 to 6 carbon atoms include linear or branched chain such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentoxy group, heptoxy group. A C1-C6 alkoxy group can be mentioned.

As the alkoxy group having 1 to 10 carbon atoms,
Linear or branched carbon number 1 such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentoxy group, heptoxy group, octoxy group, nonyloxy group, decyloxy group There may be mentioned 10 to 10 alkoxy groups.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, tert-octyl group. ,
Examples thereof include alkyl groups having 1 to 10 carbon atoms such as nonyl group and decyl group.

Specific examples of the benzotriazole compound (1) include, for example, 2- [2'-hydroxy-5'-
(Meth) acryloyloxyethylphenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2'-hydroxy -5 '-(meth) acryloyloxypropylphenyl] -5-chloro-2H-benzotriazole, 2
-[2'-hydroxy-3'-tert-butyl-5 '
-(Meth) acryloyloxyethylphenyl] -2H
-Benzotriazole, 2- [2'-hydroxy-3 '
-Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethyl Phenyl] -5-methoxy-2H-benzotriazole and the like can be mentioned.

Specific examples of the benzophenone compound (2) include 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone and 2-hydroxy-4- {2- (meth) acryloyloxy} propoxy. Benzophenone, 2-hydroxy-4- {2-
(Meth) acryloyloxy} butoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} pentoxybenzophenone, 2-hydroxy-
4- {2- (meth) acryloyloxy} hexoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} heptoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} oct Xybenzophenone, 2,2'-dihydroxy-4
-{2- (meth) acryloyloxy} ethoxybenzophenone, 2,2'-dihydroxy-4- {2- (meth) acryloyloxy} propoxybenzophenone,
2-hydroxy-4'-methoxy-4- {2- (meth)
Acryloyloxy} ethoxybenzophenone, 2-hydroxy-4'-methoxy-4- {2- (meth) acryloyloxy} propoxybenzophenone, 2-hydroxy-4'-methoxy-4- {2- (meth) acryloyloxy} propoxy Benzophenone, 2-hydroxy-4′-methoxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 4′-ethoxy-2-
Hydroxy-4- {2- (meth) acryloyloxy}
Ethoxybenzophenone, 4 '-(1-butoxy) -2
Examples thereof include -hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone and 4 '-(tert-butoxy) -2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone.

Specific examples of the triazine compound (3) include, for example, 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-.
Triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxypropoxy)]-s
-Triazine, 2,4-bis (2-hydroxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-hydroxyphenyl) -6 -[2-hydroxy-
4- (2-Acryloyloxypropoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6-
[2-Hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxypropoxy)]- s-triazine, 2,4
-Bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-
Triazine, 2,4-bis (2-methoxyphenyl)-
6- [2-hydroxy-4- (2-acryloyloxypropoxy)]-s-triazine, 2,4-bis (2-
Ethylphenyl) -6- [2-hydroxy-4- (2-
Acryloyloxyethoxy)]-s-triazine,
2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]
-S-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine, 2,4-
Bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-s-
Triazine, 2,4-bis (2-ethylphenyl) -6
-[2-Hydroxy-4- (2-methacryloyloxyethoxy)]-s-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-
Methacryloyloxyethoxy)]-s-triazine,
2,4-bis (2,4-dimethoxyphenyl) -6- [2
-Hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]- s-triazine, 2,4
-Bis (2,4-diethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]
-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine and the like can be mentioned.

Further, the ultraviolet absorbing copolymer of the present invention may contain a light stable monomer together with the ultraviolet absorbing monomer. As the light stable monomer, known compounds can be used, and examples thereof include a tetramethylpiperidine compound represented by the formula (4).

[0031]

[Chemical 8]

[In the formula, R ₄ is the same as above. R ₈ represents a hydrogen atom or a cyano group. R ₉ is a hydrogen atom, having 1 to 1 carbon atoms
An alkyl group having 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group or an aralkyl group is shown. R ₁₀ represents an oxygen atom or an imino group. ]

In the above formula (4), the alkyl group having 1 to 18 carbon atoms represented by R ₉ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl. Group, hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Examples thereof include linear or branched alkyl groups having 1 to 18 carbon atoms such as a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Specific examples of the tetramethylpiperidine compound (4) include, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and 4- (meth) acryloylamino-2,2,2. 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 etc. can be mentioned.

The amount of the tetramethylpiperidine compound (4) to be used is not particularly limited and can be appropriately selected from a wide range, but its light-stability performance can be sufficiently exerted, the mechanical strength of the obtained ultraviolet absorbing polymer, etc. In consideration of the above, the UV absorbing polymer may be usually used in an amount of 0.1 to 15% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight.

In the ultraviolet absorbing polymer of the present invention, the (meth) acrylate monomer containing a branched alkyl group which is copolymerized with the ultraviolet absorbing monomer is not particularly limited, and any known one can be used. Although a branched chain alkyl group having 3 to 10 carbon atoms is preferable, one having 3 to 4 carbon atoms is particularly preferable. Specific examples thereof include isopropyl (meth) acrylate and isobutyl (meth).
Acrylate, tert-butyl (meth) acrylate, isopropylcyclohexyl (meth) acrylate, isobutylcyclohexyl (meth) acrylate,
Examples thereof include tert-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Among these, te
rt-Butyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate and the like are preferable. The (meth) acrylate monomer containing a branched alkyl group also includes the above-mentioned bornyl (meth) acrylate and isobornyl (meth) acrylate. The (meth) acrylate monomer containing a branched alkyl group can be used alone or in combination of two or more.

Further, in the ultraviolet absorbing polymer of the present invention, a (meth) acryl other than a (meth) acrylate monomer containing a branched chain alkyl group is used as a copolymerization component as long as its preferable characteristics are not impaired. A system monomer can be used. Known compounds can be used as the (meth) acrylic monomer, and examples thereof include (meth) acrylic acid, alkyl (meth) acrylate other than methyl methacrylate, hydroxyalkyl (meth) acrylate, and cycloalkyl (meth) acrylate. , Epoxy group-containing (meth) acrylates, and the like. Specific examples of the alkyl (meth) acrylate other than methyl methacrylate include, for example, an alkyl moiety such as methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. 1-18 carbon atoms
The straight-chain alkyl of As the hydroxyalkyl (meth) acrylate, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc., in which the alkyl portion has 1 carbon atom
There may be mentioned those which are straight-chain alkyl of 4 to 4.
As the cycloalkyl (meth) acrylate, for example, a carbon atom such as cyclohexyl (meth) acrylate or methylcyclohexyl (meth) acrylate in which the cycloalkyl moiety may have a linear alkyl group having 1 to 4 carbon atoms as a substituent. Mention may be made of cycloalkyl having a number of 3 to 10. As the epoxy group-containing (meth) acrylate, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, alicyclic epoxy group-containing (meth) acrylate [trade name: CYCLOMER M-100, CYCLOME
RA-200, manufactured by Daicel Chemical Industries, Ltd.] and the like. Other copolymerizable components include caprolactone-modified hydroxy (meth) acrylate [eg, trade name: Praxel FM, Daicel Chemical Industries, Ltd.
Manufactured], (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, imide (meth) acrylate, nitrogen-containing unsaturated monomers such as N-methylol (meth) acrylamide, ethylene glycol di (meth) Examples thereof include unsaturated monomers having two polymerizable double bonds such as acrylate. In addition to the above (meth) acrylic monomers, halogen-containing unsaturated monomers such as vinyl chloride and vinylidene chloride, aromatic unsaturated monomers such as styrene, α-methylstyrene and vinyltoluene, vinyl ethers, etc. Can be mentioned. These copolymerization components can be used alone or in combination of two or more. In the ultraviolet absorbing polymer of the present invention, the content of the copolymerization component other than the (meth) acrylate monomer containing these branched chain alkyl groups is, as described above, the ultraviolet absorbing polymer of the present invention. It may be appropriately selected within a range that does not impair the preferable characteristics of No. 1, but is usually 1 to 5% by weight.

The UV-absorbing polymer of the present invention comprises a UV-absorbing monomer and a predetermined amount of a (meth) acrylate monomer containing a branched chain alkyl group, and if necessary, other copolymerization components. It can be produced by polymerizing an amount.

In the present invention, an ultraviolet absorbing monomer and a (meth) acrylate monomer containing a branched alkyl group are used, and the above two kinds of specific monomers are used in specific amounts respectively. In addition, the ultraviolet absorbing polymer of the present invention can be obtained when the three requirements that the use of a polymerization initiator is essential during the polymerization reaction and the amount used is set within a specific range.

The polymerization is carried out in the presence of a polymerization initiator according to a known radical polymerization method such as solution polymerization, dispersion polymerization, suspension polymerization and emulsion polymerization. For example, according to the solution polymerization method, each of the above-mentioned polymerization components may be dissolved or dispersed in a solvent and heated in the presence of a polymerization initiator. As the solvent, those which can dissolve or disperse the above-mentioned respective polymerization components and which do not adversely affect the polymerization reaction can be used. For example, aromatic hydrocarbons such as toluene and xylene, isopropyl alcohol, n-butyl alcohol, etc. Lower alcohols, ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellosolve, butyl cellosolve, esters such as butyl acetate, ethyl acetate, cellosolve acetate, acetone,
Examples thereof include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and dimethylformamide. As the solvent, one type may be used alone, or two or more types may be used in combination. The amount of the solvent used may be appropriately selected in consideration of the characteristics and concentration of the polymer to be produced and the amount by which the polymerization reaction proceeds smoothly. As the polymerization initiator, known compounds can be used, for example, 2,2′-azobis- (2-methylbutyronitrile), tert-butylperoxy-
2-ethylhexanoate, 2,2'-azobisisobutyronitrile, benzoyl peroxide, di-ter
A radical polymerization initiator such as t-butyl peroxide may be used. The amount of the polymerization initiator used is 0.01 to 0.2 parts by weight based on 100 parts by weight of the total amount of the polymerization components,
It is preferably 0.05 to 0.15 part by weight. If it is out of this range, an ultraviolet absorbing polymer having desired physical properties cannot be obtained. The polymerization reaction is usually at room temperature to 200 ° C,
It is preferably carried out at a temperature of 40 to 140 ° C., and 1 to 50.
It is completed in about time, preferably about 2 to 12 hours.

The laminated material of the present invention comprises, on the protective surface side of the resin substrate, a resin composition containing one or more kinds of the ultraviolet absorbing polymer of the present invention or the above ultraviolet absorbing polymer and a synthetic resin. A base material protective layer made of a material is formed. A primer (adhesive) layer may be formed between the resin base material and the base material protective layer.

If necessary, a surface protective layer formed on the base material protective layer is also included in the laminated material of the present invention. A primer layer may be formed between the base material protective layer and the surface protective layer.

The resin base material is a synthetic resin molded into a sheet or film according to a known method. As the synthetic resin, any of those commonly used in this field can be used, and examples thereof include polycarbonate, acrylic resin, polyethylene, polypropylene, polyester, ABS resin,
Examples thereof include polystyrene and vinyl chloride resin. Moreover, it is also possible to use a resin base material having a design property on which wood grain printing or the like is applied. The film thickness of the resin base material is in a wide range depending on various conditions such as the type of synthetic resin used, the material and UV absorption capacity of the base material protective layer, the presence or absence of the surface protective layer, and the intended use of the laminated material. You can select from
Usually 10 μm to 10 mm, preferably 100 μm to 5 m
It should be m.

The base material protective layer comprises the ultraviolet absorbing polymer of the present invention or an ultraviolet absorbing resin composition containing the ultraviolet absorbing polymer and a synthetic resin. As the synthetic resin, any of those commonly used in this field can be used, and examples thereof include thermoplastic resins such as vinyl chloride resin, polyester, acrylic resin, urethane resin, aminoplast resin, silicone resin, and epoxy resin. Curable resin etc. can be mentioned. These synthetic resins may be used alone or in combination of two or more. Although the content of the ultraviolet absorbing polymer in the ultraviolet absorbing resin composition is not particularly limited, it is usually 1 to 70 in consideration of compatibility with the synthetic resin and the like.
The weight ratio may be set to preferably 10 to 50% by weight.

The base material protective layer can be formed by applying the ultraviolet absorbing polymer or the ultraviolet absorbing resin composition of the present invention to a resin base material and curing it. The coating can be carried out by a known method such as dipping, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating, bar coating and electrostatic coating. Curing can also be performed by heating, irradiation with ultraviolet rays or electron beams, etc. according to known methods. Heat curing is usually from room temperature to 250 ° C.
It can be done under the temperature. UV curing is usually 1
It is usually performed by irradiating ultraviolet rays having a wavelength of 000 to 8000 angstroms for several seconds to several tens seconds. Curing by electron beam is usually 50 to 1000 kev, preferably 100 to 3
It is performed by irradiating an electron beam with an accelerating voltage of 00 kev so that the absorption line is about 1 to 20 Mrad. The electron beam irradiation is performed in the air or an inert gas such as nitrogen. Also,
You may carry out combining 2 or more types of these hardening methods.

Further, the ultraviolet absorbing polymer or the ultraviolet absorbing resin composition of the present invention is previously formed into a sheet or film according to a known method, and this and the resin base material are heated and / or heated if necessary. You may adhere | attach under pressure.

The thickness of the base material protective layer depends on the thickness of the resin base material, the type of synthetic resin used for the resin base material, the presence / absence of a primer layer, and the type of ultraviolet absorbing monomer contained in the base material protective layer. The amount can be appropriately selected from a wide range according to various conditions such as the amount and amount, the presence or absence of the surface protective layer, the intended use of the obtained laminated material, etc., but usually 0.5 to 200 μm, preferably 1 to 100 μm, and more preferably 2 to The thickness may be 30 μm.

The surface protective layer is further formed on the base material protective layer with a synthetic resin, if necessary, in order to further improve the weather resistance and scratch resistance of the laminated material. As the synthetic resin, any of those commonly used in this field can be used, but from the viewpoint of weather resistance, scratch resistance and the like, silicone resin, organic curable resin and the like are preferable.

As the silicone resin, any resin having a siloxane bond can be used. For example, a partial hydrolysis product of trialkoxysilane and tetraalkoxysilane or their alkyl compounds, a mixture of methyltrialkoxysilane and phenyltrialkoxysilane can be used. And a partially hydrolyzed condensate of colloidal silica-filled organotrialkoxysilane. Commercially available products can also be used, for example, Si coat 2 (manufactured by Daihachi Chemical Co., Ltd.), Tosgard 510, UVHC8553, U
VHC8556, UVHC8558 (manufactured by Toshiba Silicone Co., Ltd.), KP-851, KP-854, X-12-
2206, X-12-2400, X-12-2450
[Shin-Etsu Silicone Co., Ltd.], Solgard NP720,
Examples include Solgard NP730 and Solgard RF0831 (manufactured by Nippon Dacro Shamrock Co., Ltd.). These include alcohols generated during the condensation reaction, but may be dissolved or dispersed in an organic solvent, water, a mixture thereof, or the like, if necessary. Examples of the organic solvent include lower fatty acid alcohols, polyhydric alcohols and their ethers, esters and the like. In order to further improve the surface smoothness of the surface protective layer,
You may add surfactants, such as a siloxane type and an alkyl fluoride type, to silicone resin.

As the organic curable resin, any resin which can be cured by heating or irradiation with ultraviolet rays, electron beams or the like can be used. Examples thereof include melamine resin, urethane resin, alkyd resin, acrylic resin, polyfunctional acrylic resin and the like. Can be mentioned. Examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, and epoxy acrylate. The organic curable resin may contain organic polymer composite inorganic fine particles in order to improve the surface hardness of the surface protective layer. The organic polymer composite inorganic fine particles are those in which an organic polymer is fixed on the surface of the inorganic fine particles, and are described, for example, in JP-A-7-178335, JP-A-9-302257, and Japanese Patent Application No. 9-291390. ing. Among the inorganic fine particles, an inorganic oxide is preferable, an oxide of an element selected from Group II to VI of the periodic table is more preferable, an oxide of an element selected from Group III to V of the periodic table is further preferable, Si, Al, Oxides such as Ti and Zr are particularly preferable. The inorganic oxide may contain an organic group, a hydroxyl group, a part of an organic polymer, or the like. Examples of the organic group include a substituted or unsubstituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group and an aralkyl group. The inorganic fine particles can be used alone or 2
More than one species can be used together. The inorganic fine particles may have any shape such as spherical shape, needle shape, plate shape, scale shape, and crushed shape. The organic polymer is one that is soluble in an organic solvent and / or water, is composed of an organic chain and a polysiloxane group, and has at least one polysiloxane group bonded per molecule, and the polysiloxane group is contained in the polysiloxane group. At least one Si-OR
Group (R represents a hydrogen atom, an alkyl group or an acyl group.)
Those having are preferred. Specifically, for example, a polymer in which a polysiloxane group is grafted to an organic chain, a polymer in which a polysiloxane group is bonded to one end or both ends of an organic chain, or a plurality of linear or branched chains having a polysiloxane group as a core Examples thereof include a polymer having an organic chain bonded thereto. The organic chain means a portion other than the polysiloxane group in the organic polymer, and the structure of the organic chain is not particularly limited, but the main chain bond in the organic chain contains 50 to 100 mol% of carbon atoms, and the balance is N, Those composed of elements such as O, S, Si and P are preferable. The resin constituting the organic chain, for example, (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefin such as polyethylene and polypropylene, vinyl chloride, vinylidene chloride, polyester such as polyethylene terephthalate and their copolymers and amino groups, Examples thereof include resins partially modified with a functional group such as an epoxy group, a hydroxyl group, and a carboxyl group. Among these, (meth) acrylic resins, (meth) acrylic-styrene resins, (meth) acrylic- A resin containing a (meth) acrylic unit such as a polyester resin is preferable. The polysiloxane group and the organic chain in the organic polymer are S
Those chemically bonded via an i-C bond, a Si-O-C bond, or the like are preferable. Examples of commercially available curable resins containing composite inorganic fine particles include "Uudouble C-330".
0 "," Udable C-3600 "[Nippon Shokubai Co., Ltd.
Manufactured] and the like.

The synthetic resin constituting the surface protective layer includes a silane coupling agent [eg, trade name: A-187, A-
189, A-1100, A-1120, etc., manufactured by Nippon Unicar Co., Ltd.] and the like. The surface protective layer can be formed in the same manner as the base material protective layer. The thickness of the surface protective layer is not particularly limited and can be appropriately selected from a wide range, but in consideration of scratch resistance and mechanical strength (flexural strength etc.) as a laminated material, it is usually 0.1 to 200 μm, preferably 0.5-10
The thickness may be 0 μm, more preferably 1 to 50 μm.

The base material protective layer and the surface protective layer may contain various additives as long as the preferable characteristics are not impaired. As the additive, for example, leveling agent, yellow lead, molybdate orange, dark blue, cadmium pigment, titanium white, complex oxide pigment, transparent iron oxide, carbon black,
Cyclic high-grade pigment, soluble azo pigment, copper phthalocyanine pigment,
Dye pigments, pigments such as pigment intermediates, pigment dispersants, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxide decomposers, fillers, reinforcing agents, plasticizers, lubricants Agent, anticorrosive,
Examples thereof include a rust preventive agent, a fluorescent brightening agent, an organic / inorganic flameproof agent, an anti-dripping agent, a melt flow modifier and an antistatic agent.

The primer layer can be formed by an ordinary method using an adhesive resin commonly used in this field. Further, the laminated material of the present invention, a sheet made of the ultraviolet absorbent polymer or the ultraviolet absorbent resin composition of the present invention is mounted in the cavity of a mold of any shape, injection molded thermoplastic resin, It can also be manufactured by integrating the sheet and the injection resin.

The laminated material of the present invention is exposed to sunlight or light including ultraviolet rays and used in a state where the temperature changes drastically, and has transparency, surface hardness, scratch resistance, light weight, flexibility in molding and the like. It can be suitably used for required applications. In particular,
For example, substitutes for glass used for houses, facilities, automobiles and other transportation equipment, daylighting glass, lighting equipment, housing,
Interior / exterior members for facilities, automobiles, transportation equipment, etc., electronic device members, containers, agricultural and industrial members, optical device members, lenses, filters, mirrors, signboards, signage and other members, medical device members, stationery, etc. Can be mentioned. Among them, it can be preferably used as transportation equipment for automobiles, trains, airplanes, ships, windows for buildings, daylighting materials for skylights, sound insulation walls for highways, surface protection materials for solar cells, polymer batteries, etc., and windows for automobiles. It can be particularly preferably used as a substitute for glass.

[0055]

EXAMPLES The present invention will be described in detail below with reference to Synthesis Examples, Examples, Comparative Examples and Test Examples. In the following, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.

Synthesis Example 1 (Synthesis of Ultraviolet Absorbing Polymer) 2- [2'-hydroxy-5 '-(in a 500 ml flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube and a nitrogen gas inlet port. Methacryloyloxyethyl) phenyl]
-2H-benzotriazole 15 parts, methyl methacrylate 75 parts, tert-butyl methacrylate 10 parts and solvent diacetone alcohol 100 parts were charged,
Nitrogen gas was introduced and heated to 110 ° C. with stirring. To this, a mixture of 0.12 parts of AIBN (polymerization initiator) and 20 parts of diacetone alcohol was added dropwise over 2 hours, and after the addition, heating was continued for 2 hours to obtain 49.7% of the ultraviolet absorbing acrylic resin of the present invention. % Solution was obtained. The weight average molecular weight of the ultraviolet absorbing acrylic resin was 152,000. Further, a part of the solution of the ultraviolet absorbing acrylic resin was poured into 10 times the amount of methanol, and the precipitated ultraviolet absorbing acrylic resin was dried under reduced pressure and subjected to differential thermal analysis. The glass transition point was 98 ° C. It was After drying, this ultraviolet absorbing polymer is designated as Polymer 1. Table 1 shows the types and blending amounts of the monomer compositions, and the characteristic values of the obtained polymers.

Synthetic Examples 2 to 9 A solution of an ultraviolet absorbing acrylic resin was produced in the same manner as in Synthetic Example 1 except that the monomer composition and the amount used were changed as shown in Table 1. The amount of AIBN used in Synthesis Example 8 was 0.7 parts by weight. The solid content concentration, the weight average molecular weight of the ultraviolet absorbing acrylic resin and the glass transition temperature are also shown in Table 1. In Table 1, each compound represented by abbreviations is specifically as follows.

UVA1: 2- [2'-hydroxy-5 '
-(Methacryloyloxyethyl) phenyl] -2H-
Benzotriazole UVA2: 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone UVA3: 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine HALS1: 4-methacryloyloxy-2,2,6,6
-Tetramethylpiperidine M-1: methyl methacrylate M-2: isobornyl methacrylate M-3: cyclohexyl methacrylate M-4: butyl acrylate M-5: tert-butyl methacrylate M-6: 2-hydroxyethyl methacrylate

[0059]

[Table 1]

Example 1 100 parts of the ultraviolet absorbing acrylic resin obtained in Synthesis Example 1 was mixed with 150 parts of diacetone alcohol and a leveling agent (trade name: BYK300, manufactured by Big Chemie) 0.01
And agitated well to prepare a resin solution for a base material protective layer. Next, the surface of the polycarbonate resin plate was washed with ethyl alcohol, and the resin solution for the base material protective layer was coated to a thickness of 15
It was coated on the surface of the polycarbonate resin plate so as to have a thickness of μm. This was dried at room temperature for 5 hours and then at 80 ° C. for 30 minutes. Then, a silicone-based hard coating solution [trade name: UVHC8553, manufactured by Toshiba Silicone Co., Ltd.] was applied to the surface of the polycarbonate resin plate provided with the base material protective layer so that the coating film thickness would be 5 μm, and at 120 ° C. It was heat-cured for 2 hours to produce a polycarbonate resin plate.

Examples 2 to 3 Polycarbonate resin plates were produced in the same manner as in Example 1 except that the ultraviolet absorbing acrylic resin obtained in Synthesis Example 2 or 3 was used.

Example 4 To 100 parts of the ultraviolet absorbing acrylic resin obtained in Synthesis Example 4, 150 parts of diacetone alcohol, and a blocked isocyanate as a curing agent [trade name: Duranate MF-K6]
2 parts of 0X, manufactured by Asahi Kasei Co., Ltd., and 0.01 part of a leveling agent [trade name: BYK300, manufactured by Big Chemie] were added and well stirred to prepare a resin solution for a base material protective layer. Next, the surface of the polycarbonate resin plate was washed with ethyl alcohol, and the acrylic resin solution was applied to the surface of the polycarbonate resin plate so that the coating film thickness was 15 μm. This was dried at room temperature for 5 hours and then heated at 80 ° C. for 30 minutes to cure. Then, on the surface of the polycarbonate resin plate provided with the base material protective layer, a silicone-based hard coating solution [trade name: UVHC8553, Toshiba Silicone Co., Ltd.]
Manufactured] at a temperature of 120 ° C.
Then, the mixture was heated for 2 hours to cure, and a polycarbonate resin plate was manufactured.

Examples 5 to 7 Polycarbonate resin plates were produced in the same manner as in Example 4 except that the ultraviolet absorbing acrylic resin obtained in Synthesis Examples 5 to 7 was used.

Comparative Examples 1-2 A polycarbonate resin plate was produced in the same manner as in Example 4 except that the ultraviolet absorbing acrylic resin obtained in Synthesis Example 8 or 9 was used.

Comparative Example 3 To 100 parts of the acrylic resin obtained in Synthesis Example 10 was added 150 parts of diacetone alcohol and 7.5 parts of an additive type ultraviolet absorber (trade name: Tinuvin 320, manufactured by Ciba Specialty Chemicals). , 2 parts of blocked isocyanate [trade name: Duranate MF-K60X, manufactured by Asahi Kasei Co., Ltd.] as a curing material, and a leveling agent (trade name: BYK30)
0.01 part (manufactured by Big Chemie) was added and well stirred to prepare a resin solution for a base material protective layer. Next, the surface of the polycarbonate resin plate was washed with ethyl alcohol, and the acrylic resin solution was applied to the surface of the polycarbonate resin plate so that the coating film thickness was 15 μm. This was dried at room temperature for 5 hours and then heated at 80 ° C. for 30 minutes to cure. Then, on the surface of the polycarbonate resin plate with the base material protective layer,
Silicone-based hard coating solution [Product name: UVH
C8553, manufactured by Toshiba Silicone Co., Ltd.]
It was coated so as to have a thickness of μm and heated at 120 ° C. for 2 hours to be cured to produce a polycarbonate resin plate.

Test Example 1 The polycarbonate resin plates obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to a performance test and evaluated. The evaluation items are as follows. The results are shown in Table 2.

Weather resistance test A polycarbonate resin plate was used with a Duocycle sunshine weather meter [trade name: WEL-SUN-DC, manufactured by Suga Test Instruments Co., Ltd.] to obtain a black panel temperature of 60 ° C.
Then, a cycle of 2 hours without rainfall and a cycle of 18 minutes of rainfall was repeated for 24 hours, and then the cycle of leaving at 10 ° C. for 12 hours was repeated until the total exposure time reached 8000 hours. After the weather resistance test, interlayer adhesion, yellowing degree, cracks (microcracks) and surface hardness were measured to evaluate the weather resistance of the polycarbonate resin plate. <Interlayer adhesion> 100 goggles (1 mm ² ) on the coating film
And attach the cellophane tape to the eyes,
Then, the adhered cellophane tape is peeled at a right angle and rapidly. At this time, the number of remaining eyelets was counted, and the following judgment was made based on how many were left for 100 in total. Good (adhesiveness of coating film): 100 remaining marks (all remain) Poor (partial peeling): 99-50 remaining peels (half or more peeling): 50 remaining marks or less <yellowing degree (ΔYI)> Yellowness of sample before and after exposure (YI)
Was measured according to JIS K-7103 (Synthetic resin yellowness and yellowing test method), and ΔYI was calculated from the following formula.
When the degree of yellowing exceeds 5, yellowing of the polycarbonate resin plate can be visually confirmed. Yellowness (ΔYI) = Yellowness after test (YI) -Yellowness before test (YI) <Cracks (microcracks)> After exposure, the state of crack generation on the irradiated surface of the sample was observed with an optical microscope. A (no crack): No microcracks. ○ (Slightly cracked): Microcracks are observed. X (with cracks): Cracks can be visually observed. <Surface Hardness> According to ASTM D1044, the test piece was worn using a wear wheel CS-10F with a Taber abrasion tester (test load 500 gf, number of tests 500 times). The condition of the worn part of the test piece before and after the test was observed with an optical microscope, and the surface hardness was evaluated by the degree of scratching. A (sufficient surface hardness): Almost no change is observed before and after the test. ◯ (Slightly scratched): The test piece after the test is slightly scratched. X (Scratch): The test piece after the test is greatly scratched.

A cycle of immersing the hot water resistance test piece in boiling water for 1 hour and then immersing it in cold water at 20 ° C. for 30 minutes was repeated 10 times, and then interlayer adhesion, cracking, and cracking were observed in the same manner as in the weather resistance test. The surface hardness was evaluated.

[0069]

[Table 2]

As is clear from Table 2, in the resin plates of Examples 1 to 7 in which the base material protective layer containing the ultraviolet absorbing acrylic resin of the present invention was formed, after the weather resistance test for 8000 hours and in the hot water test. After heat history using cold water and cold water (Cold heat resistance cycle test)
Also showed no change in its strength (interlayer adhesion, cracking, surface hardness). Further, the yellowing degree after the 8000-hour weather resistance test was also in the range of 2 to 4, and it was proved that the material has excellent weather resistance. The above result is
It is shown that the ultraviolet-absorbing laminated resin material of the present invention does not cause a change in appearance or a decrease in strength due to irradiation with ultraviolet rays or a rapid temperature change.

On the other hand, in Comparative Examples 1 and 2, although the yellowing was relatively small, the strength decreased after the test, and the appearance such as cracking and deterioration of the interlayer adhesion was impaired. Particularly, in Comparative Example 2 in which the resin for a base material protective layer has a low glass transition point, the appearance was greatly impaired due to the heat history of the weather resistance test and the hot water resistance test, and the yellowness index (YI) could not be measured. Comparative Example 3 is a system in which an additive type ultraviolet absorber is used as the resin for the base material protective layer, but despite the molecular weight and the glass transition point being the same as those of the resins of Examples, its strength after the test, The appearance was damaged. The degree of yellowing was 7 and thus was poor.

[0072]

The UV-absorbing polymer of the present invention exhibits molding processability, lightness, surface hardness, transparency and heat resistance equivalent to or higher than those of conventional acrylic resins, and only has high UV-absorbing performance. In addition, it has excellent resistance to cold and heat cycles, and does not cause fine cracks or the like even in a use scene where a rapid temperature change occurs. Therefore, on the protective surface of the resin substrate layer,
The laminated material of the present invention provided with the base material protective layer containing the ultraviolet absorbing polymer of the present invention can be molded into any shape, and has light weight, transparency, impact resistance, abrasion resistance, heat resistance, and cold heat resistance. It has excellent cycleability, adhesion to other synthetic resins, and the like, and these characteristics do not decrease significantly even after a long period of time, and it can be particularly suitably used as a glass substitute member.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 3/00 104 C09K 3/00 104A 104B 104C F term (reference) 4F100 AA00A AA00H AK01A AK25A AK25J AK25K AK45A AK52A AL06A AL06H AT00B BA02 BA10A BA10B DE01A DE01H GB32 JB12A JD09A JJ03 JK01 JK10 JN01 4J038 CD021 CD022 CG141 CG142 CH031 CH032 CH041 CH042 CH071 CH072 DA111 DA112 DB001 DB002 DD001 DD002 DG001 DG002 DL021 DL022 DL031 DL032 GA02 GA08 NA11 NA12 NA19 PB03 PB07 PC08 4J100 AL03P AL03R AL04P AL05P AL08P AL08Q BA02Q BA03Q BA06Q BA11Q BB01Q BC04P BC43P BC65Q BC75Q CA05 JA32

Claims (8)

[Claims] 1. A (meth) acrylate monomer 5 containing 5 to 50% by weight of an ultraviolet absorbing monomer and a branched alkyl group.
A UV-absorbing polymer having a weight average molecular weight of 150,000 or more and a glass transition temperature of 90 ° C. or more, which comprises ˜60% by weight and the balance methyl methacrylate. 2. The ultraviolet absorbing monomer is selected from a benzotriazole compound represented by the formula (1), a benzophenone compound represented by the formula (2), and a triazine compound represented by the formula (3). It is 1 type or 2 or more types.
The ultraviolet-absorbing polymer described in 1. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
An aryl group, an aralkyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is shown. R ₂ represents an alkylene group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a cumyl group or an alkoxy group having 1 to 4 carbon atoms. R ₄ represents a hydrogen atom or a methyl group. ] [Chemical 2] [In formula, R < ₂ > and R < ₄ > is the same as the above. R ₅ represents a hydrogen atom or a hydroxyl group. R ₆ is a hydrogen atom, a hydroxyl group or a carbon number of 1 to
6 represents an alkoxy group. ] [Chemical 3] [Wherein R ₂ and R ₄ are the same as above. R ₇ is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
The alkyl group of 0 is shown. ] 3. A light-stable monomer represented by formula (4)
The ultraviolet absorbing polymer according to claim 1 or 2, which contains one or more kinds as a copolymerization component. [Chemical 4] [In formula, R < ₄ > is the same as the above. R ₈ represents a hydrogen atom or a cyano group. R ₉ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R ₁₀ represents an oxygen atom or an imino group. ] 4. One or more UV absorbing polymers according to claims 1 to 3 or one or more UV absorbing polymers and a synthetic resin on the protective surface side of the resin substrate. A laminated material having a base material protective layer formed of an ultraviolet absorbing resin composition containing: 5. A surface protective layer comprising a resin composition containing or not containing one or more of the ultraviolet absorbing polymer according to any one of claims 1 to 3, formed on the base material protective layer. Item 4. The laminated material according to item 4. 6. The laminated material according to claim 4, wherein the surface protective layer is a protective layer composed of one or more resins selected from silicone-based curable resins and organic-based curable resins. 7. The surface protective layer is a silicone-based curable resin,
The laminated material according to claims 4 to 6, which is a protective layer composed of one or more resins selected from organic curable resins and organic polymer composite inorganic fine particles. 8. A glass substitute member comprising the laminated material according to claim 4.