JP2000177070A - Ultraviolet absorbing laminated resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve weather resistance and scuff resistance by forming a base material protective layer and a surface protective layer on the protective surface side of a resin base material, and forming the protective layer by incorporating a polymer obtained by polymerizing a monomer component selected from specific ultraviolet absorbing monomer. SOLUTION: A base material protective layer is formed on the protective surface side of a resin base material, and a surface protective layer is formed on the protective layer to form the laminated resin material. In this case, the protective layer is formed by incorporating a polymer obtained by polymerizing a monomer component selected from an ultraviolet absorbing monomer represented by a formula I or II, wherein R1 is a hydrogen atom or a hydrocarbon group, R2 is a lower alkylene group, R3 is a hydrogen atom or a methyl group, X is a hydrogen atom, a halogen or the like, R4 is a lower alkylene group, and R5 is a hydrogen atom or a methyl group. The base material protective layer is preferably made of a crosslinked cured material. As a constituting material of the protective layer, a silicone curable resin or the like is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-absorbing laminated resin material which suppresses coloring and deterioration by ultraviolet rays and has excellent scratch resistance.

[0002]

2. Description of the Related Art Resin materials such as polycarbonate and other resin films, resin sheets, and resin plates (hereinafter referred to as resin plates) are excellent in transparency, impact resistance, heat resistance, flame retardancy, etc. It is widely used for building materials and building materials, and its use is expected to expand in the future. However, its use is limited because it is inferior to various surface characteristics such as surface hardness, scratch resistance, and solvent resistance as compared with metals, glass, and the like, and there is a strong demand for improvement of the surface characteristics of the base resin.
As a method of improving the surface characteristics, there is a method of coating the surface of the base resin with a surface treating agent. 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 are obtained by a method of forming a surface hardened layer on the surface of a base resin using a thermosetting organopolysiloxane resin. Specifically, a partially hydrolyzed condensate of an organotrialkoxysilane alone, a partially hydrolyzed condensate of a tetraalkoxysilane and an organotrialkoxysilane, or a partially hydrolyzed condensate of a colloidal silica-filled organotrialkoxysilane is applied. By curing, a laminated resin having excellent surface hardness can be obtained. These paints provide good adhesion when the base resin is polymethyl methacrylate resin, but have a problem with adhesion to polycarbonate resins, and may cause peeling of the hardened surface layer.

As a method of improving the adhesion, for example, Japanese Patent Publication No. 63-5155 and Japanese Patent Publication No. 63-66868
Japanese Patent Laid-Open Publication No. H11-19764 and the like have proposed a method of forming a primer layer by pretreating the surface of a polycarbonate resin plate. This method certainly improves the adhesion of the surface hardened layer.

[0005] On the other hand, the resin plate generally has a defect in weather resistance. In particular, another problem arises in that the surface of the resin plate is deteriorated or colored 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 can absorb ultraviolet rays, so that the transmitted ultraviolet rays deteriorate the resin plate surface and should have been improved. Adhesion deteriorates,
A problem of weather resistance such as coloring and reduction in strength occurs.

In order to prevent ultraviolet rays which deteriorate the resin plate from reaching the surface of the resin plate, for example, Japanese Patent Publication No. 60-53701 and Japanese Patent Publication No. 2-37938 disclose surface layers such as a primer layer and a surface hardened layer. There has been proposed a method in which an ultraviolet absorber is added to a constituent material to absorb ultraviolet light in a surface layer. Also, a number of methods have been proposed for preventing the solvent resistance and the like of the surface layer from deteriorating due to the added ultraviolet absorber and improving the compositions of the surface-hardened layer and the primer layer in order to further improve the adhesiveness (for example, Japanese Patent Publication No. HEI-Hei). 1-758
No. 2, Japanese Patent Publication No. 1-32246, Japanese Patent Publication No. 1-1
No. 8944, Japanese Patent Publication No. 2-37938, etc.). By these methods, the deterioration of the resin plate 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 into these layers. For this reason, the surface-hardened layer and the primer layer are colored or become turbid, and when viewed as a whole of the surface-hardened resin plate, there are problems such as loss of transparency, which is a characteristic of the resin plate, and conspicuous coloring. It is also pointed out that the interlayer adhesion between the surface hardened layer and the primer layer and between the primer layer and the resin plate is deteriorated.
Further, since the ultraviolet absorber itself is not high in hardness, there is also a problem that the addition of a large amount of the ultraviolet absorber lowers the excellent surface hardness of the surface hardened layer. In other words, if the ultraviolet absorber is not added, the surface of the resin plate is deteriorated by the ultraviolet light, and the adhesion of the surface hardened layer is deteriorated. Conversely, if the ultraviolet absorber is added, the coloring and the surface hardness are reduced, which is a contradictory problem. Was.

In order to solve such a problem, for example, Japanese Patent Application Laid-Open Nos. 9-3135 and 10-34840 propose that an acrylic resin copolymerized with a reactive ultraviolet absorber is used for the surface layer. ing. A large amount of UV absorbers can be used by these techniques, but the acrylic resins copolymerized with these UV absorbers are all thermoplastic and have insufficient hardness and insufficient scratch resistance as a coating layer for surface protection. However, it cannot be said that heat resistance, hot water resistance, weather resistance, and the like are satisfactory.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has an object to improve weather resistance without causing coloring by ultraviolet rays, a decrease in surface hardness, and a decrease in interlayer adhesion. And to provide a laminated resin material having high surface hardness and excellent scratch resistance.

[0010]

According to the present invention, there is provided a laminated resin material having a substrate protective layer formed on the protective surface side of a resin substrate and a surface protective layer formed thereon. The base material protective layer contains a polymer obtained by polymerizing a monomer component containing at least one selected from ultraviolet absorbing monomers represented by the following general formula (1) or (2). An ultraviolet-absorbing laminated resin material is provided.

[0011]

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

[0013]

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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.) At this time, the monomer component is represented by the following general formula (3) or (4). It is desirable to further include at least one selected from ultraviolet stable monomers.

[0015]

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

[0017]

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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).

The substrate protective layer is particularly preferably composed of a cross-linked cured product. From the viewpoint of improving weather resistance and scratch resistance, the constituent material of the surface protective layer is a silicone-based curable resin or an organic-based resin. It is preferable to use at least one resin selected from the group consisting of a curable resin and a curable resin containing organic polymer composite inorganic fine particles.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have considered that while retaining the excellent properties inherent in a resin plate, such as transparency and impact resistance, the surface hardness and weather resistance, which have been regarded as problems in the past, have been considered. As a result of diligent studies to improve, a layer containing a UV-absorbing polymer formed by polymerizing a monomer component containing a specific UV-absorbing monomer is formed on a resin base material, and a resin plate surface is formed. By forming a protective layer on, the knowledge that it is possible to improve the surface hardness and weather resistance of the resin plate,
The present invention has been accomplished.

One of the major features of the present invention is that a polymer obtained by polymerizing a monomer component containing at least one selected from ultraviolet absorbing monomers represented by the general formula (1) or (2). This is in that a base material protective layer containing the coalesced is formed on the surface of the resin base material. With this configuration, the ultraviolet rays are absorbed by the base material protective layer before reaching the resin base material, and the deterioration and discoloration of the resin base material due to the ultraviolet rays are suppressed. In addition, since it does not bleed out unlike the conventional additive type ultraviolet absorber, excellent interlayer adhesion can be obtained.

The polymer has the general formula (3) or (4)
And at least one selected from ultraviolet stable monomers represented by the following formula (I). The copolymerization of these UV stable monomers can further improve the weather resistance.

The resin substrate used in the present invention is not particularly limited as long as it is a resin plate. For example, polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, ABS resin, polystyrene resin, vinyl chloride Resins and the like can be mentioned. In addition, the shape and manufacturing method of the resin substrate may be any, and are not particularly limited. Further, it is also possible to use a resin base material having a design and subjected to grain printing or the like.

In the present invention, the compound is represented by the general formula (1).
The ultraviolet absorbing monomer represented by the formula: ¹Is a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms;^TwoIs lower al
Composed of a kylene group;^ThreeIs a hydrogen atom or a methyl group
X is hydrogen, halogen, hydrocarbon having 1 to 8 carbon atoms
Group, a lower alkoxy group, a cyano group or a nitro group.
Benzotriazoles formed.

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 : Alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group: aromatic hydrocarbon groups such as phenyl group, tolyl group, xylyl group, benzyl group and phenethyl group; methoxy 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; and a nitro group.

Specific examples of the ultraviolet absorbing monomer represented by the general formula (1) include, for example, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl]
-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl]-
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(methacryloyloxypropyl) phenyl]-
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(methacryloyloxyhexyl) phenyl]-
2H-benzotriazole, 2- [2′-hydroxy-
3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole,
-[2'-hydroxy-5'-tert-butyl-3 '
-(Methacryloyloxyethyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl]
-5-methoxy-2H-benzotriazole, 2-
[2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-tert-butyl −
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(methacryloyloxyethyl) phenyl] -5
-Nitro-2H-benzotriazole and the like, but are not particularly limited thereto. These UV-absorbing monomers represented by the general formula (1) may be used alone or in combination of two or more.

In the ultraviolet absorbing monomer represented by the general formula (2), the substituent represented by R ⁴ is a lower alkylene group, and the substituent represented by R ⁵ is a hydrogen atom or Benzotriazoles which are methyl groups.

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, and a propylene group.

Specific examples of the ultraviolet absorbing monomer represented by the general formula (2) include, for example, 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy)-
3'-tert-butylphenyl] -4-tert-butyl-2H-benzotriazole, but is not particularly limited thereto. These UV-absorbing monomers represented by the general formula (2) may be used alone or in combination of two or more.

In the UV-stable monomers of the general formulas (3) and (4) used in the present invention, the substituent represented by R ⁶ is a hydrogen atom or a cyano group, R ⁷ , R ⁸ , R ^{7 '} , R ^8'
Are 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 a piperidine which is an oxygen atom or an imino group.

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. Alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; phenyl group, tolyl group, xylyl group,
Non-limiting examples include aromatic hydrocarbon groups such as a benzyl group and a phenethyl group.

Specific examples of the UV-stable monomer represented by the general formula (3) include, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, ) 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. One of these may be used alone, or two or more of them may be appropriately mixed and used. You may. Of course, the UV stable monomer of the general formula (3) is not limited to these compounds.

Specific examples of the UV-stable monomer represented by the general formula (4) include, for example, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6
6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-
2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like. The above may be appropriately mixed and used. The UV-stable monomer of the general formula (4) is not limited to these.

The amount of the UV-absorbing monomer represented by the general formulas (1) and (2) is not particularly limited, but may be 1 to 90 wt% in the total monomer. desired. Describing a more preferable range, the lower limit is preferably 5 wt%, more preferably 10 wt%. On the other hand, the upper limit is preferably 70 wt%, more preferably 50 wt%. If the amount of the ultraviolet absorbing monomer used is less than 1 wt%, it is necessary to increase the thickness of the base material protective layer in order to prevent the resin base material from being deteriorated by ultraviolet rays. Cracks are likely to occur, and cracks may occur even after long-term use. On the other hand, if it exceeds 90 wt%, the physical properties of the base material protective layer may be reduced.

The amount of the UV-stable monomer represented by the general formulas (3) and (4) is not particularly limited, but is 0.1 to 15% by weight based on the UV-absorbing polymer. It is desired to do. Describing a more preferable range, the lower limit is preferably 0.5 wt%, more preferably 1 wt%. On the other hand, the upper limit is preferably 5
wt%, more preferably 3 wt%. If the total amount of the UV-stable monomer is less than 0.1% by weight, deterioration of the base material protective layer may not be prevented.
If it exceeds 5 wt%, the physical properties of the base material protective layer may be reduced.

Other unsaturated copolymerizable monomers other than the above-mentioned monomers do not impair various physical properties required for a polymer containing an ultraviolet absorbing monomer as a part of a repeating unit. Any of these can be used as long as the unsaturated monomer is represented by the following general formula (5) from the viewpoint of weather resistance.

[0037]

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(In the formula, R ¹⁰ 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 straight-chain alkyl group having 6 or more carbon atoms are preferred.

Specific examples of the unsaturated monomer represented by the general formula (5) 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, and the like. Alternatively, two or more types can be used.

The amount of the unsaturated monomer represented by the general formula (5) is not particularly limited, but is preferably in the range of 3 to 70% by weight, more preferably 5 to 50% by weight, based on the ultraviolet absorbing polymer. % Range. If the amount is less than 3 wt%, desired weather resistance may not be easily obtained, while if it exceeds 70 wt%, the interlayer adhesion to the resin substrate may be reduced.

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 can be 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.

Other unsaturated monomers copolymerizable include carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, itaconic acid, maleic acid and maleic anhydride;
-Acid phosphate unsaturated monomers such as (meth) acryloyloxyethyl acid phosphate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, caprolactone-modified hydroxy (meth)
Acrylate (for example, manufactured by Daicel Chemical Industries, Ltd .;
Unsaturated monomers containing a group having active hydrogen, such as trade name "Placcel FM"); methyl (meth) acrylate,
(Meth) acrylic acid lower alkyl esters such as ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate; (meth) acrylamide, N, N'-dimethylaminotyl (meth) acrylate, imide (meth) Nitrogen-containing unsaturated monomers such as acrylate and N-methylol (meth) acrylamide; unsaturated monomers having two polymerizable double bonds such as ethylene glycol di (meth) acrylate; vinyl chloride, vinylidene chloride, etc. Halogen-containing unsaturated monomers of: styrene,
Examples include aromatic unsaturated monomers such as α-methylstyrene and vinyltoluene; vinyl ethers, but are not particularly limited thereto. As the other monomer, only one kind may be used as needed, or two or more kinds may be used.

Among these other monomers, particularly preferred for enhancing the physical properties of the substrate protective layer are monomers having a crosslinkable functional group together with a polymerizable double bond, for example, hydroxyalkyl (meth) acrylate , Epoxy group-containing (meth) acrylates and the like, and copolymers obtained by using these monomers as copolymerizable monomers are combined with a curing agent such as a polyisocyanate compound or a cationic polymerization catalyst as described later. By combining them, they exhibit crosslinking curing reactivity, and can further enhance the surface hardness, weather resistance, adhesion to the surface protective layer, abrasion resistance of the surface protective layer, and the like of the substrate protective layer. Of these, particularly preferred from the viewpoint of cost performance are hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

The method of mixing the above monomers is not particularly limited, and a conventionally known mixing method can be employed.

The polymerization method for copolymerizing the monomer composition is not particularly limited, and a conventionally known polymerization method can be employed. For example, polymerization methods such as solution polymerization, dispersion polymerization, suspension polymerization, and emulsion polymerization can be used. Solvents that can be used when polymerizing the monomer composition using the solution polymerization method include toluene, xylene, and other aromatic solvents; alcohol solvents such as isopropyl alcohol and n-butyl alcohol; Ether solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellosolve and butyl cellosolve; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol Solvent: dimethylformamide and the like. Of course, solvents that can be used are not limited to these solvents, but solvents that attack the resin substrate are not preferred. These solvents may be used alone or in combination of two or more. The amount of the solvent used may be appropriately determined in consideration of the concentration of the product and the like.

When copolymerizing the monomer composition, a polymerization initiator is used. As the polymerization initiator, for example, 2,
2'-azobis- (2-methylbutyronitrile), te
rt-butylperoxy-2-ethylhexanoate,
Examples include ordinary radical polymerization initiators such as 2,2'-azobisisobutyronitrile, benzoyl peroxide, and di-tert-butyl peroxide. The amount of the polymerization initiator to be used should be appropriately determined from the required characteristic values of the polymer and the like, and is not particularly limited, but is preferably in the range of 0.01 to 50 wt% based on the total amount of the monomer components. Preferably, it is in the range of 0.05 to 20 wt%.

The reaction temperature is not particularly limited, but is preferably in the range of room temperature to 200 ° C, and is preferably 40 to 140 ° C.
Is more preferred. The reaction time may be appropriately set according to the composition of the monomer composition to be used, the type of the polymerization initiator, and the like so that the polymerization reaction is completed.

The weight average molecular weight (M
w) is not particularly limited, but 2,000 to 500,0.
00, more preferably 4,000 to 300,
5,000, more preferably 5,000 to 250,
000. Note that the weight average molecular weight is a value measured by polystyrene standard GPC.

Next, the formation of the base material protective layer will be described.
The UV-absorbing polymer obtained as described above is mixed with another polymer, if necessary, to obtain a base material protective layer composition, which is applied onto a resin base material. At this time, the base material protective layer may be formed directly on the resin base material, or a primer layer may be formed on the surface of the resin base material and formed thereon. 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. Thereafter, the applied base material protective layer is heated or irradiated with ultraviolet rays or electron beams to be cured to obtain a molded product.

Here, when the ultraviolet absorbing polymer can be cured alone, for example, the copolymer may be an epoxy group or (meth)
In the case of having an acryloyl group, these are cured by causing cationic polymerization or radical polymerization by heat or ultraviolet / electron beam irradiation using a cationic polymerization catalyst or a radical polymerization catalyst as necessary.

When the ultraviolet absorbing polymer is a polymer that cannot be cured alone, it is necessary to add a curing agent. Such a curing agent contains two functional groups capable of crosslinking and curing with a curable functional group present in the ultraviolet absorbing polymer, for example, a hydroxyl group, an amino group, a carboxyl group or an anhydride thereof, an epoxy group or an amide group. The compound or polymer contained above is selected and used depending on the type of the functional group present in the ultraviolet absorbing polymer. For example, when the functional group present in the ultraviolet absorbing polymer is a carboxyl group or an anhydride thereof, a polyisocyanate compound or a modified product thereof, an aminoplast resin, an epoxy resin, a cross-linking curing agent such as an oxazoline group-containing resin, When the functional group is an epoxy group, amine, carboxylic acid, amide, N
-A cross-linking curing agent comprising a compound containing a methylol alkyl ether or the like, and when the functional group is a hydroxyl group or an amino group, a cross-linking curing agent such as a polyisocyanate compound or a modified product thereof, an epoxy resin, and an aminoplast resin. Can be. Among these curing agents, in combination with a group having active hydrogen, an isocyanate compound,
Epoxy resins and aminoplast resins are preferred.

Examples of the polymer which can be used in combination with the ultraviolet absorbing polymer include a thermoplastic polymer or a thermosetting polymer which is crosslinked and cured by itself or by a crosslinking agent. The type and amount of the polymer may be appropriately determined depending on the use and required characteristics of the resin plate of the present invention. Examples of the polymer include thermoplastic polymers such as vinyl chloride resin, polyester resin, acrylic resin, and silicone resin;
Examples thereof include thermosetting polymers that are individually cured such as urethane resin, aminoplast resin, silicone resin, and epoxy resin; and thermosetting polymers that are cured by a curing agent such as polyester resin, acrylic resin, and epoxy resin.

The crosslinking curing agents may be used alone or in combination of two or more. The amount of the cross-linking curing agent used is appropriately determined depending on the type of the cross-linking curing agent and the like, and is 0.1% by the molar ratio of the curable functional group present in the base material protective layer to the functional group in the cross-linking curing agent. It is preferably in the range of 8 to 1.2. Further, a crosslinking catalyst may be added to promote the crosslinking reaction. Examples of such a crosslinking catalyst include salts, inorganic substances, organic substances, acid substances, and alkaline substances.

When the substrate protective layer is cured by heating, the curing temperature varies depending on the type of the crosslinkable functional group and the type of the curing agent used, but it is preferable to cure at a temperature of room temperature to 250 ° C., for example.

The curing method in the case of curing by irradiation with ultraviolet rays varies depending on conditions such as the photopolymerization initiator used, the type of light source for generating ultraviolet rays, and the distance between the light source and the coating surface. A method of irradiating with ultraviolet rays of 000 to 8,000 angstroms for several seconds, at most for several tens of seconds can be mentioned.

When curing by electron beam irradiation,
For example, usually 50 to 1000 kev, preferably 100
With an acceleration voltage of ~ 300 keV, the absorption line is 1 ~ 20Mra
For example, a method of irradiating an electron beam so as to be about d may be used. The electron beam irradiation may be performed in the air, but is preferably performed in an inert gas such as nitrogen.

After the irradiation of the ultraviolet rays or the irradiation of the electron beam, the curing may be further advanced by heating if necessary.

The thickness of the base material protective layer is Lambert-B
Since it depends on the amount of the ultraviolet absorbent to be copolymerized according to the Eer's law, there is no particular limitation as long as the weather resistance of the desired resin base material and the performance of the surface 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 base material may be reduced. On the other hand, when the thickness is less than 0.5 μm, it is difficult to apply the resin uniformly on the resin substrate, and the ultraviolet absorbing ability may be insufficient.

Another feature of the present invention is that a surface protective layer is provided. By forming the surface protective layer having a high surface hardness on the surface of the resin plate, the surface hardness and the scratch resistance, which have been problematic in the past, are remarkably improved.

The resin forming the surface protective layer is not particularly limited, but from the viewpoints of weather resistance, scratch resistance and the like, it is more preferable to use a silicone curable resin, an organic curable resin, and a curable resin containing organic polymer composite inorganic fine particles. At least one resin selected from the group consisting of:

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" (all 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. Lower fatty alcohols, polyhydric alcohols and ethers and esters thereof, and the like can be mentioned. In order to obtain a smooth surface state, various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the surface protective layer.

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

The organic polymer composite inorganic fine particles mean composite inorganic fine particles in which an 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. Can be achieved. Here, the term "fixation" does not mean mere adhesion and adhesion, but means that the organic polymer is not detected in the washing liquid obtained by washing the composite inorganic fine particles with an arbitrary solvent, which means that the organic polymer and the inorganic fine particles are not detected. Strongly suggests that a chemical bond has been formed between the two.

The inorganic fine particles that can be used are not particularly limited as long as they are inorganic fine particles composed of an arbitrary element, and inorganic oxides are preferably used as the inorganic material. Inorganic oxides are defined as various oxygen-containing metal compounds in which a metal element mainly forms a three-dimensional network through a bond with an oxygen atom. As the metal element constituting the inorganic oxide, for example, an element selected from Groups II to VI of the periodic table is preferable, and an element selected from Groups III to V of the periodic table is more preferable. Among them, an element selected from Si, Al, Ti, and Zr is preferable, and Si is particularly preferable. The inorganic oxide may include an organic group or a hydroxyl group, or may include a part of an organic polymer. The organic group is at least one selected from the group consisting of an optionally substituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. One or two inorganic oxides
More than one species may be used. The shape of the inorganic fine particles may be any shape such as a sphere, a needle, a plate, a scale, and a crushed shape, and is not particularly limited.

The organic polymer is particularly composed of an organic chain and a polysiloxane group, wherein at least one polysiloxane group is bonded per molecule, and at least one Si—OR ¹ group is contained in the polysiloxane group. (R ¹ is a hydrogen atom or an alkyl group, selected from acyl group, optionally substituted at least one group may, when R ¹ are a plurality in one molecule, a plurality of R ¹ are identical to each other And may be different). The structure of the organic chain in the organic polymer is not particularly limited. Also, for reasons such as availability of the organic polymer, the polysiloxane group and the organic chain in the organic polymer are
Those chemically bonded via an i-C bond, a Si-O-C bond or the like are preferable. In particular, the bonding site is excellent in hydrolysis resistance and is less susceptible to undesired reactions such as an exchange reaction at the bonding site. From the viewpoint of desirability and the like, it is more preferable that the polysiloxane group and the organic chain are chemically bonded via a Si-C bond.

The structure of the organic polymer is not particularly limited as long as it is soluble in an organic solvent and / or water. For example, a polymer having a polysiloxane group grafted to an organic chain, A plurality of linear or branched organic chains (the plurality of organic chains may be the same or different) are bonded with a polymer or polysiloxane group bonded to one or both ends as a core. Polymers and the like. Here, the organic chain refers to a portion other than the polysiloxane group in the organic polymer.
The main chain in the organic chain is centered on carbon, and carbon atoms participating in the main chain bond occupy 50 to 100 mol%, and the remainder is composed of elements such as N, O, S, Si, and P. Is easily obtained. Examples of the resin constituting the organic chain include (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefins such as polyethylene and polypropylene, vinyl chloride, vinylidene chloride, polyesters such as polyethylene terephthalate, and copolymers and amino groups thereof. Resins partially modified with functional groups such as epoxy groups, hydroxyl groups and carboxyl groups are exemplified. Among these, a resin containing a (meth) acrylic unit such as a (meth) acrylic resin, a (meth) acryl-styrene resin, and a (meth) acryl-polyester resin is preferable.

The composite inorganic fine particles having the organic polymer fixed on the surface of the inorganic fine particles can be produced by, for example, hydrolyzing / condensing the above organic polymer alone or hydrolyzing / condensing both the metal compound and the organic polymer. Can be. Examples of the metal compound include metal halides, metal nitrate salts, metal ammonium salts, organometallic compounds, alkoxymetal compounds, and derivatives of these metal compounds. The metal compounds can be used alone or in combination of two or more.

The details of the composite inorganic fine particles and the method for producing the same are described in JP-A-7-178335 and JP-A-9-178335.
No.-302257 and Japanese Patent Application No. 9-291390.

The curable resin containing the organic polymer composite inorganic fine particles is not particularly limited, and examples thereof include the organic resin-based curable resins described above.

Commercial products of the curable resin containing the composite inorganic fine particles include, for example, “Udable C-330”.
0 "and" U-double C-3600 "(all manufactured by Nippon Shokubai Co., Ltd.).

The method for forming the surface protective layer on the resin plate includes a thermosetting method in which the layer forming composition is applied to the surface of the base material protective layer and cured by heating, or a method such as ultraviolet ray, electron beam, or radiation. An active energy ray curing method for curing by irradiation with an active energy ray is exemplified.
Of these, the thermosetting method is mainly used for silicone-based curable resins,
An active energy ray curing method using ultraviolet rays is mainly used for the organic resin-based curable resin. In the case of a curable resin containing organic polymer composite inorganic fine particles, a thermosetting method and an active energy ray curing method using ultraviolet rays and electron beams are mainly used. Generally, the thermal curing method has a disadvantage that it takes longer time to cure than the active energy ray curing method. However, if the base material protective layer is excessively cured, the interlayer adhesion to the surface protective layer and the heat resistance tend to decrease, so that it is recommended to appropriately select the curing time.

The method for applying the composition for forming a surface protective layer to a resin plate includes a dipping method, a spray coating method, a flow coating method, a roll coating method, and a spin coating method. In order to improve the interlayer adhesion, the surface protective layer may be formed on an intermediate layer called an undercoat layer, a primer layer, an adhesive layer, or the like, and formed thereon.
In addition, silane coupling agents (for example, trade names “A-187”, “A-189”, and “A-11” manufactured by Nippon Unicar Co., Ltd.)
00, "A-1120" etc.).

The thickness of the surface protective layer is 0.1 to 200 μm.
m, preferably 0.5-100 μm, more preferably 1
５０50 μm. When the layer thickness of the surface protective layer is 0.1
When the thickness is less than μm, the surface hardness is low and there is no effect as a surface protective layer. On the other hand, when the thickness is more than 200 μm, the physical properties of the resin plate, particularly the mechanical strength such as bending strength, are reduced.

The substrate protective layer and the surface protective layer may further contain various additives. As an additive, for example, a leveling agent generally used in a composition for forming a layer such as a paint; graphite, molybdate orange, navy blue, cadmium-based pigment, titanium white, composite oxide pigment, transparent iron oxide, carbon black , Cyclic high-grade pigments, soluble azo pigments, copper phthalocyanine pigments, dye pigments, pigment intermediates and other pigments; pigment dispersants; antioxidants; viscosity modifiers; light stabilizers; Decomposers; Fillers; Reinforcing agents; Plasticizers; Lubricants; Corrosion inhibitors; Rust inhibitors; Fluorescent brighteners; Organic and inorganic flame retardants; And the like.

[0076]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" described in Examples and Comparative Examples are parts by weight and "%"
Represents "% 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 5 parts, methyl methacrylate 30 parts, butyl acrylate 24 parts, n-butyl methacrylate 30 parts, 2-hydroxyethyl methacrylate 10 parts, methacrylic acid 1
And 80 parts of dipropylene glycol methyl ether, nitrogen gas was introduced, and the mixture was heated to 110 ° C. while stirring. As an initiator, a mixture of 1 part of t-butyl peroxy-2-ethylhexanoate and 20 parts of dipropylene glycol methyl ether was added dropwise to the charge over 2 hours, and after the addition, the mixture was heated for another 2 hours to give 49 parts of acrylic resin. .
A 7% solution was obtained. The weight average molecular weight of this product was 4
It was 8,000. This ultraviolet absorbing polymer is referred to as polymer 1. Table 1 shows the types and amounts of the monomer compositions and the characteristic values of the obtained polymers.

(Synthesis Examples 2 to 8) Ultraviolet-absorbing polymers were produced in the same manner as in Synthesis Example 1 using the monomer compositions and amounts shown in Table 1. Polymers 2-8 each produced
And In addition, about the synthesis example 7, after synthesize | combining an ultraviolet-absorbing polymer similarly to the synthesis example 1, introducing the mixed gas of nitrogen and oxygen, and stirring at 110 degreeC, 15 parts of acrylic acid, tetraphenyl phosphonium Bromide 0.2
And a mixture of 0.01 part of methquinone were added dropwise over 30 minutes, and the mixture was further reacted for 4 hours to produce a polymer 7 having an acryloyl group in the side chain of the polymer.

[0079]

[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-2 , 2,6,
6-tetramethylpiperidine HALS2: 1-methacryloyl-4-methacryloylamino-2,2,6,6-tetramethylpiperidine CHMA: cyclohexyl methacrylate MMA: methyl methacrylate BA: butyl acrylate n-BMA: n-butyl methacrylate IA: imide Acrylate ("Aronix TO-142
9 "manufactured by Toa Gosei Co., Ltd.) HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid GMA: glycidyl methacrylate VAc: vinyl acetate Initiator: tert-butyl peroxy-2-ethylhexanoate Reaction solvent 1: dipropylene glycol methyl ether Reaction solvent 2: butyl acetate

Example 1 To 100 parts of the ultraviolet absorbing polymer obtained in Synthesis Example 1, 7 parts of the curing agent A and 0.01 part of a leveling agent (“BYK300” manufactured by Big Chemie) were added, and the mixture was stirred well. The acrylic resin solution was adjusted to have a predetermined viscosity. Next, the surface of the polycarbonate resin plate is washed with ethyl alcohol,
The acrylic resin solution is applied to the surface of the polycarbonate resin plate so that the coating thickness becomes 15 μm, and after air-drying, 80 ° C.
For 30 minutes. Then, a silicone-based hard coating solution ("Tosgard 510" manufactured by Toshiba Silicone Co., Ltd.) was applied to the surface of the polycarbonate resin plate on which the base material protective layer was applied so that the coating film thickness was 5 μm.
The composition was cured by heating at 0 ° C. for 2 hours. The obtained polycarbonate resin plate was evaluated for the following evaluation items.

(Weather Resistance Test) A test piece was used under the condition that a cycle of 2 hours without rainfall and 18 minutes of rainfall was repeated at a constant temperature of 63 ° C. using a Sunshine weather meter manufactured by Suga Test Instruments Co., Ltd. using Sunshine Super Long Life Carbon. For 2,000 or 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) 100 pieces of squares (1 mm ² ) are applied to the coating film, a cellophane tape is adhered to the parts of the squares, and then the adhered cellophane tape is perpendicularly and rapidly peeled off. 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 is 4
When it exceeds, yellowish color is conspicuous visually.

(Yellowness (△ Y1)) Indicates a 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) A test piece is worn with a Taber abrasion tester using a wear wheel CS-10F in accordance with ASTM D 1044. 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 above-mentioned interlayer adhesion was performed. The evaluation criteria are the same as in the case of interlayer adhesion.

Examples 2 to 8, Comparative Examples 1 and 2 In the same manner as in Example 1, a base material protective layer containing a predetermined polymer was formed on a resin base material shown in Table 2, and further formed thereon. A surface protective layer made of a predetermined curable resin was formed, and an ultraviolet-absorbing laminated resin plate was prepared. The test was performed in the same manner as in Example 1. Table 2 shows the test results.

[0089]

[Table 2]

Additive type UV absorber: "MARK LA3"
1 "(made by Adeka Argus Chemical Co., Ltd.) Curing agent A: Isocyanate (" Sumidur N-32
00 "(manufactured by Sumitomo Bayer Urethane Co., Ltd.)) Curing agent B: blocked isocyanate (" Duranate MF-K60X "(manufactured by Asahi Kasei Kogyo)) Curing agent C: melamine (" Cymel 212 "(manufactured by Mitsui Sinamid)) Curable resin A: "Tosgard 510" (manufactured by Toshiba Silicone Co., Ltd.) Curable resin B: "UVHC8553" (manufactured by Toshiba Silicone Co., Ltd.) Curable resin C: "NK Oligo U4H" (manufactured by Shin-Nakamura Chemical Co., Ltd.) / "ARONIX TO-1429" (Toa Gosei Co., Ltd.)
= 7/3 (weight ratio) Curable resin D: "U-Double C-3600" (manufactured by Nippon Shokubai Co., Ltd.) Curable resin E: "Solgard NP730" (manufactured by Nippon Dacro Shamrock Co.) UV curing 1: Surface is ethyl alcohol A radical photoinitiator (“Darocur 117”)
3 "from Ciba-Geigy Co., Ltd.), and applying a UV-absorbing polymer solution adjusted to a predetermined viscosity.
Dry with hot air for 0 minutes, place on a conveyor moving at a speed of 5 m / min, and use a high-pressure mercury lamp (120 W / c
m), ultraviolet irradiation was performed twice from a height of 20 cm. UV curing 2: Adjust to predetermined viscosity, "UVHC8553"
(Manufactured by Toshiba Silicone Co., Ltd.) is applied to the surface of the base material protective layer formed on the resin base material, left at room temperature for 5 minutes, and then placed on a conveyor moving at a speed of 5 m / min. Ultraviolet irradiation was performed twice from a height of 20 cm using a mercury lamp (120 W / cm). UV curing 3: radical photoinitiator (Darocur 117
3 "Ciba Geigy Co., Ltd.), apply a curable resin C solution adjusted to a predetermined viscosity, apply a solution, then dry with hot air at 80 ° C. for 30 minutes, and place on a conveyor moving at a speed of 5 m / min. UV irradiation was performed twice from a height of 20 cm using a high-pressure mercury lamp (120 W / cm). Thermal curing 1: 17 parts of curing agent A and 0.01 part of leveling agent "BYK300" were added to 100 parts of resin "U-double C-3600" containing the composite inorganic fine particles, and the mixture was stirred and adjusted to a predetermined viscosity. On the surface of the base material protective layer,
The composition was cured by heating at 80 ° C. for 2 hours.

As is clear from Table 2, Examples 1 to 5, 7 to 7 in which the base material protective layer containing the ultraviolet absorbing polymer was formed.
In the resin plate of No. 9, the results of the interlayer adhesion, which is one of the indexes of weather resistance, are as excellent as A or B rank after 2000 hours and 8000 hours. In addition, the yellowing degree after 2,000 hours has passed is in the range of 1 to 3, indicating good weather resistance. In addition, the surface hardness of the resin plates of Examples 1 to 10 showed excellent values for both A and B ranks, and the hot water resistance also showed excellent interlayer adhesion to A rank.

Among these, Examples 1 to 5 and 7 to 9 in which the base material protective layer becomes a cured coating film by heat or ultraviolet rays.
Shows a particularly excellent weather resistance, in which the yellowing degree after 8000 hours has passed is in the range of 1 to 3. However, in Example 6,
After 8000 hours, the interlayer adhesion and the surface hardness became C rank, and showed a tendency to decrease. In Example 10 in which the curing of the surface protective layer was advanced, the interlayer adhesion and heat resistance tended to decrease.

On the other hand, in Comparative Examples 1 and 2 in which an additive type ultraviolet absorber was added to the base material protective layer, Comparative Example 2 in which the amount of addition was large showed a C rank after 2,000 hours. And both the interlayer adhesion and hot water resistance are C
It was unbearable for rank and practicality. The yellowing degree is also 6
And 8 were inferior. After a lapse of 2500 hours, cracks and whitening occur in the coating film, and the film cannot be evaluated.

[0094]

According to the resin plate of the present invention, it is possible to improve weather resistance without causing coloring and deterioration by ultraviolet rays, a decrease in interlayer adhesion and a decrease in surface hardness, and a high surface hardness and excellent scratch resistance. Parts that used to be made of metal or glass, such as automobiles, trains, airplanes, ships, etc., transportation systems such as automobiles, trains, aircraft, ships, etc., windows, skylights, etc., noise barriers on highways, etc. It has become possible to provide an ultraviolet absorbing resin material which can be widely and effectively utilized as a surface protective material for batteries and polymer batteries. The resin material can also be attached to any other member, for example, a wood-grained building material using an adhesive or an adhesive.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/14 C08L 33/14 // C08F 220/12 C08F 220/12

Claims (4)

[Claims] 1. A laminated resin material having a base material protective layer formed on the protective surface side of a resin base material and a surface protective layer formed thereon, wherein the base material protective layer comprises the following general An ultraviolet-absorbing laminated type comprising a polymer obtained by polymerizing a monomer component containing at least one selected from ultraviolet-absorbing monomers represented by formula (1) or (2). Resin material. 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.) 2. The ultraviolet-absorbing material according to claim 1, further comprising at least one selected from the ultraviolet-stable monomers represented by the following general formula (3) or (4) as another monomer component. Laminated resin material. 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. ) 3. The surface protective layer is formed of at least one resin selected from the group consisting of a silicone-based curable resin, an organic-based curable resin, and a curable resin containing organic polymer composite inorganic fine particles. The ultraviolet-absorbing laminated resin material according to claim 1. 4. The ultraviolet-absorbing laminated resin material according to claim 1, wherein the base material protective layer is made of a cross-linked cured product.