JP2002154182A - Ultraviolet resistant resin laminate and resin composition for forming ultraviolet shielding layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet resistant resin laminate which is improved in adhesion to a hard coat layer while the deterioration of a resin base material by ultraviolet rays is prevented, resistant to ultraviolet rays, and excellent in scratch resistance when the scratch resistance, etc., are improved by forming the hard coat layer on the surface of the resin base material in the laminate in which a resin which is easily disclored and deteriorated by ultraviolet rays such as a polycarbonate is used as the base material. SOLUTION: In the ultraviolet resistant resin laminate in which the hard coat layer is formed on the surface side of the base material vulnerable to ultraviolet rays through an ultraviolet shielding layer, a copolymer produced by polymerizing a momomeric component comprising (1) 50-90 mass% of a monomer having a reactive silyl group, (2) 10-50 mass% of a monomer having an ultraviolet absorbent group, and (3) 0-40 mass% of another monomer is incorporated as the ultraviolet shielding layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-stable resin laminate, and a resin composition for forming an ultraviolet-shielding resin layer used for forming an ultraviolet-shielding resin layer when manufacturing the laminate. For example, a laminate in which an ultraviolet ray shielding layer for preventing ultraviolet ray deterioration and a hard coat layer for improving scratch resistance are formed on the surface of a substrate made of an ultraviolet ray degradable resin such as a polycarbonate resin or a polyester resin. And a resin composition used for forming an ultraviolet shielding layer when producing the laminate.

[0002]

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

As a method for preventing ultraviolet rays that degrade the base resin from reaching the surface of the resin member, for example, Japanese Patent Publication No. 60-53701, Japanese Patent Publication No. 2-37938.
JP-A-10-245521, JP-A-10-245521
Japanese Patent Application Laid-Open No. 58654/1994 proposes a method in which an ultraviolet absorber is contained in a surface layer such as a primer layer and a surface hardened layer, and the surface layer absorbs ultraviolet light. Also, a number of methods have been proposed for preventing the deterioration of the solvent resistance and the like of the surface layer due to the contained ultraviolet absorber and improving the composition of the surface hardened layer and the primer layer in order to further improve the adhesion (for example, Japanese Patent Application Laid-Open No. H11-157556). Japanese Patent Publication No. 1-7582, Japanese Patent Publication No. 32-246, Japanese Patent Publication No. 1-18944, Japanese Patent Publication No. 2-379
No. 38). By these methods, deterioration of the base resin surface due to ultraviolet rays can be suppressed to some extent.

[0004] However, in order to completely block ultraviolet rays with the surface-hardened layer and the primer layer, it is necessary to add a large amount of an ultraviolet absorber to these layers, and thus the surface-hardened layer and the primer layer are colored or turbid. When the resin laminate as a whole is viewed, transparency, which is a characteristic of the resin, is impaired, or further, the ultraviolet absorber bleeds out, causing a problem such as deterioration of appearance or deterioration of scratch resistance. come.

On the other hand, as means for increasing the surface hardness of the resin substrate to improve the scratch resistance, an inorganic film is formed by vacuum evaporation, a thermosetting or ultraviolet-curable silicon-based film, an electron beam, or the like. There is known a method of forming an organic hard coat layer which is cured by ultraviolet irradiation. However, while these hard coat layers have high hardness and excellent scratch resistance, they undergo large curing shrinkage during the heating and curing process to form a film with a high crosslinking density in the process of forming the hard coat layer, Cracks (hereinafter, this phenomenon is referred to as “initial cracks”) may occur in the film.

When the hard coat layer is formed on the surface of the resin substrate via the primer layer, the curing strain caused by the curing shrinkage propagates to the primer layer and accumulates as internal strain. The progress causes cracks starting from the primer layer or causes delamination from the resin substrate.

As a means for avoiding such a problem, it is conceivable to reduce the curing shrinkage during heating and curing by making the hard coat layer thinner, but if the thickness is too thin, the original effect of hardening the surface of the hard coat layer is satisfactory. And the desired scratch resistance cannot be obtained. If the thin film coating and heat curing are repeated a plurality of times when forming the hard coat layer, the amount of cure shrinkage of the entire hard coat layer can be reduced, but the operation is complicated and requires a long time, which is not practical.

For this reason, there is a demand for the development of a technique capable of forming a hard coat layer having excellent abrasion resistance on the surface of a resin substrate without causing the above-mentioned problems. No satisfactory method is given.

For example, Japanese Patent Application Laid-Open No. 4-120181 discloses a primer comprising a copolymer obtained by copolymerizing an alkoxysilyl group-containing monomer, a UV-absorbing monomer, and another acrylic monomer at a specific ratio. ing. Since this primer contains an ultraviolet-absorbing monomer as a copolymerization component, it exhibits an effect of protecting the resin base material from ultraviolet rays, and is not suitable for use when a low-molecular-weight ultraviolet absorber is mixed in the primer coating. In addition, excellent yellowing resistance can be obtained over a long period of time without causing a problem such as bleed-out of the ultraviolet absorber. According to this publication, it is described that by suppressing the copolymerization ratio of the alkoxysilyl group-containing monomer to 45% by mass or less, the adhesion to the resin substrate is also improved.

However, in the primer disclosed in the above publication,
Since the copolymerization ratio of the alkoxysilyl group-containing monomer is suppressed to 45% by mass or less, it is impossible to follow the curing shrinkage of the hard coat layer when the hard coat layer is formed on the primer layer, and the curing strain is accumulated. The occurrence of initial cracks cannot be avoided. Also, when applied to a thermoplastic resin substrate, the primer layer and the hard coat layer are required to repeatedly expand and contract according to the expansion and contraction of the resin substrate in accordance with the temperature change of the use environment. In the primer layer in which the copolymerization ratio of the alkoxysilyl group-containing monomer is suppressed to a low level, the crosslink density is low, so that it cannot withstand repeated expansion and contraction, cracks may occur in the primer layer in the weather resistance test, or the hard coat layer may become brittle. In both cases, a problem such as separation from the resin base material may occur. In addition, since the copolymerization ratio of the alkoxysilyl group-containing monomer is low, it cannot cope with a high degree of scratch resistance, which has been particularly demanded in recent years.

On the other hand, it is desired to increase the thickness of the primer layer constituting the ultraviolet absorbing layer in order to suppress the photodeterioration of the resin substrate and enhance the ultraviolet absorbing performance. When it is fleshed, it itself tends to cause initial cracks. Therefore, in order to improve both the initial crack preventing action and the abrasion resistance and weather resistance of the primer resin composition described in the above publication, it is necessary to apply a uniform thin coating on both the primer layer and the hard coat layer, It is surprisingly difficult to coat them uniformly with a thin wall, and the coating method is significantly limited. Specifically, when a normal flow coating method is employed, the film thickness can be inclined in the flow coating direction, which causes initial cracks in the thick film portion. In order to suppress such a gradient of the film thickness, it is necessary to appropriately adjust the viscosity of the coating material, but the adjustment is not easy, and the length of the flow coating substrate is naturally limited. In addition, a relatively uniform film thickness is easily obtained by spin coating, dipping, roll coating, spray coating, etc.
It is not easy to control the film thickness within a range of several μm.

Further, Japanese Patent Application Laid-Open No. Hei 7-286013 discloses that
There is disclosed a resin composition for coating obtained by copolymerizing an alkoxysilyl group-containing monomer, a UV-absorbing monomer, and another acrylic monomer at a specific ratio. This publication also states that a clear resin layer made of a dispersion containing colloidal silica and a siloxane resin can be formed on the resin film in order to improve the wear resistance and gloss of the coating layer. However, even when the coating resin composition shown as an example of the publication is used as a primer, the copolymerization ratio of the alkoxysilyl group-containing monomer is small, so that the initial ratio is the same as the technique disclosed in the above publication. Cracks easily occur, and it is inevitable that cracks occur in the film even in a weather resistance test. In addition, since the adhesion between the hard coat layer formed on the outermost layer and the primer layer is low, satisfactory scratch resistance is hardly obtained. Further, since the resin composition does not substantially have an ultraviolet absorbing ability, a function of protecting the resin substrate from ultraviolet rays cannot be expected.

Further, JP-A-7-26155 discloses a curable composition containing a copolymer obtained by copolymerizing an alkoxysilyl group-containing monomer, an ultraviolet absorbing monomer, and another acrylic monomer at a specific ratio, and a curing catalyst. A resin composition is disclosed. However, this publication does not mention the formation of a hard coat layer, and a coating film of the curable resin alone cannot provide the level of scratch resistance intended in the present invention. In addition, since this resin composition contains only a small amount of an ultraviolet-absorbing monomer and has insufficient ultraviolet-absorbing ability, a satisfactory effect cannot be expected as a protective film for a resin base material, which is likely to be deteriorated by ultraviolet rays. It is possible to increase the effect of preventing ultraviolet light deterioration by increasing the thickness of the film, but this causes deterioration of the mechanical properties and transparency of the resin base material.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a hard coat layer on the surface of a resin substrate which is liable to be discolored (colored) or deteriorated by ultraviolet rays. When forming a laminate with improved scratch resistance etc., improve the adhesion of the hard coat layer while preventing UV deterioration of the resin base, and make it stable and resistant to UV light. Another object of the present invention is to provide an excellent resin laminate and a resin composition for forming an ultraviolet shielding layer which is suitably used for producing the laminate.

[0015]

Means for Solving the Problems The ultraviolet-stable resin laminate according to the present invention, which can solve the above-mentioned problems, comprises a hard coat layer on the front side of an ultraviolet-deteriorating resin base material via an ultraviolet shielding layer. Is formed, wherein the ultraviolet shielding layer has a gist in that it contains a copolymer obtained by polymerizing the following monomer components. (1) Monomer having reactive silyl group: 50 to 90% by mass, (2) Monomer having ultraviolet absorbing group: 10 to 50
% By mass, and (3) other monomers: 0 to 40% by mass.

In the above-mentioned ultraviolet shielding layer constituting the laminate of the present invention, as a part of the monomer component (3),
(4) A monomer having a UV-stable group is contained and copolymerized so as to be 0.1 to 15% by mass with respect to 100% by mass of all monomer components, or is added in the UV shielding layer. It is preferable to include an appropriate amount of an ultraviolet stabilizer since the ultraviolet shielding layer itself can be improved in ultraviolet stability and its deterioration can be suppressed, and the performance as a laminate can be further enhanced.

In the present invention, a monomer having a hydrolyzable silyl group is preferably used as the monomer having a reactive silyl group. Further, as the hard coat layer, from the meaning of securing a high level of adhesion by utilizing the characteristics of the monomer component having a reactive silyl group that is a main component of the copolymer constituting the ultraviolet shielding layer,
A silicone-based curable resin-based resin is preferably used.

Further, the resin composition for forming an ultraviolet shielding layer according to the present invention provides a resin composition for forming an ultraviolet shielding layer in the laminate, and is formed by polymerizing the following monomer components. It has a gist where the polymer is contained. (1) Monomer having reactive silyl group: 50 to 90% by mass, (2) Monomer having ultraviolet absorbing group: 10 to 50
% By mass, and (3) other monomers: 0 to 40% by mass.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors prevent the deterioration of ultraviolet rays, which has been a problem in the past, while maintaining the excellent properties such as polycarbonate resin and the like inherently possessed of transparency and impact resistance. In addition, a hard coat layer is formed to improve abrasion resistance and the like, and in order to prevent deterioration of the base resin by ultraviolet rays when manufacturing a resin laminate that is stable to ultraviolet rays and has excellent scratch resistance. It has excellent UV shielding properties and exhibits excellent adhesion to the hard coat layer formed on the surface side of the base resin, giving a high quality UV stable resin laminate and forming a hard coat layer. The present inventors have conducted intensive studies to clarify an ultraviolet shielding layer capable of suppressing as much as possible initial cracks generated at the time and cracks and peeling generated at the time of use. As a result, as described above, a UV-shielding layer containing a copolymer obtained by copolymerizing a monomer having a reactive silyl group and a monomer having an UV-absorbing group, or another copolymerization-reactive monomer in a specific ratio, Thus, the inventors have found that the above-mentioned required characteristics are met, and have accomplished the present invention.

Therefore, the feature of the ultraviolet-stable laminate according to the present invention is that when a hard coat layer is formed on the surface of an ultraviolet-degradable resin substrate, it is formed on the lower layer side of the hard coat layer. This is characterized in that a shielding layer for blocking ultraviolet rays from being applied to the resin base material is formed. In particular, as a material constituting the ultraviolet shielding layer, a monomer having a reactive silyl group and a monomer having an ultraviolet absorbing group are contained at a specific ratio, or further obtained by polymerizing other monomers at a specific ratio. By using a copolymer, the types of these monomers and their content ratios are specified, and an ultraviolet shielding layer containing the obtained copolymer as a main component is formed adjacent to the hard coat layer to form a hard coat. Initial cracks generated during layer formation and cracks and peeling during use can be suppressed as much as possible, and a stable laminate that is stable against ultraviolet rays and has excellent scratch resistance on the outermost layer has been successfully obtained. It was done. In addition, the ultraviolet shielding layer exhibits excellent scratch resistance due to excellent adhesiveness with the hard coat layer, and has excellent adhesiveness with the base resin layer even when directly laminated on the base resin. It can withstand the expansion and contraction of the resin base material due to long-term use, and has succeeded in minimizing cracking and peeling of the ultraviolet shielding layer itself or the hard coat layer as much as possible. It is.

The ultraviolet-stable laminate of the present invention is basically a three-layer structure in which an ultraviolet shielding layer and a hard coat layer are directly laminated on the surface of a resin substrate. A laminate having a multilayer structure of four or more layers in which the ultraviolet shielding layer and the hard coat layer are formed on the surface of the substrate through a primer layer for improving adhesion, a printing layer, a heat ray shielding layer, and the like.

Therefore, as a method for producing the ultraviolet-stable resin laminate of the present invention, a method of forming the above-mentioned ultraviolet shielding layer on the surface of a resin substrate and then forming a hard coat layer thereon, or a method of producing a resin substrate After forming a primer layer, a printing layer, a heat ray shielding layer, and the like on the surface of the substrate, a method of forming an ultraviolet ray shielding layer and a hard coat layer thereon is included.

In the state of the layer structure of the ultraviolet shielding layer formed adjacent to the hard coat layer, the excellent adhesion between the specific ultraviolet shielding layer and the hard coat layer in the present invention, Other layers may be interposed between the base material and the heat ray shielding layer as long as they do not affect the effect of suppressing the initial cracks generated at the time of forming the coat layer and the cracks generated at the time of use, peeling and the like as much as possible. . However, in order to achieve “excellent adhesion between a specific ultraviolet shielding layer and a hard coat layer” which is a factor of the effect in the present invention, the layer structure of the ultraviolet shielding layer formed adjacent to the hard coat layer is required. Preferably, the state is a state in which the layers are directly laminated.

In the present invention, a monomer having a reactive silyl group used as a monomer component of a copolymer which is a main component of the ultraviolet ray shielding layer or the resin composition for forming the shielding layer is preferably a polymerizable compound in the molecule. It has a double bond and a hydrolyzable silyl group, more specifically, at least one monomer represented by the following general formulas (1) to (3) alone or in combination of two or more. used. Here, the hydrolyzable silyl group is a functional group that generates a silanol group by a hydrolysis reaction.

[0025]

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(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having 1 to 6 carbon atoms, and a
Represents an integer of 1 to 3, and b represents 0 or 1.)

[0027]

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(Wherein, R ³ has the same meaning as R ² or an alkyloxyalkyl group, and c represents 0 or 1)

[0029]

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(Wherein, R ⁴ has the same meaning as R ^2, and d represents 0 or 1).

The monomer represented by the general formula (1) is an acrylic monomer having a hydrolyzable alkoxysilyl group. In the general formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 6 carbon atoms (an alkyl group such as a methyl group, an ethyl group, and a propyl group;
An alkenyl group such as a vinyl group, an isopropenyl group or an allyl group; including an aryl group such as a phenyl group);
Integer of 3, b represents 0 or 1.

Specific examples of the acrylic monomer having an alkoxysilyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyl Tributoxysilane, 3- (meth) acryloxypropyltriisopropenoxysilane, (meth)
Acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltributoxysilane and the like are exemplified.

Among these, ease of handling and reactivity,
Particularly preferred in consideration of the crosslinking density and the like are 3- (meth) acryloxypropyltrimethoxysilane,
(Meth) acryloxytriethoxysilane.

The monomer represented by the general formula (2) is a vinyl functional compound having a hydrolyzable alkoxysilyl group, and the monomer represented by the general formula (3) is a vinyl functional alkoxysilane compound. In these general formulas (2) and (3), R ³ and R ⁴ have the same meaning as R ² or an alkyloxyalkyl group, and c and d
Is a vinyl-functional monomer representing 0 or 1.

Specific examples of these vinyl-functional monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldiethoxysilane. Examples thereof include methyldibutoxysilane, vinylmethylbis (2-methoxyethoxy), 3-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane, and 3-vinyloxypropylmethyldimethoxysilane. Among them, vinyl trimethoxy silane, vinyl triethoxy silane, 3-vinyloxy propyl trimethoxy silane and the like are particularly preferable in consideration of ease of handling and reactivity.

By using these monomers having a hydrolyzable silyl group as a copolymerization component, silanol groups generated by the hydrolysis reaction condense and crosslink with the copolymer constituting the ultraviolet shielding layer, This imparts thermosetting properties and enhances the mechanical properties and weather resistance of the thin film. In particular, if the ultraviolet ray shielding layer contains a copolymer containing a specific amount or more of the hydrolyzable silyl group-containing monomer component, the initial cracks can be formed because the hard coat layer can follow a large curing shrinkage generated during the temperature rise and curing process. Is suppressed. In particular, even when the thickness of the ultraviolet shielding layer or the hard coat layer is increased, initial cracks hardly occur, and the laminate is free from cracks even in a weather resistance test. Further, the adhesion to the hard coat layer is further strengthened, and the scratch resistance is dramatically improved. In addition, since the adhesiveness to the base resin when the ultraviolet shielding layer is formed in direct contact with the resin base becomes strong, it can follow the expansion and contraction of the resin base after long-term use.

The monomer having an ultraviolet absorbing group copolymerized with the monomer having a hydrolyzable silyl group includes:
Although all monomers having a polymerizable double bond and an ultraviolet absorbing group in the molecule at the same time can be used, particularly preferably used in the present invention are represented by the following general formulas (4), (5) and (6). At least one selected from monomers having an ultraviolet-absorbing group to be used, and by using these monomers as a copolymerization component, the obtained copolymer is provided with an ultraviolet-absorbing ability and a resin base material The effect of preventing ultraviolet light deterioration can be further enhanced.

[0038]

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(Wherein R ⁵ is a hydrogen atom or a group having 1 to 1 carbon atoms)
It represents 8 hydrocarbon group, R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, R ⁷ is 1 to carbon atoms 12 linear or branched chain alkylene group or -O-R ⁹ - (R ⁹ is match a linear or branched chain alkylene group having 2 or 3 carbon atoms) represents, R ⁸
Represents a hydrogen atom or a methyl group).

[0040]

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(Wherein, R ⁸ has the same meaning as described above;
¹⁰ represents a linear or branched alkylene group having 1 to 12 carbon atoms, R ¹¹ represents a hydrogen atom or a hydroxyl group,
R ¹² represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms).

[0042]

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(Where R⁸Represents the same meaning as described above, and R¹³
Is a direct bond,-(CH_TwoCH_TwoO)_n-Or -CH_TwoCH
(OH) -CH_TwoRepresents O-, and n represents an integer of 1 to 5
You. R ¹⁴, R^Fifteen, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R^{twenty one}
Are each independently a hydrogen atom, an alkoxy having 1 to 10 carbon atoms
Group, alkenyl group, or alkyl group)
Azine compounds.

Accordingly, the thin film containing the copolymer as a main component exhibits excellent ultraviolet light shielding properties by itself and exhibits an effect of preventing deterioration of the substrate by ultraviolet light. Therefore, when a thin film made of this copolymer is formed between the resin base material and the hard coat layer, ultraviolet rays are absorbed by the shielding layer before reaching the resin base material, thereby suppressing deterioration and discoloration of the resin base material due to the ultraviolet rays. It becomes possible. In addition, the UV absorber does not bleed out as in the conventional material containing the additive UV absorber, so that the durability of the UV shielding performance is enhanced and the adhesion to the hard coat layer formed thereon is improved. Is also good.

The ultraviolet ray shielding layer containing the above copolymer as a main component preferably contains an ultraviolet ray stabilizer from the viewpoint of preventing cracks in a weather resistance test. Particularly preferred is a copolymer obtained by copolymerizing at least one kind of a monomer having an ultraviolet light-stable group as a monomer component constituting the copolymer, which is preferable because the weather resistance of the copolymer can be further enhanced. .

The monomer having an ultraviolet light-stable group used herein may be of any type as long as it has both a polymerizable double bond and an ultraviolet light-stable group in the molecule. It is a monomer having an ultraviolet light-stable group represented by the following general formulas (7) and (8).

[0047]

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(Wherein, R ²² represents a hydrogen atom or a cyano group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a methyl group, R ²⁵ represents a hydrogen atom or a hydrocarbon group, and Y represents Represents an oxygen atom or an imino group.)

[0049]

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(Wherein, R ²² represents a hydrogen atom or a cyano group, R ²³ , R ²⁴ , R ^{23 ′} and R ^{24 ′} each independently represent a hydrogen atom or a methyl group, and Y represents an oxygen atom or an imino group. Represents a group).

Preferred specific examples of the monomer represented by the general formula (4) include, for example, 2- [2'-hydroxy-
5 '-(meth) acryloyloxymethylphenyl]-
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(meth) acryloyloxyethylphenyl]-
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(meth) acryloyloxypropylphenyl]
-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-( (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′-tert-butylphenyl] -5-tert-butyl- 2H-benzotriazole and the like.

A specific example of the benzophenone compound represented by the general formula (5) is 2-hydroxy-4-
[2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] butoxybenzophenone, 2,2′-dihydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone , 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 '-(2-hydroxyethoxy)
Benzophenone and the like can be mentioned.

Specific examples of the triazine compound represented by the general formula (6) include, for example, 2,4-diphenyl-
6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) ] -S-Triazine, 2,4-bis
(2-methoxyphenyl) -6- [2-hydroxy-4-
(2-acryloyloxyethoxy)]-s-triazine and the like.

The monomer components represented by the general formulas (4), (5), and (6) each have an ultraviolet absorbing characteristic peculiar to the compound. Depending on the ultraviolet light stabilizing performance required for the resin substrate on which the ultraviolet light shielding layer and the hard coat layer are laminated, they can be used alone or in combination of two or more. Further, a polymer obtained by homopolymerizing each of the monomer components represented by the general formulas (4), (5), and (6), or by appropriately copolymerizing two or more, may be used alone or in combination of two or more. It can be blended and contained in the ultraviolet shielding layer.

Specifically, since various polymer resin base materials have an inherent deterioration wavelength, when applied to resin base materials such as polyester resin and polycarbonate resin, for example, these resin base materials Since it is most deteriorated by ultraviolet light of 280 to 370 nm, the benzophenone-based compound represented by the general formula (5) alone or the general formula (4) is used instead of the triazine-based compound represented by the general formula (6) alone. Benzotriazole-based compound used alone is more preferable,
More preferably, the compound of formula (6) and the triazine compound
Species combination is effective.

Further, in the monomers represented by the above general formulas (7) and (8) which can be copolymerized as required in the present invention, the substituent represented by R ²² is a hydrogen atom or a cyano group; ^The substituents represented by ²³ , R ²⁴ , R ^{23 ′} and R ^{24 ′} are each independently a hydrogen atom or a methyl group, the substituent represented by R ²⁵ is a hydrogen atom or a hydrocarbon group, and the substituent represented by Y is These are piperidines which are oxygen atoms or imino groups.

More specific examples of the monomer having an ultraviolet light-stable group represented by the general formula (7) include, for example, 4
-(Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2 , 2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-
1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6
6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine and the like, without limitation. These can be used alone or in combination of two or more as needed.

More specific examples of the monomer represented by the general formula (8) include, for example, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-
Tetramethylpiperidine, 1- (meth) acryloyl-
4-cyano-4- (meth) acryloylamino-2,
Examples include, but are not limited to, 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, which can be used alone or required. May be used in appropriate combination of two or more.

In the present invention, a sterically hindered piperidine compound is preferable as the above-mentioned ultraviolet stabilizer which can be contained in the ultraviolet shielding layer. Examples of commercially available products include “tinuvin 123”, “tinuvin 144”, and “tinuvin 144”. Tinuvin 765 "(all manufactured by Ciba Specialty Chemicals)," ADK STAB LA-52 "," ADK STAB LA-57 "," ADK STAB LA-62 "," ADK STAB LA-77 "(all manufactured by Asahi Denka Kogyo Co., Ltd.) And the like, and particularly preferred are the above-mentioned sterically hindered piperidine compounds having a polymerizable double bond in the molecule.

Next, in the present invention, the ratio of the monomer having a reactive silyl group in the copolymer to the total monomers is not only to enhance the mechanical and chemical properties as a thin film constituting material, but also to improve the hard coat property. It is necessary to increase the adhesion to the layer, the effect of preventing initial cracking, the effect of preventing cracking in a weather resistance test, and the abrasion resistance.
The range is preferably from 90 to 90% by mass, more preferably 5% by mass.
5 mass%, and a more preferable upper limit is 80 mass%.

When the copolymerization ratio of the monomer having a reactive silyl group is less than 50% by mass, not only the effect of improving the adhesion to the hard coat layer becomes insufficient, but also the effect of suppressing the initial crack and the weather resistance test. Crack prevention and scratch resistance are also insufficient. Conversely, if the copolymerization ratio exceeds 90% by mass, the amount of the ultraviolet-absorbing monomer component will be small, so that the ultraviolet-shielding effect will be insufficient, and the copolymer will tend to gel during synthesis.

The amount of the monomer having an ultraviolet absorbing group used in obtaining the copolymer is preferably 10% by mass or more and 50% by mass or less based on the total monomer components constituting the copolymer. More preferably, the lower limit is 15% by mass, still more preferably 22%, and the upper limit is 45% by mass. If the copolymerization ratio of the monomer having an ultraviolet absorbing group is less than 10% by mass, the ultraviolet light shielding effect when formed into a thin film or when formed as an ultraviolet light shielding layer on a resin substrate becomes insufficient, so that the film thickness is reduced. It is necessary to increase the thickness, and it is inevitable that the mechanical and optical characteristics inherent to the resin base material deteriorate. Conversely, if the content exceeds 50% by mass, the amount of copolymerization of the reactive silyl group-containing monomer decreases, so that initial cracks are likely to occur, and the adhesion and scratch resistance to the base resin and the hard coat layer are reduced. There is a risk of lowering it.

The amount of the monomer components represented by the general formulas (7) and (8) is not particularly limited, but is preferably 0.1 to 15 in the copolymer constituting the ultraviolet shielding layer.
It is desired that the content be set to mass%. More preferably, the lower limit is 0.5% by mass, more preferably 1% by mass, and the upper limit is 5% by mass, preferably 3% by mass. If the total amount of the monomer component having a UV-stable group is less than 0.1% by mass, the effect of preventing cracks in the weather resistance test of the UV-shielding layer tends to be insufficient, and if it exceeds 15% by mass,
There is a possibility that the mechanical properties of the ultraviolet shielding layer may be reduced.

When a UV stabilizer is blended together with the copolymer in the UV shielding layer, a preferable blending amount is 0.1 to 100% by mass of the copolymer which is a main component of the UV shielding layer.
A range of 1 to 15% by mass is preferred. By the way, if it is less than 0.1% by mass, the effect of preventing cracks in the weather resistance test is not effectively exhibited. Conversely, if it exceeds 15% by mass, bleed-out is liable to occur, and the interlayer adhesion to the hard coat layer and This may cause a decrease in scratch resistance.

In the copolymer of the present invention, other copolymerizable reactive monomers other than the above-mentioned monomer components also inhibit the ultraviolet absorbing ability required for the ultraviolet shielding layer and the adhesion to the hard coat layer. 1 or 2 if not
More than one species can be copolymerized. As the other monomer components, a monomer represented by the following general formula (9) is exemplified as a preferable one from the viewpoints of weather resistance of the copolymer and adhesion to the resin substrate.

[0066]

Embedded image

(Wherein, R ²⁶ represents a hydrogen atom or a methyl group, and Z represents a hydrocarbon group having 4 or more carbon atoms).

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

More specific examples of the monomer represented by the general formula (9) include, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-
Butylcyclohexyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. are not limited. One or more of these can be used.

The amount of the monomer represented by the general formula (9) is also not particularly limited, but is preferably 40% by mass or less, more preferably 5 to 5% by mass in the copolymer.
It is in the range of 35% by mass, more preferably 5 to 30% by mass. The monomer is effective particularly in increasing the adhesion to the base resin layer, but when the amount used exceeds 40% by mass, a monomer having a relatively reactive silyl group or a monomer having an ultraviolet absorbing group is relatively used. , The effect of improving the weather resistance of the ultraviolet shielding layer and the effect of improving the adhesion to the hard coat layer are not significantly exerted.

The above other copolymerizable monomers include:
Monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic acid, and maleic anhydride; 2-
Acidic phosphoric ester monomers such as (meth) acryloyloxyethyl acid phosphate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, caprolactone-modified hydroxy (meth)
Acrylate (for example, manufactured by Daicel Chemical Industries, Ltd .;
Monomer having a group having active hydrogen such as trade name "Placcel FM"); lower (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate Alkyl esters; nitrogen-containing monomers such as (meth) acrylamide, N, N'-dimethylaminomethyl (meth) acrylate, imide (meth) acrylate, and N-methylol (meth) acrylamide; and 2 such as ethylene glycol di (meth) acrylate. Monomers having two polymerizable double bonds; halogen-containing monomers such as vinyl chloride and vinylidene chloride; aromatic monomers such as styrene, α-methylstyrene, and vinyltoluene; and vinyl ethers, but are not particularly limited thereto. Not something. These other monomers can be used alone or in combination of two or more as necessary.

The polymerization method for producing the above copolymer is not particularly limited, and conventionally known polymerization methods such as a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used. Solvents used when polymerizing monomer components by employing a solution polymerization method include toluene, xylene, and other aromatic solvents; iso-propyl alcohol, n-
Alcohol solvents such as butyl alcohol, propylene glycol methyl ether, dipropylene glycol methyl ether, diacetone alcohol, ethyl cellosolve, butyl cellosolve; ester solvents such as butyl acetate, ethyl acetate, cellosolve acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents; dimethylformamide and the like can be used. Of course, the type of solvent used is not limited to these. One of these solvents may be used alone, or two or more thereof may be used as a mixed solvent. The amount of the solvent used may be appropriately determined in consideration of the concentration of the obtained copolymer and the like.

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

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

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

Although the molecular weight (Mw) of the copolymer is not particularly limited, it may be 2,000 to 500,000 in terms of mass average molecular weight.
0, more preferably 4,000 to 250,0.
00 range. Here, the mass average molecular weight means a value measured by polystyrene standard GPC.

The application of the resin composition for forming an ultraviolet shielding layer can be carried out by a method such as dipping, spraying, brushing, curtain flow coating, gravure coating, roll coating, spin coating, bar coating, electrostatic coating and the like. .

In the present invention, the resin which is used as a resin substrate and degrades by ultraviolet rays means that the main chain is cut by ultraviolet rays, a molecular weight is reduced, a gel is formed by cross-linking, a chemical structure is changed, and a mechanical strength, yellowing , A resin that causes a decrease in physical properties such as transparency, for example, a polycarbonate resin,
Polyarylate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin,
Resin base materials which are photodegraded by ultraviolet rays, such as ABS resin, polystyrene resin, and vinyl chloride resin, can be used. In addition, the shape and manufacturing method of the resin substrate are not particularly limited, and those having high versatility are plate-like or curved plate-like, corrugated plate-like or film-like ones. . Further, it is also possible to use a resin base material having a design property, such as wood grain printing.

The copolymer constituting the ultraviolet shielding layer or the resin composition for forming the shielding layer exhibits curing reactivity due to the presence of the reactive silyl group introduced into the molecule.
It is also effective to use a curing catalyst to promote further curing. Examples of the curing catalyst include organotin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, and tin octylate; phosphoric acid or phosphoric acid ester such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, and monobutyl phosphate; alkyl Titanates; organoaluminum compounds such as tris (ethylacetoacetate) aluminum; organozirconium compounds such as tetrabutylzirconate, tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium Acetic acid, propionic acid, maleic acid and their acid anhydrides, acidic compounds such as paratoluenesulfonic acid; hexylamine, di-
Amines such as 2-ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphoric acid esters; non-limiting examples of alkaline compounds such as sodium hydroxide and potassium hydroxide Is exemplified.

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

The curing catalyst is preferably used in an amount of 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, based on the monomer unit having a reactive silyl group in the copolymer.
% By mass.

When a resin obtained by hydrolysis using an alkoxysilane as described below as a starting material is used as the silicone resin, the water and silanol group condensation catalyst contained therein are also used as the resin composition for forming an ultraviolet shielding layer. It becomes a curing catalyst. Therefore, by selecting the drying conditions of the ultraviolet shielding layer forming resin composition, the curing catalyst contained in the hard coat layer laminated thereon soaks into the ultraviolet shielding layer, and not only accelerates the curing of the ultraviolet shielding layer. And the adhesion to the hard coat layer is improved. For example, in the case of a two-coat one-bake method in which a resin composition for forming an ultraviolet shielding layer is applied to a base material, a hard coat layer is laminated, and then heat-cured, weather crack resistance and weather resistance are improved.

In the above-mentioned resin composition for forming an ultraviolet shielding layer containing the copolymer into which a reactive silyl group has been introduced,
It is also effective to include a dehydrating agent, if necessary, in order to suppress hydrolysis during storage and the resulting decrease in storage stability. Examples of such a dehydrating agent include, but are not limited to, hydrolyzable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, 3-methacryloxypropyltrimethoxysilane, methyl silicate, and ethyl silicate. These may be used alone or in combination of two or more. When these hydrolyzable ester compounds include a vinyl monomer having a reactive silyl group as a copolymerization component, they may be added at any stage before, during or after copolymerization.

The copolymer used as the resin composition for forming the ultraviolet shielding layer is as described above. When the copolymer is put to practical use as an ultraviolet shielding layer forming agent, at least the copolymerization reaction is required. It is also possible to use another polymer together with the copolymer into which a silyl group and an ultraviolet absorbing group are introduced. Examples of such another polymer include a thermoplastic polymer and a thermosetting polymer which is crosslinked and cured by the action of the polymer itself or a crosslinking agent. The type and amount of these other polymers may be appropriately determined according to the use and required characteristics of the ultraviolet-stable resin laminate. Examples of the other polymer include thermoplastic polymers such as vinyl chloride resin, polyester resin, acrylic resin, and silicone resin; and thermosetting polymers such as urethane resin, aminoplast resin, silicone resin, and epoxy resin. Polymer: a thermosetting polymer that is cured by a curing agent such as a polyester resin, an acrylic resin, and an epoxy resin.

The copolymer contained in the ultraviolet shielding layer is
It is desirable that 50% by mass or more, preferably 80% by mass or more is contained in 100% by mass of the resin constituting the ultraviolet ray shielding layer or the resin composition for forming the ultraviolet ray shielding layer. If it is less than 50% by mass, the initial crack and the adhesion to the hard coat layer tend to be insufficient, and as a result, the abrasion resistance and weather resistance become insufficient.

When the ultraviolet ray shielding layer-forming agent containing the copolymer is applied in the form of a thin film and cured, the curing temperature depends on the amount of the crosslinkable functional group contained in the polymer, which is the main component of the ultraviolet ray shielding layer forming agent. It varies depending on the type, amount used, type of curing catalyst to be used, and heat resistance of the resin base material.
Curing at a temperature of 0 ° C. is preferred.

The thickness of the ultraviolet shielding layer is Lambert-
Because it depends on the amount of the ultraviolet absorber copolymerized according to Beer's law, it is not particularly limited as long as the weather resistance and the ultraviolet shielding performance required for the ultraviolet stable resin laminate are satisfied. The preferred thickness when forming is 40 μm or less, more preferably 0.5 to 20 μm.
m, more preferably 2 to 10 μm. 40μ thick
If it exceeds m, the problem of deteriorating the mechanical and optical properties inherent to the resin base material tends to occur. On the other hand, when the thickness is less than 0.5 μm, it is difficult to uniformly coat the substrate, and the ultraviolet absorbing ability may be insufficient.

The ultraviolet-stable resin laminate of the present invention was formed directly on the surface of the resin substrate as described above, or via an adhesion improving layer (such as a primer layer), a printing layer, a heat ray shielding layer, and an adhesive layer. A hard coat layer is further formed on the ultraviolet shielding layer in order to increase abrasion resistance and surface hardness. Therefore, in order to obtain the UV-stable laminate of the present invention, the UV-shielding layer is formed or coated on the surface of the resin substrate as described above, and a hard coat is further formed thereon to enhance abrasion resistance and surface structure. The method of forming or applying a layer is a preferred embodiment.

The hard coat layer is formed in order to increase the surface hardness as a final laminated product to improve the scratch resistance. The type of the resin constituting the hard coat layer is high hardness and scratch resistance. Regardless of the type of the resin, it can be a silicone-type curable resin or an organic-type curable resin, regardless of its type, as long as it is a generally curable resin having an improving effect. But,
A silicon-based curable resin is particularly preferable in order to effectively utilize the above-described effects of improving the adhesion of the ultraviolet ray shielding layer to the hard coat layer, the scratch resistance, the initial crack resistance, the weather crack resistance, and the like. The silicon-based curable resin is a curable resin having a siloxane bond, for example, a trialkoxysilane or tetraalkoxysilane or a partial hydrolyzate of an alkylated product thereof, or a mixture of methyltrialkoxysilane or phenyltrialkoxysilane. And a partially hydrolyzed condensate of colloidal silica-filled organotrialkoxysilane. Commercially available products include, for example, “Si Coat 2” (manufactured by Daihachi Chemical Co., Ltd.); “Tosgard 510”, “UVHC8553”,
"UVHC8556", "UVHC8558" (or more,
"KP-851", "KP-8"
54 "," X-12-2206 "," X-12-240 "
0 "," X-12-2450 "(all manufactured by Shin-Etsu Silicone Co., Ltd.);" Solgard NP720 "," Solgard NP "
730 "," Solgard RF0831 "(both manufactured by Nippon Dacro Shamrock Co., Ltd.) and the like.

Examples of the organic curable resin include, for example, melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Examples of the polyfunctional acrylic resin include polyol acrylate, polyester acrylate, urethane acrylate, and the like. Resins such as epoxy acrylate are exemplified as preferred.

In particular, when the hard coat layer is made of a silicone resin, the hardness, the scratch resistance, and the weather resistance are determined according to the performance level.
The above-mentioned organic curable resin and the above-mentioned copolymer which is a main component of the ultraviolet shielding layer can be blended. However, a curable resin having a siloxane bond is used for 100% by mass of the resin constituting the hard coat layer. It is desirable that the content be 60% by mass or more, more preferably 80% by mass or more.
By the way, if it is less than 60% by mass, hardness, scratch resistance and weather resistance will be insufficient.

Further, the ultraviolet ray shielding layer forming agent or the hard coat layer forming agent used in the present invention may contain various other additives in addition to the above-mentioned components. Examples of the additive include silane, titanate, and aluminate-based coupling agents. Examples of the silane coupling agent include "A-1" manufactured by Nippon Unicar Co., Ltd.
87, A-189, A-1100, A-1
120 "and the like. Also, a leveling agent generally used in a layer forming composition such as a paint, an antioxidant, a filler such as talc, a rust inhibitor, a fluorescent brightener, an antioxidant, an antistatic agent, a pigment, a dye, It may contain a thickener or the like, and may further contain a benzotriazole-based, benzophenone-based, or triazine-based ultraviolet absorber or an ultraviolet stabilizer.

In order to further enhance the abrasion resistance and stain resistance of the hard coat layer, it is also effective to include colloidally dispersed silica sol or alumina in the ultraviolet shielding layer or the hard coat layer. Examples of these commercially available products include “Nalcoag 1034A” (manufactured by Nalco Chemical Co., USA) and “Cataloid-OSCAL”.
-1432 "(manufactured by Catalyst Chemical Industry Co., Ltd.) and" Snowtex C "(manufactured by Nissan Chemical Industry Co., Ltd.). Further, composite inorganic fine particles having an organic polymer fixed on the surface of inorganic fine particles as described in JP-A-7-178335 and JP-A-9-302257 can also be added.

The above-mentioned ultraviolet ray shielding layer forming agent is used for protecting a resin base material which is deteriorated by ultraviolet rays,
In some cases, UV degradation of the contents may be prevented. In the former case,
An ultraviolet ray shielding layer is formed on one or both sides of a resin substrate that is degraded by ultraviolet light or a resin substrate on which a printed layer that is degraded by ultraviolet light is applied, and a hard coat is further formed on the resin substrate to impart abrasion resistance and high hardness. Used to form a layer.
Also, in the latter case, it is used as a laminate having the same configuration as the former case.However, if a heat ray shielding layer is further provided in the laminated structure and applied to a resin window glass of a building, for example, indoor furniture etc. In addition to preventing UV deterioration, it also prevents indoor temperature rise and is effective in reducing cooling and heating costs.

In order to provide a heat ray shielding function, for example, when the above-mentioned resin base material is molded, a heat ray shielding substance is kneaded and then molded to form a film or sheet having a heat ray shielding function. Use a resin substrate, or, on one or both sides of the resin substrate preformed, form a heat ray shielding layer by applying a coating material containing a heat ray shielding substance, and further form an ultraviolet ray shielding layer thereon. It is also effective to form a hard coat layer.

The heat ray shielding material used here is not particularly limited as long as it has absorption in the near infrared region (700 to 1800 nm), but depending on the application, coloring in the visible light region (400 to 700 nm). It is desirable to use those substances having a low molar absorption coefficient and a small molar absorption coefficient, and these substances can be used alone or in combination of two or more. Further, depending on the application, a substance having an absorption in the visible light region can be contained in the visible light region in order to perform toning in the visible light region or to obtain a desired color.

Examples of the heat ray shielding material include an organic heat ray shielding substance and an inorganic heat ray shielding substance.

Preferred organic heat ray shielding materials include
For example, a metal complex compound, phthalocyanine, naphthalocyanine, an aminium salt, anthraquinone, naphthoquinone and the like can be mentioned. Among these, particularly preferred are at least one or more, preferably 4 or more, phthalocyanine skeletons.
Phthalocyanine with more than one nitrogen atom attached (for example,
Phthalocyanine substituted with a phenylamino group or an alkylamino group). Further, Japanese Unexamined Patent Publication No.
JP, JP-A-6-264050, JP-A-6-255
Phthalocyanine described in No. 48 and the like can also be preferably used.

Further, the kind of the inorganic heat ray shielding material is not particularly limited. For example, metals, metal nitrides, metal oxynitrides,
Metal carbides, metal oxides and the like can be mentioned, but as the inorganic heat ray shielding material, those having good solubility in a dispersion medium and having weather resistance are preferable, and fine particles of metal oxides are particularly preferably used. Is done. Examples of such preferred metal oxides include indium oxide or an indium oxide-based oxide containing an IV-valent metal element and / or F; tin oxide or a tin oxide containing a V-valent metal element and / or F therein. Oxides: Group IIIB metal elements and IV in zinc oxide
Examples thereof include a zinc oxide-based oxide containing at least one element of F and C and a trivalent metal element such as a group B metal element; and a metal oxide such as cadmium stannate.

The amount of the organic and inorganic heat ray-shielding substances used varies depending on the purpose of use, the difference in the molar extinction coefficient of the substance used, and the combination of the organic and inorganic heat ray-shielding substances. Therefore, it is not determined uniformly, but is usually selected from the range of 0.001 to 100 g / m ² in the total use amount of the heat ray shielding substance with respect to the base resin. Particularly preferred amounts are 0.05 to 30.
g / m ² .

[0101]

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

[Synthesis example] (Synthesis example 1 of ultraviolet ray shielding layer forming agent) 500 ml equipped with a stirrer, a dropping port, a thermometer, a cooling pipe and a nitrogen gas inlet.
90 g of 3-methacryloxypropyltrimethoxysilane (trade name “KBM5” manufactured by Shin-Etsu Chemical Co., Ltd.)
03 "), 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (trade name" RUVA93 "manufactured by Otsuka Chemical Co., Ltd.) 10
g, 120 g of diacetone alcohol, and the temperature was raised to 110 ° C. while introducing nitrogen gas and stirring. To this, 4.0 g of t-butyl peroxy-2-ethylhexanoate and 30 g of diacetone alcohol were used as initiators.
Was added dropwise over 2 hours, and the mixture was further heated for 4 hours to obtain a copolymer resin solution having a nonvolatile content of 39.8%. The weight average molecular weight of this copolymer was 52,000. The UV-absorbing copolymer (solution) having the reactive silyl group is referred to as copolymer 1. Table 1 shows the types and the amounts of the monomers and the amounts thereof, and the properties of the obtained copolymer 1.

(Synthesis Examples 2 to 14) Copolymer resin solutions were produced in the same manner as in Synthesis Example 1 using the monomer composition and the like and the compounding amounts shown in Table 1, and their properties are also shown in Table 1. The produced copolymers (solutions) are referred to as copolymers 2 to 14, respectively.

[0104]

[Table 1]

(Synthesis of Thermosetting Silicon Hard Coating Agent A) A 1000 equipped with a stirrer, a dropping port, a thermometer, and a cooling pipe.
164 parts of methyltriethoxysilane and 46 parts of isobutanol were charged into a flask having a temperature of 5 ° C. or less while stirring under ice-cooling, and an aqueous dispersion of colloidal silica cooled to 5 ° C. or less (SiO 2 ₂ , 20%) 13
8 parts were dropped from the dropping port, and the mixture was further cooled for 20 hours under ice cooling for 2 hours.
Stir at 25 ° C. for 8 hours. Thereafter, 45 parts of diacetone alcohol and 50 parts of isobutanol were added.
After adding 1.5 parts of a 1.5% aqueous sodium propionate solution, the pH is adjusted to 6 to 7 with acetic acid. Next, isobutanol is added to the resulting solution to adjust the concentration so that the nonvolatile content becomes 15%, and the solution is aged at room temperature for 3 days to produce a hard coat agent A.

Example 1 100 g of the copolymer 1 obtained in Synthesis Example 1 was diluted with diacetone alcohol to a nonvolatile concentration of 15%, and the thickness was adjusted to 10%.
0 μm polyethylene terephthalate (manufactured by Toray Industries, Inc.
After coating with a bar coater to a dry thickness of about 5 μm on a product name “Lumirror T”, and drying at room temperature for 10 minutes,
Heat and dry at 120 ° C. for 20 minutes. Then, the thermosetting silicone hard coat layer forming agent obtained above was applied using a bar coater to a thickness of about 5 μm, dried at room temperature for 10 minutes, and dried by heating at 120 ° C. for 60 minutes to obtain a resin laminate. Get. The obtained laminate (polyethylene terephthalate laminated film) is evaluated for the following items.

(1) Initial crack A hard coat layer is laminated, and the appearance of the coated film after baking and drying is evaluated according to the following criteria. 〇: No abnormality, △: Slight cracks, ×: Cracks on entire surface of coating film.

(2) Primary Adhesion An adhesion test is performed in accordance with JIS K5400 (1990) 8.5.2 (cross-cut tape method), and the appearance of the coating film is evaluated according to the following criteria. ；: No abnormality, △: Slight peeling between ultraviolet shielding layer and substrate, ×: Complete peeling between ultraviolet shielding layer and substrate.

(3) Water resistance The laminated film on which the ultraviolet shielding layer and the hard coat layer were formed in the same manner as in (1) was immersed in warm water at 60 ° C. for 7 days, and then treated in the same manner as in (2). An adhesion evaluation test is performed, and the water resistance and the appearance of the coating film are evaluated according to the following criteria. [Evaluation of water resistance] ○: No abnormality △: Slight peeling between ultraviolet shielding layer and substrate ×: Complete peeling between ultraviolet shielding layer and substrate [Evaluation of coating film appearance] Δ: No abnormality ×; There are gloss, discoloration, and blisters.

(4) Scratch resistance Using the coated film prepared in the above (1), ASTM
In accordance with D 1044, the test piece is worn by a Taber abrasion tester using a wear wheel CS-10F. The test load at this time was 500 gf, and the number of tests was 500 times and 10 times.
00 times. The change in haze (haze value) of the worn portion of the test piece before and after the test is measured in accordance with JIS K-7105, and the scratch resistance is evaluated.

(5) Weather Resistance The laminated film prepared in the above (1) was tested using a super energy irradiation tester manufactured by Suga Test Instruments Co., Ltd. [temperature 70 ° C. × humidity 70%, light intensity: 100 m / w: 6 Time irradiation] → [Temperature 8
[0 ° C. × 6 hours at 90% humidity] as one cycle, and the test pieces were exposed under the conditions of repeating 40 cycles and 80 cycles, and as evaluations before and after the weather resistance test, the following weather crack resistance, weather adhesion, and weather yellowing were evaluated. Find out. [Weather resistance cracking] The appearance of the coating film after the weathering test was evaluated according to the following criteria. ○: No abnormality, Δ: Slight cracking, ×: Cracking on the entire coating film [Weather resistance] About coating film after weathering test An adhesion test is performed by the method (2), and the appearance of the coating film is evaluated according to the following criteria. ；: No abnormality, △ 1: Slight peeling between hard coat and ultraviolet shielding layer, △ 2: Slight peeling between ultraviolet shielding layer and substrate, × 1: Peeling between hard coat and ultraviolet shielding layer, ×
2: Complete separation between the ultraviolet shielding layer and the substrate.

[Weathering Resistance Yellowing] Yellowness: Y1 The yellowness (Y1) showing coloration (especially yellowishness) of the test specimen at an ambient temperature of 23 ° C. was measured in accordance with JIS K-7103. Yellowing degree: ΔY1 weathering It indicates the change from the initial yellowness after the sex test, and is determined by “yellowing degree (ΔY1) = (yellowness after test) − (initial yellowness)”. A large value of the yellowing degree (） Y1) means that the coloration was higher than that of the initial value (the yellowish color became deeper). It is clearly visible.

Examples 2 to 18, Comparative Examples 1 to 6 In the same manner as in Example 1 above, a polyethylene terephthalate film (the same as above), a polyarylate sheet (PA: manufactured by Unitika Ltd., trade name "U-100", 3 mm) or a polycarbonate sheet (PC: manufactured by Asahi Glass Co., Ltd., trade name “Lexan 9034” clear, thickness 3 mm).
After forming an ultraviolet shielding layer containing a predetermined copolymer shown in Nos. 1 to 4, a hard coat layer was formed thereon, and an evaluation test was performed in the same manner. The results are shown in Tables 2 to 4.

[0114]

[Table 2]

[0115]

[Table 3]

[0116]

[Table 4]

From the results of Tables 2 to 4, the following can be considered.

Examples 1 to 18 are examples satisfying the requirements of the present invention, and it can be seen that they have an excellent substrate protection effect when viewed comprehensively. Among them, in Example 4, the thickness of the ultraviolet shielding layer was larger than that in Example 3, and cracks tend to occur slightly after the weather resistance test as compared with Example 3. In Example 5, a curing catalyst for an alkoxysilyl group as a crosslinking functional group in the ultraviolet shielding layer of Example 4 was added. Compared with Example 4, scratch resistance and weather crack resistance were improved. Example 6 differs from Example 4 in that the methacryloxysilyl group-containing monomer of the copolymer which is a component of the ultraviolet shielding layer in Example 4 was changed to an acrylic alkoxysilyl group-containing monomer. Is improving.

In Example 7, the curing catalyst component of the hard coat agent contained in the hard coat layer was easily impregnated into the ultraviolet shielding layer to promote the curing of the ultraviolet shielding layer.
In this example, the drying temperature at the time of forming the ultraviolet light shielding layer was room temperature, and then the drying temperature of the hard coat layer was 120 ° C., and the drying conditions of two coats and one bake were selected. Has improved. Example 8 is a composition obtained by copolymerizing cyclohexyl methacrylate as a copolymer component with the ultraviolet ray shielding layer constituent component of Example 5;
The weather crack resistance is improved. Examples 9 and 10 are examples in which an ultraviolet ray stabilizer was added to the components of the ultraviolet ray shielding layer of Example 5, and examples in which an ultraviolet ray stable monomer component was copolymerized. The weather cracking resistance and the weathering yellowing resistance are improved.
The weather resistance adhesion is improved as compared with Example 9. Example 11 was obtained by copolymerizing cyclohexyl methacrylate and an ultraviolet-stable monomer as copolymerization components in the ultraviolet-ray shielding layer component with respect to the ultraviolet-ray shielding layer component of Example 4, and was subjected to weathering yellowing and weathering cracking. And weather resistance are improved.

Examples 12 and 13 are examples using an ultraviolet ray shielding layer forming agent obtained by copolymerizing the ultraviolet ray absorbing group-containing monomer represented by the general formula (5) or (6) alone. In all cases, the weathering yellowing resistance was slightly inferior to that of Example 3. Example 14 is a copolymer obtained by copolymerizing the UV-absorbing group-containing monomer represented by the general formula (4) alone, and the UV-absorbing group-containing monomer represented by the general formula (6) alone This is an example in which a copolymer obtained by copolymerization is used by blending, and shows superior weather crack resistance, weather adhesion, and weather yellowing as compared with Example 3. In Example 15, the hard coat layer was obtained by blending the copolymer 3 which is a component of the ultraviolet light shielding layer, and showed much better weather resistance and adhesion than Example 3. Example 16
Is obtained by blending a hard coat agent A, which is a component of a hard coat layer, on the ultraviolet shielding layer side. The weather crack resistance is further improved as compared with Example 3.

Example 17 is an example in which the hard coat layer of Example 10 is made thicker, but has the same performance as Example 10.

Further, in Example 18, 0.5 parts of “EEX Color IR-10” (manufactured by Nippon Shokubai Co., Ltd.), which is a phthalocyanine compound, was used as an organic heat ray shielding material, and “U-double S-A”, an acrylic resin, was used. 5141 "(manufactured by Nippon Shokubai Co., Ltd.), and further diluted with diacetone alcohol to a nonvolatile content of 3%, and then a 3 mm-thick polycarbonate resin sheet (trade name" Lexan 90 "manufactured by Asahi Glass Co., Ltd.)
34) Clear) with a bar coater so as to have a dry thickness of about 5 μm, leave at room temperature for 10 minutes, heat and dry for 10 minutes, then apply an ultraviolet shielding layer containing a predetermined copolymer shown in Table 3 This is a laminate obtained by forming a hard coat layer thereon after formation. As is clear from Example 18, the laminate having a heat ray shielding layer formed between the base resin and the ultraviolet ray shielding layer also has the same performance. It can be confirmed that a laminate excellent in heat ray shielding properties can be obtained.

On the other hand, Comparative Examples 1 to 5 are comparative examples lacking any of the requirements specified in the present invention.
Is insufficient in the amount of the monomer having a reactive silyl group in the copolymer constituting the ultraviolet shielding layer, so that initial cracks are observed, the weather resistance between the resin substrate and the ultraviolet shielding layer is low, and the scratch resistance is low. Low level of weatherability, weather cracking and weathering yellowing. In Comparative Example 2, the ultraviolet ray shielding layer was made thinner in order to improve the initial cracking property of Comparative Example 1, and although the initial cracking property was improved, the abrasion resistance, weather cracking resistance, and weather resistance were hardly improved. And the weathering yellowing is significantly reduced. Comparative Example 3 is also an example in which the hard coat layer is made thinner in order to improve the initial cracking property of Comparative Example 1.
No improvement in weathering adhesion and yellowing resistance was observed, and the scratch resistance was significantly reduced.

In Comparative Example 4, an attempt was made to improve the initial crack by increasing the amount of the monomer having a reactive silyl group in the copolymer constituting the ultraviolet shielding layer as compared with Comparative Example 1. The improvement effect is insufficient, and the abrasion resistance, weather cracking resistance and weather adhesion cannot be improved. Comparative Example 5
Is an example in which the hard coat layer was not formed with the ultraviolet shielding layer as the outermost layer, and the scratch resistance was poor. In Comparative Example 6, the copolymer constituting the ultraviolet ray shielding layer did not contain a monomer having an ultraviolet ray absorbing group, so that the ultraviolet ray shielding ability was not exhibited, the weathering yellowing resistance was poor, and the substrate was broken. .

[0125]

The present invention is constituted as described above. When a hard coat layer is formed on the surface side of a resin base material which is liable to be colored or degraded by ultraviolet rays, an ultraviolet ray is used to improve the scratch resistance. As a shielding layer, by using a UV-absorbing resin composition containing a copolymer containing a monomer having a reactive silyl group and a monomer having a UV-absorbing group in a specific ratio, it is possible to prevent UV deterioration of the substrate. While improving the adhesion to the hard coat layer and the adhesion to the resin substrate, it is possible to provide a resin laminate having significantly improved weather resistance, scratch resistance, crack resistance and the like. In particular, when a silicone resin-based hard coat layer is formed on the surface of a resin base material that is easily deteriorated by ultraviolet light to improve the scratch resistance, the use of an ultraviolet light shielding layer as a base layer enables discoloration of the base resin. A hard coat layer that is laminated on the UV-shielding layer even if the hard-coat layer and the UV-shielding layer are thickened, as well as increasing the weather resistance by suppressing deterioration etc. and greatly increasing the adhesion with the hard-coat layer. Many effects are exhibited, including the effect of preventing cracks that occur during the temperature rise and curing processes, the effect of preventing cracks that occur during the weather resistance test, and the improvement in the adhesion between the ultraviolet shielding layer and the resin substrate.

Accordingly, the ultraviolet-stable resin laminate of the present invention can be used, for example, for packaging (packaging materials for various foods, solar cells, polymer batteries, etc.), for electrical connection, for optics (such as lenses), and for building materials (for sound insulation). Walls, etc., antifouling sheets and tents, marking films, outdoor expansion (agricultural houses, etc.), indoor and outdoor overlays (display materials, illuminated signs, etc.), windows (vehicles, architecture, daylighting materials, etc.) It can be widely used for various applications that are easily exposed to friction while being exposed to ultraviolet rays.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 230/08 C08F 230/08 C08K 5/3435 C08K 5/3435 C08L 43/04 C08L 43/04 F term ( reference) 4F100 AH03B AH03K AH06B AH06K AK01A AK42A AK52B AK52C AK52K AL01B AR00B AR00C BA03 BA07 BA15 CA05B CA07B EH46 GB07 GB90 JB07 JB14A JD09B JK06 JK12 JK12C JK14 JL09 JL09A YY00B 4J002 BG071 BQ001 EU076 FD046 FD056 GF00 GL00 4J100 AB02R AB03R AB04R AC03R AC04R AE02R AE09P AJ02R AJ08R AJ09R AK32R AL03R AL04R AL05R AL08P AL08Q AL08R AL09R AL62R AM15R AM21R AM23R AP16P BA02Q BA03Q BA03R BA08Q BA12Q BA31R BA40R BA65R BA77P BC02R BC04R BC07R BC43Q BC65JA05

Claims (5)

[Claims] 1. An ultraviolet-stable laminate having a hard coat layer formed on the surface side of an ultraviolet-degradable resin substrate via an ultraviolet-shielding layer, wherein the ultraviolet-shielding layer is obtained by polymerizing the following monomer components. An ultraviolet-stable resin laminate comprising a copolymer comprising: (1) Monomer having reactive silyl group: 50 to 90% by mass, (2) Monomer having ultraviolet absorbing group: 10 to 50
% By mass, and (3) other monomers: 0 to 40% by mass. 2. As part of the monomer (3), (4) a monomer having an ultraviolet light-stable group is contained in an amount of 0.1 to 15% by mass when the monomer component is 100% by mass. The ultraviolet-stable resin laminate according to claim 1, wherein 3. The ultraviolet-stable resin laminate according to claim 1, wherein the ultraviolet-shielding layer contains an ultraviolet stabilizer. 4. The ultraviolet-stable resin laminate according to claim 1, wherein the hard coat layer contains a silicone resin. 5. A resin composition for forming an ultraviolet shielding layer in producing the laminate according to any one of claims 1 to 4, wherein the resin composition is obtained by polymerizing the following monomer components. A resin composition for forming an ultraviolet shielding layer, comprising a coalescence. (1) Monomer having reactive silyl group: 50 to 90% by mass, (2) Monomer having ultraviolet absorbing group: 10 to 50
% By mass, and (3) other monomers: 0 to 40% by mass.