JP2002309211A - Weather-resistant film laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a weather-resistant film laminate capable of imparting long-lasting weather resistance to various molded articles, by using a polymer adhering well to a weather-resistant film. SOLUTION: This weather-resistant film laminate is prepared by forming a pressure-sensitive adhesive layer containing a polymer for a pressure-sensitive adhesive on the surface of a weather-resistant film obtained from a weather- resistant polymer. The weather-resistant polymer is prepared by polymerizing a monomer component essentially containing at least one cycloalkyl (meth) acrylate, at least one ultraviolet-stable monomer, and at least one hydroxyl- group-containing monomer. The polymer for a pressure-sensitive adhesive is prepared by polymerizing a monomer component essentially containing an alkyl (meth)acrylate as the main component and maleic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film laminate having a pressure-sensitive adhesive layer and having excellent weather resistance. More specifically, the present invention relates to a film laminate having good adhesiveness between the pressure-sensitive adhesive layer and the film and providing weather resistance. The present invention relates to a weather-resistant film laminate having excellent adhesion to a body.

[0002]

2. Description of the Related Art For example, acrylic resin, PC (polycarbonate), vinyl chloride, polystyrene, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, PET (polyethylene terephthalate), PP (polypropylene) And F
Various plastics such as RP (fiber reinforced plastic),
As a method of imparting various properties such as weather resistance, scratch resistance, solvent resistance, aesthetic appearance, gloss, etc. to a molded product obtained from stone or metal, a spray resin is generally applied to the molded product by a spray method. And a method of laminating a film by hot press, heat lamination, or an adhesive.

[0003] However, in the case of lamination by coating, there is a problem in environmental hygiene such as scattering of an organic solvent, and in addition, appearance defects such as uneven coating are liable to occur. In addition, in the method of laminating a film, materials that can be used in a hot press or the like are limited, and when laminating through an adhesive, a problem of poor adhesion between the film and a molded product occurs, and the adhesive application process is not performed. Since it is necessary, it is a problem in terms of environmental hygiene as in the case of painting.

Therefore, it is conceivable to form an adhesive layer on a weather-resistant film in advance. If the pressure-sensitive adhesive layer is formed in advance, the weather-resistant film can be attached to the molded product while unwinding from the wound state or by simply peeling off the release film on the surface of the pressure-sensitive adhesive layer. It is easy. However, the adhesion between the pressure-sensitive adhesive layer and the weather-resistant film becomes important.

[0005]

Therefore, in the present invention, a polymer for a pressure-sensitive adhesive having good adhesion to a weather-resistant film is found, and a weather-resistant polymer capable of imparting weather resistance to various molded articles for a long period of time. The object was to provide a functional film laminate.

[0006]

Means for Solving the Problems The weather-resistant film laminate of the present invention, which has solved the above-mentioned problems, comprises one or more cycloalkyl (meth) acrylates and the following general formula (1) or (2):
The surface of a weather-resistant film obtained from a weather-resistant polymer obtained by polymerizing a monomer component for a weather-resistant polymer essentially containing at least one ultraviolet-stable monomer represented by The gist lies in that a pressure-sensitive adhesive layer containing a polymer for pressure-sensitive adhesive formed by polymerizing a monomer component for pressure-sensitive adhesive mainly containing alkyl (meth) acrylate and essentially containing maleic anhydride is formed.

[0007]

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(Wherein R ¹ represents a hydrogen atom or a cyano group, R ² and R ³ each independently represent a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a hydrocarbon group,
X represents an oxygen atom or an imino group. )

[0009]

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(Wherein R ¹ represents a hydrogen atom or a cyano group, R ² , R ³ , R ^{2 ′} and R ^{3 ′} each independently represent a hydrogen atom or a methyl group, and X represents an oxygen atom or an imino group. The combination of a weather-resistant film and a pressure-sensitive adhesive polymer containing alkyl (meth) acrylate and maleic anhydride as essential constituents forms a pressure-sensitive adhesive layer having excellent adhesion to the weather-resistant film. Could be laminated. It is preferable to use a UV-absorbing monomer in combination as a constituent of the weather-resistant film because the weather resistance of the obtained film is further improved. The weather-resistant film of the present invention is specifically an acrylic weather-resistant film.

100% by mass of the monomer component for the pressure-sensitive adhesive
Medium, alkyl (meth) acrylate is 40-9
The composition containing 6.9% by mass, 1 to 10% by mass of maleic anhydride, 2 to 35% by mass of vinyl acetate and 0.1 to 15% by mass of a functional group-containing monomer other than maleic anhydride is an adhesive. This is a preferred embodiment of the agent polymer.

Further, the polymer for pressure-sensitive adhesive of the preferred embodiment is characterized in that 70 to 100% by mass of vinyl acetate used as a monomer for pressure-sensitive adhesive and a part of monomers other than vinyl acetate are put into a reactor. It is preferable that the monomer is obtained by charging the mixture first to start the polymerization, then charging the remaining monomer components into the reactor and performing polymerization.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a method for forming a pressure-sensitive adhesive layer having good adhesion to a weather-resistant film on the surface of a weather-resistant film composed of an ultraviolet-stable monomer having a specific structure. Has features. In particular, the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer has excellent adhesion to the weather-resistant film used in the present invention and shows good adhesion to various substrates (adherends). Therefore, weather resistance can be imparted to these substrates over a long period of time.

First, the weather resistant film of the present invention will be described. The weather-resistant film used in the present invention comprises one or more cycloalkyl (meth) acrylates, and an ultraviolet-stable monomer 1 represented by the general formula (1) or (2).
It is obtained from a weather-resistant polymer obtained by polymerizing a monomer component for a weather-resistant polymer that essentially contains at least one kind and one or more hydroxyl group-containing monomers. In addition, the word "polymer" other than the case where "homopolymer" is not specifically mentioned,
It is intended to represent a multi-component copolymer such as a copolymer or a terpolymer.

The cycloalkyl (meth) acrylate is an essential component for imparting sufficient surface hardness, aesthetic appearance such as gloss and stickiness, and weather resistance to the film. The cycloalkyl (meth) acrylate has a cyclohexyl group or a cyclododecyl group which may have a substituent (meth)
Acrylate, specifically, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, (meth)
Tert-butylcyclohexyl acrylate and the like can be mentioned, and one or more of these can be used. (Meta)
The cycloalkyl acrylate is preferably used in an amount of 5 to 95% by mass based on 100% by mass of the monomer component for a weather-resistant polymer.

The ultraviolet light-stable monomer is a piperidine compound represented by the above formula (1) or (2) and has no ability to absorb ultraviolet light, but has an excellent ultraviolet light stability due to a function different from that of the ultraviolet light absorber. Demonstrate. Although this ultraviolet light stabilizing action has not yet been sufficiently elucidated, it is considered that the N-oxyl radical generated by oxidizing the N-substituent of the piperidine skeleton captures the radical generated by the ultraviolet light. . In the present invention, in order to introduce a UV-stable group into the polymer skeleton constituting the film using a UV-stable monomer, compared with the case where a low-molecular UV stabilizer or UV absorber that easily bleeds out is mixed. A decrease in weather resistance over time is suppressed as much as possible.

In the general formula (1) or (2), R
^The substituent represented by ⁴ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group preferably has 1 to 18 carbon atoms. Specifically, it may be any of an alkyl group such as a methyl group and an ethyl group, an alicyclic hydrocarbon group such as a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group and a phenethyl group.

Specific examples of the ultraviolet-stable monomer represented by the general formula (1) 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
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.

The UV-stable monomer represented by the general formula (2) includes, for example, 1- (meth) acryloyl-
4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4
-Cyano-4- (meth) acryloylamino-2,2,
6,6-tetramethylpiperidine, 1-crotonoyl-
4-crotoyloxy-2,2,6,6-tetramethylpiperidine and the like.

As the UV-stable monomer, any one of the compounds represented by the above general formulas (1) and (2) may be used alone, or two or more of them may be appropriately mixed and used. Good. The UV-stable monomer is preferably used in an amount of 0.1 to 10% by mass based on 100% by mass of the monomer component for a weather-resistant polymer. If the amount is less than 0.1% by mass, the weather resistance of the film may be insufficient. 10% by mass
Even if added in excess of the above, the effect of improving weather resistance saturates,
This is not preferable because the gloss and the durability of the film gradually decrease, and the appearance may be impaired. A more preferred lower limit of the amount of the UV-stable monomer used is 0.2% by mass, and an upper limit is 5% by mass.

The hydroxyl group-containing monomer is used for the purpose of introducing a crosslinking point (hydroxyl group) for improving physical properties such as film strength, water resistance and chemical resistance into the weather-resistant polymer. Specific examples include 2-hydroxyethyl (meth) acrylate and 3 (meth) acrylic acid.
-Placcel F series, which is a modified polycaprolactone of hydroxypropyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate (Daicel Chemical Industries, Ltd.) And the like, and one or more of these can be used. The hydroxyl group-containing monomer is a monomer component for weatherable polymer 100
It is preferable to use 6 to 35% by mass of the mass%. If the amount is less than 6% by mass, the crosslink density of the weather-resistant polymer becomes low, and the above-mentioned properties such as film strength may be insufficient. If it is used in excess of 35% by mass, polymerization stability is deteriorated and the water resistance of the film is undesirably reduced. In addition, storage stability after blending a crosslinking agent may be reduced. The lower limit of the more preferred amount of the hydroxyl group-containing monomer is 10% by mass, and the upper limit is 30% by mass.

When obtaining a weather-resistant polymer, an ultraviolet absorbing monomer may be used. The ultraviolet-absorbing monomer refers to a monomer that can absorb ultraviolet light and re-radiate its energy mainly as harmless heat energy, and has radical polymerizability. The use of these monomers as a copolymer component imparts an ultraviolet absorbing ability to the resulting film.

Examples of the UV-absorbing monomer include a benzotriazole-based monomer represented by the following general formula (3).

[0024]

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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 A straight-chain or branched-chain alkylene group of 12 or —O—R ⁹ — (R ⁹ represents a straight-chain or branched-chain alkylene group having 2 or 3 carbon atoms); ⁸ represents a hydrogen atom or a methyl group).

A benzophenone-based monomer represented by the following general formula (4) is also an ultraviolet-absorbing monomer.
Can be used.

[0027]

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(Where R^Five, R⁸Has the same meaning as above
Then R^TenIs a straight or branched chain having 1 to 12 carbon atoms
Represents an alkylene group of¹¹Represents a hydrogen atom or a hydroxyl group
Represents, R ¹²Is a hydrogen atom or an alkoxy having 1 to 6 carbon atoms
Represents a group).

Further, a triazine-based monomer represented by the following general formula (5) may be used as an ultraviolet absorbing monomer.

[0030]

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[0031] (wherein, R ⁸ are as defined above, R ¹³
A direct bond, is _{- (CH 2 CH 2 O)} n- or -CH ₂ CH
(OH) -CH ₂ O- and represents, n is an integer of 1-5. ^{R 14, R 15, R 16} , R 17, R 18, R 19, R 20, R 21
Each independently represents a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group, or an alkyl group).

Preferred specific examples of the benzotriazole-based monomer represented by the general formula (3) include, for example, 2
-[2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -2H-benzotriazole,
-[2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole,
-[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.

Specific examples of the benzophenone-based monomer represented by the general formula (4) include 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, 2-hydroxy-3-
tert-butyl-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-3-t
tert-butyl-4- [2- (meth) acryloyloxy] butoxybenzophenone and the like.

Specific examples of the triazine monomer represented by the general formula (5) 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 above-mentioned UV-absorbing monomers each have specific UV-absorbing properties, and may be used in various combinations. The UV-absorbing monomer is preferably used in an amount of 20% by mass or less based on 100% by mass of the monomer component for a weather-resistant polymer. Use of more than 20% by mass is not preferable because the gloss and the stickiness of the film are reduced. A more preferred upper limit of the amount is 10% by mass.

The monomer component for a weather-resistant polymer may contain other monomers in addition to the above essential monomers and the preferably used ultraviolet-absorbing monomers as long as the object of the present invention is not impaired. Specifically, monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, and maleic anhydride; acidic phosphate ester monomers such as 2- (meth) acryloyloxyethyl acid phosphate; and (meth) (Meth) acrylic acid alkyl esters such as methyl acrylate and ethyl (meth) acrylate; (meth) acrylamide, N,
Nitrogen-containing monomers such as N'-dimethylaminomethyl (meth) acrylate, imide (meth) acrylate and N-methylol (meth) acrylamide; nitrile group-containing monomers such as (meth) acrylonitrile; ethylene glycol di (meth) acrylate Polyfunctional monomers; halogen-containing monomers such as vinyl chloride; aromatic monomers such as styrene and α-methylstyrene; vinyl ethers; vinyl propionate; and the like, and one or more of these can be used.

The polymerization method for obtaining a weather-resistant polymer is as follows:
Not particularly limited, conventionally known various polymerization methods, for example,
A solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like can be employed, but the solution polymerization method is preferred. This is because the solution polymerization method can easily remove the heat of polymerization during polymerization and has good operability. Specific examples of the solvent include toluene,
Aromatic hydrocarbons such as xylene; aliphatic esters such as ethyl acetate and butyl acetate; alicyclic hydrocarbons such as cyclohexane; and aliphatic hydrocarbons such as hexane and pentane. Is not particularly limited as long as it is not inhibited. These solvents may be used alone or in a combination of two or more. In addition,
The amount of the solvent used may be appropriately determined.

Examples of the polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide,
Cumene hydroperoxide, t-butyl peroxy octoate, t-butyl peroxy benzoate, lauroyl peroxide, trade name "Niiper BMT-K
Organic peroxides such as "40" (manufactured by NOF Corporation; a mixture of m-toluoyl peroxide and benzoyl peroxide), azobisisobutyronitrile, trade name "ABN-
E "[Nippon Hydrazine Industry; 2,2'-azobis (2-
Methylbutyronitrile)], trade name “ABN-V” [manufactured by Nippon Hydrazine Industry Co., Ltd .; 2,2′-azobis (2,4-
A known radical polymerization initiator such as an azo compound such as dimethylvaleronitrile)] can be used. It is preferable to use the initiator in an amount of 0.01 to 1% by mass based on the mass of the monomer. The polymerization conditions such as the polymerization temperature and the polymerization time may be appropriately set according to, for example, the type of the polymerization solvent and the polymerization initiator, and are not particularly limited. Also, the reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure. The polymerization reaction is desirably performed in an atmosphere of an inert gas such as a nitrogen gas. The molecular weight of the weather resistant polymer is preferably about 2,000 to 300,000 in terms of weight average molecular weight (Mw).

After obtaining the weather-resistant polymer, a weather-resistant polymer composition is prepared by blending a crosslinking agent for a weather-resistant polymer and formed into a film to obtain a weather-resistant film. The crosslinking agent for a weather-resistant polymer is not particularly limited as long as it has reactivity with a hydroxyl group, but a polyisocyanate compound having two or more isocyanate groups or a modified product thereof or an aminoplast resin is preferable. Can be used. The amount of the crosslinking agent for the weather-resistant polymer is not particularly limited, and may be appropriately increased or decreased according to the amount of the hydroxyl group-containing monomer used.

Specific examples of the polyisocyanate compound include tolylene diisocyanate (TDI), 4,4'-
Diisocyanate compounds such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; "Sumijur N"
(Desmodur IL) and "Desmodur HL" (both manufactured by Bayer AG), such as Buret polyisocyanate compounds (manufactured by Sumitomo Bayer Urethane Co., Ltd.);
A polyisocyanate compound having an isocyanurate ring known as "Coronate EH" (manufactured by Nippon Polyurethane Industry); an adduct polyisocyanate compound such as "Sumidur L" (manufactured by Sumitomo Bayer Urethane);
Adduct polyisocyanate compounds such as "Coronate L" and "Coronate L-55E" (both manufactured by Nippon Polyurethane Co., Ltd.) can be mentioned. These can be used alone or in combination of two or more. Also, a so-called blocked isocyanate obtained by reacting an isocyanate group of these compounds with a masking agent having active hydrogen and inactivating them may be used.

As the aminoplast resin, methyl etherified melamine resin, butyl etherified melamine resin,
Examples include butyl etherified benzoguanamine resin, butyl etherified cyclohexyl benzoguanamine resin, and the like, and water-soluble products thereof.

In addition to the crosslinking agent for the weather-resistant polymer, a known catalyst, an organic solvent, a filler, a leveling agent, a plasticizer, a stabilizer, a dye, a pigment and the like may be added to the weather-resistant polymer composition, if necessary. May be added.

The obtained weather-resistant polymer composition is continuously applied to a process film such as a polyethylene terephthalate film (PET film) or a surface of various smooth and releasable base materials such as metal and glass to a constant thickness. A weather-resistant film can be obtained by forming into a film using a cast method of coating and heating and drying, or an extrusion method of extruding a melt (or solution) from a die into a sheet and heating and drying. The heating conditions are not particularly limited,
Since the crosslinking reaction proceeds during heating and drying, it is preferable to dry at a temperature at which the crosslinking reaction proceeds promptly depending on the type of the crosslinking agent. The thickness of the film is not particularly limited and can be appropriately changed depending on the application, but is usually about 10 to 100 μm.

Next, the pressure-sensitive adhesive composition used for forming a pressure-sensitive adhesive layer on the surface of the weather-resistant film will be described. The pressure-sensitive adhesive composition essentially contains a specific pressure-sensitive adhesive polymer. This particular adhesive polymer is (meth)
It is obtained by polymerizing a monomer component for a pressure-sensitive adhesive mainly containing an alkyl acrylate and essentially containing maleic anhydride. The pressure-sensitive adhesive layer formed on the weather-resistant film of the present invention is different from a normal pressure-sensitive adhesive that is used on the assumption that the pressure-sensitive adhesive film is peeled cleanly after application, and is applied to the substrate (adherend) for a long period of time. It is used for the purpose of bonding, and is used like an adhesive. However, in order to distinguish it from an adhesive which initially has plasticity and hardens after bonding, such as a curable adhesive, it is referred to as a "pressure-sensitive adhesive (layer)" in the present invention for convenience.

(Meth) contained in the monomer component for the pressure-sensitive adhesive
The acrylic acid alkyl ester is a main component for exhibiting adhesive strength. Specifically, a (meth) acrylate having 1 to 12 carbon atoms in an alkyl group is preferable, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- (meth) acrylate -Octyl, isooctyl (meth) acrylate,
Dodecyl (meth) acrylate, stearyl (meth) acrylate and the like. One or more of these can be used.

Maleic anhydride was used as an essential component because it was useful for improving the adhesion between the weather-resistant film and the pressure-sensitive adhesive layer. Close 2 formed by ring-opening of the anhydride group of maleic anhydride
It is thought that each carboxyl group contributes to the adhesion to the weather-resistant film. Maleic anhydride is
1 to 10% by mass in 100% by mass of monomer component for adhesive
Preferably, it is used. If the amount is less than 1% by mass, the effect of improving the adhesion to the weather-resistant film becomes insufficient, and the amount becomes 10% by mass.
If used in excess of this, the pressure-sensitive adhesive becomes undesirably hard due to the effects of hydrogen bonding due to the carboxyl group, and is not preferred.

When the polymer for an adhesive is formed only with maleic anhydride and an alkyl (meth) acrylate, the preferred amount of the alkyl (meth) acrylate is 99 to 90% by mass. In consideration of the adhesive properties, it is preferable that the monomer component for an adhesive further contains vinyl acetate and a functional group-containing monomer. When these monomers are contained in the pressure-sensitive adhesive monomer component, the content of the alkyl (meth) acrylate in 100% by mass of the pressure-sensitive adhesive monomer component is adjusted to 4%.
It is preferably from 0 to 96.9% by mass. Outside this range, the adhesion to the weather-resistant film tends to decrease, and the adhesive strength tends to decrease.

It is preferable to use vinyl acetate because the temperature sensitivity of the pressure-sensitive adhesive can be reduced. What is temperature sensitivity?
It refers to the property that the pressure-sensitive adhesive becomes hard and easy to peel off in a low-temperature atmosphere, and the pressure-sensitive adhesive becomes soft and easily causes cohesive failure in a high-temperature atmosphere. Since vinyl acetate is not very copolymerizable with alkyl (meth) acrylate, the resulting pressure-sensitive adhesive polymer is an aggregate of polymers of various compositions having different copolymerization ratios of vinyl acetate. It is thought that the sex becomes smaller. In order to obtain the effect of reducing the temperature sensitivity, it is preferable to use 2-35% by mass of vinyl acetate in the monomer component for an adhesive.
If the amount is less than 2% by mass, the effect is not sufficiently exhibited, and 35% by mass.
If used in excess of this, the adhesion to the weather-resistant film and the adhesive properties are undesirably reduced. The lower limit of the more preferable vinyl acetate use amount is 4% by mass, and the upper limit is 30% by mass.

The functional group-containing monomer is not particularly limited as long as it has a functional group capable of reacting with the crosslinking agent for the pressure-sensitive adhesive polymer. However, it is preferable to use a carboxyl group-containing monomer, a hydroxyl group-containing monomer and the like.
This is because the crosslinking reaction proceeds promptly. The carboxyl group-containing monomer and the hydroxyl group-containing monomer are
Any of those exemplified in the description of the weather-resistant polymer can be used. The functional group-containing monomer is 0.1 to 1
It is preferable to use 5% by mass. If the amount is less than 0.1% by mass, the crosslinking is insufficient, the crosslinking density is low, and the cohesion may be insufficient. However, use of more than 15% by mass is not preferable because the pressure-sensitive adhesive becomes too hard. The lower limit of the more preferred amount is 0.2% by mass, and the upper limit is 10% by mass.
It is.

The monomer component for the pressure-sensitive adhesive may contain other monomers. The cycloalkyl (meth) acrylate used to obtain the weather-resistant polymer, the UV-stable monomer, the UV-absorbing monomer, and the monomers exemplified as “other monomers” can be used. The content is preferably set to 0 to 20% by mass. If the amount exceeds 20% by mass, the amount of the alkyl (meth) acrylate used is small, and properties such as adhesive strength are undesirably reduced.

The pressure-sensitive adhesive monomer is suitably combined with the pressure-sensitive adhesive monomer as described above to obtain a pressure-sensitive adhesive polymer. As a rule, it is preferable to combine the polymers so that the polymer has a Tg of -60 ° C. to + 30 ° C. The Tg of the polymer is
It can be determined by DSC (differential scanning calorimeter), DTA (differential thermal analyzer), and TMA (thermomechanical analyzer). Further, since the Tg of the homopolymer is described in various documents, the Tg of the copolymer can also be determined from the Tgn (K) of each homopolymer and the mass fraction (Wn) of the monomer by the following formula. .

[0052]

(Equation 1)

Incidentally, if the Tg of the main homopolymer is shown,
106 ° C for polyacrylic acid, 8 for polymethyl acrylate
° C, polyethyl acrylate 22 ° C, polyacrylic acid n
-Butyl is -54 ° C, 2-ethylhexyl polyacrylate is -70 ° C, 2-hydroxyethyl polyacrylate is -15 ° C, and 2-hydroxyethyl polymethacrylate is 5 ° C.
5 ° C., 105 ° C. for polymethyl methacrylate, 32 ° C. for polyvinyl acetate, 125 ° C. for polyacrylonitrile, 100 ° C. for polystyrene, and 130 ° C. for polymaleic acid.

Next, a preferred polymerization method for obtaining the adhesive polymer according to the present invention will be described. When vinyl acetate is not used, a polymer for a pressure-sensitive adhesive can be obtained by appropriately polymerizing using a known polymerization method (particularly a solution polymerization method is preferable) as described in the case of the weather-resistant polymer. The solvents, polymerization initiators, polymerization conditions, and the like that can be used in the solution polymerization are the same as those described above.

When vinyl acetate is used, its copolymerizability with the alkyl (meth) acrylate is small.
In a normal solution polymerization method in which a monomer mixture having a uniform composition is dropped, a large amount of unreacted vinyl acetate remains. For this reason, 70 to 1 of the vinyl acetate used is
00 mass% and a part of the monomer other than vinyl acetate (referred to as an initially charged monomer component) were first charged into a reactor to start polymerization, and then the remaining monomer component (referred to as a monomer component for charging) was added to the reactor. It is preferable to adopt a method of charging the mixture into the reactor and performing polymerization. According to this method, vinyl acetate is easily polymerized with the alkyl (meth) acrylate, and the polymerization rate is improved. The method of dropping a monomer mixture having a uniform composition and adding a post-addition initiator (booster) at the latter stage of the polymerization is preferable because polyvinyl acetate having a small molecular weight is generated and may adversely affect the properties as an adhesive. Absent.

The initially charged monomer component is the total amount of vinyl acetate (100% by mass) used as a monomer for the pressure-sensitive adhesive.
And 70 to 100% by mass of the above, and a small amount of a monomer other than vinyl acetate. This is because if 70% by mass or more of vinyl acetate is initially charged, the amount of residual monomers is effectively reduced and the polymerization rate is improved. The lower limit of the initial charge amount of vinyl acetate is preferably 80% by mass, more preferably 90% by mass, and still more preferably 95% by mass. It is most preferable to initially charge the entire amount of vinyl acetate, that is, 100% by mass. If all of the initially charged monomers are vinyl acetate alone, a homopolymer of polyvinyl acetate may be generated. Therefore, the amount of the monomer other than vinyl acetate is equal to the initial charged amount of vinyl acetate to 3 times (mass). Ratio), it is preferable to initially charge.

The input monomer component is a mixture of the remaining monomers not initially charged. It is preferable that the initial charging of the monomer component for charging be performed after the initiation of the polymerization of the initially charged monomer component charged into the reactor and at a point in time when the polymerization rate does not exceed 50%. If the polymerization rate of the initially charged monomer component exceeds 50%, a considerable amount of vinyl acetate-rich polymer is already formed in the reactor, and a well-balanced pressure-sensitive adhesive polymer cannot be obtained. May not be reduced. The start time of the polymerization can be measured as the time when the heat generation due to the polymerization is started by measuring the internal temperature of the polymerization vessel. Further, when the polymerization is carried out at the reflux temperature, it can be regarded as the point in time when the volatilization of the polymerization solvent becomes intense.

On the other hand, the monomer component for charging is preferably divided into three or more portions, and dripping is most preferable.
The polymerization initiator must be used for the initially charged monomer component and for the charging monomer component, and the initially charged monomer component is charged to the reactor, and the charging monomer component is charged when the charging monomer component is added. Add together. A booster (post-addition initiator) may be added at a later stage of the polymerization.

From the viewpoint of adhesive properties, the weight average molecular weight Mw of the entire polymer for an adhesive is preferably 200,000 or more, more preferably 300,000 or more. Although the upper limit is not particularly limited, it is difficult to synthesize a polymer exceeding 2,000,000 in solution polymerization, and therefore it is preferably 2,000,000 or less, more preferably 1,000,000 or less.

The pressure-sensitive adhesive layer on the surface of the weather-resistant film is preferably formed from a pressure-sensitive adhesive composition containing the polymer for a pressure-sensitive adhesive and a predetermined amount of a crosslinking agent. When cross-linked with a cross-linking agent,
This is because various physical properties such as cohesive force are improved. As the cross-linking agent, a compound having two or more functional groups in one molecule, which is a functional group of the functional group-containing monomer and has a reactivity with a functional group introduced into the pressure-sensitive adhesive polymer, can be used. . Examples of such a functional group include an isocyanate group, an epoxy group, an amino group, a methylol group, an alkoxymethyl group, an imino group, a metal chelate group, and an aziridinyl group. Specific compounds include a polyfunctional isocyanate compound, a polyfunctional epoxy compound, a polyfunctional melamine compound, a metal crosslinking agent, an aziridine compound, and the like.

As the polyfunctional isocyanate compound having two or more isocyanate groups, any of those exemplified as the crosslinking agent for the weather-resistant polymer can be used.

The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups per molecule. Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N ', N'-tetraglycidyl-
m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine and the like.

The polyfunctional melamine compound is not particularly limited as long as it has a total of two or more methylol groups, alkoxymethyl groups or imino groups per molecule. Specific examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine, and the like.

The metal crosslinking agent is not particularly limited. Specific examples include metals such as aluminum, zinc, cadmium, nickel, cobalt, copper, calcium, barium, titanium, manganese, iron, lead, zirconium, chromium, tin, acetylacetone, methyl acetoacetate, ethyl acetoacetate, and lactic acid. Metal chelate compounds coordinated with ethyl, methyl salicylate, and the like.

Examples of the aziridine compound include N, N'-hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, bisisophthaloyl-1 − (2-
Methylaziridine), tri-1-aziridinyl phosphoxide, N, N′-diphenylethane-4,4′-bis (1-aziridinecarboxamide) and the like.

A crosslinking system using a functional group-containing monomer as a carboxyl group-containing monomer and a polyfunctional epoxy compound as a crosslinking agent is most preferred. The amount of the cross-linking agent is not particularly limited, but is preferably 0.05 to 15% by mass based on the pressure-sensitive adhesive polymer (nonvolatile content). If the amount is less than 0.05% by mass, the crosslinking is insufficient, the crosslinking density is low, and the cohesive strength may be insufficient.
If it exceeds 15% by mass, the crosslink density may be too high and the adhesive strength may be low. A more preferred lower limit is 0.1.
% By mass, and the upper limit is 10% by mass.

The pressure-sensitive adhesive composition containing the pressure-sensitive adhesive polymer and the crosslinking agent may optionally contain a tackifier. As the tackifier, (polymerized) rosin,
(Polymerization) Rosin ester type, terpene type, terpene phenol type, coumarone type, coumarone indene type, styrene resin type, xylene resin type, phenol resin type, petroleum resin type and the like can be mentioned. These can be used alone or in combination of two or more.

The amount of the tackifier is not particularly limited.
Usually, 5-1 to 100 parts by mass of the polymer for adhesive is used.
Preferably it is 00 parts by mass. If the amount of the tackifier is less than 5 parts by mass, the effect of improving the adhesive strength by the tackifier may not be exhibited. On the other hand, when the addition amount of the tackifier is more than 100 parts by mass, the tack may be reduced and the adhesive strength may be reduced. More preferably, it is in the range of 10 to 50 parts by mass.

If necessary, conventionally known additives such as fillers, pigments, diluents, antioxidants, ultraviolet absorbers, ultraviolet stabilizers and the like may be added to the pressure-sensitive adhesive composition. You may. One or two of these additives may be used.
More than species can be used. The amount of these additives
What is necessary is just to set suitably so that desired physical property may be obtained.

A pressure-sensitive adhesive composition prepared by mixing the above-mentioned various additives, solvents and the like, if necessary, with the polymer for a pressure-sensitive adhesive and the crosslinking agent is applied to the surface of the weather-resistant film by a roll coating method, a spray coating method, or the like. By coating and heating and drying by a known method such as a dipping method, the weather-resistant film laminate of the present invention can be obtained. The heating and drying conditions are not particularly limited, but since the crosslinking reaction proceeds during heating and drying, it is preferable to dry at a temperature at which the crosslinking reaction proceeds promptly depending on the type of the crosslinking agent.

Further, a weather-resistant film is manufactured on a process film such as a PET film by a casting method, and then, the adhesive composition is applied on the weather-resistant film layer on the process film, dried, and dried. It is also possible to adopt a method of forming an agent layer or a method of forming a weather-resistant film and a pressure-sensitive adhesive layer on separate process films and bonding them together.

In addition, between the weather-resistant film and the pressure-sensitive adhesive layer,
For example, a weather-resistant film laminate having a configuration in which another layer such as a primer layer is interposed is also included in the present invention, but the weather-resistant film and the pressure-sensitive adhesive layer used in the present invention have excellent adhesion, so that the process is simplified. From the viewpoint of formation, a weather-resistant film laminate in which a weather-resistant film and an adhesive layer are directly laminated is most preferable.

The weather-resistant film laminate of the present invention is used for attaching weather resistance to a substrate (adherend). As the base material, acrylic resin, PC (polycarbonate), vinyl chloride, polystyrene, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, PET (polyethylene terephthalate), PP (polypropylene), and known materials And molded articles obtained from various plastics such as FRP (fiber reinforced plastic), stones, metals and the like.

In order to laminate the weather-resistant film laminate on the substrate, a pressing method or a hot pressing method may be employed. When a process film is provided, the process film may be pressed and the process film may be attached until immediately before using the product, and also serves as a surface protection film. Heat lamination is preferred for laminating a weather-resistant film laminate on a substrate having an uneven surface. Since the weather-resistant film is flexible and easily follows the surface shape of the substrate, it can be laminated neatly. Before laminating the weather-resistant film laminate, the substrate may be subjected to a known primer treatment.

[0075]

The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples. Hereinafter, unless otherwise specified, “%” indicates “% by mass” and “parts” indicates “parts by mass”.

Example 1 In order to synthesize a weatherable polymer, 173 parts of ethyl acetate was charged as a solvent into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser, and a dropping funnel. It is. Then, cyclohexyl methacrylate 258.
6 parts, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine (ultraviolet-stable monomer) 6 parts,
48.6 parts of 2-hydroxyethyl acrylate, 15 parts of 2-hydroxypropyl acrylate, butyl acrylate 2
90 parts of 600 parts of a monomer component consisting of 44.6 parts and 67.2 parts of styrene were added to the flask. Then, the mixture was stirred under a nitrogen gas flow, and when the temperature was raised to 80 ° C., 2,2′-azobis (2,4-dimethylvaleronitrile) (azo polymerization initiator; trade name “ABN-
V ": manufactured by Nippon Hydrazine Industry Co., Ltd.) and polymerization was initiated. 10 minutes after the start of the polymerization, 510 parts of the remaining monomer components, 41 parts of ethyl acetate and ABN-V1
A mixture of 2.24 parts was continuously added dropwise over 2 hours. After the addition, 30 parts of ethyl acetate and ABN-V1.
8 parts were added and further reacted under reflux for 3 hours to obtain a weather-resistant polymer solution (A). The non-volatile content of this solution is 7
0.3%, viscosity 7450 mPa · s (25 ° C., B-type viscometer, the same applies hereinafter), weight-average molecular weight (M
w) was 1.1 × 10 ⁴ (GPC measurement: standard polystyrene conversion).

The conditions for measuring the molecular weight by GPC are as follows. The sample concentration was 0.2%, and the injection volume was 200 microliter / time. GPC measuring device: Liquid Chromatography Model 510 (manufactured by Waters) Detector: M410 differential refractometer Column: Ultra Styragel Linear (7.8 mm × 30 cm) Ultra Styragel 100A (7.8 mm × 30 cm) Ultra Styragel 500A (7.8 mm ×) 30 cm) Solvent: THF (tetrahydrofuran) Then, a polyfunctional isocyanate (trade name "Sumidur N-
3200 ": manufactured by Sumitomo Bayer Urethane Co., Ltd.) such that the equivalent ratio of isocyanate to hydroxyl group of the weather-resistant polymer was 1: 1 to prepare a weather-resistant polymer composition (A).

Next, 480 parts of butyl acrylate and methacrylic acid were placed in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser and a dropping funnel for synthesizing a polymer for an adhesive. 180 parts of a mixture of 540 parts consisting of 12 parts of methyl, 12 parts of maleic anhydride and 36 parts of acrylic acid, 60 parts of vinyl acetate and 3 parts of ethyl acetate
15 parts and 45 parts of toluene were charged, and when the temperature was raised to 80 ° C. under a nitrogen gas stream, a peroxide-based initiator (trade name “Niper BMT-K40”: manufactured by NOF CORPORATION) was added.
48 parts were added to initiate polymerization for the initial charge. After 15 minutes from the start of the polymerization, 360 parts of the remaining monomer was added to 0.1 part of the monomer.
A mixture consisting of 72 parts of Niper BMT-K40 and 20 parts of ethyl acetate was added dropwise over 1.5 hours, and at the end of the addition, 85 parts of ethyl acetate were added to the reactor. As the viscosity of the contents increased after further reacting for 90 minutes,
248.2 parts of toluene and ethyl acetate 4 as a diluting solvent
Add 5.4 parts, and use as an booster an azo-based polymerization initiator (trade name “ABN-E”: manufactured by Nippon Hydrazine Industry Co., Ltd.)
A mixture consisting of 1.8 parts and 41.7 parts of toluene was added in five portions every 30 minutes, and the reaction was continued for 4 hours. At the end of the polymerization, 28 parts of toluene was added, followed by cooling. As a result, the nonvolatile content was 40.2% and the viscosity was 19900 mPa ·
s, weight average molecular weight (Mw) 57.9 × 10 ⁴ (GPC
(Measurement: standard polystyrene conversion) 1 was obtained. This adhesive polymer has a Tg of -37.
° C (calculated value). One in one
To 100 parts (present), a 3% ethyl acetate solution of a polyfunctional epoxy compound (trade name “TETRAD-C”: manufactured by Mitsubishi Gas Chemical Company: 100% active ingredient) was used as a crosslinking agent.
No. 75 parts, and the pressure-sensitive adhesive composition No. 1 was prepared.

On a polyethylene terephthalate (PET) film having a thickness of 50 μm, the thickness after drying was 40 μm.
The weather-resistant polymer composition (A) was applied so as to be as follows, and dried at 80 ° C. for 3 minutes. Then, the pressure-sensitive adhesive composition No. was placed on the weather-resistant film so that the thickness after drying was 25 μm. 1 was coated and dried at 80 ° C. for 5 minutes to obtain a weather-resistant film laminate.

Examples 2 to 4 The same procedures as in Example 1 were carried out except that the composition of the polymer for the pressure-sensitive adhesive was changed as shown in Table 1. 2-N
o. 4 was prepared, and a weather-resistant film laminate was obtained using the weather-resistant polymer composition (A) in the same manner as in Example 1.

Example 5 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the composition of the pressure-sensitive adhesive polymer was changed as shown in Table 1, and a mixture of all the monomers was dropped over 1.5 hours. No. 5 was prepared, and a weather-resistant film laminate was obtained using the weather-resistant polymer composition (A) in the same manner as in Example 1.

Example 6 A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser and a dropping funnel was prepared in order to synthesize a polymer for a weather-resistant film combined with an ultraviolet absorbing monomer. And 173 parts of ethyl acetate as a solvent.
Then, 258.6 parts of cyclohexyl methacrylate, 4
-Methacryloyloxy-2,2,6,6-tetramethylpiperidine 6 parts, 2- as an ultraviolet absorbing monomer
12 parts of [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole,
48.6 parts of 2-hydroxyethyl acrylate, 15 parts of 2-hydroxypropyl acrylate, 1 butyl acrylate
90 parts of 600 parts of a monomer component consisting of 92.6 parts and 67.2 parts of styrene were added to the flask. Then, the mixture was stirred under a nitrogen gas stream, and when the temperature was raised to 80 ° C., 2.16 parts of ABN-V was added to initiate polymerization. After a lapse of 10 minutes from the start of the polymerization, a mixture composed of 510 parts of the remaining monomer components, 41 parts of ethyl acetate and 12.24 parts of ABN-V was continuously dropped over 2 hours. After completion of the dropwise addition, 30 parts of ethyl acetate and 1.8 parts of ABN-V were added, and the mixture was further reacted under reflux for 3 hours to obtain a weather-resistant polymer solution (B). The non-volatile content of this solution is 69.8%,
The weight-average molecular weight (Mw) of the weatherable polymer having a viscosity of 7020 mPa · s was 1.0 × 10 ⁴ (GPC measurement: standard polystyrene conversion).

In the above weather-resistant polymer solution (B), a polyfunctional isocyanate “Sumidur N-32” was used as a crosslinking agent.
"00" was added so that the equivalent ratio of isocyanate to hydroxyl group of the polymer was 1: 1 to prepare a polymer composition (B) for a weather-resistant film. The pressure-sensitive adhesive composition No. 1 prepared in Example 1 was mixed with the polymer composition (B) for a weather-resistant film. Using Example 1, a weather-resistant film laminate was obtained in the same manner as in Example 1.

Comparative Examples 1-2 The adhesive composition No. was prepared in the same manner as in Example 1 except that the composition of the polymer for the adhesive was changed as shown in Table 1. 6-N
o. 7 was prepared, and a weather-resistant film laminate was obtained using the weather-resistant polymer composition (A) in the same manner as in Example 1.

Comparative Example 3 A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser, and a dropping funnel for synthesizing a polymer for a non-weatherproof film without using an ultraviolet-stable monomer. Was charged with 173 parts of ethyl acetate as a solvent, and then 300 parts of methyl methacrylate, 48.6 parts of 2-hydroxyethyl acrylate, 15 parts of 2-hydroxypropyl acrylate, 179.2 parts of butyl acrylate, and 67.2 parts of styrene. Of 600 parts of the two-part monomer component,
90 parts were added to the flask. Then, the mixture was stirred under a nitrogen gas flow, and when the temperature was raised to 80 ° C., the ABN-
2.16 parts of V was added to initiate polymerization. After a lapse of 10 minutes from the start of the polymerization, a mixture composed of 510 parts of the remaining monomer components, 41 parts of ethyl acetate and 12.24 parts of ABN-V was continuously dropped over 2 hours. After completion of the dropwise addition, 30 parts of ethyl acetate and 1.8 parts of ABN-V were added, and the mixture was further reacted under reflux for 3 hours to obtain a polymer solution (C) for a non-weatherproof film. The nonvolatile content of this solution was 69.5%, the viscosity was 5870 mPa · s, and the weight-average molecular weight (Mw) of this polymer was 1.2 × 10 ⁴ (GPC measurement: standard polystyrene conversion).

A polyfunctional isocyanate “Sumidur N-3200” was added to the polymer solution (C) as a crosslinking agent.
The polymer was added so that the equivalent ratio of isocyanate to hydroxyl group of the polymer was 1: 1 to prepare a polymer composition (C) for a non-weatherproof film. The pressure-sensitive adhesive composition No. 1 prepared in Example 1 was mixed with the polymer composition (C) for a non-weather resistant film. Using No. 1 in the same manner as in Example 1, a non-weatherproof film laminate was obtained.

Characteristic Evaluation Method The weather-resistant film laminate or the non-weather-resistant film laminate obtained in each of the examples and comparative examples was subjected to an ABS plate (thickness: 3).
mm) with a heating roll at 140 ° C. After cooling, the PET film was removed, and the following characteristics were evaluated.

[Film Adhesion] Only the weather-resistant film portion or the non-weather-resistant film portion of the above-mentioned laminated product was
By making cuts at 1mm intervals vertically and horizontally with a cutter,
I chopped 100 grids. Next, a cellophane tape was stuck on the grid, and the tape was vigorously peeled off. The number of grids where the weather-resistant (or non-weather-resistant) film portion was peeled off from the pressure-sensitive adhesive layer by the peeling operation was examined. Table 2 shows the results, that is, “the number of eyes not peeled / 100”.

[Weather Resistance] Using a sunshine weatherometer, a black panel temperature of 60 ° C., a cycle of 2 hours, a rainfall time of 18 minutes per cycle, and 2,000
After the time (1000 cycles), the surface state of the weather-resistant (or non-weather-resistant) film layer of the laminate was observed.
も の indicates that there was no change in the film surface, Δ indicates that some cracks occurred, and X indicates that cracks occurred on the entire surface. The results are shown in Table 2.

[Cooling and Heating Cycle] A thermo-hygrostat (PL-2)
F: manufactured by Tabaispec)
After leaving at -20 ° C for 4 hours, leaving at 80 ° C for 4 hours as one cycle, 10 cycles were repeated. The adhesion between the weather-resistant (or non-weather-resistant) film and the pressure-sensitive adhesive layer of the laminate was observed.異常 indicates that there was no abnormality such as film peeling, Δ indicates that partial peeling occurred, and x indicates that significant peeling occurred. The results are shown in Table 2.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

The weather-resistant film laminate of the present invention has a pressure-sensitive adhesive layer having good adhesion to the weather-resistant film on the surface of the weather-resistant film composed of a UV-stable monomer having a specific structure. It has features in the place where it is formed. In particular, the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer,
Since it has excellent adhesion to the weather-resistant film used in the present invention and exhibits good adhesion to various substrates (adherends), it is possible to impart weather resistance to these substrates over a long period of time. Can be granted.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 131/04 C09J 131/04 135/00 135/00 // (C08F 220/18 C08F 220: 34 220: 34 220: 28 220: 28) C08F 220: 58 (C08F 220/18 220: 58 220: 28) (72) Inventor Yoichi Inaba 992, Nishioki, Okihama, Aboshi-ku, Himeji-shi, Hyogo F-term (Nippon Shokubai Co., Ltd.) 4F100 AK24B AK25A AK25B BA02 BA07 CB05B GB90 JL09A 4J004 AA09 AA10 AB01 CA03 CC02 CC03 EA06 FA08 4J040 DF061 GA04 GA05 GA07 LA02 LA06 LA07 4J100 AL08P AL08Q AL08R AM23R BA02 BA03 BA12 BC02 BC04 BC04 BC04

Claims (4)

[Claims] 1. Essentially, at least one cycloalkyl (meth) acrylate, at least one ultraviolet-stable monomer represented by the following general formula (1) or (2), and at least one hydroxyl group-containing monomer: Monomer composition for pressure-sensitive adhesives, mainly composed of alkyl (meth) acrylate and essentially containing maleic anhydride And a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive polymer formed by polymerizing the pressure-sensitive adhesive. Embedded image (Wherein, R ¹ represents a hydrogen atom or a cyano group, R ^2, R
³ each independently represents a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or a hydrocarbon group, and X represents an oxygen atom or an imino group. ) (Wherein, R ¹ represents a hydrogen atom or a cyano group, R ^2, R
³ , R ^{2 ′} and R ^{3 ′} each independently represent a hydrogen atom or a methyl group, and X represents an oxygen atom or an imino group. ) 2. The weather-resistant film laminate according to claim 1, wherein the monomer component for a weather-resistant polymer further contains a UV-absorbing monomer. 3. The monomer component for the pressure-sensitive adhesive of 100% by mass.
Medium, alkyl (meth) acrylate is 40-9
6.9% by mass, 1 to 10% by mass of maleic anhydride, 2 to 35% by mass of vinyl acetate, and 0.1 to 15% by mass of a functional group-containing monomer other than maleic anhydride. 3. The weatherable film laminate according to 2. 4. The pressure-sensitive adhesive polymer is prepared by charging 70 to 100% by mass of vinyl acetate used as a pressure-sensitive adhesive monomer and a part of a monomer other than vinyl acetate into a reactor first. 4. The weather-resistant film laminate according to claim 3, which is obtained by charging the remaining monomer components into a reactor and polymerizing them after the start of the reaction.