JPH07278523A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition containing an adhesive polymer and a copolymer composed of specific monomer components, having an ultraviolet rays-absorbing function which is stable for a long period and good adhesiveness and useful for composite films. CONSTITUTION:This adhesive composition consists of (A) an adhesive polymer (preferably polyester) and (B) a copolymer composed of at least (i) a benzophenone-based monomer of the formula [X is O or ORO (R is a 1-10C alkylene or a 1-10C alkylene having one or more OH groups); Y is H or methyl] (e.g. 2-hydroxy-4-acryloxybenzophenone) and (ii) a compound having a hydroxyl group and/or carboxyl group [e.g. 2-hydroxyethyl-(meth)acrylate] as monomer components. Furthermore, the component B is preferably included in an amount of 1-50 pts.wt. component B based on 100 pts.wt.% component A. The component B contains preferably 5-90wt.% component (i) and 0.1-50wt.% component (ii).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition which absorbs ultraviolet rays, and also relates to a composite film obtained by applying an adhesive composition to a film.

[0002]

2. Description of the Related Art It is possible to prevent deterioration of the film itself by providing various films with an ultraviolet ray absorbing function, and to use a film having an ultraviolet ray absorbing function as a protective material to protect a film or printed matter which is a protected material. Deterioration and fading are prevented.

As a method of imparting an ultraviolet absorbing function to a film, a method of dispersing an ultraviolet absorbent in the film (for example, Japanese Patent Laid-Open No. 3-281685) is applied, and a layer containing various ultraviolet absorbents is applied on the surface of the film. (For example, JP-A-57-1777027 and JP-A-57-17)
However, the former method has a problem of clouding or bleeding out if the compatibility between the ultraviolet absorber and the resin to be the film is not compatible. In the latter method, various methods are used. There is a problem that the surface is soiled because the layer containing the ultraviolet absorber is on the surface.

Therefore, there is known a method of protecting a resin by giving an ultraviolet ray absorbing function to an adhesive composition to prevent the ultraviolet ray from transmitting or preventing the ultraviolet ray from being reflected. For that purpose, it has been attempted to add an ultraviolet absorber, but the molecular weight is 200 to 40.
Since it is about 0, there is a problem that it is transferred to the material to be protected or bleeds out on the film surface.

[0005]

An object of the present invention is to provide an adhesive composition having a stable UV absorbing function for a long period of time, and particularly to an adhesive composition and an adhesive which can be applied on a film. To provide a composite film coated with.

[0006]

The object of the present invention is as follows.
"Adhesive composition characterized by containing the following components A and B. A. Adhesive polymer B. Copolymer containing at least a benzophenone monomer and a compound having a hydroxyl group and / or a carboxyl group as monomer components It is solved by a polymer "or a composite film obtained by applying the adhesive composition to a film.

As the adhesive polymer which is the component A, all known adhesive polymers can be used, but polyester, polyurethane, epoxy, melamine, urea,
Examples thereof include thermosetting resins such as phenol, vinyl acetate, cellulose, polyamide, acrylic, polyvinyl acetate, chloroprene, nitrile, and silicone, thermoplastic resins, elastomers, and the like. It can also be used. Among these, polyester is preferable from the viewpoint of the adhesiveness between the adhesive composition and the film (polyethylene terephthalate etc.). Polyesters include saturated polyesters and unsaturated polyesters.

The saturated polyester is synthesized from saturated carboxylic acid and its derivative or aromatic carboxylic acid and its derivative and polyhydric alcohol, and is a hydrocarbon such as benzene, toluene, xylene, n-hexane, carbon tetrachloride and the like. Polyester resin which can be dissolved in one or more of ordinary organic solvents such as halogenated hydrocarbons, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, alcohols such as methyl ether. . Therefore, since polyethylene terephthalate used for synthetic fibers and films is insoluble in organic solvents, polyesters other than polyethylene terephthalate are preferable.

Unsaturated polyesters include maleic acid, maleic anhydride, fumaric acid, mesaconic acid, citraconic acid,
Synthesized from unsaturated carboxylic acids such as itaconic acid and chlorinated maleic acid and their derivatives, and polyhydric alcohols,
Hydrocarbons such as benzene, toluene, xylene and n-hexane, halogenated hydrocarbons such as carbon tetrachloride, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, alcohols such as methyl ether Is an unsaturated polyester resin which can be dissolved in one or more organic solvents alone or in a mixed system.

The component B is a copolymer containing at least a benzophenone monomer and a compound having a hydroxyl group and / or a carboxyl group as a monomer component. The benzophenone-based monomer exhibits an ultraviolet absorption function, and the compound having a hydroxyl group and / or a carboxyl group promotes compatibility with polyester and adhesion function, and becomes a copolymer, which is extracted by an organic solvent or water. Is considered to be prevented.

As the benzophenone type monomer, a compound represented by the general formula (1), that is, a 2-hydroxybenzophenone compound is preferably used.

[Chemical 2] (Here, X represents oxygen or -ORO-, Y represents hydrogen or a methyl group. R represents a linear or branched alkylene group having 1 to 10 carbon atoms, or 1 carbon atom having at least one hydroxyl group.
10 represents a linear or branched alkylene group. )

Specific examples of the 2-hydroxybenzophenone compound represented by the general formula (1) include 2-hydroxy-4-acryloxybenzophenone and 2-hydroxy-.
4-methacryloxybenzophenone, 2-hydroxy-
4- (2-acryloxyethoxy) benzophenone, 2
-Hydroxy-4- (2-methacryloxyethoxy) benzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone and the like can be mentioned, but not limited to them, and the general formula (1) It may have a substituent other than those represented by.
Of these, particularly preferred is 2-hydroxy-4.
-Acryloxybenzophenone, 2-hydroxy-4-
Methacryloxybenzophenone, 2-hydroxy-4-
(2-acryloxyethoxy) benzophenone and 2-hydroxy-4- (2-methacryloxyethoxy) benzophenone.

As the compound having a hydroxyl group and / or a carboxyl group, a known acrylic or methacrylic monomer having a hydroxyl group and / or a carboxyl group can be used. Specific examples include the following (however, acrylate and methacrylate are represented as (meth) acrylate). Monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate, acrylic acid, and methacrylic acid. And monomers having a carboxyl group such as 2- (meth) acryloyloxyethylsuccinic acid and 2- (meth) acryloyloxyethylphthalic acid.

Further, as a copolymerization component, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate. Ester monomers such as acrylate and butoxyethyl (meth) acrylate, acrylamide monomers such as diacetone acrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropyl acrylamide and N, N-dimethylaminoethyl acrylamide are used together. It can be polymerized.

The benzophenone type monomer and the compound having a hydroxyl group and / or a carboxyl group can be easily copolymerized by a general method such as a radical reaction to obtain a copolymer of the component B. For example, solution polymerization, suspension polymerization,
Emulsion polymerization and the like. Solution polymerization is particularly preferable, and toluene, an aromatic solvent such as xylene, ethyl acetate, etc.
Ester solvent such as butyl acetate, methyl ethyl ketone,
A ketone solvent such as methyl isobutyl ketone can be used. As the polymerization initiator, a peroxide such as benzoyl peroxide or an azo compound such as azobisisobutylnitrile can be used. If necessary, a chain transfer agent such as lauryl mercaptan or octyl thioglycolate can be added.

In the copolymer which is the component B, the structural unit composed of the benzophenone monomer is 5 to 9 in the copolymer component.
A content of 0% by weight, more preferably 10 to 80% by weight is preferable. If the amount is less than 5% by weight, a large amount must be added to the composition in order to exhibit the function as a light absorber, which may change the physical properties of the composition, which is not preferable. If it exceeds 90% by weight, the properties of the benzophenone skeleton become strong, and the compatibility with the composition decreases. Further, the structural unit composed of a compound having a hydroxyl group and / or a carboxyl group is 0.1 to 50% by weight in the copolymerization component, and 0.1 to 50% by weight.
A content of 10% by weight is preferred. If it is less than 0.1% by weight, the adhesive force is often lowered, which is not preferable. Fifty
If it is more than wt%, the stability of the composition is often impaired, which is not preferable.

The copolymer as the component B preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 10,000 to 100,000. Three
If it is less than 000, it often shifts to the protected layer.
When it is larger than 0,000, compatibility in the composition is often lowered.

The copolymer which is the component B is preferably added in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the component A. When the amount is less than 1 part by weight, the function as an ultraviolet absorber is not easily exhibited, which is not preferable. If the amount is more than 50 parts by weight, the physical properties often change such as a decrease in adhesive strength.

Two or more kinds of the component B copolymers can be mixed and used.

In order to impart water resistance and solvent resistance to the adhesive composition, it is preferable to add a polyvalent isocyanate having two or more isocyanate groups in the molecule.

As the polyvalent isocyanate compound, all compounds having two or more isocyanate groups in the molecule can be used. Specific examples include, but are not limited to, the following. 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Isophorone diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenyl isocyanate, and these polyisocyanates are synthesized by addition such as trimethylolpropane. It is an adduct body. It is also possible to use a so-called blocked polyvalent isocyanate in which an isocyanate group is blocked with phenols and these blocking agents are dissociated when heated.

The polyisocyanate is preferably added in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the adhesive polymer as the component A. Polyvalent isocyanate reacts with hydroxyl groups or carboxyl groups at the ends of the adhesive polymer (polyester, etc.) of component A, reacts with isocyanate groups, and reacts with hydroxyl or carboxyl groups of component B to form a crosslinked structure. The adhesive is then given water resistance and solvent resistance. Therefore, if the addition amount is less than 5 parts by weight, the crosslink density becomes insufficient, so that the water resistance or solvent resistance of the adhesive tends to be insufficient. Further, if it exceeds 200 parts by weight, the crosslink density becomes excessive, so that a problem occurs such that the gap between the adhesive and the material to be protected becomes brittle and cracks and dissociates. For this reason, the amount of the polyisocyanate added is preferably 5 to 200 parts by weight, more preferably 10 to 10 parts by weight, relative to 100 parts by weight of the component A.
0 parts by weight. It is also possible to use a mixture of two or more kinds of polyvalent isocyanates.

In order to improve the adhesiveness of the adhesive composition and the resistance to water and solvents, it is also preferable to add a compound having two or more epoxy groups in the molecule.

Examples of the compound having two or more epoxy groups in the molecule include bisphenol type epoxy such as bisphenol A and bisphenol F, hydroxyphenyl type epoxy such as tetrahydroxyphenyl, resorcin type epoxy, novolac type epoxy and polyglycol type. Epoxy, polyolefin type epoxy and glycidyl ether type epoxy compounds are all included. It is also possible to use two or more of these in combination. The amount of the compound having two or more epoxy groups is preferably 0.5 to 150 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the component A polyester. If it is less than 0.5 part by weight, the effect of addition will not be exhibited, and if it exceeds 150 parts by weight, the crosslinking density becomes excessive, which is not preferable.

For the same purpose, a compound having an ethylenically unsaturated bond in the molecule can be added. Examples of the compound having an ethylenically unsaturated bond in the molecule include, but are not limited to, the following compounds. Monofunctional vinyl monomers having a hydroxyl group such as hydroxymethyl (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate such as methoxyethylene glycol (meth) acrylate, polyalkylene glycol di (such as ethylene glycol di (meth) acrylate) (Meth) acrylate, butanediol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol diglycidyl ether and other polyvalent glycidyl ethers and (meth) acrylics Polyfunctional vinyl monomer obtained by addition reaction of acid, addition reaction product of glycidyl (meth) acrylate and acrylic acid, addition reaction product of xylylenediamine and glycidyl (meth) acrylate, addition reaction product of alcohols and glycidyl (meth) acrylate , (Meta)
(Meth) acrylamides such as acrylamide and methylenebisacrylamide, and monofunctional or polyfunctional vinyl monomers such as divinylbenzene. Further, an oligomer having an unsaturated group in the molecule and a resin having an unsaturated group such as unsaturated polyester or unsaturated polyurethane can also be used. It is also possible to use two or more of these in combination. The addition amount of the compound having an ethylenically unsaturated bond in the molecule is preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the component A polyester. If it is less than 0.1 part by weight, the effect of addition is not exhibited, and if it exceeds 50 parts by weight, the crosslinking density becomes excessive, which is not preferable. Therefore, the addition amount is preferably in the range of 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, relative to 100 parts by weight of the component A. A compound having an ethylenically unsaturated compound in the molecule causes a polymerization reaction to occur due to heat treatment when the composition of the adhesive layer of the present invention is used or when it is applied to a substrate as an adhesive layer. Sometimes it has been transformed into a coalesce.

Other minor components can be added to the adhesive composition. Such additives include plasticizers,
Examples include pigments, dyes, surfactants, and the like. Further, it is effective to add a thermal polymerization initiator to accelerate the thermal polymerization and a photopolymerization initiator to accelerate the photopolymerization. As such a thermal polymerization initiator and a photopolymerization initiator, all known ones can be used.

The adhesive composition of the present invention is applied to a film to form a composite film comprising the adhesive composition and the film.

The film to be applied is not particularly limited. For example, polyethylene, polypropylene, polyester, polyamide, polyesteramide,
Polyvinyl acetal, polyvinyl chloride, polyacrylic acid ester, polyimide, polyurethane, polycarbonate, polystyrene, polymethylpentene, polyolefin, halogenated polyolefin, polyamideimide,
Examples thereof include melamine resin, epoxy resin, PPS resin and the like. Among them, polyester, polyethylene, polypropylene, polyvinyl chloride, polyurethane,
Polyacrylic ester film is preferred.

The composite film of the present invention is further used as a coating material. Examples of the material to be coated include the following. Metal materials such as steel, aluminum, zinc, copper, plastic materials such as polyethylene terephthalate, polyamide, polypropylene, paper,
Woven cloth, glass, etc. In the case of metal materials, plating treatment such as chrome plating, chemical treatment such as phosphoric acid treatment,
Those that have been surface treated such as graining are also included. It is also possible to apply and cure an epoxy-based paint or the like on the surface of the metal substrate in advance for the purpose of preventing rust. In the case of a plastic material, those subjected to surface treatment such as sand blasting treatment, chemical etching treatment, discharge treatment such as corona discharge, and plasma treatment are also included. Further, from the viewpoint of the ultraviolet shielding ability and durability of the composite film of the present invention, a composite transparent material obtained by laminating the composite film with glass or another film can be used. It also includes a material having a printing pattern of oil-based ink or water-based ink on the surface of the material to be coated.

The simplest method for providing the adhesive on the film is to apply the adhesive composition to a predetermined thickness and then remove the solvent. As a coating method, a roll coater, a curtain flow coater, a slit die coater,
Known methods such as gravure coater, comma coater, spray, vinyl coating can be applied. For removing the solvent, a method of blowing hot air in a drying furnace is generally used. It is considered that during the drying, a part of the polyvalent isocyanate of the component C has reacted, and the hydroxyl group and / or the carboxyl group of the component B are also thermally polymerized with the isocyanate of the component C. Furthermore, in order to impart water resistance and solvent resistance to the adhesive, it is possible to add a compound having two or more epoxy groups in the molecule or a compound having an ethylenically unsaturated bond in the molecule as described above. It is valid.

The thickness of the adhesive layer is usually 0.5 to 100 μm.
m. When the thickness is less than 0.5 μm, the adhesive force between the material to be protected and the adhesive layer is often not expressed. 100 μm
If it exceeds, it becomes difficult to apply the coating with high thickness accuracy.

As the method for bringing the composite film provided with the adhesive layer into close contact with the object to be coated, all known methods can be used. It is common practice to heat laminate with what is coated using heated rolls.

[0033]

EXAMPLES The present invention will be described in more detail with reference to examples.

(Synthesis Example 1) A known formulation (for example, Japanese Patent Laid-Open No. Hei 3)
A copolymer composed of the following components was synthesized based on JP-A-281685 and JP-A-2-180909).

Copolymer of 2-hydroxy-4-methacryloxybenzophenone, methyl methacrylate and 2-hydroxyethyl methacrylate 2-in a separable flask equipped with a stirrer, Dimroth, nitrogen introducing tube, thermometer, dropping funnel. Hydroxy-4-
128 g methacryloxybenzophenone and 293 g methyl methacrylate, 4 g 2-hydroxyethyl methacrylate, 0.4 g lauryl mercaptan, 4 ethyl acetate
30 g was added, the temperature of this solution was raised to 70 ° C. under a nitrogen stream, 0.25 g of azobisisobutylnitrile was dissolved in a small amount of ethyl acetate, and the solution was added dropwise with a dropping funnel and reacted for 8 hours.

After the reaction was completed, the solution was returned to room temperature and used. The solution after the reaction had a residue (nonvolatile content) after volatilization of ethyl acetate of 47.9%, 372 cps by a B-type viscometer at 23 ° C., and a weight average molecular weight of 2.4 × 10 ⁴ by GPC analysis. Met. The weight percentage of the structure formed by 2-hydroxy-4-methacryloxybenzophenone is 31%.
Thus, the weight percentage of the 2-hydroxyethyl methacrylate structure was 0.9%. The weight% of the 2-hydroxybenzophenone-based monomer was calculated from the Lambert-Beer equation from the obtained value and the molar absorption coefficient of each 2-hydroxybenzophenone-based monomer after obtaining the absorbance at 290 nm of the copolymer. The weight% of the compound having a hydroxyl group and / or a carboxyl group is obtained from the integrated intensity value of NMR spectrum.

(Synthesis Example 2) A copolymer of 128 g of 2-hydroxy-4-methacryloxybenzophenone and 298 g of methyl methacrylate was obtained in the same manner as in Synthesis Example 2.

The solution after the reaction had a nonvolatile content of 47.0% and 2
It was 175 cps by a B-type viscometer at 3 ° C., and the weight average molecular weight was 2.3 × 10 ⁴ by GPC analysis. The weight% of the structure formed by 2-hydroxy-4-methacryloxybenzophenone was 31%.

(Synthesis Example 3) A homopolymer of 426 g of 2-hydroxy-4-methacryloxybenzophenone was obtained in the same manner as in Synthesis Example 2.

The solution after the reaction had a nonvolatile content of 46.5% and 2
It was 345 cps by B-type viscometer at 3 ° C., and the weight average molecular weight was 3.4 × 10 ⁴ from GPC analysis.

(Synthesis Example 4) 128 g of 2-hydroxy-4-methacryloxybenzophenone, 293 g of methyl methacrylate and 4 g of 2-hydroxyethyl methacrylate.
A copolymer of 1 g of methacrylic acid and 1 g of methacrylic acid was obtained in the same manner as in Synthesis Example 2.

The solution after the reaction had a nonvolatile content of 49.4% and 2
The viscosity was 560 cps by a B-type viscometer at 3 ° C., and the weight average molecular weight was 2.4 × 10 4 by GPC analysis. The weight% of the structure of 2-hydroxy-4-methacryloxybenzophenone was 30%, the weight% of the structure of 2-hydroxyethyl methacrylate was 0.9%, and the weight% of methacrylic acid was 0.2%.

(Synthesis Example 5) A copolymer of 340 g of 2-hydroxy-4-methacryloxybenzophenone and 85 g of 2-hydroxyethyl methacrylate was obtained in the same manner as in Synthesis Example 2.

The solution after the reaction had a nonvolatile content of 49.3% and 2
It was 363 cps by B-type viscometer at 3 ° C., and the weight average molecular weight was 2.6 × 10 ⁴ from GPC analysis. The weight% of the structure with 2-hydroxy-4-methacryloxybenzophenone was 81% and the weight% of the structure with 2-hydroxyethyl methacrylate was 19%.

Synthesis Example 6 Synthesis of Copolymer of 2-Hydroxy-4-methacryloxybenzophenone, Butyl Acrylate and 2-Hydroxyethyl Methacrylate Stirrer, Dim funnel, Nitrogen introduction tube, Thermometer, Drop funnel 2-hydroxy-4-in a separable flask
Methacryloxybenzophenone 292 g and butyl acrylate 180 g, 2-hydroxyethyl methacrylate 4 g, lauryl mercaptan 0.2 g, ethyl acetate 48
0 g was added, and this solution was heated to 70 ° C. under a nitrogen stream,
0.23 g of azobisisobutylnitrile was dissolved in a small amount of ethyl acetate and added dropwise with a dropping funnel, and the reaction was carried out for 8 hours.

After the reaction was completed, the solution was returned to room temperature and used. The solution after the reaction has a nonvolatile content of 49.1% and 23 ° C.
920 cps by B-type viscometer, and the weight average molecular weight was 6.2 × 10 ⁴ by GPC analysis. The weight% of the structure with 2-hydroxy-4-methacryloxybenzophenone was 61% and the weight% of the structure with 2-hydroxyethylmethacrylate was 0.8%.

Synthesis Example 7 Synthesis of Copolymer of 2-Hydroxy-4-acryloxybenzophenone, Butyl Acrylate and 2-Hydroxypropyl Acrylate A stirrer, Dimroth, nitrogen introduction tube, thermometer, dropping funnel are provided. 2-hydroxy-4-in a separable flask
121 g of acryloxybenzophenone, 180 g of butyl acrylate, 4-hydroxypropyl acrylate 4
g, 1020 g of ethyl acetate were added, the solution was heated to 70 ° C. under a nitrogen stream, 0.40 g of azobisisobutylnitrile was dissolved in a small amount of ethyl acetate and added dropwise with a dropping funnel, and reacted for 8 hours. .

After completion of the reaction, the solution was returned to room temperature and used. The solution after the reaction has a nonvolatile content of 29.8% and 23 ° C.
By a B-type viscometer at 350 cps, and the weight average molecular weight by GPC analysis was 3.0 × 10 ⁵ . The weight% of the structure with 2-hydroxy-4-acryloxybenzophenone was 40% and the weight% of the structure with 2-hydroxypropyl acrylate was 1.2%.

(Synthesis Example 8) Synthesis of copolymer of 2-hydroxy-4- (2-acryloxy) ethoxybenzophenone, methyl methacrylate, 2-hydroxypropyl acrylate and 2-acryloyloxyethyl succinic acid Stirrer, Dimroth, In a separable flask equipped with a nitrogen introduction tube, a thermometer, and a dropping funnel, 2-hydroxy-4-
135 g of (2-acryloxy) ethoxybenzophenone
And 210 g of methyl methacrylate, 8 g of 2-hydroxypropyl acrylate, 17 g of 2-acryloyloxyethyl succinic acid, 0.4 g of lauryl mercaptan, and 374 g of ethyl acetate were added, and the solution was heated to 70 ° C. under a nitrogen stream to give a solution of 0. 40 g of azobisisobutylnitrile was dissolved in a small amount of ethyl acetate and added dropwise with a dropping funnel, and the reaction was carried out for 8 hours.

After completion of the reaction, the solution was returned to room temperature and used. The solution after the reaction has a nonvolatile content of 49.2% and 23 ° C.
520 cps by B-type viscometer, and the weight average molecular weight was 4.5 × 10 ⁴ by GPC analysis. The weight% of the structure with 2-hydroxy-4- (2-acryloxy) ethoxybenzophenone is 37%, the weight% of the structure with 2-hydroxypropyl acrylate is 2.1%, the weight of the structure with 2-acryloyloxyethyl succinic acid. % Was 4.6%.

Example 1 An adhesive composition solution was prepared as follows. As a saturated polyester resin, "Byron" 300 (product of Toyobo Co., Ltd., molecular weight 20000)
25,000) 100 parts by weight to 8 parts by weight of toluene / methyl ethyl ketone = 80/20 (weight ratio) mixed solvent 200 parts by weight
It was heated to 0 ° C. and dissolved. After cooling, 15 parts by weight of "Coronate" 3015 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyvalent isocyanate, 9 parts by weight of 2-ethylene glycol methacrylate and the copolymer 30 obtained in Synthesis Example 1 were used.
Parts by weight were added and thoroughly mixed with stirring.

The adhesive composition solution thus obtained was coated on a polyethylene terephthalate film having a thickness of 100 μm by a comma coater so that the dry film thickness was 15 μm, and passed through an oven at 150 ° C. for 5 minutes to remove the solvent. 250μm with a pattern printed with alcohol ink on the surface by a laminator heated to 110 ℃ after removing
The polyethylene terephthalate film of was adhered.

The resulting film was transparent. The ultraviolet transmittance of the non-patterned portion of this film was 18%. The ultraviolet transmittance is a value calculated from the ultraviolet transmittance (using a Macbeth densitometer TR-927, manufactured by Sakata Inx Co., Ltd., for filter ultraviolet rays).

The film obtained was made 1 cm wide and
"Tensilon" RTM-100 (ORIENTEC CORPRATION
18) at a peeling speed of 100 cm / min.
When the peeling adhesive strength in the 0 ° direction was measured, it was 0.8 kg / c.
It was m.

The obtained film was left outdoors for 183 days. The pattern of the film was good without fading.

Comparative Example 1 An adhesive composition solution was obtained without adding the copolymer obtained in Synthesis Example 1 of Example 1. The adhesive composition solution thus obtained was applied in the same manner as in Example 1 to obtain a film having a dry film thickness of 15 μm, and in the same manner as in Example 1, a polyethylene terephthalate film having a printed pattern was formed. Laminated.

The resulting film was transparent. The ultraviolet transmittance of the non-patterned portion of this film was 76%.

The film thus obtained was left outdoors under the same conditions as in Example 1. After the lapse of time, the fading of the film design was observed.

It is considered that the ink was discolored by passing ultraviolet rays through the film because it did not contain an ultraviolet absorber.

(Comparative Example 2) Instead of 30 parts by weight of the copolymer obtained in Synthesis Example 1 of Example 1, a benzotriazole type ultraviolet absorber "Tinuvin" 327 having a molecular weight of 357.9 was used.
30 parts by weight (manufactured by CIBA-GEIGY) was used to obtain an adhesive composition solution. The adhesive composition solution thus obtained was applied to a film having a dry film thickness of 15 μm in the same manner as in Example 1 and laminated on a polyethylene terephthalate film having a printed pattern in the same manner as in Example 1.

The resulting film was transparent. The ultraviolet transmittance of the non-patterned portion of this film was 5%.

When the film thus obtained was left outdoors under the same conditions as in Example 1, discoloration of the printed pattern was observed. It is considered that the ultraviolet absorber migrated to the printed pattern and the ultraviolet absorbing function was lowered, and the ultraviolet rays penetrated the film to discolor the ink.

(Comparative Example 3) Instead of 30 parts by weight of the copolymer obtained in Synthesis Example 1 of Example 1, a benzotriazole type ultraviolet absorber "Adeka Stab" LA- having a molecular weight of 659 was used.
31 (manufactured by Asahi Denka Co., Ltd.) to 30 parts by weight to obtain an adhesive composition solution. The adhesive composition solution thus obtained was applied to a film having a dry film thickness of 15 μm in the same manner as in Example 1 and laminated on a polyethylene terephthalate film having a printed pattern in the same manner as in Example 1.

The resulting film was transparent. The ultraviolet transmittance of the non-patterned portion of this film was 6%.

When the film thus obtained was left outdoors as in Example 1, discoloration of the printed pattern was observed. It is considered that the ultraviolet absorber migrated to the printed pattern and the ultraviolet absorbing function was lowered, and the ultraviolet rays penetrated the film to discolor the ink.

Comparative Example 4 An adhesive composition solution was obtained by using 30 parts by weight of the copolymer obtained in Synthesis Example 2 instead of 30 parts by weight of the copolymer obtained in Synthesis Example 1 of Example 1. . The adhesive composition solution thus obtained was dried on a polyethylene terephthalate film having a thickness of 100 μm to give a dry film thickness of 15
After coating with a comma coater so as to have a thickness of 5 μm, the solution was passed through an oven at 150 ° C. for 5 minutes to remove the solvent, and then a polyethylene terephthalate film having a pattern printed with an alcohol ink on the surface was adhered by a laminator heated at 110 ° C.

The film obtained was treated with "Tensilon" RTM.
The peel adhesive strength in the 180 ° direction was measured with a -100 (manufactured by ORIENTEC CORPORATION) under a peel speed of 100 cm / min to find that it was 0.1 kg / cm. Synthesis example 2
It is considered that since the copolymer obtained in (1) had neither a hydroxyl group nor a carboxyl group, the adhesive strength of the saturated polyester resin was lowered.

Comparative Example 5 An adhesive composition solution was obtained by using 30 parts by weight of the copolymer obtained in Synthesis Example 3 instead of 30 parts by weight of the copolymer obtained in Synthesis Example 1 of Example 1. . This adhesive composition solution became cloudy. The adhesive composition solution thus obtained was applied in the same manner as in Example 1 so that the dry film thickness was 15 μm, the solvent was removed, and then 250 μm of polyethylene terephthalate having a printed pattern as in Example 1 was applied. The film was stuck.

The resulting film was slightly opaque.
For this reason, the printed pattern was fluttered and was not at a practical level.

It is considered that this is because the copolymer of Synthesis Example 3 had poor compatibility with the saturated polyester resin and the adhesive composition solution became cloudy.

Example 2 An adhesive composition solution was prepared as follows. "Byron" as polyester resin 20
0 (Toyobo Co., Ltd. product, molecular weight 15,000-2000
0) 100 parts by weight of toluene / methyl ethyl ketone = 8
It was dissolved in 200 parts by weight of a 0/20 (weight ratio) mixed solvent by heating at 80 ° C. After cooling, as a polyisocyanate, "Coronate" L (product of Nippon Polyurethane Industry Co., Ltd.)
10 parts by weight, 2-ethylene glycol methacrylate 5
By weight, 30 parts by weight of the copolymer obtained in Synthesis Example 4 was added and thoroughly mixed with stirring.

The adhesive composition solution thus obtained was coated on a polyethylene terephthalate film having a thickness of 100 μm by a slit die coater so that the dry film thickness would be 15 μm, and passed through an oven at 150 ° C. for 5 minutes. The solvent was removed and the adhesive layer was heat-cured. In this way, a film coated with the adhesive layer was obtained. The adhesive surface had no tackiness and was transparent and easy to handle.

A 250 μm polyethylene terephthalate film having a pattern printed with alcohol ink was adhered to the surface of this film by a laminator heated to 110 ° C.

The obtained film was transparent. The ultraviolet transmittance of the non-patterned portion of this film was 12%.

The film obtained was made 1 cm wide and
"Tensilon" RTM-100 (ORIENTEC CORPRATION
18) at a peeling speed of 100 cm / min.
When the peeling adhesive strength in the 0 ° direction was measured, it was 0.7 kg / c.
It was m.

When the obtained film was left under the same conditions as in Example 1, the pattern of the film was good without fading.

Example 3 An adhesive composition solution was prepared as follows. As a saturated polyester resin, 100 parts by weight of "Nichigo Polyester" LP-035 (product of Nippon Synthetic Chemical Industry Co., Ltd., number average molecular weight: 16000) was added to 200 parts by weight of toluene / methyl ethyl ketone = 80/20 (weight ratio) mixed solvent at 80 ° C. It was warmed and dissolved. After cooling, 20 parts by weight of the copolymer obtained in Synthesis Example 5 was added and thoroughly mixed with stirring.

The adhesive composition solution was coated on a 70 μm thick polypropylene film by a vinyl coater so that the dry film thickness was 6 μm, and passed through an oven at 150 ° C. for 5 minutes to remove the solvent. The transparency of this film was good. The ultraviolet transmittance of this film was 8%.

This film and a coated paper having a pattern printed with an oil-based ink were adhered to each other with a heating roller at 110 ° C.

The coated paper laminated with the film could not be peeled off between the film and the coated paper.

When the coated paper was left under the same conditions as in Example 1, the printed pattern was good without fading.

Example 4 An adhesive composition solution was prepared as follows. As a saturated polyester resin, 100 parts by weight of "Nichigo Polyester" LP-035 (product of Nippon Synthetic Chemical Industry Co., Ltd., number average molecular weight: 16000) was added to 200 parts by weight of toluene / methyl ethyl ketone = 80/20 (weight ratio) mixed solvent at 80 ° C. It was warmed and dissolved. After cooling, 20 parts by weight of the copolymer obtained in Synthesis Example 6 was added and sufficiently stirred and mixed.

The adhesive composition solution was coated on a polypropylene film having a thickness of 70 μm by a vinyl coater so that the dry film thickness would be 6 μm, and passed through an oven at 150 ° C. for 5 minutes to remove the solvent. The transparency of this film was good. The ultraviolet transmittance of this film was 10%.

This film and a coated paper having a pattern printed with an oil-based ink were brought into close contact with each other with a heating roller at 110 ° C.

The coated paper laminated with the film could not be peeled off between the film and the coated paper.

When the coated paper laminated with the film was allowed to stand under the same conditions as in Example 1, the printed pattern was good without fading.

Example 5 An adhesive composition solution was prepared as follows. As a saturated polyester resin, 100 parts by weight of "Nichigo Polyester" LP-033 (product of Nippon Synthetic Chemical Industry Co., Ltd., number average molecular weight: 16000) is added to 200 parts by weight of toluene / methyl ethyl ketone = 80/20 (weight ratio) mixed solvent at 80 ° C. It was warmed and dissolved. After cooling, 30 parts by weight of the copolymer obtained in Synthesis Example 7 was added, and the mixture was sufficiently stirred and mixed.

The adhesive composition solution was applied on a polypropylene film having a thickness of 70 μm by a vinyl coater so that the dry film thickness would be 6 μm, and passed through an oven at 150 ° C. for 5 minutes to remove the solvent. Many particles were found on the surface of this film. It is considered that Synthetic Example 7 had a large molecular weight and therefore did not exist stably in the adhesive composition. . The ultraviolet transmittance of this film was 19%.

This film and a coated paper having a pattern printed with an oil-based ink were adhered to each other with a heating roller at 110 ° C.

The coated paper laminated with the film could not be peeled off between the film and the coated paper.

When the coated paper laminated with the film was allowed to stand under the same conditions as in Example 1, the printed pattern was good without fading.

Example 6 An adhesive composition solution was prepared as follows. As a saturated polyester resin, 100 parts by weight of "Nichigo Polyester" LP-033 (product of Nippon Synthetic Chemical Industry Co., Ltd., number average molecular weight: 16000) is added to 200 parts by weight of toluene / methyl ethyl ketone = 80/20 (weight ratio) mixed solvent at 80 ° C. It was warmed and dissolved. After cooling, 30 parts by weight of the copolymer obtained in Synthesis Example 8 was added, and the mixture was sufficiently stirred and mixed.

The adhesive composition solution was coated on a 70 μm-thick polypropylene film by a vinyl coater so that the dry film thickness was 6 μm, and passed through an oven at 150 ° C. for 5 minutes to remove the solvent. The transparency of this film was good. The ultraviolet transmittance of this film was 19%.

This film and a coated paper having a pattern printed with an oil-based ink were brought into close contact with each other with a heating roller at 110 ° C.

The coated paper laminated with the film could not be peeled off between the film and the coated paper.

When the coated paper laminated with the film was allowed to stand under the same conditions as in Example 1, the printed pattern was good without fading.

[0097]

EFFECTS OF THE INVENTION The present invention is an adhesive composition having an ultraviolet absorbing function, capable of sustaining the function for a long period of time, and having a good adhesive force, since the adhesive composition is constituted as described above. In particular, it is applied on a film and used, and is suitably used as a composite film having a long-term stable ultraviolet absorbing function.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C09J 175/04 JFC

Claims (7)

[Claims] 1. An adhesive composition containing the following components A and B: A. Adhesive polymer B. Copolymer containing at least a benzophenone-based monomer and a compound having a hydroxyl group and / or a carboxyl group as monomer components 2. The adhesive composition according to claim 1, wherein the component A is polyester. 3. One part of B component is added to 100 parts by weight of A component.
The adhesive composition according to claim 1, wherein the adhesive composition is contained in an amount of -50 parts by weight. 4. The adhesive composition according to claim 1, wherein the component B contains a structure containing a benzophenone-based monomer in an amount of 5 to 90% by weight. 5. The adhesive composition according to claim 1, wherein the component B contains 0.1 to 50% by weight of a structure composed of a compound having a hydroxyl group and / or a carboxyl group. 6. The adhesive composition according to claim 1, wherein the benzophenone-based monomer is a compound represented by the general formula (1). [Chemical 1] (Here, X represents oxygen or -ORO-, Y represents hydrogen or a methyl group. R represents a linear or branched alkylene group having 1 to 10 carbon atoms, or 1 carbon atom having at least one hydroxyl group.
10 represents a linear or branched alkylene group. ) 7. The weight average molecular weight of component B is 3,000 to 2.
The adhesive composition according to claim 1, wherein the adhesive composition is 0,000.