TW201343833A - Adhesive composition and surface-protective adhesive film - Google Patents

Abstract

The invention provides an adhesive composition and a surface-protective adhesive film, which is excellent in the balance of adhesive force when being stripped at low and high speeds, and is thus also excellent in durability and reworking performance. The invention is characterized by being composed of an acrylic acid polymer comprising a copolymer of: (A) a (meth)acrylate monomer having a C4-C10 alkyl group, (B) a copolymeriable monomer having a hydroxyl group, (C) a copolymeriable monomer having a carboxyl group, (D) a polyalkylene glycol mono(meth)acrylate monomer, and (E) a nitrogen-containing vinyl monomer having no hydroxyl group or an alkoxy group-containing (meth)acrylate monomer, and further comprising (F) an isocyanate compound having 3 or more functional groups, (G) a cross-linking retardant agent, (H) a cross-linking catalyst, and (I) a polyether-modified siloxane compound, wherein the acrylic acid polymer has an acid value of 0.01-8.0.

Description

Adhesive composition and surface protective film

The present invention relates to a surface protective film used in a manufacturing step of a liquid crystal display. More specifically, it is composed of an adhesive for a surface protective film which is bonded to the surface of an optical member such as a polarizing plate or a retardation film which constitutes a liquid crystal display, and which protects the surface of an optical member such as a polarizing plate or a phase difference plate. And the surface protective film using it.

In the manufacturing process of an optical member such as a polarizing plate or a retardation film which is a member constituting a liquid crystal display, the surface protective film is temporarily bonded to the surface of the optical member. When the optical member is assembled into the liquid crystal display, the surface protective film is peeled off from the optical member and removed. The surface protective film for protecting the surface of the optical member is used only in the manufacturing step, and is therefore also referred to as a step film.

The surface protective film used in the step of producing the optical member forms an adhesive layer on one surface of a polyethylene terephthalate (PET) resin film having optical transparency. Further, the release film for protecting the adhesive layer from being peeled off is bonded to the upper side of the adhesive layer until it is bonded to the optical member.

Further, in the optical member such as a polarizing plate or a retardation film, the product inspection of the optical evaluation such as the display capability, chromaticity, contrast, and impurity incorporation of the liquid crystal display panel is performed in a state in which the surface protective film is bonded. Therefore, the necessary performance for the surface protective film is to adhere No bubbles or impurities are attached to the agent layer.

In addition, when the surface protective film is bonded to an optical member such as a polarizing plate or a retardation plate, the surface protective film may be temporarily peeled off and the surface protective film may be reattached for various reasons. At this time, a surface protective film which is easily peeled off from the optical member (having reworkability) is sought.

Further, when the surface protective film is peeled off from an optical member such as a polarizing plate or a phase difference plate, it is sought to be peeled off quickly. In other words, in order to remove the peeling at a high speed, it is necessary to quickly peel off, and it is necessary to have a small peeling speed of the adhesive force.

As described above, in recent years, as a required performance for the adhesive layer constituting the surface protective film, (1) balance between adhesion at low-speed peeling and high-speed peeling, (2) prevention of occurrence of adhesive residue, and (3) It is necessary to have rework performance and the like.

However, although these (1) to (3) can satisfy the respective required properties, it is very difficult to simultaneously provide all of the required properties (1) to (3) required in the adhesive layer of the surface protective film.

For example, (1) the balance of the adhesive force obtained in the low-speed peeling and the high-speed peeling; and (2) the prevention of the occurrence of the adhesive residue, and the following proposals are known.

An acrylic acid obtained by crosslinking a copolymer of a (meth)acrylic acid alkyl ester having an alkyl group having 7 or less carbon atoms and a carboxyl group-containing copolymerizable compound as a main component and crosslinking the mixture with a crosslinking agent When the adhesive is applied for a long period of time after the bonding, there is a problem that the adhesive moves toward the adhesive side and the adhesive force to the adhesive increases with time. In order to prevent this problem, a copolymer of a (meth)acrylic acid alkyl ester having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group is known, and such a crosslinking agent is known. A cross-linking adhesive (pressure-sensitive adhesive) (Patent Document 1).

Further, it is proposed to mix a small amount of a copolymer of an alkyl (meth) acrylate and a carboxyl group-containing copolymerizable compound in the same copolymer as described above, and crosslink it as a crosslinking agent. Adhesives, etc. However, these surface tensions are low, and if they are used for surface protection such as a smooth plastic plate, there is a problem that peeling occurs due to heating during processing or storage, or high-speed peeling by manual peeling. There is a problem of poor removability.

In order to solve such problems, an adhesive composition is proposed which comprises (a) 100 parts by weight of an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms as a main component. (b) 1 to 15 parts by weight of a carboxyl group-containing copolymerizable compound, and (c) 3 to 100 parts by weight of an aliphatic carboxylic acid having 1 to 5 carbon atoms in the (meth)acrylic acid alkyl ester A copolymer of a monomer mixture of a vinyl ester is obtained by mixing a crosslinking agent having an equivalent weight or more with respect to the carboxyl group of the component (b) in the copolymer (Patent Document 2).

The adhesive composition described in Patent Document 2 does not cause peeling such as floating during processing or storage, and further has a small increase in adhesion over time and excellent removability, even in long-term storage, especially in Long-term storage under high temperature environment can also be peeled off with a small force. At this time, no adhesive residue remains on the adhesive, and it can be peeled off with a small force even at high speed peeling.

Further, (3) an adhesive composition having reworkability, for example, a curable agent of an isocyanate compound in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the acrylic resin in the acrylic resin, and specific The phthalate oligomer is mixed (Patent Document 3).

In Patent Document 3, an alkyl acrylate having an alkyl group having a carbon number of from 2 to 12 or an alkyl methacrylate having an alkyl group having a carbon number of from 4 to 12 is used as a main monomer component, for example, A monomer component containing a carboxyl group-containing monomer or the like and containing other functional groups may be contained. In general, it is preferable to contain 50% by weight or more of the above-mentioned main monomer, and it is more preferable that the content of the monomer component containing a functional group is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, and further preferably It is 0.01 to 25% by weight. The adhesive composition described in Patent Document 3 is even high Under the temperature or high temperature and high humidity, the cohesive force and the adhesive force change little with time, and the adhesion to the curved surface also shows excellent effects, and thus has reworkability.

In general, when the adhesive layer is made into a soft property, adhesive residue is likely to occur, and reworkability is liable to lower. In other words, when the bonding is wrong, it is easy to cause peeling and it is difficult to reattach. Therefore, it is necessary to crosslink a monomer having a functional group such as a carboxyl group to a host agent, and to form a certain hardness to the adhesive layer to have reworkability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 63-225677

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-256111

[Patent Document 3] Japanese Patent Laid-Open No. Hei 8-199130

In the prior art, as a required performance for an adhesive layer constituting a surface protective film, it has been sought to obtain a balance of adhesion between low-speed peeling and high-speed peeling, and reworkability. Although each of the required properties can be individually satisfied, it is not possible to satisfy all of the required properties required in the adhesive layer of the surface protective film.

The present invention has been made in view of the above circumstances. An object of the present invention is to provide an adhesive composition and a surface protective film which are excellent in balance of adhesion at low-speed peeling and high-speed peeling, and further excellent in durability and reworkability.

In order to solve the above problems, the present invention provides an adhesive composition comprising: (A) a (C) alkyl group having a C4 to C10 (meth) acrylate monomer, (B) a hydroxyl group Copolymerizable monomer, (C) carboxyl group-containing copolymerizable monomer, (D) polyalkylene glycol mono(meth)acrylate monomer, and (E) hydroxyl-free nitrogen-containing vinyl group An acrylic polymer comprising at least one of a monomer or an alkoxy-containing (meth) acrylate monomer, further comprising (F) a trifunctional or higher isocyanate compound, (G) a cross-linking resistance a retarder, (H) a crosslinking catalyst, and (I) a polyether modified siloxane compound, and the acrylic polymer has an acid value of 0.01 to 8.0.

The above (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxy(meth)acrylic acid octyl ester, 6-hydroxy(meth)acrylic acid hexyl ester, 4-hydroxy(meth)acrylic acid butyl ester, and 2- a compound consisting of ethyl hydroxy (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide At least one or more of the above (B) hydroxyl group-containing (C)-containing (meth) acrylate monomer having a C4 to C10 carbon number is preferably contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the (A) alkyl group. Copolymerizable monomer, and among the above (B) hydroxyl group-containing copolymerizable monomers, 8-hydroxy(meth)acrylic acid octyl ester, 6-hydroxy(meth)acrylic acid hexyl ester, and 4-hydroxy group (A) The total amount of butyl acrylate is 0 to 0.9 parts by weight.

The above (C) carboxyl group-containing copolymerizable monomer is selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2-(methyl) propylene oxime Ethyl hexahydrofurfuric acid, 2-(methyl) propylene methoxy propyl hexahydro decanoic acid, 2-(methyl) propylene methoxy methoxy citric acid, 2-(methyl) propylene decyloxy Ethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2-(methyl) propylene methoxyethyl tetrahydro phthalic acid At least one or more of the compound groups of the composition; preferably, the C4 to C10 (meth) acrylate monomer having a carbon number of the (A) alkyl group is 0.35 to 1.0 part by weight based on 100 parts by weight of the above (C) a carboxyl group-containing copolymerizable monomer.

The above (D) polyalkylene glycol mono(meth)acrylate monomer is selected from the group consisting of polyalkylene glycol mono(meth)acrylate, methoxypolyalkylene glycol (meth)acrylate Ester, ethoxy extension At least one or more of alkyl diol (meth) acrylates; preferably a C4 to C10 (meth) acrylate monomer having 100 parts by weight of the (A) alkyl group; ~20 parts by weight of the above (D) polyalkylene glycol mono(meth)acrylate monomer.

The (E) hydroxyl group-containing nitrogen-containing ethylene is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the (A) alkyl group having a carbon number of C4 to C10 (meth) acrylate monomer. A monomer or an alkoxy-containing alkyl (meth)acrylate monomer.

The above (F) trifunctional or higher isocyanate compound is an isocyanurate body selected from the group consisting of a hexamethylene diisocyanate compound, an isocyanurate body of an isophorone diisocyanate compound, and a hexamethylene diisocyanate compound. At least one of an adduct body, an adduct of an isophorone diisocyanate compound, a biuret body of a hexamethylene diisocyanate compound, and a biuret compound of an isophorone diisocyanate compound The above (F) trifunctional or higher isocyanate compound is preferably contained in an amount of 0.4 to 5.0 parts by weight based on 100 parts by weight of the above copolymer.

The polyether modified siloxane compound of the above (I) is a polyether modified siloxane compound having an HLB value of 7 to 12, preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the above copolymer. The above (I) polyether modified oxoxane compound.

The (G) crosslinking retarder is a keto-enol tautomer compound, and preferably contains 1.0 to 5.0 parts by weight of the above (G) crosslinking retarder per 100 parts by weight of the above copolymer.

The (H) crosslinking catalyst is an organotin compound, and preferably contains 0.01 to 0.5 part by weight of the above (H) crosslinking catalyst based on 100 parts by weight of the above copolymer.

Preferably, the adhesive layer obtained by crosslinking the above-mentioned adhesive composition has an adhesive force of 0.05 to 0.1 N/25 mm at a low-speed peeling speed of 0.3 m/min, and an adhesive force of 1.0 at a high-speed peeling speed of 30 m/min. N/25mm or less.

Moreover, the present invention provides an adhesive film which is formed on one or both sides of a resin film. An adhesive film of an adhesive layer obtained by crosslinking the above adhesive composition.

Moreover, the present invention provides a surface protective film which is formed on a surface of a resin film to form a surface protective film of an adhesive layer obtained by crosslinking the above-mentioned adhesive composition, and is coated on the surface by a ballpoint pen through the above adhesive layer. After the film is painted on the protective film, there is no pollution transfer to the adhesive.

The surface protective film can be used as a surface protective film for a polarizing plate.

Preferably, antistatic and antifouling treatment is performed on the opposite surface of the resin film from the side on which the adhesive layer is formed.

According to the present invention, all of the properties required in the adhesive layer of the surface protective film which cannot be solved by the prior art can be satisfied. Further, excellent performance for preventing the occurrence of adhesive residue can be obtained. Specifically, the performance of preventing the occurrence of adhesive residue can be further improved.

Hereinafter, the present invention will be described based on preferred embodiments.

The adhesive composition of the present invention is characterized in that the main component is a (meth) acrylate monomer having a CA-C10 carbon number of (A) alkyl group, (B) a hydroxyl group-containing copolymerizable monomer, (C) a carboxyl group-containing copolymerizable monomer, (D) a polyalkylene glycol mono(meth)acrylate monomer, and (E) a hydroxyl group-free nitrogen-containing vinyl monomer or an alkoxy group ( The acrylic polymer of a copolymer of a methyl acrylate monomer, further comprising (F) a trifunctional or higher isocyanate compound, (G) a crosslinking retarder, (H) a crosslinking catalyst, and I) A polyether modified oxoxane compound, and the acid value of the above acrylic polymer is from 0.01 to 8.0.

Examples of the (meth) acrylate monomer having a carbon number of (A) alkyl group of C4 to C10 include butyl (meth)acrylate, isobutyl (meth)acrylate, and amyl (meth)acrylate. , (hexyl) (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, hexyl 2-ethyl(meth)acrylate, (methyl) Ethyl acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, and the like.

Examples of the (B) hydroxyl group-containing copolymerizable monomer include 8-hydroxy(meth)acrylic acid octyl ester, 6-hydroxy(meth)acrylic acid hexyl ester, 4-hydroxy(meth)acrylic acid butyl ester, and 2 - hydroxyalkyl (meth) acrylates such as ethyl hydroxy (meth) acrylate, N-hydroxy (meth) acrylamide, N- hydroxymethyl (meth) acrylamide, N- hydroxyethyl A hydroxyl group-containing (meth) acrylamide such as (meth)acrylamide or the like.

It is preferably selected from octyl 8-hydroxy(meth)acrylate, hexyl-hydroxy(meth)acrylate, butyl 4-hydroxy(meth)acrylate, ethyl 2-hydroxy(meth)acrylate, N At least one of a compound group consisting of hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.

The (B) hydroxyl group-containing copolymerizable monomer is preferably contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the (A) alkyl group having a carbon number of C4 to C10 (meth) acrylate monomer. body.

Further, among the (B) hydroxyl group-containing copolymerizable monomers, 8-hydroxy(meth)acrylic acid octyl ester, 6-hydroxy(meth)acrylic acid hexyl ester, and 4-hydroxybutyl (meth)acrylate The total amount is preferably less than 1 part by weight (may not be contained), and is preferably 0 to 0.9 parts by weight.

(C) The carboxyl group-containing copolymerizable monomer is selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2-(methyl) propylene decyloxy group Ethyl hexahydrophthalic acid, 2-(methyl)propenyloxypropyl hexahydrophthalic acid, 2-(meth) propylene methoxyethyl decanoic acid, 2-(methyl) propylene methoxy ethoxylate Succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2-(methyl) propylene oxiranyl ethyl tetrahydro hydrazine At least one or more of the acid compound compounds.

The (meth) acrylate monomer having a C4 to C10 carbon number per 100 parts by weight of the (A) alkyl group is preferably contained in an amount of 0.35 to 1.0 part by weight, more preferably 0.35 to 0.6 part by weight (C). a carboxyl group-containing copolymerizable monomer.

As the (D) polyalkylene glycol mono(meth)acrylate monomer, in the polyalkylene glycol having a plurality of hydroxyl groups, it may be a hydroxyl group as a (meth) acrylate esterified compound. . Since the (meth) acrylate group becomes a polymerizable group, it can be copolymerized to the main agent polymer. The other hydroxyl group can maintain OH, and can also be an alkyl ether such as methyl ether or diethyl ether or a saturated carboxylic acid ester such as acetate.

Examples of the alkylene group which the polyalkylene glycol has are an exoethyl group, a propyl group, a butyl group, and the like, but are not limited thereto. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the copolymer of the polyalkylene glycol include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polymer. The butylene glycol and the like may also be a block copolymer or a random copolymer.

As the (D) polyalkylene glycol mono(meth) acrylate monomer, preferably selected from polyalkylene glycol mono(meth) acrylate, methoxy polyalkylene glycol (A) At least one of acrylate and ethoxylated polyalkylene glycol (meth) acrylate.

More specifically, polyethylene glycol mono- (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol - mono (meth) acrylate, polyethylene glycol - Polypropylene glycol-mono(meth)acrylate, polyethylene glycol-polybutylene glycol-mono(meth)acrylate, polypropylene glycol-polybutylene glycol-mono(meth)acrylate, polyethylene glycol- Polypropylene glycol-polybutylene glycol-mono(meth)acrylate; methoxypolyethylene glycol-(meth)acrylate, methoxypolypropylene glycol-(meth)acrylate, methoxy polybutylene Alcohol-(meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-(A Acrylate, methoxy-polyethylene glycol-polybutylene glycol-(meth) acrylate, methoxy-polypropylene glycol-polybutylene glycol-(meth) acrylate, methoxy-poly Ethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate; ethoxypolyethylene glycol-(meth)acrylate, ethoxypolypropylene glycol-(meth)acrylate, ethoxylate Polybutylene glycol-(meth)acrylate, ethoxy-polyethylene glycol-polypropylene glycol-(meth)acrylate, ethoxy-polyethylene glycol-polybutylene glycol-(meth)acrylic acid Ester, ethoxy-polypropylene glycol-polybutylene glycol-(meth)acrylate, ethoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate, and the like.

The (D) polyalkylene glycol monomer is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having a carbon number of the above (A) alkyl group of C4 to C10. (Meth) acrylate monomer.

In (E), examples of the (E-1) nitrogen-containing vinyl monomer include a mercapto bond-containing vinyl monomer, an amine group-containing vinyl monomer, and an ethylene having a nitrogen-containing heterocyclic structure. Base monomer and the like. More specifically, N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N -vinylpyrimidine, N-vinylpiperidone N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl a cyclic nitrogen-vinyl compound having an N-vinyl substituted heterocyclic structure such as azole, N-vinylmorpholine, N-vinyl caprolactam, N-vinyldodecanoin; N-( Methyl) propylene decyl porphyrin, N-(methyl) propylene sulfhydryl , N-(methyl) propylene fluorenylcyclopropane, N-(methyl) propylene decyltetrahydro hydrazine, N-(methyl) propylene decyl pyrrolidine, N-(methyl) propylene sulfhydryl Pyridine, N-(methyl)acrylonitrile a cyclic nitrogen-vinyl compound having a N-(meth)acrylinyl group-substituted heterocyclic ring structure such as N-(meth)acryloylyl azacyclooctane; N-cyclohexylmaleimide, N a cyclic nitrogen-vinyl compound having a heterocyclic structure having a nitrogen atom and an ethylenically unsaturated bond in the ring, such as a phenylmaleimide; (meth) acrylamide, N-methyl (methyl) Unsubstituted or monoalkyl substituted (meth) acrylamide such as acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide; N, N - dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl acrylamide, N, N-diisopropyl (methyl) Acrylamide, N,N-dibutyl(meth)acrylamide, N-ethyl-N-methyl(meth)acrylamide, N-methyl-N-propyl(methyl)propene Dialkyl substituted (meth) acrylamide such as decylamine or N-methyl-N-isopropyl (meth) acrylamide; methyl N,N-dimethylamino (meth) acrylate , N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylamino(meth)acrylate Propyl ester, N,N-dimethylamine Butyl (meth)acrylate, methyl N,N-diethylamino(meth)acrylate, ethyl N,N-diethylamino(meth)acrylate, N-ethyl-N- Ethylaminoethyl (meth)acrylate, N-methyl-N-propylaminoethyl (meth)acrylate, N-methyl-N-isopropylaminoethyl (meth)acrylate, Dialkylamino (meth) acrylate such as ethyl N,N-dibutylaminoethyl (meth) acrylate or ethyl ternary butylamino (meth) acrylate; N, N-dimethyl Aminopropyl (meth) acrylamide, N,N-diethylaminopropyl (meth) acrylamide, N,N-dipropylaminopropyl (meth) acrylamide, N,N-diisopropylaminopropyl (meth) acrylamide, N-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propyl N,N-dialkyl substituted aminopropyl (methyl) such as aminopropyl (meth) acrylamide or N-methyl-N-isopropylaminopropyl (meth) acrylamide Acrylamide; N-vinylcarbamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylcarboxylic acid amides; N-methoxy (meth)acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxy Methyl (meth) acrylamide, diacetone acrylamide, N, N-methylene bis(methyl) acrylamide, etc. (meth) acrylamide; (meth) acrylonitrile, etc. Saturated carboxylic acid nitriles and the like.

The (E-1) nitrogen-containing vinyl monomer preferably contains no hydroxyl group and further contains no hydroxyl group or carboxyl group. The monomer is a monomer as described above, and preferably, for example, a propylene group containing an N,N-dialkyl-substituted amine group or an N,N-dialkyl-substituted guanamine group. Acid-based monomer; N-vinyl substituted indoleamines such as N-vinyl-2-pyrrolidone, N-vinyl caprolactam, N-vinyl-2-piperidone; N-( N-(methyl)acrylenyl-substituted cyclic amines such as methyl propylene sulfoxide or N-(methyl) propylene pyrrolidine.

In (E), as the (E-2) alkoxy group-containing (meth)acrylic acid alkyl ester monomer, ethyl 2-methoxy (meth)acrylate and 2-ethoxy group (A) are mentioned. Ethyl acrylate, ethyl 2-propoxy (meth) acrylate, ethyl 2-isopropoxy (meth) acrylate, ethyl 2-butoxy (meth) acrylate, 2-methoxy Propyl (meth) acrylate, 2-ethoxy (meth) propyl acrylate, 2-propoxy (meth) propyl acrylate, 2-isopropoxy (meth) propyl acrylate, 2 -butoxy propyl (meth) acrylate, 3-methoxy (meth) propyl acrylate, 3-ethoxy (meth) propyl acrylate, 3-propoxy (meth) propyl acrylate , 3-isopropoxy propyl (meth) acrylate, 3-butoxy propyl (meth) acrylate, 4-methoxy (meth) butyl acrylate, 4-ethoxy (methyl) Butyl acrylate, butyl 4-propoxy (meth) acrylate, butyl 4-isopropoxy (meth) acrylate, butyl 4-butoxy (meth) acrylate, and the like.

The alkoxy group-containing alkyl (meth)acrylate monomer has a structure in which an atom of an alkyl group in an alkyl (meth)acrylate is substituted with an alkoxy group.

The (meth) acrylate monomer having a C4 to C10 carbon number per 100 parts by weight of the (A) alkyl group preferably contains 1 to 20 parts by weight of (E-1) nitrogen-containing one having no hydroxyl group. A vinyl monomer or (E-2) alkoxy-containing alkyl (meth)acrylate monomer. (E-1) one of a nitrogen-containing vinyl monomer not containing a hydroxyl group and (E-2) an alkoxy group-containing alkyl (meth)acrylate monomer, or a combination of two or more use.

The (F) trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three or more isocyanate (NCO) groups per molecule, and examples thereof include hexamethylene diisocyanate and isophorone diisocyanate. Diisocyanates such as phenylmethane diisocyanate, toluene diisocyanate, and xylene diisocyanate (2 NCOs in one molecule) a divalent urea modified or a cyanuric acid modified body, a trivalent or higher polyhydric alcohol such as trimethylolpropane or glycerin (a compound having at least three or more OH groups in one molecule) An adduct (polyol modified body) or the like.

(F) The trifunctional or higher isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and particularly preferably an isocyanurate compound selected from a hexamethylene diisocyanate compound. An isocyanurate body of a sulphuric acid diisocyanate compound, an adduct body of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, and a biuret body of a hexamethylene diisocyanate compound At least one or more of the compound groups consisting of the biuret body of the isophorone diisocyanate compound. It is preferred to contain 0.4 to 5.0 parts by weight of the (F) trifunctional or higher isocyanate compound per 100 parts by weight of the copolymer.

Examples of the (G) cross-linking retarder include methyl ethyl acetate, ethyl acetate, octyl acetate, oleyl acetate, lauryl acetate, and ethyl acetate. A β-ketoester such as an oxime ester or a β-diketone such as acetamidineacetone, 2,4-hexanedione or benzamidineacetone. These are keto-enol tautomer compounds, and in the adhesive composition using a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group of the crosslinking agent, the composition of the adhesive after the crosslinking agent is mixed can be suppressed. The excessive viscosity of the material rises or gels, prolonging the shelf life of the adhesive composition.

The (G) crosslinking retarder is preferably a keto-enol tautomer compound, and particularly preferably at least one selected from the group consisting of ethyl acetonide and ethyl acetate.

It is preferred to contain 1.0 to 5.0 parts by weight of a (G) crosslinking retarder with respect to 100 parts by weight of the copolymer.

In the case where a polyisocyanate compound is used as a crosslinking agent, the (H) crosslinking catalyst is a catalyst (crosslinking reaction) for the above-mentioned copolymer and a crosslinking agent as a catalyst. The functional substance may be an amine compound such as a tertiary amine, an organotin compound, an organic lead compound, or an organometallic compound such as an organic zinc compound.

As the tertiary amine, a trialkylamine, N,N,N',N'-tetraalkyldiamine, N,N-dialkylamino alcohol, triethylene glycol diamine, and morpholin are derived. Pipe Derivatives, etc.

Examples of the organotin compound include a dialkyl tin oxide, a fatty acid salt of a dialkyl tin, a fatty acid salt of stannous, and the like.

The (H) crosslinking catalyst is preferably an organotin compound, and particularly preferably at least one selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.

It is preferred to contain 0.01 to 0.5 part by weight of the (H) crosslinking catalyst relative to 100 parts by weight of the copolymer.

(I) The polyether modified siloxane compound is a siloxane compound having a polyether group, in addition to the conventional oxirane unit [-SiR ¹ ₂ -O-], a decane having a polyether group unit ^{[-SiR 1 (R 2 O (R} 3 O) n R 4) -O- ]. Here, R ¹ represents one or two or more alkyl groups or aryl groups, R ² and R ³ represent one or two or more kinds of alkylene groups, and R ⁴ represents one or two or more kinds of alkyl groups or hydrazines. Base or the like (end group). Examples of the polyether group include a polyoxyalkylene group such as a polyoxyethylene group ((C ₂ H ₄ O) _n ) or a polyoxypropylene group [(C ₃ H ₆ O) _n ].

(I) The polyether-modified siloxane compound is preferably a polyether modified siloxane compound having an HLB value of 7 to 12. Further, it is preferred to contain 0.01 to 0.5 part by weight of the (I) polyether modified siloxane compound per 100 parts by weight of the copolymer. More preferably, it is 0.1 to 0.5 part by weight.

The HLB is, for example, a hydrophilic-lipophilic balance (hydrophilic lipophilic ratio) prescribed in JIS K3211 (in the form of a surfactant).

The polyether modified oxoxane compound is, for example, obtained by grafting an organic compound having an unsaturated bond and a polyoxyalkylene group by a hydrogenation oximation reaction for a polyorganosiloxane chain having a decyl group. Specifically, dimethyl methoxyoxane can be mentioned. Methyl (polyoxyethylene) decane Copolymer, dimethyl methoxyoxane. Methyl (polyoxyethylene) decane. Methyl (polyoxypropylene) fluorene oxide copolymer, dimethyl methoxy alkane. A methyl (polyoxypropylene) decane copolymer or the like.

The adhesion and reworkability of the adhesive can be improved by mixing the (I) polyether modified oxoxane compound in the adhesive composition.

Further, as another component, a copolymerizable (meth) acrylate monomer containing an alkylene oxide, a (meth) acrylamide monomer, a dialkyl-substituted acrylamide monomer, and an interface can be appropriately mixed. A known additive such as an active agent, a hardening accelerator, a plasticizer, a filler, a hardener, a processing aid, an anti-aging agent, an antioxidant, an antistatic agent, and the like. These may be used alone or in combination of two or more.

As an antistatic agent, an ionic compound is mentioned. Further, the antistatic property can also be imparted by a copolymer in which an ionic acrylic monomer is copolymerized in a main component.

The copolymer of the main agent used in the adhesive composition of the present invention may be a (meth) acrylate monomer having a carbon number of a polymerized (A) alkyl group of C4 to C10, and (B) a hydroxyl group containing The copolymerization is carried out by copolymerizing a monomer, (C) a carboxyl group-containing copolymerizable monomer, and (D) a polyalkylene glycol mono(meth)acrylate monomer. The polymerization method of the copolymer is not particularly limited, and a suitable polymerization method such as solution polymerization or emulsion polymerization can be used.

The adhesive composition of the present invention can be used in the above-mentioned copolymer to mix (F) a trifunctional or higher isocyanate compound, (G) a crosslinking retarder, (H) a crosslinking catalyst, and (I) a polyether modification. It is prepared by a oxoxane compound, and further any suitable additives.

The above-mentioned copolymer, preferably an acrylic polymer, preferably contains 50 to 100% by weight of a (meth) acrylate monomer or an acrylic monomer such as (meth)acrylic acid or (meth) acrylamide. body.

Further, the acid value of the acrylic polymer is preferably from 0.01 to 8.0. By the acid value, the contamination property can be improved and the prevention performance of the occurrence of the adhesive residue can be improved.

Here, the "acid value" is one of the indexes of the acid content, and indicates the number of mg of potassium hydroxide required to neutralize 1 g of the carboxyl group-containing polymer.

The adhesive layer obtained by crosslinking the above adhesive composition preferably has an adhesive force of 0.05 to 0.1 N/25 mm at a low-speed peeling speed of 0.3 m/min, and an adhesive force of 1.0 at a high-speed peeling speed of 30 m/min. N/25mm or less. Thereby, the performance of the adhesive force change with the peeling speed can be obtained, and even if it peels by high speed, it can peel rapidly. Further, in order to re-bond, when the surface protective film is temporarily peeled off, excessive force is not required, and it is easy to peel off from the adhesive.

The adhesive layer (adhesive after crosslinking) in which the adhesive composition of the present invention is crosslinked has a gel fraction of preferably 95 to 100%. Thus, since the gel fraction is high, the adhesion of the peeling at low speed does not become excessive, the dissolution of the unpolymerized monomer or oligomer from the copolymer is lowered, and the reworkability or high temperature is improved. Durability in high humidity, inhibiting contamination of adhesives.

The adhesive film of the present invention is formed by crosslinking an adhesive composition of the present invention on one or both sides of a resin film. Further, the surface protective film of the present invention is a surface protective film in which an adhesive layer obtained by crosslinking the adhesive composition of the present invention is formed on one surface of a resin film. In the adhesive composition of the present invention, since the components (A) to (I) are uniformly mixed, the balance of adhesion is excellent in low-speed peeling and high-speed peeling, and further, durability and reworkability (adhesion by a ballpoint pen) The agent layer is also excellent in the transfer of the adhesive on the surface protective film without contamination of the adhesive. Therefore, the use as a surface protective film of a polarizing plate can be suitably used.

A resin film such as a polyester film or the like can be used as the base film of the adhesive layer or the release film (separator) for protecting the adhesive surface.

The base film can be implemented on the opposite side of the resin film from the side on which the adhesive layer is formed. Antifouling treatment by a decane-based, fluorine-based release agent or coating agent, cerium oxide microparticles or the like; antistatic treatment by application or kneading of an antistatic agent.

In the release film, a release treatment such as a siloxane or a fluorine-based release agent is applied to the surface of the adhesive layer on the side where it is bonded to the adhesive surface.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples.

<Preparation of acrylic acid copolymer> [Example 1]

Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen. Thereafter, 100 parts by weight of 2-ethylhexyl acrylate, 0.9 parts by weight of octyl 8-hydroxyacrylate, 0.5 parts by weight of acrylic acid, 3 parts by weight of polyethylene glycol monoacrylate, and N-vinylpyrrole were added to the reaction apparatus. 5 parts by weight of ketone and 60 parts by weight of a solvent (ethyl acetate). Thereafter, 0.1 part by weight of azobisisobutyronitrile was added dropwise as a polymerization initiator over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain an acrylic copolymer solution used in Example 1 having a weight average molecular weight of 500,000. 1. One part of the acrylic copolymer was extracted, and a measurement sample as the following acid value was used.

[Examples 2 to 9 and Comparative Examples 1 to 9]

Example 2 was obtained in the same manner as in the acrylic copolymer solution 1 used in the above Example 1, except that the composition of each monomer was set as described in (A) to (E) of Table 1. ~9 and the acrylic copolymer solution used in Comparative Examples 1-9.

<Preparation of Adhesive Composition and Surface Protective Film> [Example 1]

To the acrylic copolymer solution 1 of Example 1 prepared as described above, 0.2 parts by weight of KF-351A (polyether modified oxirane compound of HLB=12) and 2.5 parts by weight of acetamidine acetone were added and stirred. 1.5 parts by weight of CORONATE HX (isocyanurate body of hexamethylene diisocyanate compound) and 0.02 parts by weight of dioctyltin dilaurate were added, followed by stirring and mixing. The adhesive composition of Example 1 was obtained. After the adhesive composition was applied onto a release film made of a polyethylene terephthalate (PET) film coated with a siloxane resin, the solvent was removed by drying at 90 ° C to obtain an adhesive layer. Adhesive sheet having a thickness of 25 μm.

Thereafter, the adhesive sheet is transferred to the opposite side of the antistatic and antifouling treatment surface of the anti-static and anti-fouling polyethylene terephthalate (PET) film on one side, and the anti-static and anti-static surface is obtained. The surface protective film of Example 1 of the laminated structure of the antifouling treated PET film/adhesive layer/release film (silicone resin coated PET film).

[Examples 2 to 9 and Comparative Examples 1 to 9]

Examples 2 to 9 and Comparative 1 to 9 were obtained in the same manner as in the above-described surface protective film of Example 1 except that the composition of each of the additives was set to be in accordance with (F) to (I) of Table 2. Surface protection film.

Tables 1 and 2 show that the overall ratio of the mixing ratios of the respective components is divided into two, and the values of the required parts by weight of 100 parts by weight of any one of the groups (A) are indicated by parentheses. Further, the names of the compounds abbreviated as the respective components used in Tables 1 and 2 are shown in Tables 3 and 4. In addition, CORONATE (registered trademark) HX and the same HL are trade names of Japan Polyurethane Industry Co., Ltd., Takenate (registered trademark) D-140N is the trade name of Mitsui Chemicals Co., Ltd., KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are trade names of Shin-Etsu Chemical Co., Ltd.

<Test method and evaluation>

The surface protective films of Examples 1 to 9 and Comparative Examples 1 to 9 were aged for 7 days in an environment of 23° C. and 50% RH, and then the release film (silicone resin coated PET film) was peeled off to expose The adhesive layer was used as a test sample for the gel fraction.

Further, the surface protective film exposing the adhesive layer is bonded to the surface of the polarizing plate adhered to the liquid crystal cell via the adhesive layer, and left for 1 day, and then subjected to autoclaving at 50 ° C, 5 atm, and 20 minutes. It was further allowed to stand at room temperature for 12 hours as a test sample for adhesion and durability.

<acid value>

The acid value of the acrylic polymer is obtained by dissolving a sample in a solvent (a mixture of diethyl ether and ethanol in a volume ratio of 2:1), using a potentiometric automatic titrator (manufactured by Kyoto Electronics Manufacturing Co., Ltd., AT-610). 0.1 potentiometric titration apparatus, potentiometric titration with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol/l, and measuring hydrogen and oxygen required for neutralizing the sample The amount of potassium ethanol solution. Further, the acid value was obtained by the following formula.

Acid value = (B × f × 5.611) / S

B = amount of 0.1 mol/l potassium hydroxide ethanol solution used in the titration (ml)

f=0.1mol/l coefficient of potassium hydroxide ethanol solution

S = mass of the solid part of the sample (g)

<gel fraction>

After the aging treatment was completed, the quality of the test sample attached to the polarizing plate was accurately measured, and after immersing in toluene for 24 hours, it was filtered through a metal mesh of 200 mesh. Thereafter, after the filtrate was dried at 100 ° C for 1 hour, the mass of the residue was accurately measured, and the gel fraction of the adhesive layer (adhesive after crosslinking) was calculated from the following formula.

Gel fraction (%) = insoluble portion mass (g) / adhesive mass (g) × 100

<adhesion>

The measurement was carried out by using a tensile tester at a low speed peeling speed (0.3 m/min) and a high speed peeling speed (30 m/min) in the 180° direction (the surface of the polarizing plate was attached to a width of 25 mm). The peeling strength of the surface protective film was used as the adhesive strength.

<reworkability>

After drawing on the surface protective film of the measurement sample obtained above by a ballpoint pen (loading 500 g, reciprocating three times), the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed, and it was confirmed that there was no contamination transfer on the polarizing plate. The evaluation target criterion is that the case where there is no contamination transfer on the polarizing plate is evaluated as "○", and at least one of the trajectories drawn along the ballpoint pen The case where the contamination transfer was confirmed in part was evaluated as "△", and the contamination was confirmed along the trajectory drawn by the ballpoint pen, and the adhesion of the adhesive was confirmed to be "x" from the surface of the adhesive.

<Durability>

The measurement sample obtained above was allowed to stand at 60 ° C and 90% RH for 250 hours, and then taken out at room temperature, and after standing for 12 hours, the adhesion was measured, and it was confirmed that there was no significant increase compared with the initial adhesion. The evaluation target was evaluated as "○" when the adhesion after the test was 1.5 times or less of the initial adhesion, and "x" when the adhesion was more than 1.5 times.

The evaluation results are shown in Table 5.

The surface protective film of Examples 1 to 9 has an adhesive force of 0.05 to 0.1 N/25 mm at a low-speed peeling speed of 0.3 m/min, and an adhesive force of 1.0 N/25 mm or less at a high-speed peeling speed of 30 m/min, and is passed through a ballpoint pen. After the adhesive layer was drawn on the surface protective film, there was no contamination transfer on the adhesive, and the durability was excellent when left in an environment of 60 ° C and 90% RH for 250 hours.

That is, it satisfies (1) the balance of the adhesive force at the low-speed peeling speed and the high-speed peeling speed; (2) prevention of the occurrence of the adhesive residue; and (3) all required performance of the rework performance.

The surface protective film of Comparative Example 1 may be due to the absence of (D) polyalkylene glycol mono(meth)acrylate monomer and (E) nitrogen-containing vinyl monomer or alkoxy-containing (methyl group) The alkyl acrylate monomer has a low adhesion at a low-speed peeling speed of 0.3 m/min and a slightly poor reworkability.

The surface protective film of Comparative Example 2 may be due to (B) too little hydroxyl group-containing monomer, (D) polyalkylene glycol mono(meth)acrylate monomer too small, and no (E) nitrogen-containing vinyl group. The HLB value of the monomer or the alkoxy-containing alkyl (meth)acrylate monomer, (F) isocyanate compound is too large, and the (I) polyether modified siloxane compound is too small, so the stripping speed at a low speed is 0.3 m/ Adhesive force at min and excessive adhesion at a high-speed peeling speed of 30 m/min, reworkability and durability are deteriorated, and gel fraction is lowered.

The surface protective film of Comparative Example 3 may be due to (B) excessive hydroxyl group-containing monomer, (C) excessive acid-containing monomer, and (D) polyalkylene glycol mono(meth)acrylate monomer. And (E) the nitrogen-containing vinyl monomer or the alkoxy-containing alkyl (meth) acrylate monomer is excessive, and (I) the polyether modified siloxane compound has an excessive HLB value, so the acrylic polymer The acid value is high, the adhesion at a low-speed peeling speed of 0.3 m/min, and the adhesion at a high-speed peeling speed of 30 m/min are too large, and the reworkability and durability are poor.

The surface protective film of Comparative Example 4 may be due to (C) too little acid-containing monomer, no (D) polyalkylene glycol mono(meth)acrylate monomer, (E) nitrogen-containing vinyl single The amount of the alkoxy group-containing alkyl (meth) acrylate monomer is too small, so the adhesion at a low-speed peeling speed of 0.3 m/min is low, and the reworkability and durability are poor.

The surface protective film of Comparative Example 5 may be due to (B) too much hydroxyl group-containing monomer, (C) too much acid-containing monomer, and (D) polyalkylene glycol mono(meth)acrylate monomer too small, Since the (E) nitrogen-containing vinyl monomer or the alkoxy group-containing (meth)acrylic acid alkyl ester monomer and the (F) isocyanate compound are too small, the acid value of the acrylic polymer becomes high and is peeled off at a low speed. The adhesive force at a speed of 0.3 m/min and the adhesive force at a high-speed peeling speed of 30 m/min become excessive, the reworkability and durability are deteriorated, and the gel fraction is lowered.

The surface protective film of Comparative Example 6 may be such that the (G) crosslinking retarder is not mixed, so that the pot life is too short, and since it is crosslinked before coating, coating is impossible.

The surface protective film of Comparative Example 7 may contain too much MA having a C1 alkyl group in (A) a (meth) acrylate monomer having an alkyl group, and (B) a hydroxyl group-containing monomer, and may not contain (D) Polyalkylene glycol mono(meth)acrylate monomer and (E) nitrogen-containing vinyl monomer or alkoxy-containing alkyl (meth)acrylate monomer without mixing (H) crosslinking The catalyst has an adhesive force at a low-speed peeling speed of 0.3 m/min and an excessive adhesion at a high-speed peeling speed of 30 m/min, and has poor reworkability and durability.

The surface protective film of Comparative Example 8 may be due to excessive (D) polyalkylene glycol mono(meth)acrylate monomer, no (E) nitrogen-containing vinyl monomer or alkoxy-containing (A) Alkyl acrylate monomer, no mixed (I) polyether modified oxirane compound, so the adhesion at a low speed peeling speed of 0.3 m / min and the adhesion at a high speed peeling speed of 30 m / min Big, rework is slightly worse.

The surface protective film of Comparative Example 9 may be due to the absence of (D) polyalkylene glycol mono(meth)acrylate monomer and (E) nitrogen-containing vinyl monomer or alkoxy-containing (methyl group) Since the alkyl acrylate monomer and the (I) polyether modified oxirane compound are too much, the adhesion at a low-speed peeling speed of 0.3 m/min is low, the reworkability is slightly poor, and the durability is poor.

Thus, the surface protective films of Comparative Examples 1 to 9 cannot simultaneously satisfy (1) the balance of the adhesive force obtained at the low-speed peeling speed and the high-speed peeling speed; (2) the prevention of the occurrence of the adhesive residue; and (3) the reworkability. All required performance.

Claims (23)

An adhesive composition comprising (A) a (meth) acrylate monomer having a C4 to C10 carbon number, (B) a hydroxyl group-containing copolymerizable monomer, and (C) a carboxyl group-containing Copolymerized monomer, (D) polyalkylene glycol mono(meth)acrylate monomer, and (E) nitrogen-containing vinyl monomer or alkoxy-containing (meth)acrylic acid containing no hydroxyl group a copolymer of an acrylic polymer of at least one of an alkyl ester monomer, further comprising (F) a trifunctional or higher isocyanate compound, (G) a crosslinking retarder, (H) a crosslinking catalyst, and (I) A polyether modified oxirane compound having an acid value of from 0.01 to 8.0. The adhesive composition of claim 1, wherein the (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxy(meth)acrylic acid octyl ester and 6-hydroxy(methyl)acrylic acid. Ester, butyl 4-hydroxy(meth)acrylate, ethyl 2-hydroxy(meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N- At least one or more of a compound group consisting of hydroxyethyl (meth) acrylamide; and a (meth) acrylate monomer having a C4 to C10 carbon number per 100 parts by weight of the (A) alkyl group; 0.1 to 5.0 parts by weight of the above (B) hydroxyl group-containing copolymerizable monomer, and (B) the hydroxyl group-containing copolymerizable monomer, 8-hydroxy(meth)acrylic acid octyl ester, 6-hydroxyl group ( The total amount of hexyl methacrylate and butyl 4-hydroxy(meth)acrylate is 0 to 0.9 parts by weight. The adhesive composition according to claim 1 or 2, wherein the (C) carboxyl group-containing copolymerizable monomer is selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth) acrylate, and carboxy pentane. (meth) acrylate, 2-(meth) propylene methoxyethyl hexahydro phthalic acid, 2-(methyl) propylene methoxy propyl hexahydro phthalic acid, 2-(methyl) propylene hydride Oxyethyl phthalic acid, 2-(meth) propylene methoxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate 2-(methyl)propenyloxyethyltetrahydrofurfuric acid At least one or more of the compound groups of the composition; (C) is contained in an amount of 0.35 to 1.0 part by weight based on 100 parts by weight of the (meth) acrylate monomer having a C4 to C10 carbon number of the (A) alkyl group; A copolymerizable monomer having a carboxyl group. The adhesive composition according to claim 1 or 2, wherein the (D) polyalkylene glycol mono(meth)acrylate monomer is selected from the group consisting of polyalkylene glycol mono(methyl) At least one or more of an acrylate, a methoxy-alkylene glycol (meth) acrylate, and an ethoxy-polyalkylene glycol (meth) acrylate; and the above (A) with respect to 100 parts by weight The alkyl group has a C4 to C10 (meth) acrylate monomer and contains 1 to 20 parts by weight of the above (D) polyalkylene glycol mono(meth) acrylate monomer. The adhesive composition according to claim 1 or 2, wherein the (A) alkyl group has a carbon number of C4 to C10 (meth) acrylate monomer, and contains 1 to 20 parts per 100 parts by weight. The above (E) is a nitrogen-containing vinyl monomer having no hydroxyl group or an alkoxy-containing alkyl (meth)acrylate monomer. The adhesive composition according to claim 1 or 2, wherein the (F) trifunctional or higher isocyanate compound is selected from the group consisting of isocyanurate and hexanone from a hexamethylene diisocyanate compound. An isocyanurate body of an isocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, and an isophor At least one or more of the compound groups of the biuret composition of the keto diisocyanate compound; and 0.4 to 5.0 parts by weight of the above (F) trifunctional or higher isocyanate compound per 100 parts by weight of the above copolymer. The adhesive composition according to claim 1 or 2, wherein the (I) polyether modified siloxane compound is a polyether modified siloxane compound having an HLB value of 7 to 12; Parts of the above copolymer, containing 0.01 to 0.5 parts by weight of the above (I) The polyether is modified with a oxoxane compound. The adhesive composition according to claim 1 or 2, wherein the (G) crosslinking blocker is a keto-enol tautomer compound; and 1.0 to 100 parts by weight of the above copolymer; 5.0 parts by weight of the above (G) cross-linking retarder. The adhesive composition according to claim 1 or 2, wherein the (H) crosslinking catalyst is an organotin compound; and 0.01 to 0.5 part by weight of the above (H) is contained with respect to 100 parts by weight of the above copolymer. Cross-linking catalyst. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has an adhesive force of 0.05 to 0.1 N/25 mm at a low-speed peeling speed of 0.3 m/min. The adhesive force at a high-speed peeling speed of 30 m/min is 1.0 N/25 mm or less. An adhesive film obtained by forming an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 1 or 2 on one surface or both surfaces of a resin film. An adhesive film obtained by forming an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of the third aspect of the patent application on one or both sides of a resin film. An adhesive film obtained by forming an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 4 in one or both sides of a resin film. An adhesive film formed on an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 5 in one or both sides of a resin film. An adhesive film obtained by forming an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 6 in one or both sides of a resin film. An adhesive film formed on one or both sides of a resin film to enable a patent application scope The adhesive film of the adhesive layer obtained by crosslinking the adhesive composition of the seventh item. An adhesive film formed on an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 8 on one or both sides of a resin film. An adhesive film formed on an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 9 in one or both sides of a resin film. An adhesive film obtained by forming an adhesive film of an adhesive layer obtained by crosslinking an adhesive composition of claim 10 in one or both sides of a resin film. A surface protective film which is formed on a surface of a resin film and which has an adhesive layer which is obtained by crosslinking an adhesive composition of claim 1 or 2, and which is adhered to the adhesive layer via a ballpoint pen. After the surface protection film is painted, there is no contamination transfer to the adhesive. For example, the surface protective film of claim 20 is used as a surface protective film for a polarizing plate. The surface protective film of claim 20, which is subjected to an antistatic and antifouling treatment on a surface of the resin film opposite to the side on which the adhesive layer is formed. The surface protective film of claim 21, which is subjected to an antistatic and antifouling treatment on a surface of the resin film opposite to the side on which the adhesive layer is formed.