TW201534679A - Adhesive composition and surface-protective adhesive film - Google Patents

Abstract

The invention provides an adhesive composition and a surface-protective adhesive film, which have excellent electrical resistance and excellent adhesive balance, durability and rework performance during peeling in high speed and low speed. The adhesive composition contains (A) acrylate monomer (methyl) containing alkyl carbons of C4-C10, (B) comonomer containing hydroxyl, (C) comonomer containing carboxyl and (D) acrylic polymer of copolymer of poly alkylene glycol single (meth) acrylate monomer. The adhesive composition further contains (E) over three-functional isocyanate compound, (F) crosslinking inhibitor, (G) Crosslinking catalyst, (H) antistatic agent and (I) polyether modified siloxane compound, wherein the acid value of the acrylic polymer ranges from 0.01-8.0.

Description

Adhesive composition, adhesive film 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, the present invention relates to adhesion of a surface protective film for bonding the surface of an optical member such as a polarizing plate or a retardation plate which constitutes a polarizing plate or a phase difference plate of a liquid crystal display. The composition of the agent, and a surface protective film using the same.

Conventionally, in the manufacturing step of an optical member for forming a polarizing plate or a phase difference plate of a liquid crystal display, a surface protective film is temporarily bonded to the surface of the optical member. When the optical member is assembled in 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. Therefore, it is also generally referred to as a step film.

The surface protective film used in the step of producing an optical member has an adhesive layer formed on one surface of an optically transparent polyethylene terephthalate (PET) resin film. Further, the release film for protecting the adhesive layer and being subjected to the release treatment is bonded to the upper surface of the adhesive layer until it is bonded to the optical member.

In addition, in the optical member such as a polarizing plate or a retardation film, the display capability, chromaticity, contrast, and impurity mixing accompanying the liquid crystal display panel are performed in a state in which the surface protective film is bonded. In the optical inspection of the product inspection, the necessary performance for the surface protective film is that no bubbles or impurities adhere to the adhesive layer.

In addition, in recent years, when the surface protective film is peeled off from an optical member such as a polarizing plate or a phase difference plate, it is necessary to prevent the occurrence of excellent antistatic performance of static electricity. This is because when the adhesive layer is peeled off from the adherend, the electrification at the time of peeling accompanying the generated static electricity may cause the electrical control circuit of the liquid crystal display to malfunction.

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, it is desirable to have a surface protective film which can be easily peeled off from the optical member to be adhered (having heavy workability).

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 required to be peeled off quickly. It is required that even high-speed peeling can be quickly peeled off, and the influence on the peeling speed of the adhesive force is small.

As described above, in recent years, the performance of the following (1) to (4) is required as a required performance for the adhesive layer constituting the surface protective film.

(1) A balance of adhesion in low-speed peeling and high-speed peeling is obtained.

(2) Prevent the occurrence of adhesive residue.

(3) It has excellent antistatic properties.

(4) Has heavy work performance.

However, although the respective required performances of the above (1) to (4) can be satisfied, it is extremely difficult to have all the required performances of (1) to (4) required in the adhesive layer of the surface protective film. of.

For example, the following proposals are known regarding (1) obtaining an adhesive balance in low-speed peeling and high-speed peeling; and (2) preventing occurrence of adhesive residue.

An acrylic adhesive prepared 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. If it takes a long time after the bonding, there is a problem that the adhesive moves toward the adherend side, and the adhesion to the adherend increases with time. In order to prevent this problem, an adhesive (pressure-sensitive adhesive) is known which uses an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group. The copolymer is obtained by crosslinking treatment with a crosslinking agent (Patent Document 1).

Further, an adhesive or the like is proposed in which a copolymer in which a small amount of a (meth)acrylic acid alkyl ester and a carboxyl group-containing copolymerizable compound are blended in a copolymer similar to the above is obtained by crosslinking treatment with a crosslinking agent. However, when it is used for surface protection such as a plastic sheet having a low surface tension and a smooth surface, there is a problem of peeling phenomenon such as floating due to heating during processing or storage, or peeling at a high speed by manual peeling. Poor peelability.

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

The adhesive composition described in Patent Document 2 does not cause a peeling phenomenon such as floating during processing or storage, and the adhesion time rises little, and the removability is excellent, that is, It can be stored for a long period of time, especially in a high-temperature environment, and can be peeled off with a small force. At this time, no adhesive residue remains on the adherend, and it can be peeled off with a small force when performing high-speed peeling. .

Further, (3) has an excellent antistatic property, and as a method of imparting antistatic properties to the surface protective film, a method of kneading an antistatic agent to a base film is shown. As the antistatic agent, for example, various cationic antistatic agents having (a) a cationic group having a quaternary ammonium salt, a pyridinium salt, a first to third amino group, and the like; (b) having a sulfonate group or a sulfate salt are disclosed. An anionic antistatic agent such as an anion group such as a phosphate group, a phosphonate group or a phosphonate group; (c) an amphoteric antistatic agent such as an amino acid or an aminosulfate group; (d) an amino alcohol or a glycerin And a nonionic antistatic agent such as a polyethylene glycol; and (e) a polymer type antistatic agent which is obtained by polymerizing an antistatic agent as described above (Patent Document 3).

Further, in recent years, it has been proposed not only to contain such an antistatic agent on a substrate film or to apply it to the surface of a substrate film, but it has been proposed to directly include the antistatic agent in the adhesive layer.

Further, (4) has a rework property, for example, an adhesive composition is proposed, which is a hardener in which an isocyanate compound is blended in an acrylic resin, and is specific to 0.0001 to 10 parts by weight based on 100 parts by weight of the acrylic resin. Citrate oligomer (Patent Document 4).

In Patent Document 4, an alkyl acrylate having an alkyl group having about 2 to 12 carbon atoms, an alkyl methacrylate having an alkyl group having about 4 to 12 carbon atoms, or the like is used as a main monomer component, and for example, A monomer component containing another functional group in a monomer such as a carboxyl group. In general, it is preferable to contain 50% by weight or more of the above-mentioned main monomer, and it is 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 0.01 to 25% by weight. weight % is better. The adhesive composition described in Patent Document 4 has a small change in cohesive force and adhesive force over a high temperature or high temperature and high humidity, and exhibits an excellent effect in adhesion to a curved surface, and thus has reworkability. .

In general, when the adhesive layer is made into a soft property, the adhesive residue tends to occur, and the workability is also liable to lower. That is, it is difficult to peel off and re-attach when it is erroneously bonded. 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 of the adhesive layer to have a 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 11-070629

[Patent Document 4] Japanese Patent Laid-Open No. Hei 8-199130

In the prior art, as a required performance for the adhesive layer constituting the surface protective film, it is desired to achieve a balance of adhesion in low-speed peeling and high-speed peeling, excellent antistatic properties, and reworkability. However, although the respective required properties can be respectively satisfied, the required performance required in the adhesive layer of the surface protective film cannot be satisfied.

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 the above adhesive composition and surface protective film. The antistatic property is excellent in the balance of adhesion in low-speed peeling and high-speed peeling, and is excellent in durability and reworkability.

In order to solve the above problems, the present invention provides an adhesive composition comprising (A) a (meth) acrylate monomer having an alkyl group having a carbon number of C4 to C10, and (B) a copolymerizable monomer having a hydroxyl group. And (C) an acrylic polymer comprising a carboxyl group-containing copolymerizable monomer and (D) a polyalkylene glycol mono(meth)acrylate monomer copolymer, further comprising (E)3 An isocyanate compound having a functional group or more, (F) a crosslinking inhibitor, (G) a crosslinking catalyst, (H) an antistatic agent, (I) a polyether modified siloxane compound, and an acid value of the above acrylic polymer It is 0.01~8.0.

The above (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (A) a group of compounds consisting of 2-hydroxyethyl acrylate, N-hydroxy(meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide At least one or more; preferably, the (A) alkyl (C)-C10 (C)-C10 (meth) acrylate monomer having 0.1 to 5.0 parts by weight of the above (B) hydroxyl group-containing monomer The monomer may be copolymerized, and among the above (B) hydroxyl group-containing copolymerizable monomers, 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and (meth)acrylic acid 4- The total content of the hydroxybutyl ester 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 hexahydrophthalic acid, 2-(methyl) propylene methoxypropyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalate, 2-(A Acryloxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2-(methyl) propyl At least one or more of the group consisting of enelicoxyethyltetrahydrophthalic acid is preferably a (meth) group having (C) a C4 to C10 (meth) group with respect to 100 parts by weight of the (A) alkyl group. The acrylate monomer contains 0.35 to 1.0 part by weight of the above (C) 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 At least one or more of an ester and an ethoxylated polyalkylene glycol (meth) acrylate, wherein the (A) alkyl group having a CA to C10 alkyl group has a C4 to C10 The body contains 1 to 20 parts by weight of the above (D) polyalkylene glycol mono(meth)acrylate monomer.

The above (E) trifunctional or higher isocyanate compound is an isocyanurate body selected from a hexamethylene diisocyanate compound, an isocyanurate body of an isophorone diisocyanate compound, and hexamethylene diisocyanate. a compound composed of an adduct of a compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, and a biuret of an isophorone diisocyanate compound At least one or more of them preferably contain 0.5 to 5.0 parts by weight of the above (E) trifunctional or higher isocyanate compound per 100 parts by weight of the copolymer.

Preferably, the (H) antistatic agent is an ionic compound having a content of the copolymer of 0.1 to 5.0 parts by weight and a melting point of 30 to 80 ° C with respect to 100 parts by weight of the copolymer, or 0.1 to 5.0 in the above copolymer. A quaternary ammonium salt type ionic compound containing an acrylonitrile group copolymerized by weight%.

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

The above (F) crosslinking inhibitor is a ketoenol tautomerizing compound, preferably relative to 100 parts by weight of the above copolymer contains 1.0 to 5.0 parts by weight of the above (F) crosslinking inhibitor.

The (G) crosslinking catalyst is an organotin compound, and preferably contains 0.01 to 0.5 part by weight of the above (G) crosslinking catalyst based on 100 parts by weight of the 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 N at a high-speed peeling speed of 30 m/min. /25mm or less.

Preferably, the adhesive layer obtained by crosslinking the above-mentioned adhesive composition has a surface resistivity of 5.0 × 10 ^{+ 10} Ω / □ or less and a peeling tape voltage of ± 0 to 0.3 kV.

Further, the present invention provides an adhesive film obtained by forming an adhesive layer obtained by crosslinking the above-mentioned adhesive composition on one or both sides of a resin film.

Further, the present invention provides a surface protective film in which a surface protective film of an adhesive layer obtained by crosslinking the above-mentioned adhesive composition is formed on one surface of a resin film, and the surface protective film is passed through the adhesive layer to be a ballpoint pen After being painted on the surface protective film, it will not be contaminated by the transfer of the adhesive.

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

Preferably, antistatic and anti-pollution treatment is performed on the opposite side of the side on which the above-mentioned adhesive layer is formed on the resin film.

According to the present invention, it is possible to satisfy the prior art that it is impossible to solve all the properties required in the adhesive layer of the surface protective film. In addition, excellent antistatic properties and excellent performance against sticking of adhesives are obtained. In particular, it is possible to maintain excellent antistatic properties while reducing the amount of addition of the antistatic agent, and further improve the performance of preventing the occurrence of adhesive residue.

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

The adhesive composition of the present invention is mainly composed of a (meth) acrylate monomer having (A) an alkyl group having a carbon number of C4 to C10, (B) a hydroxyl group-containing copolymerizable monomer, and (C) An acrylic polymer containing a copolymerizable monomer of a carboxyl group and a copolymer of (D) a polyalkylene glycol mono(meth)acrylate monomer, further containing (E) 3 functional groups or more Isocyanate compound, (F) crosslinking inhibitor, (G) crosslinking catalyst, (H) antistatic agent, (I) polyether modified siloxane compound, the acid value of the above acrylic polymer is 0.01 to 8.0 .

Examples of the (meth) acrylate monomer having (A) an alkyl group having a carbon number of C4 to C10 include butyl (meth)acrylate, isobutyl (meth)acrylate, and amyl (meth)acrylate. , (meth) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (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-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylate, N-hydroxy(methyl) acrylamide, N-methylol (meth) acrylamide, N-hydroxyl A hydroxyl group-containing (meth) acrylamide such as a (meth) acrylamide or the like.

Preferably, it is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate and 6-hydroxyhexyl (meth)acrylate. 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyl At least one or more of the group consisting of a group of (meth)acrylamides.

The (B) (4) 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) (C)-C10-C10 (meth) acrylate monomer. .

Further, in (B) a hydroxyl group-containing copolymerizable monomer, a total of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate The content is preferably less than 1 part by weight (may not be contained), and 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 fluorenyloxy group Ethyl hexahydrophthalic acid, 2-(methyl)propenyloxypropyl hexahydrophthalic acid, 2-(meth) propylene methoxyethyl phthalate, 2-(methyl ) acryloxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2-(methyl) propylene methoxy ethoxylate At least one or more of the group consisting of tetrahydrophthalic acid.

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

The (D) polyalkylene glycol mono(meth)acrylate monomer may be a compound in which a hydroxyl group is esterified as a (meth)acrylate in a plurality of hydroxyl groups of the polyalkylene glycol. Since the (meth) acrylate group becomes a polymerizable group, it can be copolymerized with the main agent polymer. Other hydroxyl groups can maintain OH or become an alkyl ether or an ether. Alkyl 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 polyethyl diol, poly propyl diol, and polybutylene glycol. Examples of the copolymer of the polyalkylene glycol include a polyethylene glycol-polypropylene glycol, a polyethylene glycol-polybutylene glycol, and a poly(propylidene glycol)-polymer. Stretching butyl diol, polyethyl propylene glycol - poly propylene glycol - polybutylene glycol, etc., the copolymer may be a block copolymer or a random copolymer.

As the (D) polyalkylene glycol mono(meth) acrylate monomer, preferably selected from the group consisting of polyalkylene glycol mono(meth)acrylates, methoxypolyalkylene glycols (methyl groups) At least one of an acrylate and an ethoxylated polyalkylene glycol (meth) acrylate.

More specifically, polyethyl epoxide-mono (meth) acrylate, poly propyl diol-mono (meth) acrylate, polybutylene butyl diol - mono (meth) acrylic acid Ester, polyethyl epoxide - poly propyl diol - mono (meth) acrylate, polyethyl propylene glycol - polybutylene diol - mono (meth) acrylate, poly propyl Glycol-polybutylene glycol-mono(meth)acrylate, polyethylene glycol-polypropylene glycol-polybutylene glycol-mono(meth)acrylate; methoxy Polyethyl epoxide-(meth) acrylate, methoxy-poly-propyl diol-(meth) acrylate, methoxy-polybutylene glycol-(meth) acrylate, methoxy Base-polyethyl diol-poly propyl diol-(meth) acrylate, methoxy-polyethyl diol-polybutylene glycol-(meth) acrylate, methoxy -Polymeric propyl diol-polybutylene glycol-(meth) acrylate, methoxy-polyethyl diol-poly propylene glycol-polybutylene glycol-(A Acrylate; ethoxylated polyethylene glycol-(meth)acrylate, ethoxylated polypropylene glycol-(meth)acrylate, ethoxylate Polyethylene glycol extending butyl - (meth) acrylate, ethoxy - extending poly ethylene glycol - poly extending propyl Glycol-(meth) acrylate, ethoxy-polyethyl diol-polybutylene glycol-(meth) acrylate, ethoxy-poly propylene glycol-polybutylene Glycol-(meth) acrylate, ethoxy-polyethyl diol-poly propyl diol-polybutylene glycol-(meth) acrylate, and the like.

Preferably, it is a (meth) acrylate monomer having a C4 to C10 carbon number in the above (A) alkyl group, and contains 1 to 20 parts by weight of the above (D) polyalkylene glycol monomer. (Meth) acrylate monomer.

The (E) trifunctional or higher isocyanate compound may have at least three or more isocyanate (NCO) groups in one molecule, and examples thereof include hexamethylene diisocyanate and isophorone diisocyanate. Biuret modified or isocyanuric acid of diisocyanate (compound having two NCO groups in one molecule) such as diphenylmethane diisocyanate, phenylene diisocyanate or xylylene diisocyanate An adduct (polyol modified body) of a trivalent or higher polyvalent alcohol (a compound having at least three or more OH groups in one molecule) such as an ester modified product, trimethylolpropane or glycerin.

The (E) 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 body selected from a hexamethylene diisocyanate compound, An isocyanurate body of an isophorone diisocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, and a biuret of a hexamethylene diisocyanate compound At least one or more of the compound group consisting of a biuret body of a body or an isophorone diisocyanate compound. The (E) trifunctional or higher isocyanate compound is preferably contained in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer.

Examples of the (F) crosslinking inhibitor include methyl ethyl acetate and ethyl acetate. Β-ketoesters such as octyl acetate, ethyl acetoacetate, lauryl acetate, stearyl acetate, acetamidine, 2,4-hexanedione, benzamidine, etc. Beta-diketone. These are ketoenol tautomer compounds, and in the adhesive composition using a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group having a crosslinking agent, it is possible to suppress the adhesion agent composition after the crosslinking agent is blended. The excessive viscosity rises or gels, prolonging the shelf life of the adhesive composition.

(F) The crosslinking inhibitor is preferably a ketoenol tautomer compound, and particularly preferably at least one selected from the group consisting of ethyl acetate and ethyl acetate.

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

In the case where the polyisocyanate compound is used as the crosslinking agent, the (G) crosslinking catalyst may be a substance that functions as a catalyst in the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and may be exemplified: An amine compound such as a tertiary amine, an organometallic compound such as an organotin compound, an organic lead compound or an organozinc compound.

As the tertiary amine, there may be mentioned: a trialkylamine, N,N,N',N'-tetraalkyldiamine, N,N-dialkylamino alcohol, tri-ethylenediamine, morpholine Derivatives, oxazine derivatives, and the like.

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.

(G) The 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 preferable to contain 0.01 to 0.5 part by weight of the (G) crosslinking catalyst with respect to 100 parts by weight of the copolymer.

The (H) antistatic agent is preferably (H1) an ionic compound having a melting point of 30 to 80 ° C or (H2) a quaternary ammonium salt type ionic compound containing an acrylonitrile group.

In the present invention, as the (H) antistatic agent, (H1) an ionic compound having a melting point of 30 to 80 ° C or (H2) a quaternary ammonium salt type ionic compound containing an acrylonitrile group is added to the copolymer. Medium copolymerization. Since these (H) antistatic agents have a low melting point and a long-chain alkyl group, it is presumed to have high affinity with an acrylic copolymer.

The ionic compound having a (H1) melting point of 30 to 80 ° C is an ionic compound having a cation and an anion, and examples thereof include a pyridinium cation, an imidazolium cation, a pyrimidine cation, a pyrazolium cation, and a pyrrole. a nitrogen-containing phosphonium cation such as a phosphonium cation or an ammonium cation, or a compound such as a phosphonium cation or a sulfonium cation; the anion is a hexafluorophosphate (PF ₆ ^- ), a thiocyanate (SCN ^- ), an alkylbenzene sulfonate. A compound of an inorganic or organic anion such as an acid radical (RC ₆ H ₄ SO ₃ ^- ), perchlorate (ClO ₄ ^- ), or tetrafluoroborate (BF ₄ ^- ). Preferably, it is a solid at normal temperature (for example, 30 ° C), and a material having a melting point of 30 to 80 ° C can be obtained by selection of an alkyl chain length or a substituent position and number. The cation is preferably a quaternary nitrogen-containing cerium cation, and examples thereof include a quaternary pyridinium cation such as 1-alkylpyridinium (the carbon atom at the 2nd to 6th position may have a substituent or may be unsubstituted), and 1,3-dioxane. A quaternary ammonium cation such as a quaternary imidazolium cation or a tetraalkylammonium group such as a carbaryl imidazolium group (the carbon atom at the 2, 4, and 5 positions may have a substituent or may be unsubstituted).

It is preferred to contain 0.1 to 5.0 parts by weight of (H1) an ionic compound having a melting point of 30 to 80 ° C with respect to 100 parts by weight of the copolymer.

The (H2) quaternary ammonium salt type ionic compound containing an acrylonitrile group is an ionic compound having a cation and an anion, and examples thereof include a compound: (cation) (meth) propylene decyloxyalkyltrialkylammonium ( a quaternary ammonium compound containing a (meth)acryl fluorenyl group such as R ₃ N ⁺ -C _n H _2n -OCOCQ=CH ₂ , but Q=H or CH ₃ , R=alkyl group, and an anion of hexafluorophosphate (PF ₆ ^- ), thiocyanate (SCN ^- ), organic sulfonate (RSO ₃ ^- ), perchlorate (ClO ₄ ^- ), tetrafluoroborate (BF ₄ ^- ), yttrium imide containing F A compound of an inorganic or organic anion such as (R ^F ₂ N ^- ). As R F of the yttrium imine salt (R ^F ₂ N ^- ) containing ^F , a perfluoroalkylsulfonyl group such as a trifluoromethylsulfonyl group or a pentafluoroethylsulfonyl group, or a fluorosulfonate can be exemplified.醯基. Examples of the yttrium imide salt containing F include bis(fluorosulfonyl) quinone imide salt ((FSO ₂ ) ₂ N ^- ), bis(trifluoromethylsulfonyl) ruthenium salt [(CF). ₃ SO ₂ ) ₂ N ^- 〕, bis(pentafluoroethylsulfonyl) sulfinium imide salt ((C ₂ F ₅ SO ₂ ) ₂ N ^- ) and the like.

(H2) A quaternary ammonium salt type ionic compound containing an acrylonitrile group, preferably copolymerized in the copolymer in an amount of 0.1 to 5.0% by weight.

Specific examples of the (H) antistatic agent are not particularly limited, and specific examples of the ionic compound having a (H1) melting point of 30 to 80 ° C include 1-octylpyridinium hexafluoride phosphate, and 1 - mercaptopyridinium hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecyl Pyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like. Further, specific examples of the (H2) quaternary ammonium salt type ionic compound containing an acrylonitrile group include dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt [(CH ₃ ) ₃ N ⁺ CH ₂ OCOCQ=CH ₂ ‧PF ₆ ^- , however, Q=H or CH ₃ ], dimethylaminoethyl (meth) acrylate bis(trifluoromethylsulfonyl) fluorene Base salt [(CH ₃ ) ₃ N ⁺ (CH ₂ ) ₂ OCOCQ=CH ₂ ‧(CF ₃ SO ₂ ) ₂ N ^- , but, Q=H or CH ₃ ], dimethylaminomethyl methacrylate Ester bis(fluorosulfonyl) quinone imine methyl salt [(CH ₃ ) ₃ N ⁺ CH ₂ OCOCQ = CH ₂ ‧ (FSO ₂ ) ₂ N ^- , but Q = H or CH ₃ ] and the like.

(I) The polyether-modified oxirane compound is a polyoxyl group-containing oxirane compound, in addition to the conventional oxime unit [-SiR ¹ ₂ -O-], a polyether-based oxirane 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 and hydrazines. Base or the like (end group). The polyether group may, for example, be 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 oxime compound is preferably a polyether-modified oxirane 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 above (I) polyether modified oxoxane compound with respect to 100 parts by weight of the copolymer. More preferably, it is 0.1 to 0.5 part by weight.

The HLB system is, for example, a hydrophilic-lipophilic balance (ratio of hydrophilicity to lipophilicity) prescribed in JIS K3211 (surfactant terminology).

The polyether-modified siloxane 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 (polyethylene oxide) alkane copolymer, dimethyl methoxy alkane. Methyl (polyoxyethylene) oxirane. Methyl (polyoxypropylene) siloxane copolymer, dimethyl methoxy alkane. A methyl (polyoxypropylene) siloxane copolymer or the like.

The adhesion and reworkability of the adhesive can be improved by blending the (I) polyether-modified siloxane compound to the adhesive composition.

Further, as other components, a copolymerizable (meth)acrylic monomer, a (meth)acrylamide monomer, a dialkyl-substituted acrylamide monomer, and an interface containing an olefin oxide may be appropriately blended. Active agent, hardening accelerator, plasticizer, filler, hardening inhibitor, processing A well-known additive such as an auxiliary agent, an anti-aging agent, an antioxidant, and the like. These may be used alone or in combination of two or more.

The copolymer of the main component used in the adhesive composition of the present invention can be copolymerized by (A) a (meth) acrylate monomer having an alkyl group having a C4 to C10 carbon number, and (B) a copolymerizable group having a hydroxyl group. A monomer, (C) a carboxyl group-containing copolymerizable monomer, and (D) a polyalkylene glycol mono(meth)acrylate monomer are synthesized. The polymerization method of the copolymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used.

When (H2) a quaternary ammonium salt type ionic compound containing an acrylonitrile group is used as the (H) antistatic agent, the copolymer of the main agent used in the adhesive composition of the present invention can be polymerized (A). a (meth) acrylate monomer having an alkyl group having a carbon number of C4 to C10, (B) a copolymerizable monomer having a hydroxyl group, (C) a copolymerizable monomer having a carboxyl group, and (D) a polyalkylene oxide A diol mono(meth) acrylate monomer and (H2) a quaternary ammonium salt type ionic compound containing an acryl oxime group are synthesized.

The adhesive composition of the present invention may be obtained by blending (E) a trifunctional or higher isocyanate compound, (F) a crosslinking inhibitor, (G) a crosslinking catalyst, (H) an antistatic agent, or the like in the above copolymer. (I) A polyether-modified siloxane compound is further prepared by appropriately adding an optional additive. Further, when (H2) a quaternary ammonium salt type ionic compound containing an acrylonitrile group is polymerized in a copolymer of a main component, the (H) antistatic agent may be added to the copolymer.

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

Further, the acid value of the acrylic polymer is preferably from 0.01 to 8.0. Thereby improving pollution Improves the performance of preventing the occurrence of adhesive residue.

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

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 N at a high-speed peeling speed of 30 m/min. /25mm or less. Thereby, it is possible to obtain a performance in which the adhesive force changes little with the peeling speed, and even if it is peeled off at a high speed, it can be peeled off quickly. Further, in order to re-bond, when the surface protective film is temporarily peeled off, excessive force is not required, and it is also easy to peel off from the adherend.

Preferably, the adhesive layer obtained by crosslinking the above-mentioned adhesive composition has a surface resistivity of 5.0 × 10 ^{+ 10} Ω / □ or less and a peeling tape voltage of ± 0 to 0.3 kV. Further, in the present invention, the above "±0 to 0.3 kV" means 0 to -0.3 kV and 0 to +0.3 kV, that is, -0.3 to +0.3 kV. When the surface resistivity is large, the performance of electrostatic escaping due to charging at the time of peeling is poor. Therefore, by sufficiently lowering the surface resistivity, peeling of static electricity generated when the adhesive layer is peeled off from the adherend can be reduced. With voltage, it suppresses the influence on the electrical control circuit of the adherend.

The adhesive layer (adhesive after crosslinking) obtained by crosslinking the adhesive composition of the present invention preferably has a gel fraction of 95 to 100%. Thus, since the gel fraction is high, the adhesive force at the low-speed peeling speed can be prevented from becoming excessively large, the dissolution of the unpolymerized monomer or oligomer from the copolymer is lowered, and the workability and high temperature are improved. Durability in high humidity, inhibiting contamination of adherends.

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. The adhesive composition of the present invention has excellent antistatic properties by blending the components of the above (A) to (I) in a well-balanced manner, and is excellent in balance of adhesion at a low-speed peeling speed and a high-speed peeling speed, and is durable. The performance and the rework performance (except that the ballpoint pen is drawn on the surface protective film through the above adhesive layer is not contaminated by the adherend) is also excellent. Therefore, the surface protective film of the present invention can be suitably used as a surface protective film for a polarizing plate.

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

In the base film, an antifouling treatment by an anthrone, a fluorine-based release agent or a coating agent, cerium oxide microparticles or the like may be applied to the opposite side of the resin film on the side where the adhesive layer is formed; Antistatic treatment by coating or kneading of an antistatic agent.

In the release film, a release treatment is applied to the surface on the side where the adhesive surface of the adhesive layer is adhered by an anthrone or a fluorine-based release agent.

[Examples]

Hereinafter, the present invention will be specifically described based on examples.

<Preparation of acrylic acid copolymer> [Example 1]

For a reaction device equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube Nitrogen gas was introduced to replace the air in the reaction device with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 0.9 parts by weight of 8-hydroxyoctyl acrylate, 0.5 parts by weight of acrylic acid, 3 parts by weight of polyethylene glycol monoacrylate, and a solvent (acetic acid B) were added to the reaction apparatus. Ester) 60 parts by weight. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was dropped over 2 hours, and reacted at 65 ° C for 6 hours to obtain an acrylic copolymer used in Example 1 having a weight average molecular weight of 500,000. Solution 1. A part of the acrylic copolymer was sampled and used as an acid value measurement sample to be described later.

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

The composition was carried out in the same manner as in the acrylic copolymer solution 1 used in the above Example 1 except that the composition of the monomers was set as described in (A) to (D) and (H2) of Table 1, respectively. The acrylic copolymer solutions used in Examples 2 to 9 and Comparative Examples 1 to 9.

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

According to the acrylic copolymer solution 1 prepared above (in which the acrylic copolymer is 100 parts by weight), 1.5 parts by weight of 1-octylpyridinium hexafluorophosphate, KF-351A (HB=12 polyether modified) 0.1 parts by weight of oxirane compound and 2.5 parts by weight of acetamidine acetone, and stirred, and then added 1.5 parts by weight of CORONATE HX (isocyanurate body of hexamethylene diisocyanate compound) and dioctyltin dilaurate. The adhesive composition of Example 1 was obtained by mixing 0.02 parts by weight with stirring. The adhesive composition is applied onto a release film composed of an oxime resin coated polyethylene terephthalate (PET) film, and then dried at 90 ° C to remove the solvent to obtain an adhesive. The layer has an adhesive sheet having a thickness of 25 μm.

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

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

Except that the composition of the additive was set as described in (E) to (I) of Table 1, the same manner as in the surface protective film of Example 1 was carried out, and Examples 2 to 9 and Comparative Examples 1 to 9 were obtained. Surface protection film.

In Table 1, the mixing ratio of each component is indicated by parentheses in the numerical value of the required part by weight of 100 parts by weight of the total of the group (A). Further, Table 2 shows the compound names corresponding to the abbreviations of the respective components used in Table 1. In addition, CORONATE HX (registered trademark) and the same HL are trade names of Nippon Polyurethane Industry Co., Ltd., and Takenate D-140N (registered trademark) is a trade name of Mitsui Chemicals Co., Ltd. DURANATE 24A-100 (registered trademark) is the trade name of Asahi Kasei Chemicals Corporation, KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are Shin-Etsu Chemical Co., Ltd. The company's trade name.

In Table 1, in the (H) antistatic agent, the (H2) quaternary ammonium salt type ionic compound containing the acryl fluorenyl group copolymerized in the copolymer and the (H1) melting point added after the polymerization are 30 The ionic compounds at ~80 ° C are described in different columns. Further, H1-8 used in Comparative Example 9 is a melting point of less than 30 ° C (liquid at normal temperature), and is described in the same column as (H1) for convenience.

<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 (PET film coated with an anthrone resin) was peeled off to expose the adhesive. The layer material was used as a test sample for gel fraction and surface resistivity.

Further, the surface protective film exposing the adhesive layer is bonded to the surface of the polarizing plate bonded to the liquid crystal cell through the adhesive layer, and left for 1 day, and then subjected to autoclaving at 50 ° C, 5 atm, and 20 minutes. After further standing at room temperature for 12 hours, the material obtained above was used as a test sample for adhesion, peeling tape voltage and durability.

<acid value>

The acid value of the acrylic polymer is obtained by dissolving a sample in a solvent (a substance obtained by mixing diethyl ether and ethanol in a volume ratio of 2:1), using a potential difference automatic titrator (manufactured by Kyoto Electronics Industrial Co., Ltd., AT-610), using 0.1. The potentiometric titration apparatus described above was subjected to potentiometric titration with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol/l, and the amount of the potassium hydroxide ethanol solution required for neutralizing the sample was measured. Then, 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 factor of potassium hydroxide ethanol solution

S = quality of the solid component of the sample (g)

<gel fraction>

After the aging 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. Then at 100 ° C After drying the filtrate 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 mass (g) / adhesive mass (g) × 100

<adhesion>

The peel strength measured as follows was used as the adhesive force: the test sample obtained above was peeled off in the 180° direction at a low speed peeling speed (0.3 m/min) and a high speed peeling speed (30 m/min) using a tensile tester (in polarized light) The surface of the board was bonded to a surface protective film having a width of 25 mm) and the peel strength measured was measured.

<surface resistivity>

After the aging, the release film (PET film of the fluorenone resin coating) was peeled off to expose the adhesive layer, and the adhesive was measured using a resistivity meter Hiresta UP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The surface resistivity of the layer.

<Peel strip voltage>

When the test sample obtained above was peeled off at a tensile speed of 180° at a tensile rate of 30 m/min, the voltage generated by the polarizing plate was charged using a high-precision electrostatic sensor SK-035, SK-200 (manufactured by KEYENCE CORPORATION). The maximum value of the measured value is taken as the peeling strip voltage.

<Reworkability>

After drawing on a surface protective film of the test sample obtained above with a ballpoint pen (loading weight: 500 g, reciprocating three times), the surface of the polarizing plate was observed from the polarizing plate peeling off the surface protective film, and it was confirmed that Contaminated polarizing plates transfer pollution. The evaluation target was evaluated as "○" when no contamination was transferred to the polarizing plate, and it was confirmed that the contamination was traced along at least a part of the trajectory drawn by the ballpoint pen as "△", and it was confirmed that the contamination was traced along the trajectory drawn by the ballpoint pen. The case where the adhesive was detached on the surface of the agent was evaluated as "x".

<Durability>

The test sample obtained above was allowed to stand at 60 ° C and 90% RH for 250 hours, and then taken out at room temperature. After further 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 adhesive strength after the test was 1.5 times or less of the initial adhesive force, and "x" when it was more than 1.5 times.

The evaluation results are shown in Table 3. Further, the surface resistivity is marked by setting "m × 10 ^{+ n} " to "mE + n" (where m is an arbitrary real number and n is a positive integer).

The surface protective films of Examples 1 to 9 had 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 strength of 1.0 N/25 mm or less at a high-speed peeling speed of 30 m/min. Further, the surface resistivity is 5.0 × 10 ^{+ 10} Ω / □ or less, and the peeling tape voltage is ± 0 to 0.3 kV. After the ballpoint pen was drawn on the surface protective film through the above-mentioned adhesive layer, it was not contaminated by the adherend, and was excellent in durability when placed in an environment of 60 ° C and 90% RH for 250 hours.

That is, (1) achieving a balance between the low-speed peeling speed and the high-speed peeling speed; (2) preventing the occurrence of the adhesive residue; (3) having excellent antistatic properties; and (4) having rework performance, At the same time, it also meets all the required performance.

The surface protective film of Comparative Example 1 seems to contain no (D) polyalkylene glycol mono(meth)acrylate monomer, and the adhesion at a low-speed peeling speed of 0.3 m/min is low, and the peeling tape voltage is high. Heavy work is also slightly worse.

In the surface protective film of Comparative Example 2, it is considered that (B) the monomer having a hydroxyl group is too small, (D) the polyalkylene glycol mono(meth)acrylate monomer is too small, and (E) the isocyanate compound is excessive (I). The HLB value of the polyether-modified helioxane compound is too small, and the adhesion at a low-speed peeling speed of 0.3 m/min and the adhesive force at a high-speed peeling speed of 30 m/min become too large, the peeling strip voltage becomes high, and the rework The properties and durability are deteriorated, and the gel fraction is lowered.

In the surface protective film of Comparative Example 3, it is considered that (B) the monomer having a hydroxyl group is excessive, (C) the acid-containing monomer is excessive, and (D) the polyalkylene glycol mono(meth)acrylate monomer is excessively large. (I) The HLB value of the polyether-modified siloxane compound is too large, so that the acid value of the acrylic polymer is high, the adhesion at a low-speed peeling speed of 0.3 m/min is low, the surface resistivity is high, and the peeling band voltage is high. , heavy workability and poor durability.

In the surface protective film of Comparative Example 4, it was found that the (C) acid-containing monomer was too small, and the (D) polyalkylene glycol mono(meth)acrylate monomer was not contained, and the low-speed peeling speed was 0.3 m/ The adhesion at min is low, the stripping voltage is high, and the workability and durability are poor.

In the surface protective film of Comparative Example 5, it is considered that (B) the monomer having a hydroxyl group is excessive, (C) the acid-containing monomer is excessive, and (D) the polyalkylene glycol mono(meth)acrylate monomer is too small. (E) The isocyanate compound is too small, and the acid value of the acrylic polymer is high, and the adhesive force at a low-speed peeling speed of 0.3 m/min and the adhesive force at a high-speed peeling speed of 30 m/min become excessively large, and the peeling band voltage becomes high. The workability and durability are deteriorated, and the gel fraction is lowered.

The surface protective film of Comparative Example 6 may be a cause of unmixed (F) crosslinking inhibitor, so that the storage The shelf life is too short and cross-linking is not possible before coating.

The surface protective film of Comparative Example 7 seems to contain MA having a C1 alkyl group in (A) a (meth) acrylate monomer having an alkyl group, (B) a monomer having a hydroxyl group, and no (D) poly The alkyl diol mono(meth) acrylate monomer and the unmixed (G) crosslinking catalyst have an adhesive force at a low-speed peeling speed of 0.3 m/min and an adhesive force at a high-speed peeling speed of 30 m/min, High surface resistivity, high strip voltage, poor workability and durability.

In the surface protective film of Comparative Example 8, the (D) polyalkylene glycol mono(meth)acrylate monomer was excessively mixed, and the (I) polyether modified naphthenic compound was not mixed, and the low-speed peeling was caused. The adhesion at a speed of 0.3 m/min and the high-speed peeling speed at 30 m/min are too high, the surface resistivity is high, the stripping voltage is high, and the reworkability is poor.

In the surface protective film of Comparative Example 9, it is considered that the (D) polyalkylene glycol mono(meth)acrylate monomer and the (H) antistatic agent have a melting point of less than 30 ° C (liquid at normal temperature). (I) The polyether-modified polyoxane compound is too much, and the adhesion at a low-speed peeling speed of 0.3 m/min is low, the peeling tape voltage is high, the workability is slightly poor, and the durability is poor.

As described above, in the surface protective films of Comparative Examples 1 to 9, it is impossible to simultaneously satisfy (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; (3) excellent Antistatic performance; and (4) heavy performance and other required performance.

Claims (12)

An adhesive composition comprising (A) a (meth) acrylate monomer having an alkyl group having C4 to C10, (B) a copolymerizable monomer having a hydroxyl group, and (C) a carboxyl group; An acrylic polymer comprising a copolymer of a copolymerizable monomer and (D) a polyalkylene glycol mono(meth)acrylate monomer, further containing an (E) trifunctional or higher isocyanate compound, ( F) a crosslinking inhibitor, (G) a crosslinking catalyst, (H) an antistatic agent, (I) a polyether-modified oxirane compound having an HLB value of 7 to 12, wherein the acid of the above acrylic polymer The value is 0.01 to 8.0, and the above (H) antistatic agent is an ionic compound having a melting point of 30 to 80 ° C and a solid at a temperature of 30 ° C and having a cation and an anion. The adhesive composition of claim 1, wherein the (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate and 6-hydroxyhexyl (meth)acrylate. Ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N- At least one or more of the group of compounds consisting of hydroxyethyl (meth) acrylamide, and the (meth) acrylate monomer having a C4 to C10 alkyl group having the above (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, (meth)acrylic acid 8-hydroxyoctyl ester, (A) The total content of 6-hydroxyhexyl acrylate and 4-hydroxybutyl (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-(methyl) propylene methoxyethyl hexahydrophthalic acid, 2-(methyl) propylene methoxy propyl hexahydrophthalic acid, 2- (A) Acryloxyethyl phthalic acid, 2-(methyl) propylene methoxyethyl succinic acid, 2-(methyl) propylene methoxyethyl At least one or more of the group consisting of maleic acid, carboxypolycaprolactone mono(meth)acrylate, and 2-(meth)acryloxyethyltetrahydrophthalic acid, relative to 100 The (A) (C) alkyl group having a C4 to C10 alkyl group has a C4 to C10 content, and contains 0.35 to 1.0 part by weight of the above (C) carboxyl group-containing copolymerizable monomer. 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-polyalkylene glycol (meth) acrylate, and an ethoxy-polyalkylene glycol (meth) acrylate; and the above (A) with respect to 100 parts by weight The (meth) acrylate monomer having an alkyl group having a carbon number of C4 to C10 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 (E) trifunctional or higher isocyanate compound is an isocyanurate or isophorone selected from a hexamethylene diisocyanate compound. An isocyanurate body of a diisocyanate compound, an adduct body of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret body of a hexamethylene diisocyanate compound, and a different Buddha At least one or more of the group consisting of biuret bodies of the ketone diisocyanate compound; and 0.5 to 5.0 parts by weight of the above (E) trifunctional or higher isocyanate compound per 100 parts by weight of the copolymer . The adhesive composition of claim 1 or 2, wherein the cation of the (H) antistatic agent is selected from the group consisting of pyridinium cations, imidazolium cations, pyrimidine cations, pyrazolium cations, pyrrole cations One of the group consisting of ammonium cation, phosphonium cation, and sulfonium cation; the above anion is selected from the group consisting of hexafluorophosphate (PF ₆ ^- ), thiocyanate (SCN ^- ), alkyl benzene sulfonate (RC ₆ H ₄ SO ₃ ^- ), a group of perchlorate (ClO ₄ ^- ), and tetrafluoroborate (BF ₄ ^- ). The adhesive composition according to claim 1 or 2, wherein 0.01 to 0.5 part by weight of the polyether modified by the above (I) HLB value of 7 to 12 is contained with respect to 100 parts by weight of the above copolymer. A siloxane compound. The adhesive composition according to claim 1 or 2, wherein the (F) crosslinking inhibitor is a ketoenol tautomerizing compound, and contains 1.0 to 5.0 parts by weight based on 100 parts by weight of the copolymer. The above (F) crosslinking inhibitor; the (G) crosslinking catalyst is an organotin compound, and 0.01 to 0.5 part by weight of the above (G) crosslinking catalyst is contained per 100 parts by weight of the copolymer. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has an adhesive force at a low-speed peeling speed of 0.3 m/min of 0.05 to 0.1 N/25 mm. The adhesive force at a high-speed peeling speed of 30 m/min is 1.0 N/25 mm or less. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has a surface resistivity of 5.0 × 10 ^{+ 10} Ω / □ or less, and the peeling strip voltage is ±0~0.3kV. An adhesive film comprising an adhesive layer formed by crosslinking an adhesive composition according to any one of claims 1 to 10 on one or both sides of a resin film. A surface protective film in which an adhesive layer obtained by crosslinking an adhesive composition according to any one of claims 1 to 10 is formed on one surface of a resin film.