KR20130113372A - Adhesive composition and surface-protective adhesive film - Google Patents

Abstract

PURPOSE: An adhesive composition has excellent antistatic performance, has excellent adhesion balance at low peeling rate and high peering rate, and has excellent durability and reworkability. CONSTITUTION: An adhesive composition comprises C4-10 (meth)acrylic acid ester monomer; a hydroxyl group-containing copolymerizable monomer; a carboxyl-containing copolymerizable monomer; a polyalkylene glycolmono(meth)acrylic acid ester monomer; and an acrylic polymer which is a copolymer including a nitrogen-containing vinyl monomer and/or alkoxy group-containing alkyl(meth)acrylate monomer; and additionally contains a trifunctional isocyanate compound, a crosslinking retarder, a crosslinking catalyst, an antistatic agent, and a polyester-modified siloxane compound.

Description

Adhesive composition and surface protection film {ADHESIVE COMPOSITION AND SURFACE-PROTECTIVE ADHESIVE FILM}

This invention relates to the surface protection film used for a liquid crystal display manufacturing process. In more detail, the adhesive composition for surface protection films which stick to the surface of optical members, such as a polarizing plate and retardation plate which comprise a liquid crystal display, and protects the surface of optical members, such as a polarizing plate and a retardation plate, and uses it It relates to a surface protective film.

Conventionally, in the process of manufacturing optical members, such as a polarizing plate and retardation plate which are members which comprise a liquid crystal display, a surface protection film is temporarily stuck on the surface of an optical member. At the time of mounting the optical member on the liquid crystal display, the surface protective film is peeled off and removed from the optical member. Since the surface protection film for protecting the surface of an optical member is used only for a manufacturing process, it may be called a process film.

As for the surface protection film used at the process of manufacturing an optical member, the adhesive layer is formed in one surface of the polyethylene terephthalate (PET) resin film which has optical transparency. Moreover, the peeling process with the peeling process for protecting the adhesive layer is bonded together on an adhesive layer until it bonds to an optical member.

In addition, the optical member, such as a polarizing plate and a retardation plate, is a product test | inspection accompanying optical evaluation, such as the display capability of a liquid crystal display plate, a hue, contrast, and a foreign material mixing, in the state which bonded the surface protection film. Therefore, the performance required for a surface protection film is that a bubble and a foreign material do not adhere to an adhesive layer.

Moreover, in recent years, the excellent antistatic performance which prevents generation | occurrence | production of static electricity when peeling a surface protection film from optical members, such as a polarizing plate and a retardation plate, is needed. This is because charging at the time of peeling caused by static electricity generated when the adherend peels off the pressure-sensitive adhesive layer may cause the electric control circuit of the liquid crystal display to fail.

In addition, when bonding a surface protection film to optical members, such as a polarizing plate and a retardation plate, for a variety of reasons, a surface protection film may be peeled off once and a surface protection film may be stuck again. At that time, the surface protection film which has easy to peel (having rework property) from the optical member of a to-be-adhered body is calculated | required.

Moreover, when peeling a surface protection film from optical members, such as a polarizing plate and a phase difference plate, what can be peeled quickly is calculated | required. So-called peeling at a high speed also requires that the effect of the peeling speed of the adhesive force is small so that the peeling can be performed quickly.

Thus, in recent years, the performance of following (1)-(4) is required as a required performance with respect to the adhesive layer which comprises a surface protection film.

(1) Balance of adhesive force in peeling at low speed and peeling at high speed.

(2) It can prevent generation of adhesive residue.

(3) Having excellent antistatic performance.

(4) Having rework performance.

However, although each of these (1)-(4) can satisfy | fill individual required performance, it is very difficult to simultaneously provide the required performance of all (1)-(4) required for the adhesive layer of a surface protection film. Do.

For example, the following proposals are known about the balance of adhesive force in (1) peeling at low speed and peeling at high speed, and (2) being able to prevent generation | occurrence | production of an adhesive residue.

In an acrylic pressure sensitive adhesive comprising 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 with a crosslinking agent, the adhesive is avoided when a long time passes after bonding. There existed a problem which adhered to the side surface of a complex, and also the adhesive force with respect to a to-be-adhered body rises with time. In order to prevent this problem, the adhesive (pressure sensitive adhesive) which crosslinked this with the crosslinking agent using the copolymer of the (meth) acrylic-acid alkylester which has a C8-C10 alkyl group, and an alcoholic hydroxyl group is known, and it is known. (Patent Document 1).

Moreover, the adhesive etc. which mix | blended a small amount of the copolymer of a (meth) acrylic-acid alkylester and a carboxyl group-containing copolymerizable compound with the same copolymer as above and crosslinked this with the crosslinking agent are proposed. However, when they are used for surface protection of a plastic plate or the like having a smooth surface due to low surface tension, problems such as lifting phenomenon such as lifting due to heating during processing or storage, or when peeling at high speed to peel manually There is a problem of poor re-peelability.

In order to solve these problems, (a) 100 weight part of (meth) acrylic-acid alkylester which has the (meth) acrylic-acid alkylester which has a C8-C10 alkyl group as a main component, (b) carboxyl group-containing copolymerizable compound 1-15 The adhesive which mix | blended the crosslinking agent equivalent or more with respect to the carboxyl group of the said (b) component to the copolymer of the monomer mixture which consists of a weight part and (c) 3-100 weight part of vinyl esters of a C1-C5 aliphatic carboxylic acid. A composition is proposed (patent document 2).

In the pressure-sensitive adhesive composition described in Patent Literature 2, no peeling phenomenon such as lifting occurs during processing, storage, etc., and the adhesive force rises little over time, and is excellent in re-peelability, and long-term storage, especially under a high temperature atmosphere. Even if it is stored for a long time, it can be re-peeled with a small force, and it is said that it can be re-peeled with a small force even in peeling at high speed, without generating adhesive residue on a to-be-adhered body at that time.

Moreover, about (3) having excellent antistatic performance, the method of kneading an antistatic agent to a base film as a method for providing antistatic property to a surface protection film, etc. are disclosed. Examples of the antistatic agent include (a) various cationic antistatic agents having cationic groups such as quaternary ammonium salts, pyridinium salts and primary to tertiary amino groups, (b) sulfonic acid bases, sulfuric acid ester bases, phosphoric acid An anionic antistatic agent having an anionic group such as an ester base or a phosphonic acid base, (c) a positive antistatic agent such as amino acid or amino sulfate ester, (d) a nonionic antioxidant such as amino alcohol, glycerin or polyethylene glycol (E) a polymer-type antistatic agent obtained by polymerizing an antistatic agent as described above (Patent Document 3).

In recent years, it has been proposed to include such an antistatic agent in the base film or directly to the pressure-sensitive adhesive layer without applying it to the surface of the base film.

In addition, about (4) what has rework performance, the adhesive composition which mix | blended the hardening | curing agent of an isocyanate type compound and specific silicate oligomer with 0.0001-10 weight part with respect to 100 weight part of acrylic resin is proposed, for example in acrylic resin. (Patent document 4).

Patent Document 4 discloses a method for producing a polyester resin composition which comprises an acrylic acid alkyl ester having an alkyl group of about 2 to 12 carbon atoms or a methacrylic acid alkyl ester having an alkyl group of about 4 to 12 as a main monomer component, Containing functional monomer component and a functional group-containing monomer component. Generally, it is preferable to contain 50 weight% or more of the said main monomer, and content of a functional group containing monomer component is 0.001-50 weight%, Preferably it is 0.001-25 weight%, More preferably, it is 0.01-25 weight % Is said to be preferable. The pressure-sensitive adhesive composition described in Patent Document 4 is said to have reworkability because the change in cohesion and adhesive strength over time is small even under high temperature or high temperature and high humidity, and the adhesive force to a curved surface is also excellent.

Generally, if the pressure-sensitive adhesive layer has a soft property, the pressure-sensitive adhesive residue tends to be generated, and the workability tends to decrease. That is, when bonding by mistake, it is difficult to peel and it becomes difficult to reattach. For this reason, it is necessary to bridge | crosslink monomer which has functional groups, such as a carboxyl group, with a main body, and to make a pressure sensitive adhesive layer constant hardness, in order to make rework property.

Japanese Patent Application Laid-Open No. 63-225677 Japanese Laid-Open Patent Publication No. 11-256111 Japanese Laid-Open Patent Publication No. 11-070629 Japanese Unexamined Patent Publication No. 8-199130

In the prior art, as a required performance for the pressure-sensitive adhesive layer constituting the surface protective film, balancing the adhesive force in peeling at a low speed and peeling at a high speed, excellent antistatic performance, rework performance, and the like are required. Although each required performance could be satisfied, it could not satisfy all the required performances required for the adhesive layer of a surface protection film.

The present invention has been made in view of the above circumstances. The subject of this invention is providing the adhesive composition and surface protection film which have the outstanding antistatic performance, are excellent in the balance of adhesive force in peeling at low speed, and peeling at high speed, and also excellent in durability and rework performance. will be.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention copolymerizes the (A) alkyl group's C4-C10 (meth) acrylic acid ester monomer, the copolymerizable monomer containing (B) hydroxyl group, and (C) carboxyl group. A monomer comprising at least one of a possible monomer, (D) a polyalkylene glycol mono (meth) acrylic acid ester monomer, and (E) a nitrogen-containing vinyl monomer or an alkoxy group-containing alkyl (meth) acrylate monomer not containing a hydroxyl group. It consists of an acryl-type polymer which is a copolymer, and adds (F) trifunctional or more isocyanate compound, (G) crosslinking retarder, (H) crosslinking catalyst, (I) antistatic agent, and (J) polyether modified siloxane compound It contains in, and provides the adhesive composition whose acid value of the said acrylic polymer is 0.01-8.0.

The copolymerizable monomer containing the said (B) hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy At least one selected from the group consisting of ethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide, 0.1-5.0 weight part of copolymerizable monomers containing the said (B) hydroxyl group are contained with respect to 100 weight part of (meth) acrylic acid ester monomers whose C4-C10 carbon number of the said (A) alkyl group is further mentioned, (B) ) 0-0.9 weight in total of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate among the copolymerizable monomers containing a hydroxyl group. It is desirable to disclaim.

The copolymerizable monomer containing the said (C) carboxyl group is (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxy (Meth) whose carbon number of the said (A) alkyl group is C4-C10, at least 1 sort (s) chosen from the compound group which consists of polycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid. It is preferable that 0.35-1.0 weight part of copolymerizable monomers containing the said (C) carboxyl group are contained with respect to 100 weight part of acrylate ester monomers.

The said (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is a polyalkylene glycol mono (meth) acrylate, a methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acryl It is preferable that 1-20 weight part is contained with respect to 100 weight part of (meth) acrylic acid ester monomers which are at least 1 sort (s) chosen from a rate, and a C4-C10 carbon number of said (A) alkyl group is included.

The nitrogen-containing vinyl monomer or the alkoxy group-containing alkyl (meth) acrylate monomer not containing the hydroxyl group (E) is based on 100 parts by weight of the (meth) acrylic acid ester monomer having carbon atoms of the alkyl group (A) C4 to C10. It is preferable that 1-20 weight part is included.

Isocyanurate of the hexamethylene diisocyanate compound, the isocyanurate of an isophorone diisocyanate compound, the adduct of the hexamethylene diisocyanate compound, and the isophorone diisocyanate compound of the said (F) trifunctional or more isocyanate compound It is at least 1 sort (s) or more selected from the group of compounds which consists of an adduct, the biuret of a hexamethylene diisocyanate compound, and the biuret of an isophorone diisocyanate compound, and (F) trifunctional or more is contained with respect to 100 weight part of the said copolymer. It is preferable to contain 0.4-5.0 weight part of isocyanate compounds.

The antistatic agent (I) is an ionic compound having a melting point of 30 to 80 ° C that is contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the copolymer, or 0.1 to 5.0% by weight of the copolymerized in the copolymer. It is preferable that it is a quaternary ammonium salt type ionic compound containing acryloyl group.

The said (J) polyether modified siloxane compound is a polyether modified siloxane compound whose HLB value is 7-12, and 0.01-0.5 weight part of said (J) polyether modified siloxane compounds with respect to 100 weight part of the said copolymer. It is preferred to be included.

It is preferable that the said (G) crosslinking retardant is a keto-enol tautomer, and contains 1.0-5.0 weight part of said (G) crosslinking retardants with respect to 100 weight part of said copolymers.

It is preferable that the said (H) crosslinking catalyst is an organic tin compound, and 0.01-0.5 weight part of said (H) crosslinking catalysts are contained with respect to 100 weight part of the said copolymer.

It is preferable that the adhesive force in the low speed peeling speed 0.3m / min is 0.05-0.1 N / 25mm, and the adhesive force in the high speed peeling speed 30m / min is 1.0N / 25mm or less of the adhesive layer which crosslinks the said adhesive composition. .

It is preferable that the surface resistivity of the adhesive layer which crosslinks the said adhesive composition is 5.0x10 ⁺ 10 (ohm) / square or less, and peeling electrification voltage is +/- 0 to 0.3 kPa.

Moreover, this invention provides the adhesive film which formed the adhesive layer which bridge | crosslinked the said adhesive composition in one side or both sides of a resin film.

Moreover, this invention is a surface protection film which formed the adhesive layer which bridge | crosslinked the said adhesive composition on one side of a resin film, and transfers contamination to a to-be-adhered body after overwriting a surface protection film with a ballpoint pen via the said adhesive layer. It provides a surface protective film characterized in that the absence.

The said surface protection film can be used as a use of the surface protection film of a polarizing plate.

It is preferable that antistatic and antifouling treatment are given to the surface opposite to the side in which the said adhesive layer of the said resin film was formed.

According to this invention, all the performance calculated | required by the adhesive layer of a surface protection film which could not be solved by the prior art can be satisfied. In addition, excellent antistatic performance and excellent adhesive residue prevention performance can be obtained. Specifically, the addition amount of the antistatic agent can be reduced while maintaining excellent antistatic performance, and the performance of preventing generation of the adhesive residue can be further improved.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on preferable embodiment.

The adhesive composition of this invention is copolymerizable containing the (A) alkyl group (C) -C10 (meth) acrylic acid ester monomer which has C4-C10, the copolymerizable monomer containing (B) hydroxyl group, and (C) carboxyl group. Copolymer containing at least 1 sort (s) of a monomer, the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, and the (E) nitrogen-containing vinyl monomer which does not contain a hydroxyl group, or an alkoxy group containing alkyl (meth) acrylate monomer. It consists of a chain acrylic polymer, (F) trifunctional or more isocyanate compound, (G) crosslinking retarder, (H) crosslinking catalyst, (I) antistatic agent, and (J) polyether modified siloxane compound further And the acid value of the said acrylic polymer is 0.01-8.0.

(A) As a (meth) acrylic acid ester monomer whose C4-C10 carbon number of an alkyl group is butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) Acrylates and the like.

(B) As a copolymerizable monomer containing a hydroxyl group, 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy Hydroxyalkyl (meth) acrylates, such as ethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. Hydroxyl group-containing (meth) acrylamides; and the like.

(Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy ) Acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.

It is preferable that 0.1-5.0 weight part of copolymerizable monomers containing the said (B) hydroxyl group are contained with respect to 100 weight part of the (meth) acrylic acid ester monomers whose C4-C10 carbon number of (A) alkyl group is contained.

Moreover, the total amount of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate among the copolymerizable monomers containing (B) hydroxyl group is It is preferable that it is less than 1 weight part (it is also acceptable when it is not containing), and it is preferable that it is 0-0.9 weight part.

(C) The copolymerizable monomer containing a carboxyl group is (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( Meta) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypoly It is preferable that it is at least 1 sort (s) or more chosen from the compound group which consists of caprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.

(C) 0.35-1.0 weight part, More preferably, 0.35-0.6 weight part of copolymerizable monomers containing the (C) carboxyl group with respect to 100 weight part of (meth) acrylic acid ester monomers whose C4-C10 carbon number of an alkyl group is C4-C10. It is preferred to be included.

As a (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, the compound in which one hydroxyl group was esterified as (meth) acrylic acid ester among the several hydroxyl groups which polyalkylene glycol has may be sufficient. Since a (meth) acrylic acid ester group becomes a polymeric group, it can copolymerize to a main polymer. The other hydroxyl group may be the same as OH, or may be an alkyl ether such as methyl ether or ethyl ether, or a saturated carboxylic acid ester such as acetic acid ester.

Examples of the alkylene group of the polyalkylene glycol include an ethylene group, a propylene group, and a butylene group, 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 polybutylene glycol. Examples of the copolymer of polyalkylene glycol include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polybutylene glycol. The copolymer may be a block copolymer or a random copolymer.

As the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, polyalkylene glycol mono (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylic It is preferable that it is at least 1 sort (s) or more selected from the rates.

More specifically, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylic Elate, polyethyleneglycol polybutylene glycol mono (meth) acrylate, polypropylene glycol polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylic Rate; methoxy polyethylene glycol-(meth) acrylate, methoxy polypropylene glycol-(meth) acrylate, methoxy polybutylene glycol-(meth) acrylate, methoxy- polyethyleneglycol-polypropylene glycol-(meth Acrylate, methoxy- polyethyleneglycol polybutylene glycol- (meth) acrylate, methoxy- polypropylene glycol- polybutylene Recall-(meth) acrylate, methoxy- polyethyleneglycol-polypropylene glycol-polybutylene glycol-(meth) acrylate; ethoxy polyethylene glycol-(meth) acrylate, ethoxy polypropylene glycol-(meth) acryl Ethoxy Polybutylene Glycol- (meth) acrylate, Ethoxy-Polyethylene Glycol-Polypropylene Glycol- (Meta) acrylate, Ethoxy-Polyethylene Glycol-Polybutylene Glycol- (Meta) acrylate, Ethoxy -Polypropylene glycol- polybutylene glycol- (meth) acrylate, ethoxy-polyethylene glycol- polypropylene glycol- polybutylene glycol- (meth) acrylate, etc. are mentioned.

It is preferable that 1-20 weight part of (D) polyalkylene glycol mono (meth) acrylic acid ester monomers are contained with respect to 100 weight part of (A) C4-C10 (meth) acrylic acid ester monomers of an alkyl group.

(E), examples of the nitrogen-containing vinyl monomer include an amide bond-containing vinyl monomer, an amino group-containing vinyl monomer, and a nitrogen-containing heterocyclic structure-containing vinyl monomer. More specifically, there may be mentioned N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N- vinylpyridine, N-vinylpiperidone, N- vinylpyrimidine, Substituted complexes such as N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N- A cyclic nitrogen vinyl compound having a cyclic structure; N- (meth) acryloyl morpholine, N- (meth) acryloylpiperazine, N- (meth) acryloyl aziridine, N- (meth) acryloylazetidine, N- (meth) acrylic Complex of N- (meth) acryloyl substitution, such as loyl pyrrolidine, N- (meth) acryloyl piperidine, N- (meth) acryloyl azepane, and N- (meth) acryloyl azocan Cyclic nitrogen vinyl compounds having a cyclic structure; Cyclic nitrogen vinyl compounds having a heterocyclic structure having nitrogen atoms and ethylenically unsaturated bonds such as N-cyclohexylmaleimide and N-phenylmaleimide in the ring; Unsubstituted or monoalkyl substituted (meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-t-butyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropylacrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di Dialkyl, such as butyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-methyl-N-propyl (meth) acrylamide, and N-methyl-N-isopropyl (meth) acrylamide Substituted (meth) acrylamides; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, (Meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminomethyl (Meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (Meth) acrylate, t-butylaminoethyl (meth) acrylate and the like; N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N-diisopropylaminopropyl (Meth) acrylamide, N-methyl-N-isopropylaminopropyl (meth) acrylamide, N-methyl- N, N-dialkyl-substituted aminopropyl (meth) acrylamides such as amides; N-vinylcarboxylic acid amides such as N-vinyl formamide, N-vinylacetamide and N-vinyl-N-methylacetamide; N-methoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, N, N-methylenebis (meth) acrylamide, etc. (Meth) acrylamides of; Unsaturated carboxylic acid nitriles such as (meth) acrylonitrile; And the like.

The nitrogen-containing vinyl monomer (E-1) preferably contains no hydroxyl group, and more preferably contains no hydroxyl group and carboxyl group. As such a monomer, the monomer illustrated above, for example, an acryl-type monomer containing a N, N-dialkyl substituted amino group or an N, N-dialkyl substituted amide group; N-vinyl substituted lactams, such as N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and N-vinyl-2- piperidone; N- (meth) acryloyl-substituted cyclic amines such as N- (meth) acryloylmorpholine and N- (meth) acryloylpyrrolidine are preferred.

(Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate and the like can be given as examples of the alkyl (meth) (Meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (Meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-isopropoxypropyl (meth) acrylate, 2-butoxypropyl Propyl (meth) acrylate, 3-butoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, Acrylate, 4-ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxybutyl And the like methacrylate, 4-butoxy-butyl (meth) acrylate.

These alkoxy group-containing alkyl (meth) acrylate monomers have a structure in which the atom of the alkyl group in the alkyl (meth) acrylate is substituted with an alkoxy group.

(E-1) Nitrogen-containing vinyl monomer or (E-2) alkoxy group-containing alkyl (meth) acrylate monomer that does not contain a hydroxyl group is a (meth) acrylic acid ester monomer having (C) to C10 It is preferable to contain 1-20 weight part with respect to 100 weight part. The nitrogen-containing vinyl monomer which does not contain the (E-1) hydroxyl group, and the (E-2) alkoxy group containing alkyl (meth) acrylate monomer can also use together 1 type (s) or 2 or more types, respectively.

(F) The trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and may be hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, Trivalent or more polyols (at least three or more in one molecule), such as biuret-modified or isocyanurate-modified, trimethylolpropane or glycerin such as diisocyanates (compounds having two NCO groups in one molecule) such as xylylene diisocyanate An adduct (polyol modified body) with the compound which has an OH group, etc. are mentioned.

(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 isocyanurate of hexamethylene diisocyanate compound and isocyanurate of isophorone diisocyanate compound It is preferable that it is at least 1 sort (s) or more selected from the group which consists of a body, the adduct of a hexamethylene diisocyanate compound, the adduct of an isophorone diisocyanate compound, the burette body of a hexamethylene diisocyanate compound, and the burette body of an isophorone diisocyanate compound. Do. (F) It is preferable that 0.4-5.0 weight part of trifunctional or more than trifunctional isocyanate compounds are contained with respect to 100 weight part of copolymers.

(G) As the crosslinking retarder, β-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoate, oleyl acetoacetate, lauryl acetoacetate and stearyl acetoate, acetyl acetone, 2,4- Dione, and benzoyl acetone. These are keto-enol tautomers, and in the adhesive composition which uses a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group which a crosslinking agent has, the excess viscosity rise and gelation of the adhesive composition after mix | blending of a crosslinking agent are suppressed, and an adhesive composition is carried out. You can extend your port life.

The crosslinking retardant (G) is preferably a keto-enol tautomer, and particularly preferably at least one or more selected from the group of compounds consisting of acetylacetone and ethyl acetoacetate.

(G) It is preferable to contain 1.0-5.0 weight part with respect to 100 weight part of copolymers.

(H) crosslinking catalyst may be any substance that functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent in the case where the polyisocyanate compound is used as the crosslinking agent, and may be an amine compound such as a tertiary amine, , An organic lead compound, an organic zinc compound, and the like.

Examples of tertiary amines include trialkylamines, N, N, N ', N'-tetraalkyldiamines, N, N-dialkylaminoalcohols, triethylenediamine, morpholine derivatives and piperazine derivatives .

Examples of the organic tin compound include dialkyl tin oxide, fatty acid salts of dialkyl tin, fatty acid salts of stannous, and the like.

(H) The crosslinking catalyst is preferably an organic tin compound, and particularly preferably at least one or more selected from the group of compounds consisting of dioctyl tin oxide and dioctyl tin dilaurate.

(H) It is preferable to contain 0.01-0.5 weight part of crosslinking catalysts with respect to 100 weight part of copolymers.

The antistatic agent (I) is preferably an ionic compound having a melting point of 30 to 80 ° C (I-1) or a quaternary ammonium salt type ionic compound containing (I-2) acryloyl group.

In the present invention, (I) an ionic compound having a melting point of 30 to 80 ° C as an antistatic agent is added to the copolymer, or (I-2) a quaternary ammonium salt type ionic compound containing acryloyl group. Is copolymerized in the copolymer. Since these (I) antistatic agents have a low melting | fusing point and also have a long chain alkyl group, it is estimated that affinity with an acrylic copolymer is high.

(I-1) As an ionic compound having a melting point of 30 to 80 ° C., an ionic compound having a cation and an anion, the cation is pyridinium cation, imidazolium cation, pyrimidinium cation, pyrazollium cation one, pyrrolidinyl ninyum cation, ammonium cation also including on a nitrogen onium cation or a phosphonium cation, sulfonium cation or the like on the anion is hexafluorophosphate phosphate (PF ₆ ^-), thiocyanate (SCN ^-) , alkyl benzene sulfonate ^{_{(RC 6 H 4 SO 3 -}} ) may be an inorganic anion or an organic phosphorus compound, such as, perchlorate (ClO ₄ ^{- -),} ₄ fluoride borate (BF _4). It is preferable that it is solid at normal temperature (for example, 30 degreeC), and it can obtain that melting | fusing point is 30-80 degreeC according to selection of the chain length of an alkyl group, the position, the number of substituents, etc. The cation is preferably a quaternary ammonium onium cation, a quaternary pyridinium cation or a quaternary pyridinium cation such as 1-alkyl pyridinium (the carbon atom at 2-6 may have a substituent or may be unsubstituted) Quaternary imidazolium cation such as 3-dialkyl imidazolium (the carbon atom at the 2, 4 and 5 positions may have a substituent or may be unsubstituted), quaternary ammonium cation such as tetraalkylammonium, etc. .

(I-1) It is preferable that the ionic compound whose melting | fusing point is 30-80 degreeC is contained 0.1-5.0 weight part with respect to 100 weight part of copolymers.

The quaternary ammonium salt type ionic compound containing (I-2) acryloyl group is an ionic compound having a cation and an anion, the cation being (meth) acryloyloxyalkyltrialkylammonium [R ₃ N ⁺ -C _n H _2n —OCOCQ = CH ₂ , provided that (meth) acryloyl group-containing quaternary ammonium such as Q = H or CH ₃ , R = alkyl], and the anion is hexafluorophosphate (PF ₆ ⁻ ) or thiocyanate (SCN ^-), organic acid salts (RSO ₃ ^-), perchlorate (ClO ₄ ^-), ₄ fluoride borate (BF ₄ ^-), F-containing already deuyeom (R ^F ₂ N ^-) inorganic or organic anion compounds such as Can be mentioned. F-containing already deuyeom (R ^F ₂ N ^-) roneun of R ^F, can be given as a trifluoromethanesulfonyl group, a pentafluorophenyl perfluoroalkyl ethane sulfonyl group, such as an alkane sulfonyl group or a fluoroalkyl sulfonyl group. F contained in an already deuyeom include bis (sulfonyl fluorophenyl) already deuyeom [(FSO _{2) 2} N ^-], bis (trifluoromethane sulfonyl) already deuyeom _{[(CF 3 SO 2) 2 N} - ], bis (Pentafluoroethanesulfonyl) imide salt [(C ₂ F ₅ SO ₂ ) ₂ N ^- ], and the like.

(I-2) It is preferable that the quaternary ammonium salt type ionic compound containing acryloyl group is copolymerized 0.1 to 5.0 weight% in a copolymer.

Although it does not specifically limit as a specific example of (I) antistatic agent, (I-1) As a specific example of the ionic compound whose melting | fusing point is 30-80 degreeC, 1-octylpyridinium hexafluorophosphate and 1-nonyl Pyridinium hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecylpyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzene Sulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like. Further, (I-2) as a specific example of the quaternary ammonium salt type ion-crystalline compounds of the group comprising for example, acrylic is, dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt ^{_{[(CH 3) 3 N + CH}} 2 OCOCQ = CH ₂ · PF ₆ ⁻ , provided that Q = H or CH ₃ ], and dimethylaminoethyl (meth) acrylate bis (trifluoromethanesulfonyl) imidemethyl salt [(CH ₃ ) ₃ N ⁺ (CH ₂ ) ₂ OCOCQ = CH ₂ · (CF ₃ SO ₂ ) ₂ N ⁻ , provided that Q = H or CH ₃ ], dimethylaminomethylmethacrylate bis (fluorosulfonyl) imidemethyl salt [(CH ₃ ) ₃ N ⁺ CH ₂ OCOCQ = CH ₂ · (FSO ₂ ) ₂ N ⁻ , provided that Q = H or CH ₃ ].

(J) The polyether modified siloxane compound is a siloxane compound having a polyether group, and in addition to the usual siloxane unit [-SiR ¹ ₂ -O-], a siloxane unit having a polyether group [-SiR ¹ (R ² O (R ³⁾ O) _n R ⁴ ) -O-]. (Wherein R ¹ represents one or two or more kinds of 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 acyl groups . Examples of the polyether group include polyoxyalkylene groups such as a polyoxyethylene group [(C ₂ H ₄ O) _n ] and a polyoxypropylene group [(C ₃ H ₆ O) _n ].

(J) It is preferable that a polyether modified siloxane compound is a polyether modified siloxane compound whose HLB value is 7-12. Moreover, it is preferable that 0.01-0.5 weight part of (J) polyether modified siloxane compounds are contained with respect to 100 weight part of copolymers. More preferably, it is 0.1 to 0.5 parts by weight.

HLB is a hydrophilic lipophilic balance (hydrophilic lipophilic ratio) defined by, for example, JIS K3211 (surfactant term).

The polyether-modified siloxane compound can be obtained, for example, by grafting an organic compound having an unsaturated bond and a polyoxyalkylene group to a polyorganosiloxane main chain having a hydrogenated silicon group by a hydrosilylation reaction. Specific examples thereof include dimethylsiloxane · methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane · methyl (polyoxyethylene) siloxane · methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane · methyl (polyoxypropylene) .

(J) By mix | blending a polyether modified siloxane compound with an adhesive composition, the adhesive force and rework performance of an adhesive can be improved.

(Meth) acrylate monomer, a (meth) acrylamide monomer, a dialkyl substituted acrylamide monomer, a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid , An antioxidant, and an antioxidant may be appropriately added. They may be used alone or in combination of two or more.

(A) a (meth) acrylic acid ester monomer having an alkyl group of C4 to C10, (B) a copolymerizable monomer containing a hydroxyl group, (C) a carboxyl group , And (D) a polyalkylene glycol mono (meth) acrylic acid ester monomer. The polymerization method of the copolymer is not particularly limited, and suitable polymerization methods such as solution polymerization and emulsion polymerization can be used.

When the quaternary ammonium salt type ionic compound (I-2) containing an acryloyl group is used as the antistatic agent (I), the copolymer of the subject used in the pressure-sensitive adhesive composition of the present invention preferably has (A) (B) a copolymerizable monomer containing a hydroxyl group, (C) a copolymerizable monomer containing a carboxyl group, (D) a polyalkylene glycol mono (meth) acrylate monomer, and , And (I-2) an acryloyl group-containing quaternary ammonium salt type ionic compound.

The pressure-sensitive adhesive composition of the present invention further comprises (F) a trifunctional or higher isocyanate compound, (G) crosslinking retardant, (H) crosslinking catalyst, (I) antistatic agent, (J) polyether modified siloxane compound, It can prepare by mix | blending arbitrary arbitrary additives. In addition, when the (I-2) acryloyl group-containing quaternary ammonium salt type ionic compound is polymerized in the main copolymer, (I) an antistatic agent may be further added or not added to the copolymer.

The copolymer is preferably an acrylic polymer, and it is preferable that the copolymer contains 50 to 100% by weight of an acrylic monomer such as (meth) acrylic acid ester monomer, (meth) acrylic acid or (meth) acrylamide.

The acid value of the acrylic polymer is preferably 0.01 to 8.0. This makes it possible to improve stain resistance and improve the ability to prevent the occurrence of adhesive residue.

Here, " acid value " is one of indices showing the content of acid, and is expressed in mg of potassium hydroxide necessary for neutralizing 1 g of a carboxyl group-containing polymer.

It is preferable that the adhesive force in the low speed peeling speed 0.3m / min is 0.05-0.1 N / 25mm, and the adhesive force in the high speed peeling speed 30m / min is 1.0N / 25mm or less of the adhesive layer which crosslinks the said adhesive composition. . Thereby, performance with little change also in adhesive force by peeling speed can be obtained, and it becomes possible to peel quickly also by high speed peeling. Further, even when the surface protective film is once peeled off for reattaching, an excessive force is not required and it is easy to peel off from the adherend.

It is preferable that the surface resistivity of the adhesive layer which crosslinks the said adhesive composition is 5.0x10 ⁺ 10 (ohm) / square or less, and peeling electrification voltage is +/- 0 to 0.3 kPa. In the present invention, "± 0 to 0.3 kV" means 0 to -0.3 kPa and 0 to +0.3 kPa, that is, -0.3 to +0.3 kPa. If the surface resistivity is large, the ability to escape static electricity generated by charging at the time of peeling is inferior. Therefore, by sufficiently reducing the surface resistivity, the peeling electrification voltage generated with the static electricity generated when the adherend peels off the adhesive layer is reduced. The influence on the electric control circuit of the adherend can be suppressed.

The gel fraction of the pressure-sensitive adhesive layer (pressure-sensitive adhesive after crosslinking) to be crosslinked with the pressure-sensitive adhesive composition of the present invention is preferably 95 to 100%. Thus, the gel fraction is high, the adhesive force does not become excessive in peeling at low speed, the elution of the unpolymerized monomer or oligomer from a copolymer is reduced, the rework property and durability in high temperature, high humidity are improved, and a to-be-adhered body is improved. Contamination can be suppressed.

The adhesive film of this invention forms the adhesive layer which bridge | crosslinked the adhesive composition of this invention on one side or both surfaces of a resin film. Moreover, the surface protection film of this invention is a surface protection film which provided the adhesive layer which bridge | crosslinked the adhesive composition of this invention in one side of a resin film. Since the adhesive composition of this invention mix | blends each component of said (A)-(J) in balance, it is equipped with the outstanding antistatic performance, and it is excellent in the adhesive force balance in peeling at low speed, and peeling at high speed. Moreover, durability and rework performance (thing which has not carried out contamination to a to-be-adhered body after overwriting a surface protection film with a ballpoint pen via an adhesive layer) also becomes excellent. Therefore, it can be preferably used as a surface protective film of a polarizing plate.

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

Antistatic treatment with an antifouling treatment with a silicon-based or fluorine-based releasing agent, a coating agent, fine silica particles, antistatic treatment by application or incorporation of an antistatic agent, etc. can be performed on the surface of the base film opposite to the side where the pressure-

A release process is performed to a peeling film with a silicone type, a fluorine-type release agent, etc. to the surface of the side joined with the adhesive face of an adhesive layer.

Example

Hereinafter, the present invention will be described in detail with reference to Examples.

≪ Preparation of acrylic copolymer >

[Example 1]

Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube to replace the air in the reactor with nitrogen gas. Thereafter, 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 5 parts by weight of N-vinylpyrrolidone were added to the reaction apparatus. And 60 weight part of solvents (ethyl acetate) were added together. Then, 0.1 weight part of azobisisobutyronitrile is dripped over 2 hours as a polymerization initiator, it is made to react at 65 degreeC for 6 hours, and the acrylic copolymer solution (1) used for Example 1 of 500,000 of weight average molecular weights is Got it. A part of acrylic copolymer was extract | collected and used for the measurement sample of the acid value mentioned later.

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

Example was carried out similarly to the acrylic copolymer solution (1) used for the said Example 1 except having carried out composition of a monomer similarly to description of (A)-(E) and (I-2) of Table 1, respectively. The acrylic copolymer solution used for 2-9 and Comparative Examples 1-9 was obtained.

≪ Preparation of pressure-sensitive adhesive composition and surface protective film &

[Example 1]

1.5 parts by weight of 1-octylpyridinium hexafluorophosphate, 0.2 part by weight of KF-351A (a polyether-modified siloxane compound of HLB = 12) with respect to the acrylic copolymer solution (1) of Example 1 prepared as described above, acetyl After adding 2.5 parts by weight of acetone and stirring, 1.5 parts by weight of coronate HX (isocyanurate of hexamethylene diisocyanate compound) and 0.02 part by weight of dioctyl tin dilaurate were added, followed by stirring and mixing. A composition was obtained. This pressure-sensitive adhesive composition was coated on a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin and dried at 90 캜 to remove the solvent to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 25 탆.

After that, the pressure-sensitive adhesive sheet was transferred to a surface opposite to the antistatic and antifouling surface of the antistatic and antifouling polyethylene terephthalate (PET) film on one surface thereof, and thus the "antistatic and antifouling PET film / The surface protection film of Example 1 which has a laminated constitution of "A pressure sensitive adhesive layer / peeling film (PET film coated with silicone resin)" was obtained.

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

The surface protection of Examples 2-9 and Comparative Examples 1-9 was carried out similarly to the surface protection film of Example 1 except having made the composition of an additive like the description of Tables (F)-(J) of Table 2, respectively. A film was obtained.

Table 1 and Table 2 divide | divided all the table | surface which shows the compounding ratio of each component into two, and both show the numerical value of the weight part which calculated | required the sum total of (A) group as 100 weight part in parentheses. In addition, the compound name of the symbol of each component used for Table 1 and Table 2 is shown in Table 3 and Table 4. Meanwhile, Coronate® HX and HL are trade names of Nippon Polyurethane Industries, Ltd., and Takenate D-140N is a trade name of Mitsui Chemicals, Inc., KF-351A, KF-352A, KF-353, and KF. -640 and X-22-6191 are trademarks of Shin-Etsu Chemical Co., Ltd.

In Table 1, the (I-1) melting | fusing point added after superposition | polymerization of the (I-2) acryloyl group containing quaternary ammonium salt type | mold ionic compound copolymerized in the copolymer among (I) antistatic agents is 30-80 degreeC It is described in the column different from a phosphorus ionic compound. In addition, although I-1-8 used for the comparative example 9 has melting | fusing point less than 30 degreeC (liquid at normal temperature), it described in the same column as (I-1) for convenience.

<Test Method and Evaluation>

After aging the surface protective films in Examples 1-9 and Comparative Examples 1-9 for 7 days in 23 degreeC and 50% RH atmosphere, peeling film (silicone resin-coated PET film) was peeled off and an adhesive layer was What was expressed was made into the measurement sample of a gel fraction and surface resistivity.

Moreover, after bonding the surface protection film which expressed this adhesive layer to the surface of the polarizing plate pasted on the liquid crystal cell via the adhesive layer, and leaving it for 1 day, it autoclave-processes 50 degreeC, 5 atmospheres for 20 minutes, and again at room temperature. What was left to stand for 12 hours was used as the measurement sample of adhesive force, peeling electrification voltage, and durability.

<Acid value>

The acid value of an acryl-type polymer dissolves a sample in a solvent (mixing diethyl ether and ethanol in volume ratio 2: 1), and uses the potentiometric automatic titration apparatus (Kyoto Electronics Co., Ltd., AT-610), and 0.1 the said potential difference Potentiometric titration was carried out with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol / L using a titration apparatus, and the amount of potassium hydroxide ethanol solution required to neutralize the sample was measured. From the following equation, the acid value was calculated.

Acid value = (B x f x 5.611) / S

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

f = 0.1 mol / l A factor of the potassium hydroxide ethanol solution

S = mass of solids in the sample (g)

<Gel fraction>

After the end of aging, the mass of the measurement sample before bonding to the polarizing plate is accurately measured, and after immersion in toluene for 24 hours, it is filtered through a 200 mesh wire mesh. Then, after drying a filtrate at 100 degreeC for 1 hour, the mass of a residue was measured correctly and the gel fraction of the adhesive layer (pressure-sensitive adhesive after crosslinking) was computed from the following formula | equation.

Gel fraction (%) = insoluble partial mass (g) / adhesive mass (g) x 100

<Adhesion>

The peeling rate (0.3 m / min) and the high speed peeling rate (30 m / min) of the measurement sample (what bonded the 25 mm width surface protection film on the surface of a polarizing plate) obtained above using the tensile tester in 180 degree direction The peeling strength measured by peeling) was measured as the adhesive force.

<Surface resistivity>

After aging, before bonding to a polarizing plate, the peeling film (silicone resin coat PET film) was peeled off and an adhesive layer was exposed, and an adhesive layer was used using the resistivity meter Hirestar UP-HT450 (made by Mitsubishi Chemical Analyte). The surface resistivity of was measured.

<Peeling Voltage>

The voltage (voltage) generated as a result of charging the polarizing plate was measured with a high-precision electrostatic sensor SK-035, SK-200 (manufactured by KYOSEN CO., LTD.) At 180 ° peeling at a tensile speed of 30 m / , And the maximum value of the measured value was taken as the peeling electrification voltage.

<Rework property>

After overwriting the surface protection film of the measurement sample obtained above with a ballpoint pen (load 500g, 3 round trips), the surface protection film was peeled off from the polarizing plate, the surface of the polarizing plate was observed, and it was confirmed whether there was no migration of a polarizing plate. The evaluation target criterion is "○" when there is no contamination migration on the polarizing plate, and "△" when at least part of the contamination is confirmed along the trace added with a ballpoint pen, and the contamination transfer is confirmed along the trace added with a ballpoint pen. Also evaluated the case where release of an adhesive was confirmed from "x".

<Durability>

The measurement sample thus obtained was allowed to stand in an atmosphere at 60 DEG C and 90% RH for 250 hours, taken out at room temperature, left for another 12 hours, and then measured for adhesion to confirm that there was no clear increase compared with the initial adhesion. Evaluation target criteria evaluated "(circle)" and the case where it exceeded 1.5 times as "(circle)" when the adhesive force after a test is 1.5 times or less of initial stage adhesive force.

Table 5 shows the results of the evaluation. In addition, the surface resistivity was described by the method of making "m * 10 ^{+ n} " into "mE + n" (but m is arbitrary real value and n is a positive integer).

The surface protection films of Examples 1-9 are 0.05-0.1 N / 25mm of adhesive force in the low speed peeling speed 0.3m / min, and the adhesive force of 1.0N / 25mm or less in the high speed peeling speed 30m / min, and surface The resistivity is 5.0 × 10 ⁺¹⁰ Ω / □ or less, the peeling electrification voltage is ± 0 to 0.3 kPa, and the adherend has no transfer of contamination after being overlaid with a ballpoint pen on the surface protective film via the pressure-sensitive adhesive layer. The durability at the time of standing for 250 hours in the atmosphere of% RH was also excellent. In addition, in these Examples, the peeling electrification voltage could be reduced to ± 0 to 0.2 kV.

That is, (1) low-speed peeling speed and high-speed peeling speed, balance of adhesive force, (2) prevention of adhesive residue generation, (3) excellent antistatic performance, and (4) all required performances of rework performance Is satisfying at the same time.

Is the surface protection film of the comparative example 1 not because it contains (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, and (E) nitrogen-containing vinyl monomer or an alkoxy group containing alkyl (meth) acrylate monomer? The adhesive force at the peeling speed of 0.3 m / min was low, the peeling electrification voltage was high, and the rework property was slightly inferior.

In the surface protection film of the comparative example 2, (B) hydroxyl group containing monomer is under, (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is under, (E) nitrogen-containing vinyl monomer or alkoxy group containing alkyl (meth) ) It does not contain an acrylate monomer, and it is because the (F) isocyanate compound is excessive and the (H) HLB value of the (J) polyether modified siloxane compound is too low, or the adhesive force at a low peeling speed of 0.3 m / min and a high peeling speed of 30 m / The adhesive force in min was too large, the peeling electrification voltage was high, the rework property and durability were inferior, and the gel fraction was low.

In the surface protection film of the comparative example 3, (B) hydroxyl-containing monomer is excessive, (C) acid-containing monomer is excessive, (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is excessive, and (E) nitrogen containing Whether the vinyl monomer or the alkoxy group-containing alkyl (meth) acrylate monomer is excessive, or the HLB value of the (J) polyether-modified siloxane compound is excessive or the acid value of the acrylic polymer is high and the adhesive force at a low peeling speed of 0.3 m / min And the adhesive force at the high-speed peeling speed of 30 m / min was too large, the surface resistivity was high, the peeling electrification voltage was high, and reworkability and durability were inferior.

In the surface protection film of the comparative example 4, (C) acid-containing monomer is too small, (D) does not contain the polyalkylene glycol mono (meth) acrylic acid ester monomer, (E) nitrogen-containing vinyl monomer or an alkoxy group containing alkyl It was because the (meth) acrylate monomer was too small, the adhesive force at the low speed peeling rate 0.3 m / min was low, the peeling electrification voltage was high, and rework property and durability were inferior.

In the surface protection film of the comparative example 5, (B) hydroxyl-containing monomer is excessive, (C) acid-containing monomer is excessive, (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is under, (E) nitrogen-containing It does not contain a vinyl monomer or an alkoxy group containing alkyl (meth) acrylate monomer, and it is because the (F) isocyanate compound is under or the acid value of an acryl-type polymer is high, and the adhesive force and high speed peeling speed in a low peeling speed of 0.3 m / min are high. The adhesive force at 30 m / min was too large, the peeling electrification voltage was high, the rework property and durability fell, and the gel fraction fell.

The surface protection film of the comparative example 6 was not able to apply coating because it did not mix | blend the (G) crosslinking retardant, or since pot life was too short and crosslinking advanced before application | coating.

The surface protection film of the comparative example 7 contains MA which has a C1 alkyl group in the (meth) acrylic acid ester monomer which has an (A) alkyl group, (B) the hydroxyl group containing monomer is excessive, (D) polyalkylene glycol mono ( It is because it does not contain a meta) acrylic acid ester monomer, (E) nitrogen-containing vinyl monomer, or an alkoxy group containing alkyl (meth) acrylate monomer, and does not mix | blend (H) crosslinking catalyst, Adhesive force and adhesive force in the high speed peeling speed of 30 m / min were too big, the surface resistivity was high, the peeling electrification voltage was high, and rework property and durability were inferior.

In the surface protection film of the comparative example 8, (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is excessive, does not contain the (E) nitrogen containing vinyl monomer or the alkoxy group containing alkyl (meth) acrylate monomer, (J) It is because the polyether modified siloxane compound is not mix | blended, the adhesive force at the low speed peeling speed of 0.3 m / min, and the adhesive force at the high speed peeling speed of 30 m / min are too big, the surface resistivity is high, the peeling charge voltage is high, Rework was a bit off.

In the surface protection film of the comparative example 9, it does not contain the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, (E) nitrogen-containing vinyl monomer, or the alkoxy group containing alkyl (meth) acrylate monomer, and (I) The melting point of the antistatic agent is less than 30 ° C. (liquid at room temperature), (J) whether the polyether-modified siloxane compound is excessive, the low adhesive force at a low peeling speed of 0.3 m / min, the peeling electrification voltage is high, and the rework The castle fell slightly, and the durability was poor.

Thus, in the surface protection films of Comparative Examples 1-9, (1) balancing the adhesive force in a low peeling speed and a high peeling speed, (2) prevention of generation | occurrence | production of an adhesive residue, and (3) excellent antistatic performance , And (4) all required performance of the rework performance could not be satisfied at the same time.

Claims (27)

(A) a C4-C10 (meth) acrylic acid ester monomer having an alkyl group, a copolymerizable monomer containing a hydroxyl group (B), a copolymerizable monomer containing a (C) carboxyl group, and (D) a polyalkylene glycol It consists of an acryl-type polymer which is a copolymer containing a mono (meth) acrylic acid ester monomer and at least 1 sort (s) of the (E) nitrogen-containing vinyl monomer or alkoxy-group containing alkyl (meth) acrylate monomer which does not contain a hydroxyl group, (F) The trifunctional or higher isocyanate compound, (G) crosslinking retardant, (H) crosslinking catalyst, (I) antistatic agent, and (J) polyether modified siloxane compound are further contained, and the acid value of the acrylic polymer is 0.01 Adhesive composition which is -8.0. The method of claim 1,
The copolymerizable monomer containing the said (B) hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy At least one selected from the group consisting of ethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide,
0.1-5.0 weight part of copolymerizable monomers containing the said (B) hydroxyl group are contained with respect to 100 weight part of (meth) acrylic acid ester monomers whose C4-C10 carbon number of the said (A) alkyl group is further mentioned, (B) ) 0-0.9 weight in total of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate among the copolymerizable monomers containing a hydroxyl group. Mrs. pressure-sensitive adhesive composition. 3. The method according to claim 1 or 2,
The copolymerizable monomer containing the said (C) carboxyl group is (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxy At least one or more selected from the group consisting of polycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid,
The adhesive composition containing 0.35-1.0 weight part of copolymerizable monomers containing the said (C) carboxyl group with respect to 100 weight part of C4-C10 (meth) acrylic acid ester monomers of the said (A) alkyl group. 3. The method according to claim 1 or 2,
The said (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is a polyalkylene glycol mono (meth) acrylate, a methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acryl It is at least 1 sort (s) chosen from the rate, and the adhesive composition which contains 1-20 weight part with respect to 100 weight part of (meth) acrylic acid ester monomers whose C4-C10 carbon number of the said (A) alkyl group is contained. 3. The method according to claim 1 or 2,
The nitrogen-containing vinyl monomer or the alkoxy group-containing alkyl (meth) acrylate monomer not containing the hydroxyl group (E) is based on 100 parts by weight of the (meth) acrylic acid ester monomer having carbon atoms of the alkyl group (A) C4 to C10. Pressure-sensitive adhesive composition containing 1 to 20 parts by weight. 3. The method according to claim 1 or 2,
The (F) trifunctional or higher isocyanate compound is an isocyanurate of a hexamethylene diisocyanate compound, an isocyanurate of an isophorone diisocyanate compound, an adduct of an hexamethylene diisocyanate compound, an isophorone diisocyanate compound It is at least 1 sort (s) or more selected from the compound group which consists of an adduct, the biuret of a hexamethylene diisocyanate compound, and the biuret of an isophorone diisocyanate compound,
The adhesive composition containing 0.4-5.0 weight part of said (F) trifunctional or more isocyanate compounds with respect to 100 weight part of the said copolymers. 3. The method according to claim 1 or 2,
Wherein the antistatic agent (I) is an ionic compound having a melting point of 30 to 80 DEG C, which is contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the copolymer, or 0.1 to 5.0% Wherein the quaternary ammonium salt type ionic compound is an acryloyl group-containing quaternary ammonium salt type ionic compound. 3. The method according to claim 1 or 2,
Said (J) polyether modified siloxane compound is a polyether modified siloxane compound whose HLB value is 7-12,
The adhesive composition containing 0.01-0.5 weight part of said (J) polyether modified siloxane compounds with respect to 100 weight part of the said copolymers. 3. The method according to claim 1 or 2,
The crosslinking retardant (G) is a keto-enol tautomer,
The adhesive composition containing 1.0-5.0 weight part of said (G) crosslinking retardants with respect to 100 weight part of said copolymers. 3. The method according to claim 1 or 2,
The (H) crosslinking catalyst is an organic tin compound,
The adhesive composition containing 0.01-0.5 weight part of said (H) crosslinking catalysts with respect to 100 weight part of said copolymers. 3. The method according to claim 1 or 2,
The pressure-sensitive adhesive composition having a pressure-sensitive adhesive force at a low-speed peeling speed of 0.3 m / min of 0.05 to 0.1 N / 25 mm and a pressure-sensitive adhesive force at a high speed of peeling speed of 30 m / min of 1.0 N / 25 mm or less. 3. The method according to claim 1 or 2,
The adhesive composition whose surface resistivity of the adhesive layer which crosslinks the said adhesive composition is 5.0x10 ⁺ 10 (ohm) / square or less, and peeling electrification voltage is +/- 0 to 0.3 kPa. The adhesive film which formed the adhesive layer which bridge | crosslinked the adhesive composition of Claim 1 or 2 in one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 3 is formed on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 4 is formed on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 5 is formed on one side or both sides of a resin film. The adhesive film which formed the adhesive layer which bridge | crosslinked the adhesive composition of Claim 6 on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 7 is formed on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 8 is formed on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 9 is formed on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 10 is formed on one side or both sides of a resin film. A pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition of claim 11 is formed on one side or both sides of a resin film. The adhesive film which formed the adhesive layer which bridge | crosslinked the adhesive composition of Claim 12 on one side or both sides of a resin film. The surface protection film which formed the adhesive layer which bridge | crosslinked the adhesive composition of Claim 1 or 2 in one side of the resin film, and transfers the contamination to a to-be-adhered body after overwriting the surface protection film with a ballpoint pen via the said adhesive layer. Surface-protective film. 25. The method of claim 24,
The surface protection film used as a use of the surface protection film of a polarizing plate. 25. The method of claim 24,
The surface protection film which has been given antistatic and antifouling treatment on the surface opposite to the side in which the said adhesive layer of the said resin film was formed. The method of claim 25,
The surface protection film which has been given antistatic and antifouling treatment on the surface opposite to the side in which the said adhesive layer of the said resin film was formed.