CN105440988B - Adhesive composition and surface protective film - Google Patents

Adhesive composition and surface protective film Download PDF

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Publication number
CN105440988B
CN105440988B CN201510429028.1A CN201510429028A CN105440988B CN 105440988 B CN105440988 B CN 105440988B CN 201510429028 A CN201510429028 A CN 201510429028A CN 105440988 B CN105440988 B CN 105440988B
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meth
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acrylate
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CN105440988A (en
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长仓毅
长谷川良
吉田弘幸
菱沼昌世
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Fujimori Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides an adhesive composition and a surface protective film which have excellent antistatic performance, excellent balance of adhesive force under low peeling speed and high peeling speed, long service life and excellent durability and reprocessing property. The adhesive composition contains 50-95 parts by weight of a (meth) acrylate monomer having an alkyl group and having a carbon number of C4-C18, 0.1-10 parts by weight of a monomer containing a hydroxyl group, 0.1-1.0 part by weight of a monomer containing a carboxyl group, 8-50 parts by weight of a polyalkylene glycol mono (meth) acrylate monomer, 0.1-20 parts by weight of a vinyl monomer containing nitrogen and not containing a hydroxyl group or an alkyl (meth) acrylate monomer containing an alkoxy group, and contains no silicone compound, a bifunctional or higher isocyanate compound, a crosslinking catalyst, a keto-enol tautomer compound, and an antistatic agent, relative to 100 parts by weight of an acrylic polymer.

Description

Adhesive composition and surface protective film
Technical Field
The present invention relates to a surface protective film used in a manufacturing process of a liquid crystal display. More specifically, the present invention relates to an adhesive composition for a surface protective film used for protecting the surface of an optical member such as a polarizing plate or a retardation plate constituting a liquid crystal display by adhering the composition to the surface of the optical member, and a surface protective film obtained by using the adhesive composition.
Background
Conventionally, in a process of manufacturing an optical member such as a polarizing plate or a retardation plate as a member constituting a liquid crystal display, a surface protective film for temporarily protecting a surface of the optical member is bonded. Such a surface protective film is used only in a process of manufacturing an optical member, and is peeled and removed from the optical member when the optical member is incorporated in a liquid crystal display. Such a surface protective film for protecting the surface of an optical member is used only in a manufacturing process, and is therefore generally referred to as a process film.
In the surface protective film used in the process of producing an optical member, a pressure-sensitive adhesive layer is formed on one surface of a polyethylene terephthalate (PET) resin film having optical transparency, and a release film subjected to a release treatment for protecting the pressure-sensitive adhesive layer is bonded to the pressure-sensitive adhesive layer before bonding to the optical member.
In addition, since optical components such as a polarizing plate and a retardation plate are subjected to product inspection in accordance with optical evaluation such as display capability, color tone, contrast, and contamination of foreign substances of a liquid crystal display panel in a state where a surface protective film is bonded, it is required that no air bubbles or foreign substances are adhered to an adhesive layer as performance required for the surface protective film.
In addition, in recent years, when a surface protective film is peeled from an optical member such as a polarizing plate or a retardation plate, there is a fear that peeling electrification generated by static electricity generated when an adherend is peeled from an adhesive layer affects a failure of an electric control circuit of a liquid crystal display, and excellent antistatic performance is required for the adhesive layer.
When a surface protective film is bonded to an optical member such as a polarizing plate or a retardation plate, the surface protective film is peeled off and then the surface protective film is bonded again for various reasons, and in this case, it is required to be easily peeled off from the optical member of an adherend (reworkability).
In addition, when the surface protective film is finally peeled from an optical member such as a polarizing plate or a retardation plate, it is required to be quickly peeled. As the adhesive strength is required to be less changed by a change in the peeling speed, as in the case of rapid peeling even by high-speed peeling.
Therefore, in recent years, as performance required for an adhesive layer constituting a surface protective film, from the viewpoint of ease of use when using the surface protective film, it is required to (1) maintain balance of adhesive force at a low peeling speed and a high peeling speed, (2) prevent generation of paste residue, (3) excellent antistatic performance, and (4) reworkability, and the like.
However, even if the required performances of the above-mentioned (1) to (4) for the required performances of the pressure-sensitive adhesive layer constituting the surface protective film are satisfied, it is a very difficult problem to satisfy all the required performances of (1) to (4) required for the pressure-sensitive adhesive layer of the surface protective film at the same time.
For example, the following proposals are known for (1) maintaining the balance of adhesive force at a low peeling speed and a high peeling speed, and (2) preventing the occurrence of paste residue.
In an acrylic pressure-sensitive adhesive layer comprising, as a main component, a copolymer of an alkyl (meth) acrylate having an alkyl group having 7 or less carbon atoms and a copolymerizable compound having a carboxyl group, which is crosslinked with a crosslinking agent, there is a problem that the pressure-sensitive adhesive migrates to the adherend side during long-term adhesion and the adhesive strength to the adherend increases greatly with time. In order to avoid this, a pressure-sensitive adhesive layer is known which is formed by using a copolymer of an alkyl (meth) acrylate having an alkyl group with 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group and crosslinking the copolymer with a crosslinking agent (patent document 1).
Further, there has been proposed a pressure-sensitive adhesive layer and the like, which is obtained by blending a copolymer containing a small amount of an alkyl (meth) acrylate and a carboxyl group-containing copolymerizable compound in the same copolymer as described above and crosslinking the resulting copolymer with a crosslinking agent. However, when these are used for surface protection of plastic sheets or the like having a smooth surface with a low surface tension, there are problems such as a peeling phenomenon of floating due to heating at the time of processing or storage and/or a poor removability at the time of peeling at a high speed in a manual operation area.
In order to solve these problems, a binder composition has been proposed, which is obtained by adding 100 parts by weight of an alkyl (meth) acrylate containing a) an alkyl (meth) acrylate having an alkyl group with 8 to 10 carbon atoms as a main component, b) 1 to 15 parts by weight of a copolymerizable compound having a carboxyl group and c) 3 to 100 parts by weight of a vinyl ester of an aliphatic carboxylic acid with 1 to 5 carbon atoms to prepare a copolymer of a monomer mixture, and adding an equivalent amount of a crosslinking agent to the carboxyl group of the component b) or more to the copolymer of the monomer mixture (patent document 2).
The pressure-sensitive adhesive composition described in patent document 2 does not cause a peeling phenomenon such as floating during processing, storage, or the like, and in addition, has a small increase in adhesive strength with time and excellent removability, and can be peeled off with a small force even after long-term storage, particularly even after long-term storage in a high-temperature atmosphere, and at this time, does not cause paste residue on an adherend, and can be peeled off again with a small force even when high-speed peeling is performed.
In addition, as a method for imparting an antistatic property to the surface protective film with respect to the excellent antistatic property of (3), a method of mixing an antistatic agent into a base film, and the like are disclosed. Examples of the antistatic agent include (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group, (b) anionic antistatic agents having an anionic group such as a sulfonate group, a sulfate group, a phosphate group, or a phosphonate group, (c) amphoteric antistatic agents such as amino acid-based and aminosulfate-based agents, (d) nonionic antistatic agents such as amino alcohol-based, glycerol-based, and polyethylene glycol-based agents, and (e) polymeric antistatic agents obtained by polymerizing the above-mentioned antistatic agents (patent document 3).
In recent years, it has been proposed to contain such an antistatic agent in a base film or to directly contain such an antistatic agent in an adhesive layer without applying it to the surface of the base film.
In order to address the reworkability (4), for example, a pressure-sensitive adhesive composition has been proposed in which an isocyanate-based compound curing agent and a specific silicate oligomer are blended in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of an acrylic resin (patent document 4).
In patent document 4, an alkyl acrylate having an alkyl group with a carbon number of about 2 to 12, an alkyl methacrylate having an alkyl group with a carbon number of about 4 to 12, or the like is used as a main monomer component, and for example, a monomer component containing another functional group such as a carboxyl group-containing monomer may be included. In general, the main monomer is preferably contained in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is preferably 0.001 to 50% by weight, more preferably 0.001 to 25% by weight, and still more preferably 0.01 to 25% by weight. The pressure-sensitive adhesive composition described in patent document 4 has reworkability because it shows little change over time in cohesive force and adhesive force even at high temperature or high temperature and high humidity, and also shows excellent adhesive force to a curved surface.
In general, when the pressure-sensitive adhesive layer is made flexible, paste residue is likely to occur, and the reworkability is likely to be lowered. That is, peeling is difficult in the case of erroneous attachment, and reattachment is easy to be difficult. Therefore, it is considered that crosslinking a monomer having a functional group such as a carboxyl group with a base compound to make the adhesive layer have a certain hardness is necessary for providing reworkability.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 63-225677
Patent document 2: japanese laid-open patent publication No. 11-256111
Patent document 3: japanese laid-open patent publication No. 11-070629
Patent document 4: japanese laid-open patent publication No. 8-199130
Disclosure of Invention
Technical problem
In the prior art, as required performance of an adhesive layer constituting a surface protective film, excellent antistatic performance, reworkability and the like are required by maintaining a balance of adhesive force at a low peeling speed and a high peeling speed, but even if the required performance can be satisfied individually, all the required performance required for the adhesive layer of the surface protective film cannot be satisfied.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition and a surface protective film which have excellent antistatic properties, are excellent in the balance of adhesive force at a low peeling speed and a high peeling speed, have a long pot life, and are excellent in durability and reworkability.
Technical scheme
In order to solve the above problems, the present invention provides an adhesive composition comprising an acrylic polymer comprising a copolymer of a copolymerizable monomer containing 50 to 95 parts by weight of (a) a (meth) acrylate monomer having an alkyl group and having a carbon number of C4 to C18, 0.1 to 10 parts by weight of (B) a copolymerizable monomer containing a hydroxyl group, 0.1 to 1.0 part by weight of (C) a copolymerizable monomer containing a carboxyl group, 8 to 50 parts by weight of (D) a polyalkylene glycol mono (meth) acrylate monomer, 0.1 to 20 parts by weight of (E) at least one of a nitrogen-containing vinyl monomer not containing a hydroxyl group or an alkyl (meth) acrylate monomer containing an alkoxy group, based on 100 parts by weight of the acrylic polymer, and further comprising a silicone compound, contains (F) an isocyanate compound having two or more functional groups, (G) a crosslinking catalyst, (H) a keto-enol tautomer compound, (I) an ionic compound having a melting point of 25 to 50 ℃ and/or an ionic compound having an acryloyl group as an antistatic agent.
Preferably, the acrylic polymer contains 0.1 to 10 parts by weight of the difunctional or higher isocyanate compound (F), 0.001 to 0.5 part by weight of the crosslinking catalyst (G), and 0.1 to 300 parts by weight of the keto-enol tautomer compound (H) per 100 parts by weight of the acrylic polymer, the antistatic agent (I) is contained in the adhesive composition, and the total amount of the ionic compound with the melting point of 25-50 ℃ and the ionic compound containing acryloyl copolymerized in the copolymer is 0.01-5.0 parts by weight, the average number of repetitions of an alkylene oxide constituting a polyalkylene glycol chain of the polyalkylene glycol mono (meth) acrylate monomer (D) is 3 to 14, the diester moiety in the monomer is 0.3% or less, the water content is 0.1% or less, and the water solubility is 2% or less in a 20% aqueous solution state.
Preferably, the crosslinking catalyst (G) is a metal chelate crosslinking catalyst, and the weight ratio (H)/(G) of the crosslinking catalyst (G) to the keto-enol tautomer compound (H) is 70 to 1000.
The hydroxyl group-containing copolymerizable monomer (B) is preferably at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
The carboxyl group-containing copolymerizable monomer (C) is preferably at least one monomer selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
The polyalkylene glycol mono (meth) acrylate monomer (D) is preferably at least one monomer selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate, and ethoxypolyalkylene glycol (meth) acrylate.
The gel fraction of the adhesive composition after crosslinking is preferably 95 to 100%.
Preferably, among the above-mentioned (F) difunctional or higher isocyanate compounds, the difunctional isocyanate compound is a non-cyclic aliphatic isocyanate compound which is a compound produced by reacting a diisocyanate compound with a diol compound, the aliphatic diisocyanate compound is one selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, and the diol compound is one selected from the group consisting of 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol and 2-ethyl-2-butyl-1, one of 3-propanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol monohydroxypivalate, polyethylene glycol and polypropylene glycol, and the trifunctional isocyanate compound includes isocyanurate of hexamethylene diisocyanate compound, isocyanurate of isophorone diisocyanate compound, adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, biuret of hexamethylene diisocyanate compound, biuret of isophorone diisocyanate compound, isocyanurate of toluene diisocyanate compound, isocyanurate of xylylene diisocyanate compound, isocyanurate of hydrogenated xylylene diisocyanate compound, and the like, An adduct of a toluene diisocyanate compound, an adduct of a xylylene diisocyanate compound, and an adduct of a hydrogenated xylylene diisocyanate compound.
The adhesive layer obtained by crosslinking the adhesive composition preferably has an adhesive strength of 0.04 to 0.2N/25mm at a low peeling speed of 0.3m/min and an adhesive strength of 2.0N/25mm or less at a high peeling speed of 30 m/min.
The surface resistivity of the pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition is preferably 9.0X 10+11Omega/□ below, and the stripping charge voltage is + -0-0.5 kV.
The present invention also provides an adhesive film, wherein the adhesive layer is formed by crosslinking the adhesive composition on one surface or both surfaces of a resin film.
The present invention also provides a surface protective film, which is obtained by forming an adhesive layer obtained by crosslinking the adhesive composition on one surface of a resin film, wherein stains are not transferred to an adherend after the surface protective film is scraped with a ballpoint pen through the adhesive layer.
The surface protective film can be used for the purpose of a surface protective film for a polarizing plate.
Preferably, the antistatic and antifouling treatment is performed on the surface of the resin film opposite to the side on which the pressure-sensitive adhesive layer is formed.
Advantageous effects
According to the present invention, all the properties required for an adhesive layer of a surface protective film, which cannot be solved by the prior art, can be satisfied, and excellent antistatic properties and excellent prevention of the occurrence of paste residue can be obtained. Specifically, the antistatic property can be maintained, and the property of preventing the occurrence of paste residue can be further improved by reducing the amount of the antistatic agent to be added.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present invention comprises an acrylic polymer comprising a copolymer of a copolymerizable monomer, wherein the copolymerizable monomer comprises 50 to 95 parts by weight of (A) a (meth) acrylate monomer having an alkyl group and having a carbon number of C4 to C18, (B) a copolymerizable monomer having a hydroxyl group, 0.1 to 10 parts by weight of (C) a copolymerizable monomer having a carboxyl group, 8 to 50 parts by weight of (D) a polyalkylene glycol mono (meth) acrylate monomer, and 0.1 to 20 parts by weight of at least one of (E) a nitrogen-containing vinyl monomer having no hydroxyl group or an alkyl (meth) acrylate monomer having an alkoxy group, based on 100 parts by weight of the acrylic polymer, and the adhesive composition does not contain a silicone compound, and contains (F) a bifunctional or higher isocyanate compound, and (C) a polymer, (G) A crosslinking catalyst, (H) a keto-enol tautomer compound, (I) an ionic compound having a melting point of 25 to 50 ℃ and/or an ionic compound containing an acryloyl group as an antistatic agent.
Preferably, the acrylic polymer contains 0.1 to 10 parts by weight of the difunctional or higher isocyanate compound (F), 0.001 to 0.5 part by weight of the crosslinking catalyst (G) and 0.1 to 300 parts by weight of the keto-enol tautomer compound (H) per 100 parts by weight of the acrylic polymer, and further, the antistatic agent (I) is contained in the adhesive composition, the ionic compound with the melting point of 25-50 ℃ and the ionic compound containing acryloyl copolymerized in the copolymer are 0.01-5.0 parts by weight in total, the average number of repetitions of an alkylene oxide constituting a polyalkylene glycol chain of the polyalkylene glycol mono (meth) acrylate monomer (D) is 3 to 14, the diester moiety in the monomer is 0.3% or less, the water content is 0.1% or less, and the water solubility is 2% or less in a 20% aqueous solution state.
Examples of the (meth) acrylate monomer having an alkyl group of C4 to C18 include 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) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and mixtures thereof, Myristyl (meth) acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, isocetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and the like.
The copolymerizable monomer preferably contains (A) an alkyl (meth) acrylate monomer having C4-C18 in an amount of 50-95 parts by weight based on 100 parts by weight of the acrylic polymer.
Examples of the copolymerizable monomer having a hydroxyl group (B) include hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, and hydroxyl group-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
Preferably, the acrylic acid is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
The copolymerizable monomer preferably contains (B) a hydroxyl group-containing copolymerizable monomer in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.
The (C) carboxyl group-containing copolymerizable monomer is preferably at least one member selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalate.
The copolymerizable monomer preferably contains (C) a carboxyl group-containing copolymerizable monomer in an amount of 0.1 to 1.0 part by weight based on 100 parts by weight of the acrylic polymer.
The polyalkylene glycol mono (meth) acrylate monomer (D) may be any compound in which one of a plurality of hydroxyl groups of the polyalkylene glycol is esterified in the form of a (meth) acrylate. Since the (meth) acrylate group is a polymerizable group, it can be copolymerized with the main agent polymer. The other hydroxyl group may be OH, or an alkyl ether such as methyl ether or ethyl ether, or a saturated carboxylic acid ester such as acetic acid ester may be used.
Examples of the alkylene group of the polyalkylene glycol include, but are not limited to, an ethylene group, a propylene group, and a butylene group. The polyalkylene glycol may be a copolymer of two or more 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, polyethylene glycol-polypropylene glycol-polybutylene glycol, and the like, and the copolymer may be a block copolymer or a random copolymer.
The average number of repetitions of the alkylene oxide constituting the polyalkylene glycol chain of the polyalkylene glycol mono (meth) acrylate monomer (D) is preferably 3 to 14. The "average number of repetitions of alkylene oxide" means the average number of repetitions of alkylene oxide units in the portion of the "polyalkylene glycol chain" contained in the molecular structure of the (D) polyalkylene glycol mono (meth) acrylate monomer.
The polyalkylene glycol mono (meth) acrylate monomer (D) preferably has a diester moiety of 0.3% or less, a water content of 0.1% or less, and a water solubility of 2% or less in a 20% aqueous solution state.
The "diester moiety in the monomer" means the content (wt%) of the polyalkylene glycol di (meth) acrylate contained in the polyalkylene glycol mono (meth) acrylate monomer (D).
The "moisture content" means the content (wt%) of moisture contained in the polyalkylene glycol mono (meth) acrylate monomer (D).
"haze value in the state of 20% aqueous solution" means a haze value (%) of an aqueous solution in the state of making the (D) polyalkylene glycol mono (meth) acrylate monomer be a 20% by weight aqueous solution. In other words, the (D) polyalkylene glycol mono (meth) acrylate monomer not only has water solubility (solubility in water) to be a 20% aqueous solution, but also needs to have a low haze value (%) in a 20% aqueous solution (less white haze).
In the present specification, the turbidity value of a 20% aqueous solution is a value measured by a turbidity meter by adding the aqueous solution to a quartz cell having an optical path length of 10 mm. This index is introduced as the degree of hydrophilicity of the polyalkylene glycol mono (meth) acrylate monomer (D) in order to select a highly hydrophilic monomer which can give a solution free from cloudiness even at a high concentration.
The polyalkylene glycol mono (meth) acrylate monomer (D) is preferably at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate, and ethoxypolyalkylene glycol (meth) acrylate.
More specifically, there may be mentioned polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, polybutylene glycol-mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, polyethylene glycol-polybutylene glycol-mono (meth) acrylate, polypropylene glycol-polybutylene glycol-mono (meth) acrylate, polyethylene glycol-polypropylene glycol-polybutylene glycol-mono (meth) acrylate; methoxy polyethylene glycol- (meth) acrylate, methoxy polypropylene glycol- (meth) acrylate, methoxy polybutylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polybutylene glycol- (meth) acrylate, methoxy-polypropylene glycol-polybutylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol- (meth) acrylate; ethoxy polyethylene glycol- (meth) acrylate, ethoxy polypropylene glycol- (meth) acrylate, ethoxy polybutylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polybutylene glycol- (meth) acrylate, ethoxy-polypropylene glycol-polybutylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol- (meth) acrylate, and the like.
The copolymerizable monomer preferably contains (D) a polyalkylene glycol mono (meth) acrylate monomer in a proportion of 8 to 50 parts by weight based on 100 parts by weight of the acrylic polymer.
Examples of the nitrogen-containing vinyl monomer (E-1) in (E) include an amide bond-containing vinyl monomer, an amino group-containing vinyl monomer, a nitrogen-containing vinyl monomer having a heterocyclic structure, and the like. More specifically, there may be mentioned N-vinyl-substituted cyclic nitrogen vinyl compounds having a heterocyclic structure such as N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam and N-vinyldodecanoamide; n- (meth) acryloyl-substituted cyclic nitrogen vinyl compounds having a heterocyclic structure such as N- (meth) acryloyl morpholine, N- (meth) acryloyl piperazine, N- (meth) acryloyl aziridine, N- (meth) acryloyl azetidine, N- (meth) acryloyl pyrrolidine, N- (meth) acryloyl piperidine, N- (meth) acryloyl azepane, and N- (meth) acryloyl azocane; cyclic nitrogen vinyl compounds having a heterocyclic structure having a nitrogen atom and an ethylenically unsaturated bond in the ring, such as N-cyclohexylmaleimide and N-phenylmaleimide; unsubstituted or monoalkyl-substituted (meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-tert-butyl (meth) acrylamide; dialkyl-substituted (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropylacrylamide, N-diisopropyl (meth) acrylamide, N-dibutyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-methyl-N-propyl (meth) acrylamide, and N-methyl-N-isopropyl (meth) acrylamide; n, N-dimethylaminomethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, N-dimethylaminoisopropyl (meth) acrylate, N-dimethylaminobutyl (meth) acrylate, N-diethylaminomethyl (meth) acrylate, dialkylamino (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate, N-ethyl-N-methylaminoethyl (meth) acrylate, N-methyl-N-propylaminoethyl (meth) acrylate, N-methyl-N-isopropylaminoethyl (meth) acrylate, N-dibutylaminoethyl (meth) acrylate, and tert-butylaminoethyl (meth) acrylate; n, N-dialkyl-substituted aminopropyl (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide, N-dipropylaminopropyl (meth) acrylamide, N-diisopropylaminopropyl (meth) acrylamide, N-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, and N-methyl-N-isopropylaminopropyl (meth) acrylamide; n-vinylcarboxylic acid amides such as N-vinylformamide, N-vinylacetamide, and N-vinyl-N-methylacetamide; (meth) acrylamides such as N-methoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, and N, N-methylenebis (meth) acrylamide; unsaturated carboxylic acid nitriles such as (meth) acrylonitrile, and the like.
As the nitrogen-containing vinyl monomer (E-1), a monomer containing no hydroxyl group is preferable, and a monomer containing no hydroxyl group or carboxyl group is more preferable. As such monomers, the monomers exemplified above are preferable, for example, acrylic monomers containing an N, N-dialkyl-substituted amino group and/or an N, N-dialkyl-substituted amide group; n-vinyl-substituted lactams such as N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinyl-2-piperidone; n- (meth) acryloyl-substituted cyclic amines such as N- (meth) acryloyl morpholine and N- (meth) acryloyl pyrrolidine.
Examples of the alkoxy group-containing alkyl (meth) acrylate monomer (E-2) in (E) include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-isopropoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-isopropoxypropyl (meth) acrylate, 2-butoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 3-propoxypropyl (meth) acrylate, and the like, 3-isopropoxypropyl (meth) acrylate, 3-butoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxybutyl (meth) acrylate, 4-butoxybutyl (meth) acrylate, and the like.
These alkoxy group-containing (meth) acrylate monomers have a structure in which an atom of an alkyl group in an alkyl (meth) acrylate is substituted with an alkoxy group.
The copolymerizable monomer preferably contains at least one of (E) a nitrogen-containing vinyl monomer having no hydroxyl group or an alkyl (meth) acrylate monomer having an alkoxy group in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic polymer. It is also possible to use 1 or more of (E-1) a nitrogen-containing vinyl monomer having no hydroxyl group and (E-2) an alkyl (meth) acrylate monomer having an alkoxy group, respectively, in combination.
The (F) bifunctional or higher isocyanate compound may be at least 1 or two or more selected from polyisocyanate compounds having at least 2 or more isocyanate (NCO) groups in 1 molecule. The polyisocyanate compound may be any of aliphatic isocyanate, aromatic isocyanate, acyclic isocyanate, and alicyclic isocyanate.
Examples of the trifunctional or higher-functional isocyanate compound include a biuret modified product of a bifunctional isocyanate compound (a compound having 2 NCO groups in 1 molecule), an isocyanurate modified product, and an adduct (polyol modified product) of a polyhydric alcohol having a valence of 3 or more (a compound having at least 3 OH groups in 1 molecule) such as Trimethylolpropane (TMP) and glycerol. As the (F) difunctional or higher isocyanate compound, only a trifunctional isocyanate compound may be used, or only a difunctional isocyanate compound may be used. Further, a trifunctional isocyanate compound and a difunctional isocyanate compound may be used in combination.
The trifunctional isocyanate compound is preferably at least one member selected from the group consisting of an isocyanurate of a hexamethylene diisocyanate compound, an isocyanurate of an isophorone diisocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, a biuret of an isophorone diisocyanate compound, an isocyanurate of a toluene diisocyanate compound, an isocyanurate of a xylylene diisocyanate compound, an isocyanurate of a hydrogenated xylylene diisocyanate compound, an adduct of a tolylene diisocyanate compound, an adduct of a xylylene diisocyanate compound, and an adduct of a hydrogenated xylylene diisocyanate compound.
The difunctional isocyanate compound is preferably an acyclic aliphatic isocyanate compound produced by reacting a diisocyanate compound with a diol compound. For example, when a diisocyanate compound is represented by the general formula "O ═ C ═ N — N ═ C ═ O" (where X is a 2-valent group) and a diol compound is represented by the general formula "HO — Y — OH" (where Y is a 2-valent group), examples of compounds produced by reacting the diisocyanate compound with the diol compound include compounds represented by the following general formula Z.
[ general formula Z ]
O＝C＝N-X-(NH-CO-O-Y-O-CO-NH-X)n-N＝C＝O
Here, n is an integer of 0 or more. When N is 0, the general formula Z represents "O ═ C ═ N-X-N ═ C ═ O". The difunctional non-cyclic aliphatic isocyanate compound may contain a compound in which n is 0 (a diisocyanate compound which is not reacted with respect to the diol compound) in the general formula Z, and preferably contains a compound in which n is an integer of 1 or more as an essential component. The difunctional non-cyclic aliphatic isocyanate compound may be a mixture of a plurality of compounds having different n in the general formula Z.
The diisocyanate compound represented by the general formula "O ═ C ═ N — N ═ C ═ O" is an aliphatic diisocyanate. Preferably, X is a non-cyclic and aliphatic 2-valent group. The aliphatic diisocyanate preferably includes one or more selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.
The diol compound represented by the general formula "HO-Y-OH" is an aliphatic diol. Preferably, Y is a non-cyclic and aliphatic 2-valent group. The diol compound preferably includes one or more selected from the group consisting of 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol monohydroxypivalate, polyethylene glycol, and polypropylene glycol.
The acrylic polymer preferably contains (F) a difunctional or higher isocyanate compound in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.
The crosslinking catalyst (G) may be any one that functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent when a polyisocyanate compound is used as the crosslinking agent, and examples thereof include amine compounds such as tertiary amines, metal chelates, organic tin compounds, organic lead compounds, organic zinc compounds, and other organic metal compounds.
Examples of the tertiary amine include trialkylamines, N' -tetraalkyldiamines, N-dialkylaminols, triethylenediamine, morpholine derivatives, and piperazine derivatives.
The metal chelate compound is a compound in which 1 or more polydentate ligands L are bonded to a central metal atom M. The metal chelate compound may or may not have 1 or more monodentate ligands X bonded to the metal atom M. For example, in the use of M (L)m(X)nWhen the general formula of the metal chelate compound is such that the metal atom M is 1, M is not less than 1 and n is not less than 0. When M is 2 or more, M L may be the same ligand or different ligands. When n is 2 or more, n X's may be the same ligand or different ligands.
Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, and Sn.
Examples of the polydentate ligand L include β -ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate, β -diketones such as acetylacetone (also called 2, 4-pentanedione), 2, 4-hexanedione, and benzoylacetone. These are keto-enol tautomer compounds, and in the polydentate ligand L, may be enolates (e.g. acetylacetone) after deprotonation of the enolates.
Examples of the monodentate ligand X include a halogen atom such as a chlorine atom or a bromine atom, an acyloxy group such as a pentanoyl group, a hexanoyl group, a 2-ethylhexanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a dodecanoyl group, or a octadecanoyl group, and an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or a butoxy group.
Specific examples of the metal chelate compound include iron (III) tris (2, 4-pentanedionate), iron (III) triacetylacetonate, titanium (III) triacetylacetonate, ruthenium (III) triacetylacetonate, zinc (III) bisacetoacetonate, aluminum (III) triacetylacetonate, zirconium (IV) tetraacetonat, iron (III) tris (2, 4-hexanedionate), zinc (2, 4-hexanedionate), titanium (2, 4-hexanedionate), aluminum (2, 4-hexanedionate), zirconium (2, 4-hexanedionate), and the like.
Examples of the organotin compound include dialkyl tin oxide, fatty acid salt of dialkyl tin, fatty acid salt of monovalent tin, and the like.
(G) The crosslinking catalyst is preferably a metal chelate or an organotin compound. As the metal chelate compound, aluminum chelate, titanium chelate, iron chelate, tin chelate and the like are preferable. The organotin is preferably at least one member selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.
The crosslinking catalyst (G) is preferably contained in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the acrylic polymer.
Examples of the keto-enol tautomer compound (H) include β -keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate, and β -diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. (H) In the adhesive composition containing a polyisocyanate compound as a crosslinking agent, the keto-enol tautomer compound blocks the isocyanate group of the crosslinking agent, whereby excessive viscosity increase or gelation of the adhesive composition after the crosslinking agent is added can be suppressed, and the pot life of the adhesive composition can be extended.
The (H) keto-enol tautomer compound is particularly preferably at least one compound selected from the group consisting of acetylacetone and ethyl acetoacetate.
The (H) keto-enol tautomer compound is preferably contained in a proportion of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer.
Since the (H) keto-enol tautomer compound has an effect of inhibiting crosslinking in contrast to the (G) crosslinking catalyst, it is preferable to appropriately set the ratio of the (H) keto-enol tautomer compound to the (G) crosslinking catalyst. In order to prolong the pot life of the adhesive composition and improve the storage stability, it is preferable that the weight ratio (H)/(G) of the (G) crosslinking catalyst to the (H) keto-enol tautomer compound is 70 to 1000.
The antistatic agent (I) is preferably an ionic compound (I-1) having a melting point of 25 to 50 ℃ and/or an ionic compound (I-2) containing an acryloyl group.
In the present invention, (I-1) an ionic compound having a melting point of 25 to 50 ℃ is added to the copolymer and/or (I-2) an ionic compound having an acryloyl group is copolymerized in the copolymer as the antistatic agent (I). These antistatic agents (I) have a low melting point and a long-chain alkyl group, and therefore are presumed to have a high affinity for acrylic copolymers.
Examples of the antistatic agent (I) include an antistatic agent contained in the adhesive composition and an antistatic agent copolymerized in the copolymer. The adhesive composition preferably contains (I) an antistatic agent in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the acrylic polymer, the total of (I-1) an ionic compound having a melting point of 25 to 50 ℃ and (I-2) an acryloyl group-containing ionic compound copolymerized in the copolymer.
The ionic compound having a melting point of 25 to 50 ℃ in (I-1) is an ionic compound having a cation and an anion, and examples of the cation include a pyridinium cation, an imidazolium cation, a pyrimidinium cation, a pyrazolium cation, a pyrrolidinium cation, and the like,Ammonium cation or phosphonium cation, sulfonium cation, or the like, and the anion is hexafluorophosphate (PF)6 -) Thiocyanate (SCN)-) Alkyl benzene sulfonate (RC)6H4SO3 -) Perchlorate (ClO)4 -) Tetrafluoroborate (BF)4 -) Inorganic or organic anionic compounds such as bis (fluorosulfonyl) imide salt (FSI), bis (trifluoromethanesulfonyl) imide salt (TFSI), and trifluoromethanesulfonate salt (TF). Preferably, the ionic compound is solid at room temperature (e.g., 25 ℃), and the melting point of the ionic compound is 25 to 50 ℃ by selecting the chain length of the alkyl group, the position of the substituent, the number of the substituent, and the like. The cation is preferably a quaternary nitrogen-containing onium cation, and examples thereof include a quaternary pyridinium cation such as 1-alkylpyridinium (the carbon atom at the 2-6 position may or may not be substituted), a quaternary imidazolium cation such as 1, 3-dialkylimidazolium (the carbon atom at the 2,4,5 positions may or may not be substituted), and a quaternary ammonium cation such as tetraalkylammonium.
Preferably, the acrylic polymer contains (I-1) an ionic compound having a melting point of 25 to 50 ℃ in a proportion of 0.01 to 5.0 parts by weight based on 100 parts by weight of the acrylic polymer.
The ionic compound having an acryloyl group (I-2) is an ionic compound having a cation and an anion, and examples thereof include those wherein the cation is (meth) acryloyloxyalkyltrialkylammonium [ R ]3N+-CnH2n-OCOCQ＝CH2Wherein Q is H or CH3The (meth) acryloyl group-containing cation or anion such as R ═ alkyl ] is hexafluorophosphate (PF)6 -) Thiocyanate (SCN)-) Organic sulfonate (RSO)3 -) Perchlorate (ClO)4 -) Tetrafluoroborate (BF)4 -) And an imide salt containing F (R)F 2N-) And the like inorganic or organic anionic compounds. As F-containing imide salts (R)F 2N-) R of (A) to (B)FExamples thereof include a perfluoroalkylsulfonyl group and a fluorosulfonyl group such as a trifluoromethanesulfonyl group and a pentafluoroethanesulfonyl group. As the imide salt containing F, bis (fluorosulfonyl) imide is mentionedSalt [ (FSO)2)2N-Bis (trifluoromethanesulfonyl) imide salt [ (CF)3SO2)2N-Bis (pentafluoroethanesulfonyl) imide salt [ (C)2F5SO2)2N- ], etc.
It is preferable that the (I-2) acryloyl group-containing ionic compound is copolymerized in a proportion of 0.01 to 5.0 parts by weight based on 100 parts by weight of the acrylic polymer.
Specific examples of the antistatic agent (I) are not particularly limited, and specific examples of the ionic compound (I-1) having a melting point of 25 to 50 ℃ include 1-octylpyridinium hexafluorophosphate, 1-nonylphenium hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dodecylpyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzene sulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like. Specific examples of the ionic compound having an acryloyl group (I-2) include dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt [ (CH)3)3N+CH2OCOCQ＝CH2·PF6 -Wherein Q is H or CH3Bis (trifluoromethanesulfonyl) imide methyl salt of dimethylaminoethyl (meth) acrylate [ (CH)3)3N+(CH2)2OCOCQ＝CH2·(CF3SO2)2N-Wherein Q is H or CH3Dimethylaminomethylmethacrylate bis (fluorosulfonyl) imide methyl salt [ (CH ]3)3N+CH2OCOCQ＝CH2·(FSO2)2N-Wherein Q is H or CH3And the like.
Further, as other components, known additives such as a copolymerizable (meth) acrylic acid monomer containing an alkylene oxide, 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 the like may be appropriately blended. These may be used alone or in combination of two or more.
However, it is preferred that the adhesive composition of the present invention does not contain a silicone compound. Here, the silicone compound refers to a compound having a silicone structure, and includes modifications such as polyether-modified silicone compounds. In the present invention, by blending a predetermined amount of the polyalkylene glycol mono (meth) acrylate monomer (D) with the pressure-sensitive adhesive, hydrophilicity is improved even if the pressure-sensitive adhesive does not contain a silicone compound, and therefore, a pressure-sensitive adhesive layer having excellent antistatic properties can be formed.
The copolymer of the main agent that can be used in the adhesive composition of the present invention can be synthesized by polymerizing (a) a (meth) acrylate monomer having an alkyl group with a carbon number of C4 to C18, (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 (E) a nitrogen-containing vinyl monomer containing no hydroxyl group or an alkyl (meth) acrylate monomer containing an alkoxy group. 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 (I-2) an ionic compound having an acryloyl group is used as (I) the antistatic agent, (I-2) an ionic compound having an acryloyl group, and (B) a copolymerizable monomer having a hydroxyl group, (C) a copolymerizable monomer having a carboxyl group, (D) a polyalkylene glycol mono (meth) acrylate monomer, and (E) a nitrogen-containing vinyl monomer having no hydroxyl group or an alkyl (meth) acrylate monomer having an alkoxy group, can be synthesized by polymerizing (I-2) the ionic compound having an acryloyl group and (B) a (meth) acrylate monomer having an alkyl group of C4 to C18.
The adhesive composition of the present invention can also be prepared by blending (F) a bifunctional or higher isocyanate compound, (G) a crosslinking catalyst, and (H) a keto-enol tautomer compound to the above-mentioned copolymer, without containing a silicone compound, and further blending any additive as appropriate. When polymerizing the (I-2) acryloyl group-containing ionic compound in the copolymer as the main component, the (I-1) ionic compound having a melting point of 25 to 50 ℃ may be further added to the copolymer, or may not be added.
In order to reduce the mixing of water into the adhesive composition when producing the copolymer as the main component, it is preferable to carry out the polymerization reaction under anhydrous conditions using solution polymerization or the like using an anhydrous organic solvent. In particular, since the polyalkylene glycol mono (meth) acrylate monomer (D) has high hydrophilicity, it is preferable to use a compound having a low moisture content.
In order to avoid an increase in viscosity of the pressure-sensitive adhesive composition, it is preferable to reduce the amount of polyfunctional (bifunctional or higher) monomers that can function as a crosslinking agent as much as possible. In particular, since the corresponding diester moiety of the polyalkylene glycol mono (meth) acrylate monomer (D) is a di (meth) acrylate of a bifunctional monomer, it is preferable to use a compound having a small diester moiety.
The copolymer is preferably an acrylic polymer, and preferably contains an acrylic monomer such as a (meth) acrylate monomer, (meth) acrylic acid, or (meth) acrylamide in a proportion of 50 to 100 parts by weight based on 100 parts by weight of the acrylic polymer.
Further, the acid value of the acrylic polymer is preferably 0.01 to 8.0. This improves the stain resistance and improves the prevention of the generation of the residual paste.
Here, the "acid value" is one of indexes indicating the content of acid and is expressed by mg of potassium hydroxide required for neutralizing 1g of the carboxyl group-containing polymer.
The adhesive layer obtained by crosslinking the adhesive composition preferably has an adhesive strength of 0.04 to 0.2N/25mm at a low peeling speed of 0.3m/min and an adhesive strength of 2.0N/25mm or less at a high peeling speed of 30 m/min. Thus, the adhesive strength is less changed by the peeling speed, and peeling can be performed quickly even in high-speed peeling. Further, since re-adhesion is performed, an excessive force is not required even when the surface protective film is once peeled off, and the surface protective film is easily peeled off from the adherend.
The surface resistivity of the pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition is preferably 9.0X 10+11Omega/□ below, and the stripping charge voltage is + -0-0.5 kV. In the present invention, "+ -0-0.5 kV" means 0- +0.5kV and 0- +0.5kV, that is, -0.5- +0.5 kV. If the surface resistivity is large, the performance of eliminating static electricity generated by electrification at the time of peeling is poor. Therefore, by making the surface resistivity sufficiently small, the peeling electrification voltage generated by static electricity generated when peeling the adherend from the pressure-sensitive adhesive layer can be reduced, and the influence on the electrical control circuit and the like of the adherend can be suppressed.
The gel fraction of the pressure-sensitive adhesive layer (pressure-sensitive adhesive after crosslinking) obtained by crosslinking the pressure-sensitive adhesive composition of the present invention is preferably 95 to 100%. By increasing the gel fraction in this manner, the adhesive force does not become excessively large at a low peeling speed, elution of unpolymerized monomer or oligomer from the copolymer is reduced, reworkability and durability under high temperature and high humidity are improved, and staining of an adherend can be suppressed.
The adhesive film of the present invention is obtained by forming an adhesive layer obtained by crosslinking the adhesive composition of the present invention on one surface or both surfaces of a resin film. 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 pressure-sensitive adhesive composition of the present invention has excellent antistatic properties because the components (a) to (I) are blended in a well-balanced manner, has an excellent balance of adhesive force at a low peeling speed and a high peeling speed, and has excellent durability and reworkability (after being scraped on a surface protective film with a ball pen via a pressure-sensitive adhesive layer, stains are not transferred to an adherend). Therefore, the composition can be suitably used for the purpose of a surface protective film of a polarizing plate.
As the base film of the pressure-sensitive adhesive layer and the release film (separation film) for protecting the pressure-sensitive adhesive surface, a resin film such as a polyester film can be used.
The base film may be subjected to an anti-fouling treatment with a silicone-based or fluorine-based release agent, a coating agent, silica fine particles, or the like, or an antistatic treatment with an antistatic agent, for example, coating or mixing, on the surface of the base film opposite to the side of the resin film on which the pressure-sensitive adhesive layer is formed.
The release film is subjected to a release treatment with a silicone-based or fluorine-based release agent or the like on the surface of the pressure-sensitive adhesive layer on the side bonded to the pressure-sensitive adhesive surface.
Examples
The present invention will be specifically described below with reference to examples.
< production of acrylic copolymer >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, 100 parts by weight of 2-ethylhexyl acrylate, 3.0 parts by weight of 8-hydroxyoctyl acrylate, 0.2 parts by weight of acrylic acid, 10 parts by weight of polypropylene glycol monoacrylate (average repetition number N of alkylene oxides constituting a polyalkylene glycol chain is 12, diester portion in the monomer is 0.1%, solubility in water is 0.8% turbidity value in a 20% aqueous solution state, moisture content is 0.05%), 5 parts by weight of N-vinylpyrrolidone, and 60 parts by weight of a solvent (ethyl acetate) were added to the reaction apparatus. Thereafter, 0.1 part by weight of azobisisobutyronitrile was added dropwise over 2 hours as a polymerization initiator, and the reaction was carried out at 65 ℃ for 6 hours to obtain an acrylic copolymer solution having a weight average molecular weight of 50 ten thousand, which was used in example 1. A part of the acrylic copolymer was collected and used as a measurement sample of an acid value described later.
Examples 2 to 9 and comparative examples 1 to 4
Acrylic copolymer solutions used in examples 2 to 9 and comparative examples 1 to 4 were obtained in the same manner as the acrylic copolymer solution used in example 1 above, except that the monomer compositions were as described in (A) to (E) and (I-2) in Table 1, respectively.
< production of adhesive composition and surface protective film >
[ example 1]
After adding 1.0 part by weight of 1-octylpyridinium hexafluorophosphate and 8.5 parts by weight of acetylacetone to the acrylic copolymer solution of example 1 prepared as described above and stirring them, 2.5 parts by weight of Coronet HX (isocyanurate body of hexamethylene diisocyanate compound) and 0.1 part by weight of titanium triacetylacetonate were added and mixed by stirring to obtain the pressure-sensitive adhesive composition of example 1. The pressure-sensitive adhesive composition was applied to a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90 ℃ to remove the solvent, thereby obtaining a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 25 μm.
Then, on one side, the adhesive sheet was transferred to the surface of the polyethylene terephthalate (PET) film after the antistatic and antifouling treatment opposite to the surface after the antistatic and antifouling treatment, to obtain the surface protective film of example 1 having a laminated structure of "PET film after the antistatic and antifouling treatment/adhesive layer/release film (silicone resin-coated PET film)".
Examples 2 to 9 and comparative examples 1 to 4
Surface protective films of examples 2 to 9 and comparative examples 1 to 4 were obtained in the same manner as the surface protective film of example 1 described above, except that the additive compositions were as shown in (F) to (J) of table 2.
In tables 1 and 2, the blending ratio of each component is bracketed to show the values of the parts by weight obtained by assuming the total of the group (a) as 100 parts by weight. In table 1, (I-2) the acryloyl group-containing ionic compound copolymerized in the copolymer among the antistatic agents (I) and (I) the antistatic agent added after the polymerization are described in different columns.
In addition, abbreviated compound names of the respective components used in tables 1 and 2 are shown in tables 3 and 4. Coronet (registered trademark) HX, the HL and the L are trade names of Nippon polyurethane industries, Ltd., and Takenate (registered trademark) D-140N, D-127N, D-110N, D-120N is a trade name of Mitsui chemical Co., Ltd. For the group (D) of Table 3, the numerical value of "n" is the average number of repetitions of the alkylene oxide constituting the polyalkylene glycol chain. The "diester" value is the diester fraction (%) of the monomer. The "moisture" value is a moisture content (%). The value of "turbidity" is a turbidity value (%) in a 20% aqueous solution state. The values of (H)/(G) are shown in table 5.
TABLE 1
TABLE 2
Figure BDA0000763534740000211
TABLE 3
Figure BDA0000763534740000221
Figure BDA0000763534740000231
TABLE 4
Figure BDA0000763534740000232
Figure BDA0000763534740000241
TABLE 5
(H)/(G)
Example 1 85
Example 2 120
Example 3 100
Example 4 83.3
Example 5 333.3
Example 6 500
Example 7 200
Example 8 187.5
Example 9 375
Comparative example 1 -
Comparative example 2 60
Comparative example 3 3.3
Comparative example 4 -
< Synthesis of difunctional isocyanate Compound >
The bifunctional isocyanate compounds of Synthesis examples 1 to 3 were synthesized by the following method. As shown in tables 6 and 7, the molar ratio: the diisocyanate and the diol compound were mixed at an NCO/OH ═ 16 ratio, reacted at 120 ℃ for 3 hours, and thereafter, the unreacted diisocyanate was removed under reduced pressure using a thin film evaporator to obtain the objective difunctional isocyanate compound.
TABLE 6
Synthesis example 1F-1 Synthesis example 2F-2 Synthesis example 3F-3
Diisocyanate compound HDI HDI HDI
Diol compound L-1 L-2 L-3
TABLE 7
Figure BDA0000763534740000251
< test method and evaluation >
The surface protection films of examples 1 to 9 and comparative examples 1 to 4 were aged at 23 ℃ under an atmosphere of 50% RH for 7 days, and then the release film (silicone resin-coated PET film) was peeled off to expose the pressure-sensitive adhesive layer, which was used as a sample for measuring the gel fraction and the surface resistivity.
The surface protective film with the adhesive layer exposed was bonded to the surface of the liquid crystal cell-attached polarizing plate via the adhesive layer, left to stand for 1 day, then autoclaved at 50 ℃ under 5 atmospheres for 20 minutes, and left to stand at room temperature for 12 hours, and the resultant was used as a test specimen for measuring the adhesive force, the peel charging voltage, the reworkability, and the durability.
< gel fraction >
After the aging was completed, the mass of the measurement sample before being attached to the polarizing plate was accurately measured, and the measurement sample was immersed in toluene for 24 hours and then filtered through a 200-mesh wire net. Thereafter, the filtrate was dried at 100 ℃ for 1 hour, and then the mass of the residue was measured accurately, and the gel fraction of the pressure-sensitive adhesive layer (pressure-sensitive adhesive after crosslinking) was calculated from the following formula.
Gel fraction (%) — mass of insoluble fraction (g)/mass of binder (g) × 100
< adhesion >
The measurement sample obtained above (a sample obtained by bonding a 25 mm-wide surface protective film to the surface of a polarizing plate) was peeled at a low peeling speed (0.3m/min) and a high peeling speed (30m/min) in a 180 ° direction using a tensile tester, and the peel strength was determined as an adhesive force (N/25 mm).
< surface resistivity >
After aging and before bonding to a polarizing plate, the release film (silicone resin-coated PET film) was peeled off to expose the adhesive layer, and the surface resistivity (Ω/□) of the adhesive layer was measured using a resistivity meter HIRESTA UP-HT450 (manufactured by Mitsubishi Chemical Analytech).
< strip charging voltage >
When the measurement sample obtained above was peeled at a tensile speed of 30m/min by 180 degrees, the voltage (charge voltage) generated by charging the polarizing plate was measured using high-precision electrostatic sensors SK-035 and SK-200 (manufactured by Keyence corporation), and the maximum value of the measured values was defined as the peeled charge voltage (kV).
< reworkability >
The surface protective film of the measurement sample obtained above was scratched with a ball-point pen (load 500g, 3 round trips), and then the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed to confirm that the stain was not transferred to the polarizing plate, and for the evaluation target criteria, the case where the stain was not transferred to the polarizing plate was evaluated as "○", the case where the stain was transferred to at least a part along the scratch with the ball-point pen was evaluated as "△", and the case where the stain was transferred along the scratch with the ball-point pen and the adhesive was also peeled off from the adhesive surface was evaluated as "x".
< durability >
The measurement sample obtained as described above was left to stand at 60 ℃ under an atmosphere of 90% RH for 250 hours, then taken out at room temperature, and after further standing for 12 hours, the adhesive force was measured and compared with the initial adhesive force, and it was confirmed that there was no significant increase, and for the evaluation target standard, the case where the adhesive force after the test was 1.5 times or less the initial adhesive force was evaluated as "○", and the case where the adhesive force exceeded 1.5 times was evaluated as "x".
The evaluation results are shown in table 8. The surface resistivity is defined as "m.times.10+n"mE + n" (where m is an arbitrary real number and n is a positive integer) is recorded.
TABLE 8
Figure BDA0000763534740000261
Figure BDA0000763534740000271
The surface protective films of examples 1 to 9 had an adhesive force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3m/min, an adhesive force of 2.0N/25mm or less at a high peeling speed of 30m/min, and a surface resistivity of 9.0X 10+11Omega/□ or less, a peel electrification voltage of + -0 to 0.5kV, and excellent durability even when left for 250 hours in an atmosphere of 60 ℃ and 90% RH without transferring stains to an adherend after scraping the surface protective film with a ball pen through an adhesive layer.
That is, all the required performances of (1) maintaining the balance of the adhesive force at a low peeling speed and a high peeling speed, (2) preventing the occurrence of the paste residue, (3) excellent antistatic performance, and (4) reworkability are satisfied.
Since the surface protective film of comparative example 1 does not contain (F) a bifunctional or higher isocyanate compound, (G) a crosslinking catalyst, and (H) a keto-enol tautomer compound, the gel fraction is 0%, the adhesive force at a low peeling speed of 0.3m/min and a high peeling speed of 30m/min is not large, the surface resistivity and peeling electrification voltage are high, and the reworkability and durability are poor.
Since the surface protection film of comparative example 2 contains a large amount of diester moiety of the polyalkylene glycol mono (meth) acrylate monomer (D), has a high moisture content, has low solubility in water, and contains the siloxane compound (J), the adhesive force at a low peeling rate of 0.3m/min and a high peeling rate of 30m/min is too large, the surface resistivity and the peeling electrification voltage are high, and the durability is poor.
The surface protective film of comparative example 3 had a short pot life because of a large amount of diester moiety of the polyalkylene glycol mono (meth) acrylate monomer (D), a high water content, and low solubility in water, and was gelled before application, and thus could not be applied.
The surface protective film of comparative example 4 was poor in polymerizability and could not be applied due to poor tackiness because of its large average number of repetitions of alkylene oxide constituting the polyalkylene glycol chain of the polyalkylene glycol mono (meth) acrylate monomer (D), its large diester moiety, its high moisture content, its low solubility in water, and its absence of the crosslinking catalyst (G) and the keto-enol tautomer compound (H).
Accordingly, the surface protective films of comparative examples 1 to 4 could not satisfy all of the requirements of (1) maintaining the balance of adhesive force at a low peeling speed and a high peeling speed, (2) preventing the occurrence of paste residue, (3) excellent antistatic performance, and (4) reworkability.

Claims (12)

1. An adhesive composition comprising an acrylic polymer comprising a copolymer of copolymerizable monomers, wherein the acrylic polymer is obtained by copolymerizing 50 to 95 parts by weight of (A) a (meth) acrylate monomer having an alkyl group and having a carbon number of C4 to C18, (B) a copolymerizable monomer containing a hydroxyl group, 0.1 to 10 parts by weight of (C) a copolymerizable monomer containing a carboxyl group, 8 to 50 parts by weight of (D) a polyalkylene glycol mono (meth) acrylate monomer, and 0.1 to 20 parts by weight of (E) at least one of a nitrogen-containing vinyl monomer containing no hydroxyl group and an alkyl (meth) acrylate monomer containing an alkoxy group, based on 100 parts by weight of the acrylic polymer,
the (B) hydroxyl group-containing copolymerizable monomer is at least one member selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide,
the adhesive composition contains no siloxane compound, contains (F) difunctional or more isocyanate compound, (G) crosslinking catalyst, (H) keto-enol tautomer compound, (I) ionic compound with melting point of 25-50 ℃ and/or ionic compound containing acryloyl as antistatic agent,
the average number of repetitions of an alkylene oxide constituting a polyalkylene glycol chain of the polyalkylene glycol mono (meth) acrylate monomer (D) is 3 to 14, the diester moiety in the monomer is 0.3% or less, the water content is 0.1% or less, and the water-solubility is 2% or less in a 20% aqueous solution state,
the crosslinking catalyst (G) is more than one metal chelate selected from aluminum chelate, titanium chelate and iron chelate,
the adhesive composition contains 0.001 to 0.5 parts by weight of the (G) crosslinking catalyst and 6.0 to 300 parts by weight of the (H) keto-enol tautomer compound per 100 parts by weight of the acrylic polymer, and the weight ratio (H)/(G) of the (G) crosslinking catalyst to the (H) keto-enol tautomer compound is 70 to 1000.
2. The adhesive composition according to claim 1, wherein the (F) di-or higher-functional isocyanate compound is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic polymer, and further,
the antistatic agent (I) is contained in the adhesive composition, and the total amount of the ionic compound with the melting point of 25-50 ℃ and the ionic compound containing acryloyl copolymerized in the copolymer is 0.01-5.0 parts by weight.
3. The adhesive composition according to claim 1 or 2, wherein the (C) carboxyl group-containing copolymerizable monomer is at least one member selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
4. The adhesive composition according to claim 1 or 2, wherein the (D) polyalkylene glycol mono (meth) acrylate monomer is at least one or more selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate.
5. The adhesive composition according to claim 1 or 2, wherein the adhesive composition has a gel fraction after crosslinking of 95 to 100%.
6. The adhesive composition according to claim 1 or 2, wherein the difunctional or higher isocyanate compound (F) is a non-cyclic aliphatic isocyanate compound formed by reacting a diisocyanate compound with a diol compound, the diisocyanate compound is an aliphatic diisocyanate selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, and the diol compound is selected from the group consisting of 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-dimethylpropane-1, 3-diol, and lysine diisocyanate, One of 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol monohydroxypivalate, polyethylene glycol, and polypropylene glycol, and the trifunctional isocyanate compound includes isocyanurate of hexamethylene diisocyanate compound, isocyanurate of isophorone diisocyanate compound, adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, biuret of hexamethylene diisocyanate compound, biuret of isophorone diisocyanate compound, isocyanurate of toluene diisocyanate compound, isocyanurate of xylylene diisocyanate compound, isocyanurate of hydrogenated xylylene diisocyanate compound, and the like, An adduct of a toluene diisocyanate compound, an adduct of a xylylene diisocyanate compound, and an adduct of a hydrogenated xylylene diisocyanate compound.
7. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has an adhesive strength of 0.04 to 0.2N/25mm at a low peeling speed of 0.3m/min and an adhesive strength of 2.0N/25mm or less at a high peeling speed of 30 m/min.
8. The adhesive composition according to claim 1 or 2, wherein the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 9.0 x 10+11Omega/□ below, and the stripping charge voltage is + -0-0.5 kV.
9. An adhesive film characterized in that an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 8 is formed on one surface or both surfaces of a resin film.
10. A surface protective film comprising a resin film and a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition according to any one of claims 1 to 8, wherein the pressure-sensitive adhesive layer is scraped with a ballpoint pen through the pressure-sensitive adhesive layer to prevent stains from being transferred to an adherend.
11. The surface protective film according to claim 10, which is used for a surface protective film for a polarizing plate.
12. The surface protective film according to claim 11, wherein antistatic and antifouling treatment is performed on a side opposite to a side on which the adhesive layer of the resin film is formed.
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