CN115991966A - Adhesive composition and surface protective film - Google Patents

Adhesive composition and surface protective film Download PDF

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Publication number
CN115991966A
CN115991966A CN202211461135.9A CN202211461135A CN115991966A CN 115991966 A CN115991966 A CN 115991966A CN 202211461135 A CN202211461135 A CN 202211461135A CN 115991966 A CN115991966 A CN 115991966A
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meth
acrylate
weight
monomer
parts
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Inventor
长仓毅
长谷川良
吉田弘幸
菱沼昌世
大津贺健太郎
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Fujimori Kogyo Co Ltd
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

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

Abstract

The invention provides an adhesive composition for a surface protective film, which has excellent durability, reworkability and antistatic property even if used for a polarizer with an acrylic protective film on the surface, and a surface protective film. The adhesive composition for a surface protective film of a polarizing plate having an acrylic protective film on the surface thereof is formed from an acrylic polymer of a copolymer of at least one of (A) a C4-C18 (meth) acrylate monomer having an alkyl group, (B) a hydroxyl group-containing copolymerizable monomer, (C) a carboxyl group-containing copolymerizable monomer, (D) a polyalkylene glycol mono (meth) acrylate monomer, (E) a nitrogen-containing vinyl monomer having no hydroxyl group or an alkyl (meth) acrylate monomer having an alkoxy group, and contains (F) a 3-functional isocyanate compound, (G) a crosslinking catalyst, (H) a keto-enol tautomer compound, and (I).

Description

Adhesive composition and surface protective film
The present invention is a divisional application of chinese patent application having application number 201610225099.4, application date 2016, 4 and 12, and the name of "adhesive composition and surface protective film", and the present application claims priority based on patent application number 2015-096644 of japanese patent application filed 5-11.
Technical Field
The present invention relates to an adhesive composition and a surface protective film. More specifically, the present invention relates to an adhesive composition for a surface protective film and a surface protective film for a polarizing plate, which have antistatic properties, excellent balance of adhesive force at a low peeling speed and a high peeling speed, and also excellent pot life (pot life), durability, reworkability, and antistatic properties, and which have an acrylic protective film on the surface thereof instead of TAC.
Background
Conventionally, in a process for manufacturing an optical member such as a polarizing plate or a retardation plate, which is a member constituting a liquid crystal display, a surface protective film for temporarily protecting the optical member is attached to a surface of the optical member. Such a surface protective film is used only in the process of manufacturing an optical member, and is peeled off from the optical member when the optical member is assembled to a liquid crystal display. Such a surface protective film for protecting the surface of an optical component is generally called an engineering film (process film) because it is used only in a manufacturing process.
The surface protection film used in the process of manufacturing the optical member has an adhesive layer 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 adhesive layer is bonded to the adhesive layer until the adhesive layer is bonded to the optical member.
In addition, in a state where an optical member such as a polarizing plate or a retardation plate is bonded to a surface protective film, it is necessary to perform product inspection for optical evaluation such as display capability, color tone, contrast, and foreign matter mixing in a liquid crystal display panel, and as a performance required for the surface protective film, no bubbles or foreign matter is attached to an adhesive layer.
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, peeling static electricity generated by static electricity generated when an adhesive layer is peeled from an adherend may cause failure of an electric control circuit of a liquid crystal display, and excellent antistatic performance is required for the adhesive layer.
In addition, when an optical protective film is bonded to an optical member such as a polarizing plate or a retardation plate, the surface protective film may be temporarily peeled off for various reasons, and the surface protective film may be re-bonded again, and in this case, the optical member needs to be easily peeled off from 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 peeled quickly. That is, even by high-speed peeling, it is required to be able to perform quick peeling so that the change in the adhesive force due to the peeling speed is small.
Therefore, in recent years, as a performance required for an adhesive layer constituting a surface protective film, from the viewpoint of convenience in use when the surface protective film is used, there is a need for: (1) The balance of the adhesive is obtained in the peeling speed of low speed and the peeling speed of high speed; (2) preventing the generation of residual glue; (3) excellent antistatic properties; and (4) re-operability, etc.
However, as the above-mentioned (1) to (4) of the required performances for the adhesive layer constituting the surface protective film, even if each of the required performances can be satisfied, it is a very difficult problem to satisfy all the required performances (1) to (4) required for the adhesive layer of the surface protective film at the same time.
For example, the following proposals are known for (1) obtaining an adhesive balance at a low peeling speed and a high peeling speed and (2) preventing the generation of a residual adhesive.
An acrylic pressure-sensitive adhesive layer 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 being crosslinked with a crosslinking agent, has a problem in that the pressure-sensitive adhesive is transferred to the adherend side or the adhesion strength is greatly improved over time when the pressure-sensitive adhesive layer is connected over a long period of time. In order to avoid this problem, an adhesive layer formed by crosslinking a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group (alcoholic hydroxy) with a crosslinking agent is known (patent document 1).
There has been proposed an adhesive layer formed by adding a copolymer of a (meth) acrylic acid alkyl ester and a carboxyl group-containing copolymerizable compound in a small amount to the same copolymer and crosslinking the copolymer with a crosslinking agent. However, if these are used for surface protection of plastic plates or the like having a low surface tension and a smooth surface, there are problems that peeling phenomena such as warpage occur due to heating during processing or storage, or re-peelability is poor when peeling at a high speed in a manual operation region.
In order to solve these problems, there has been proposed an adhesive composition in which 1 to 15 parts by weight of b) a carboxyl group-containing copolymerizable compound and 3 to 100 parts by weight of c) a vinyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms are added to 100 parts by weight of a) an alkyl (meth) acrylate containing an alkyl group having 8 to 10 carbon atoms as a main component, to form a monomer mixture, and a crosslinking agent having an equivalent or more of carboxyl groups relative to the component b) is mixed into a copolymer of the monomer mixture (patent document 2).
In the adhesive composition described in patent document 2, peeling phenomenon such as warpage during processing or storage does not occur, and further, the adhesive strength is small in the improvement with time and excellent in the re-peeling property, and even in long-term storage, particularly in long-term storage under a high-temperature atmosphere, the adhesive composition can be re-peeled with a small force, and in this case, no adhesive residue occurs on an adherend, and the adhesive composition can be re-peeled with a small force even when peeled at a high speed.
Further, regarding (3) excellent antistatic properties, as a method for imparting antistatic properties to a surface protective film, a method of mixing an antistatic agent into a base film is disclosed. As an antistatic agent, for example, disclosed are: (a) Various cationic antistatic agents having cationic groups such as quaternary ammonium salt and pyridinium salt, primary amino group to tertiary amino group; (b) Anionic antistatic agents having anionic groups such as sulfonate groups, sulfate groups, phosphate groups, phosphonate groups, and the like; (c) Amphoteric antistatic agents such as amino acids and sulfamates; (d) Nonionic antistatic agents such as amino alcohols, glycerins, polyethylene glycols, and the like; (e) A polymer antistatic agent obtained by increasing the molecular weight of the antistatic agent as described above (patent document 3).
In recent years, it has been proposed to include such antistatic agents in the substrate film or directly in the adhesive layer, not on the surface of the substrate film.
Regarding (4) reworkability, for example, an adhesive composition is proposed in which an isocyanate compound curing agent and 0.0001 to 10 parts by weight of a specific silicate oligomer per 100 parts by weight of an acrylic resin are mixed with the 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 may be used as a main monomer component, and a monomer component containing other functional groups such as a carboxyl group-containing monomer may be contained. In general, it is desirable that the main monomer is contained in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, and more preferably 0.01 to 25% by weight. The adhesive composition described in patent document 4 has a reworkability because the cohesive force and the adhesive force change with time at high temperature or high temperature and high humidity are small, and the adhesive force to a curved surface is excellent.
In general, when the adhesive layer is soft, a residual adhesive is likely to be generated, and the reworkability is likely to be lowered. That is, peeling is difficult at the time of erroneous attachment, and re-attachment becomes difficult. Therefore, in order to provide reworkability, it is considered necessary to crosslink a monomer having a functional group such as a carboxyl group on the main agent to provide the adhesive layer with a certain hardness.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 63-225677
Patent document 2: JP-A-11-256111
Patent document 3: JP-A-11-070629
Patent document 4: JP-A-8-199130
Disclosure of Invention
Technical problem to be solved by the invention
Conventionally, as a protective film for a polarizing plate used for a liquid crystal display or the like, a polarizing plate using an acrylic film (hereinafter referred to as an acrylic polarizing plate) has been changed from a polarizing plate using a conventional TAC film (triacetyl cellulose compound) (hereinafter referred to as a TAC polarizing plate). However, a surface protective film using an acrylic adhesive having excellent optical properties for the adhesive layer tends to have higher adhesive force than that of the adhesive layer when used for the TAC-based polarizer.
In the prior art, as the required performance of the adhesive layer constituting the surface protective film, it is necessary to obtain a balance of adhesion at a low peeling speed and a high peeling speed, and excellent antistatic performance, reworkability, and the like are required, however, even if each required performance is individually satisfied, all the required performances required for the adhesive layer of the surface protective film cannot be satisfied at the same time.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide an adhesive composition for a surface protective film and a surface protective film which are excellent in durability, reworkability and antistatic properties even when used in a polarizing plate having an acrylic protective film on the surface.
Technical means for solving the technical problems
In order to solve the above-mentioned problems, the present invention provides an adhesive composition for a surface protective film of a polarizing plate having an acrylic protective film on the surface, wherein the adhesive composition is formed of an acrylic polymer of a copolymer containing (a) a (meth) acrylic acid ester monomer having a carbon number of an alkyl group of from 4 to 18, and (B) a hydroxyl group-containing copolymerizable monomer, (C) a carboxyl group-containing copolymerizable monomer, (D) a polyalkylene glycol mono (meth) acrylic acid ester monomer, and at least one of a nitrogen-containing vinyl monomer having no hydroxyl group or an alkoxy group-containing (meth) acrylic acid alkyl ester monomer having (E), the adhesive composition contains (F) a 3-functional isocyanate compound, (G) a crosslinking catalyst, (H) a ketone-tautomer compound, and (I) an ionic compound and/or an acryl-containing ionic compound having a melting point of from 25 to 50 ℃ as an antistatic agent, and the total amount of the (D) is 100 parts by weight of the polyalkylene glycol (meth) acrylic acid ester monomer relative to the total amount of the (D) the acrylic acid ester monomer.
Preferably, the acrylic polymer contains 50 to 95 parts by weight of the (A) C4 to C18 (meth) acrylate monomer having an alkyl group, 0.1 to 10 parts by weight of the (B) hydroxyl group-containing copolymerizable monomer, 0.05 to 1.0 parts by weight of the (C) carboxyl group-containing copolymerizable monomer, 5 to 50 parts by weight of the (D) polyalkylene glycol mono (meth) acrylate monomer, and 0.1 to 20 parts by weight of the (E) hydroxyl group-free nitrogen-containing vinyl monomer or alkoxy group-containing alkyl (meth) acrylate monomer, relative to 100 parts by weight of the total amount of the acrylic polymer of the copolymer, the adhesive composition contains 0.1 to 10 parts by weight of the (F) 3 functional isocyanate compound, 0.001 to 0.5 part by weight of the (G) crosslinking catalyst, 0.1 to 300 parts by weight of the (H) keto-enol tautomer compound, further contains, as the (I) antistatic agent, a total amount of the antistatic agent contained in the adhesive composition and the antistatic agent copolymerized in the copolymer, the (D) polyalkylene glycol mono (meth) acrylate monomer having an average repeating unit number of 3 to 14 of alkylene oxide (alkylene oxide) constituting a polyalkylene glycol chain, a diester component in the monomer of 0.3% or less, a moisture content of 0.1% or less, and a solubility to water of 20% aqueous solution having a haze value of 2% or less.
It is preferable to contain 0.001 to 0.5 part by weight of a polyether-modified silicone compound having an HLB value of 7 to 14, relative to 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
Preferably, the (B) hydroxyl group-containing copolymerizable monomer 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.
Preferably, the (C) carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.
Preferably, the (D) polyalkylene glycol mono (meth) acrylate monomer is at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate.
Preferably, the adhesive composition has a gel fraction of 95 to 100% after crosslinking.
The (F) 3 functional isocyanate compound is preferably at least one 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 toluene diisocyanate compound, an adduct of a xylylene diisocyanate compound, and an adduct of a hydrogenated xylylene diisocyanate compound.
Preferably, the antistatic agent (I) contains 0.01 to 5.0 parts by weight of an ionic compound having a melting point of 25 to 50 ℃ and/or 0.01 to 5.0 parts by weight of an acryl-containing ionic compound copolymerized in the copolymer, relative to 100 parts by weight of the copolymer.
Preferably, the (G) crosslinking catalyst is a metal chelate compound crosslinking catalyst, and the (H)/(G) weight ratio is 70 to 1000 based on 100 parts by weight of the copolymer containing 1.0 to 30.0 parts by weight of the (H) keto-enol tautomer compound.
The adhesive layer obtained by crosslinking the adhesive composition preferably has an adhesive force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3 m/min and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30 m/min to a polarizing plate having the acrylic protective film on the surface.
Preferably crosslinked by the adhesive compositionThe surface resistivity of the adhesive layer was 9.0X10 +11 And the stripping static voltage is +/-0-1.0 kV under omega/≡.
The present invention also provides an adhesive film, wherein the adhesive film is formed by forming an adhesive layer formed by crosslinking the adhesive composition on one or both surfaces of a resin film.
The present invention also provides a surface protective film comprising a resin film and an adhesive layer formed by crosslinking the adhesive composition formed on one surface of the resin film, wherein the surface protective film is drawn with a ballpoint pen through the adhesive layer, and there is no transfer of contamination to an adherend having a polarizing plate having the acrylic protective film on the surface.
Preferably, the resin film is subjected to antistatic treatment and antifouling treatment on the opposite surface of the side where the adhesive layer is formed.
Effects of the invention
According to the present invention, an adhesive composition for a surface protective film and a surface protective film which are excellent in durability, reworkability and antistatic properties even when used in a polarizing plate having an acrylic protective film on the surface thereof can be provided.
Detailed Description
The present invention will be described below based on appropriate embodiments.
The adhesive composition for a surface protective film of a polarizing plate having an acrylic protective film on the surface thereof is characterized by comprising an acrylic polymer of a copolymer containing (A) an acrylic acid ester monomer having an alkyl group with a carbon number of C4 to C18, (meth) an ionic compound having a melting point of 25 to 50 ℃ and/or an ionic compound having an acryl group as a copolymerizable monomer group, (B) a hydroxyl group-containing copolymerizable monomer, (C) a carboxyl group-containing copolymerizable monomer, (D) a polyalkylene glycol mono (meth) acrylic acid ester monomer, and (E) at least one of a nitrogen-containing vinyl monomer or an alkoxy group-containing (meth) acrylic acid alkyl ester monomer containing no hydroxyl group, wherein the adhesive composition contains (F) a 3-functional isocyanate compound, (G) a crosslinking catalyst, (H) a keto-enol tautomer compound, and (I) an ionic compound having a melting point of 25 to 50 ℃ and/or an acryl group-containing ionic compound, and the adhesive composition is 5 parts by weight of polyalkylene glycol (D) per 100 parts by weight of the total amount of the acrylic polymer.
Preferably, the acrylic polymer contains 50 to 95 parts by weight of the (A) C4 to C18 alkyl (meth) acrylate monomer, 0.1 to 10 parts by weight of the (B) hydroxyl group-containing copolymerizable monomer, 0.05 to 1.0 parts by weight of the (C) carboxyl group-containing copolymerizable monomer, 5 to 50 parts by weight of the (D) polyalkylene glycol mono (meth) acrylate monomer, and 0.1 to 20 parts by weight of the (E) hydroxyl group-free nitrogen-containing vinyl monomer or alkoxy group-containing alkyl (meth) acrylate monomer, relative to 100 parts by weight of the total amount of the acrylic polymer of the copolymer, the adhesive composition contains 0.1 to 10 parts by weight of the (F) 3 functional isocyanate compound, 0.001 to 0.5 part by weight of the (G) crosslinking catalyst, 0.1 to 300 parts by weight of the (H) keto-enol tautomer compound, further contains, as the (I) antistatic agent, a total amount of the antistatic agent contained in the adhesive composition and the antistatic agent copolymerized in the copolymer, the (D) polyalkylene glycol mono (meth) acrylate monomer having an average repeating unit number of alkylene oxide groups constituting a polyalkylene glycol chain of 3 to 14, a diester component in the monomer of 0.3% or less, a moisture content of 0.1% or less, and a solubility to water of 2% or less in a 20% aqueous solution state.
Examples of the (meth) acrylic acid ester monomer having a C4 to C8 carbon atom in the (a) alkyl group 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, myristyl (meth) acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, isocetyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate.
The total amount of the (a) at least one of the (meth) acrylic acid ester monomers having an alkyl group of 4 to 8 carbon atoms is preferably contained in a proportion of 50 to 95 parts by weight, more preferably 60 to 90 parts by weight, and particularly preferably 70 to 90 parts by weight, based on 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
Examples of the hydroxyl group-containing copolymerizable monomer (B) include hydroxyl group-containing (meth) acrylic amines such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like, and N-hydroxy (meth) acrylamides, N-hydroxymethyl (meth) acrylamides and N-hydroxyethyl (meth) acrylamides.
Preferably at least one compound 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 total amount of the (B) hydroxyl group-containing copolymerizable monomer is preferably at least one of 0.1 to 10 parts by weight, more preferably 2 to 8 parts by weight, and particularly preferably 2 to 6 parts by weight, based on 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
Preferably, (C) the carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.
The total amount of the (C) carboxyl group-containing copolymerizable monomer is preferably at least one of 0.05 to 1.0 parts by weight, more preferably 0.05 to 0.8 parts by weight, and particularly preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
The polyalkylene glycol mono (meth) acrylate monomer (D) may be any compound in which one hydroxyl group is esterified as a (meth) acrylate among a plurality of hydroxyl groups of the polyalkylene glycol. The (meth) acrylate group is a polymerizable group and can be copolymerized with the base polymer. The other hydroxyl groups may be OH groups, or may be alkyl ethers such as methyl ether and ethyl ether, saturated carboxylic acid esters such as acetic acid esters, or the like.
Examples of the alkylene group included in the polyalkylene glycol include, but are not limited to, ethylene, propylene, and butylene. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like. Examples of the polyalkylene glycol copolymer include polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polypropylene glycol-polytetramethylene glycol, and polyethylene glycol-polypropylene glycol-polytetramethylene glycol, and the copolymer may be a block copolymer or a random copolymer.
In the polyalkylene glycol mono (meth) acrylate monomer (D), the average number of repeating units of alkylene oxide groups constituting the polyalkylene glycol chain is preferably 3 to 14. The "average number of repeating units of an alkyleneoxy group" means the average number of repeating units of an alkyleneoxy group in the "polyalkylene glycol chain" moiety contained in the molecular structure of the (D) polyalkylene glycol mono (meth) acrylate monomer.
The amount of the (D) polyalkylene glycol mono (meth) acrylate monomer is preferably 5 parts by weight or more relative to 100 parts by weight of the total amount of the acrylic copolymer.
As the polyalkylene glycol mono (meth) acrylate monomer (D), it is preferable that the diester component in the monomer is 0.3% or less, the moisture content is 0.1% or less, and the solubility to water is 2% or less in the state of a 20% aqueous solution.
The "diester component in monomer" means the content (wt%) of polyalkylene glycol di (meth) acrylate contained in the (D) polyalkylene glycol mono (meth) acrylate monomer.
The "moisture content" means the content (wt%) of moisture contained in the (D) polyalkylene glycol mono (meth) acrylate monomer.
The "haze value in a 20% aqueous solution state" means a haze value (%) of an aqueous solution in which the (D) polyalkylene glycol mono (meth) acrylate monomer is in a 20% by weight aqueous solution state. That is, the (D) polyalkylene glycol mono (meth) acrylate monomer has not only water solubility (solubility in water) that can only form a 20% aqueous solution, but also a haze value (%) in a 20% aqueous solution is required to be low (less white turbidity).
In the present specification, the haze value of the 20% aqueous solution is a value measured by a haze meter by adding the aqueous solution to a quartz cell having an optical path length of 10 mm. The index is introduced as the degree of hydrophilicity of the (D) polyalkylene glycol mono (meth) acrylate monomer in order to select a monomer having high hydrophilicity that can give a solution free from white turbidity 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, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate.
More specifically, it is possible to list: polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, polytetramethylene glycol-mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol-mono (meth) acrylate, polypropylene glycol-polytetramethylene glycol-mono (meth) acrylate, polyethylene glycol-polypropylene glycol-polytetramethylene glycol-mono (meth) acrylate; methoxy polyethylene glycol- (meth) acrylate, methoxy polypropylene glycol- (meth) acrylate, methoxy polytetramethylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polytetramethylene glycol- (meth) acrylate, methoxy-polypropylene glycol-polytetramethylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-polytetramethylene glycol- (meth) acrylate; ethoxy polyethylene glycol- (meth) acrylate, ethoxy polypropylene glycol- (meth) acrylate, ethoxy polytetramethylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polytetramethylene glycol- (meth) acrylate, ethoxy-polypropylene glycol-polytetramethylene glycol- (meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol-polytetramethylene glycol- (meth) acrylate, and the like.
The total amount of the (D) polyalkylene glycol mono (meth) acrylate monomer is preferably contained in a proportion of 5 to 50 parts by weight, more preferably in a proportion of 5 to 40 parts by weight, and particularly preferably in a proportion of 5 to 30 parts by weight, based on 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
The acrylic polymer of the copolymer may contain, as optional components, at least one of (E) a nitrogen-containing vinyl monomer containing no hydroxyl group or an alkyl (meth) acrylate monomer containing an alkoxy group, in addition to the essential components of (a) to (D). (E) As the nitrogen-containing vinyl monomer (E-1), there may be mentioned: an amide bond-containing vinyl monomer, an amino group-containing vinyl monomer, a vinyl monomer having a nitrogen-containing heterocyclic structure, and the like. More specifically, it is possible to list: cyclic nitrogen vinyl compounds having a heterocyclic structure substituted with an N-vinyl group, such as N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methyl vinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyridine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N-vinyllaurolactam, etc.; cyclic nitrogen vinyl compounds having an N- (meth) acryloyl-substituted heterocyclic structure, such as N- (meth) acryloylmorpholine, N- (meth) acryloylpiperazine, N- (meth) acryloylaziridine, N- (meth) acryloylazetidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine, N- (meth) acryloylazepan, and N- (meth) acryloylazepan; cyclic nitrogen vinyl compounds having a heterocyclic structure having a nitrogen atom in the ring and an ethylenically unsaturated bond, 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-t-butyl (meth) acrylamide; dialkyl-substituted (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropyl acrylamide, N-diisopropyl (meth) acrylamide, N-dibutyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-methyl-N-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, and the like; 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, N, dialkylamino (meth) acrylates such as 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 t-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-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, N-methyl-N-isopropylaminopropyl (meth) acrylamide, and the like; n-vinylcarboxylic acid amides such as N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, and the like; (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; etc.
The nitrogen-containing vinyl monomer (E-1) preferably contains no hydroxyl group, more preferably contains no hydroxyl group or carboxyl group. The above-listed monomers are preferable, for example: an acrylic monomer containing an 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 morpholine or N- (meth) acryloyl pyrrolidine, and the like.
(E) Examples of the (E-2) alkoxy group-containing alkyl (meth) acrylate monomer 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) acrylic acid, 3-ethoxypropyl (meth) acrylate, 3-propoxypropyl (meth) acrylate, 3-isopropoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxyputyl (meth) acrylate, and the like.
The content of at least one of (E) a nitrogen-containing vinyl monomer containing no hydroxyl group or an alkyl (meth) acrylate monomer containing an alkoxy group is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, and particularly preferably 0.3 to 8 parts by weight, based on 100 parts by weight of the total amount of the acrylic polymer of the copolymer. The nitrogen-containing vinyl monomer (E-1) containing no hydroxyl group and the alkyl (meth) acrylate monomer (E-2) containing an alkoxy group may be used simultaneously in an amount of 1 or 2 or more, respectively.
The (F) 3 functional isocyanate compound may be at least 1 or 2 or more selected from polyisocyanate compounds having 3 isocyanate (NCO) groups in 1 molecule. The isocyanate compound may be classified into aliphatic isocyanate, aromatic isocyanate, acyclic isocyanate, alicyclic isocyanate, and the like.
Examples of the (F) 3-functional isocyanate compound include a biuret modified product or isocyanurate modified product of a 2-functional isocyanate compound (a compound having 2 NCO groups in the molecule), an adduct (polyol modified product) of a 3-or more-membered polyol (a compound having at least 3 or more OH groups in the molecule) such as Trimethylolpropane (TMP) or glycerin, and the like.
The 3-functional isocyanate compound is preferably at least one compound selected from the group consisting of an isocyanurate body of a hexamethylene diisocyanate compound, an isocyanurate body of an isophorone diisocyanate compound, an adduct of a hexamethylene diisocyanate compound, a biuret body of a isophorone diisocyanate compound, a biuret body of an isophorone diisocyanate compound, an isocyanurate body of a toluene diisocyanate compound, an isocyanurate body of a xylylene diisocyanate compound, an isocyanurate body of a hydrogenated xylylene diisocyanate compound, an adduct of a toluene diisocyanate compound, an adduct of a xylylene diisocyanate compound, and an adduct of a hydrogenated xylylene diisocyanate compound.
The (F) 3 functional isocyanate compound is preferably contained in a proportion of 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
When the polyisocyanate compound is used as the crosslinking agent, the crosslinking catalyst (G) may be any one that serves as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and examples thereof include amine compounds such as tertiary amines, metal chelate compounds, organotin compounds, organolead compounds, organozinc compounds, and other organometallic compounds.
Examples of the tertiary amine include trialkylamine, N' -tetraalkyldiamine, N-dialkylaminoalcohol, triethylenediamine, morpholine derivative, piperazine derivative, and the like.
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, the general formula of the metal chelate compound having 1 metal atom M is represented by M (L) m (X) n When expressed, m is more than or equal to 1, and n is more than or equal to 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 may be the same ligand or different ligands.
As the metal atom M, fe, ni, mn, cr, V, ti, ru, zn, al, zr, sn and the like can be mentioned.
Examples of the polydentate ligand L include beta-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate (acetoacetate oleyl), lauryl acetoacetate, stearyl acetoacetate, beta-diketones such as acetylacetone (referred to as 2, 4-pentanedione), 2, 4-hexanedione, and benzoylacetone. They are keto-enol tautomeric compounds, which in the case of polydentate ligands L can also be enol compounds (for example acetylacetonates) after deprotonation of the enol.
Examples of the monodentate ligand X include halogen atoms such as chlorine atom and bromine atom, acyloxy groups such as pentanoyl, hexanoyl, 2-ethylhexanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl and octadecanoyl, and alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy and butoxy.
Specific examples of the metal chelate compound include iron (III) tris (2, 4-pentanedione), iron triacetylacetonate, titanium triacetylacetonate, ruthenium triacetylacetonate, zinc diacetylacetonate, aluminum triacetylacetonate, zirconium tetra-acetylacetonate, iron (III) tris (2, 4-hexanedione), zinc bis (2, 4-hexanedione), titanium tris (2, 4-hexanedione), aluminum tris (2, 4-hexanedione), zirconium tetra (2, 4-hexanedione), and the like.
Examples of the organotin compound include dialkyltin oxide, a fatty acid salt of dialkyltin, a fatty acid salt of stannous, and the like.
(G) The crosslinking catalyst is preferably a metal chelating compound or an organotin compound. The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, an iron chelate compound, a tin chelate compound, or the like. The organotin compound is preferably at least one selected from the group of compounds consisting of dioctyltin oxide and dioctyltin dilaurate.
The crosslinking catalyst (G) is preferably contained in a proportion of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the total amount of the acrylic polymer of the copolymer.
Examples of the keto-enol tautomer compound include beta-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate and stearyl acetoacetate, beta-diketones such as acetylacetone, 2, 4-hexanedione and benzoylacetone. (H) The keto-enol tautomer compound can inhibit excessive viscosity rise or gelation of the adhesive composition after mixing the crosslinking agent by the isocyanate group of the block (blocking) crosslinking agent in the adhesive composition using the polyisocyanate compound as the crosslinking agent, and can prolong the pot life of the adhesive composition.
The keto-enol tautomer compound (H) is preferably at least one compound selected from the group consisting of, in particular, acetylacetone and ethyl acetoacetate.
The (H) keto-enol tautomer compound is preferably contained in a proportion of 0.1 to 300 parts by weight, more preferably in a proportion of 1.0 to 30.0 parts by weight, relative to 100 parts by weight of the total amount of the acrylic copolymer of the copolymer.
(H) Since the keto-enol tautomer compound has an effect of inhibiting crosslinking contrary to the (G) crosslinking catalyst, the ratio of the (H) keto-enol tautomer compound to the (G) crosslinking catalyst is preferably appropriately set. In order to prolong the pot life of the adhesive composition and improve the storage stability, the weight ratio (H)/(G) of the (H) keto-enol tautomer compound to the (G) crosslinking catalyst is preferably 70 to 1000.
(I) The antistatic agent is preferably (I-1) an ionic compound having a melting point of 25 to 50℃and/or (I-2) an ionic compound containing an acryl group.
In the present invention, as the (I) antistatic agent, (I-1) an ionic compound having a melting point of 25 to 50℃and/or (I-2) an ionic compound containing an acryl group is copolymerized in the copolymer are added to the copolymer. It is presumed that these (I) antistatic agents have a high affinity with acrylic copolymers due to their low melting point and long chain alkyl groups.
The antistatic agent (I) includes an antistatic agent contained in the adhesive composition and an antistatic agent copolymerized in the copolymer. Preferably, the antistatic agent (I) is contained in a proportion of 0.01 to 5.0 parts by weight of the total amount of the antistatic agent contained in the adhesive composition and the antistatic agent copolymerized in the copolymer, relative to 100 parts by weight of the acrylic polymer of the copolymer.
The ionic compound having a melting point of 25 to 50 ℃ 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, a nitrogen-containing onium cation such as an ammonium cation, a phosphonium cation, a sulfonium cation, and the like, and the anion is a phosphate hexafluoride (PF) 6 - ) Thiocyanate radical (SCN) - ) Alkylbenzenesulfonate (RC) 6 H 4 SO 3 - ) Perchlorate (ClO) 4 - ) Tetrafluoroborate (BF) 4 - ) Inorganic or organic anions such as bis (fluorosulfonyl) imide (FSI), bis (trifluoromethanesulfonyl) imide (TFSI), and Trifluoromethanesulfonate (TF). Preferably solid at ordinary temperature (e.g., 25 ℃ C.), and an ionic compound having a melting point of 25 to 50 ℃ C. Can be obtained by selecting the chain length of the alkyl group, the position, the number of substituents, and the like. The cations are preferably quaternary nitrogen-containing onium cations, which can be listed as followsExamples of the quaternary pyridinium cations include 1-alkylpyridinium (carbon atoms at 2 to 6 may have a substituent or may be unsubstituted), quaternary imidazolium cations such as 1, 3-dialkylimidazolium (carbon atoms at 2, 4 and 5 may have a substituent or may be unsubstituted), and quaternary ammonium cations such as tetraalkylammonium.
The ionic compound having a melting point of 25 to 50℃is preferably contained in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the acrylic polymer of the copolymer.
The ionic compound having an acryl group (I-2) is an ionic compound having a cation and an anion, and the cation is (meth) acryloyloxy alkyl trialkylammonium [ R ] 3 N + -C n H 2n -OCOCQ＝CH 2 Wherein q=h or CH 3 R=alkyl]The cation containing (methyl) acryloyl and the anion is hexafluorophosphate (PF) 6 - ) Thiocyanate radical (SCN) - ) Organic sulfonate (RSO) 3 - ) Perchlorate (ClO) 4 - ) Tetrafluoroborate (BF) 4 - ) Containing F imide radical (R) F 2 N - ) And inorganic or organic anions. As the F-containing imide radical (R) F 2 N - ) R of (2) F Examples thereof include perfluoroalkanesulfonyl groups such as trifluoromethanesulfonyl and pentafluoroethanesulfonyl groups, and fluorosulfonyl groups. As the F-containing imide salt, bis (fluorosulfonyl) imide salt [ (FSO) 2 ) 2 N - ]Bis (trifluoromethanesulfonyl) imide salt [ (CF) 3 SO 2 ) 2 N - ]Bis (pentafluoroethane sulfonyl) imide salt [ (C) 2 F 5 SO 2 ) 2 N - ]And bis-sulfonyl imide salts.
The ionic compound containing an acryl group (I-2) is preferably copolymerized in the copolymer in a proportion of 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the acrylic polymer.
Specific examples of the antistatic agent (I) are not particularly limited, but specific examples of the ionic compound (I-1) having a melting point of 25 to 50℃include 1-octylpyridinium hexafluorophosphate and 1-nonylPyridinium 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. As specific examples of the ionic compound having an acryl group (I-2), dimethylaminomethyl (meth) acrylate methyl hexafluorophosphate [ (CH) may be mentioned 3 ) 3 N + CH 2 OCOCQ＝CH 2 ·PF 6 - Wherein q=h or CH 3 ]Dimethylaminoethyl (meth) acrylate bis (trifluoromethanesulfonyl) imide methyl salt [ (CH) 3 ) 3 N + (CH 2 ) 2 OCOCQ＝CH 2 ·(CF 3 SO 2 ) 2 N-, wherein q=h or CH 3 Dimethylaminomethyl methacrylate bis (fluorosulfonyl) imide methyl salt [ (CH) 3 ) 3 N + CH 2 OCOCQ＝CH 2 ·(FSO 2 ) 2 N-, wherein q=h or CH 3 And the like.
The adhesive composition of the present invention may optionally contain a polyether modified silicone compound having an HLB value of 7 to 14. Polyether-modified silicone compounds are silicone compounds having polyether groups, except for the usual siloxane units [ -SiR ] 1 2 -O-]In addition, it contains siloxane units [ -SiR ] having polyether groups 1 (R 2 O(R 3 O) n R 4 )-O-]. Here, R is 1 Represents 1 or more than 2 alkyl groups or aryl groups, R 2 R is R 3 Represents 1 or more than 2 alkylene groups, R 4 Represents 1 or 2 or more kinds of alkyl groups, acyl groups, or the like (terminal groups). As polyether groups there may be mentioned polyoxyethylene [ (C) 2 H 4 O) n ]Or polyoxypropylene [ (C) 3 H 6 O) n ]And the like.
The polyether-modified silicone compound is preferably a polyether-modified silicone compound having an HLB value of 7 to 14. Further, it is preferable to contain 0.001 to 0.5 part by weight of a polyether-modified silicone compound having an HLB value of 7 to 14, relative to 100 parts by weight of the total amount of the acrylic polymer of the copolymer. More preferably 0.1 to 0.5 parts by weight. HLB refers to the hydrophilic-lipophilic balance (hydrophilic-lipophilic ratio) specified in, for example, JIS K3211 (surfactant term) and the like.
The polyether-modified silicone compound can be obtained, for example, by grafting a polyorganosiloxane main chain having a hydrogenated silicon group with an organic compound having an unsaturated bond and a polyoxyalkylene group by hydrosilylation reaction, thereby obtaining the polyether-modified silicone compound. Specifically, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxypropylene) siloxane polymer, and the like are exemplified. The HLB value of the polyether modified silicone compound can be adjusted by selecting the ratio of polyether groups to silicone groups.
By adding the polyether-modified silicone compound having an HLB value of 7 to 14 to the adhesive composition, the adhesion and the reworkability of the adhesive can be improved. The cost is lower when the adhesive composition does not contain a polyether modified silicone compound.
However, in the present invention, by adding a predetermined amount of the (D) polyalkylene glycol mono (meth) acrylate monomer to the adhesive, the hydrophilicity is improved even if the silicone compound such as the polyether-modified silicone compound is not contained, and thus an adhesive layer excellent in antistatic property can be formed.
Further, as other components, known additives such as copolymerizable (meth) acrylic monomer containing an alkyleneoxy group, (meth) acrylamide monomer, dialkyl-substituted acrylamide monomer, surfactant, curing accelerator, plasticizer, filler, curing retarder, processing aid, anti-aging agent, antioxidant and the like may be appropriately added. They may be used singly or in combination of 2 or more kinds.
The copolymer of the main agent used in the adhesive composition of the present invention can be synthesized by polymerizing the following monomers: (A) A (meth) acrylate monomer having an alkyl group having 4 to 18 carbon atoms; (B) a hydroxyl-containing copolymerizable monomer; (C) a carboxyl group-containing copolymerizable monomer; (D) Polyalkylene glycol mono (meth) acrylate monomers; optionally component (E) a hydroxyl-free nitrogen-containing vinyl monomer or an alkoxy-containing alkyl (meth) acrylate 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. The monomer (E) of the optional ingredient may be omitted.
As the (I) antistatic agent, in the case of using (I-2) an acryl-containing ionic compound, the copolymer of the main agent used in the adhesive composition of the present invention can be synthesized by polymerizing the following monomers: (A) A (meth) acrylate monomer having an alkyl group having 4 to 18 carbon atoms; (B) a hydroxyl-containing copolymerizable monomer; (C) a carboxyl group-containing copolymerizable monomer; (D) Polyalkylene glycol mono (meth) acrylate monomers; optionally component (E) a hydroxyl-free nitrogen-containing vinyl monomer or an alkoxy-containing alkyl (meth) acrylate monomer; (I-2) an acryl-containing ionic compound. The monomer (E) of the optional ingredient may be omitted.
The adhesive composition of the present invention can be prepared by further adding (F) a 3-functional isocyanate compound, (G) a crosslinking catalyst, (H) a keto-enol tautomer compound, and also suitable optional additives to the above copolymer. In addition, when the ionic compound (I-2) containing an acryl group is polymerized in the copolymer as a main agent, the ionic compound (I-1) 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 moisture into the adhesive composition when preparing the copolymer as the main agent, it is preferable to perform polymerization under anhydrous conditions such as solution polymerization using an anhydrous organic solvent. In particular, the (D) polyalkylene glycol mono (meth) acrylate monomer is preferably used with a low moisture content because of high hydrophilicity.
Among the monomers used in the preparation of the copolymer of the main agent, in order to avoid an increase in the viscosity of the adhesive composition, it is preferable to reduce the amount of the polyfunctional (difunctional or more) monomer functioning as a crosslinking agent as much as possible. In particular, since the (D) polyalkylene glycol mono (meth) acrylate monomer corresponds to a di (meth) acrylate of the di-functional monomer, it is preferable to use a small amount of the di-ester component.
The copolymer is preferably an acrylic polymer, and preferably contains an acrylic monomer such as a (meth) acrylate monomer or (meth) acrylic acid, (meth) acrylamide, etc. in an amount of 50 to 100 parts by weight relative to 100 parts by weight of the acrylic polymer.
The acid value of the acrylic polymer is preferably 0.01 to 8.0. This improves the contamination and improves the performance of preventing the generation of the residual glue.
The "acid value" is one of the indicators indicating the content of acid, and indicates the 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 force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3 m/min and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30 m/min to a polarizing plate having the acrylic protective film on the surface. Thus, the performance of small variation in adhesion with peeling speed can be obtained, and even by peeling at high speed, peeling can be performed rapidly. In addition, even when the surface protective film is temporarily peeled for re-adhesion, the surface protective film is easily peeled from the adherend without requiring excessive force.
Preferably, the adhesive layer formed by crosslinking the adhesive composition has a surface resistivity of 9.0X10 +11 And the stripping static voltage is +/-0-1.0 kV under omega/≡. In the present invention, ".+ -. 0.0 kV" to "1.0 kV" means 0 to-1.0 kV and 0 to +1.0kV, that is, -1.0 to +1.0kV. If the surface resistivity is large, the performance of dissipating static electricity due to electrification at the time of peeling is poor. Therefore, by making the surface resistivity extremely small, it is possible to reduce the peeling static voltage generated by static electricity generated when the adhesive layer is peeled from the adherend, and to suppress the influence on the electric control circuit or the like of the adherend.
The gel fraction of the adhesive composition of the present invention after crosslinking is preferably 95 to 100%. By such a high gel fraction, the adhesion at a low peeling rate is not excessively high, and the elution of unpolymerized monomers or oligomers from the copolymer is reduced, thereby improving the reworkability and durability at high temperature and high humidity, and preventing contamination of an adherend.
The adhesive film of the present invention is formed by forming an adhesive layer formed by crosslinking the adhesive composition of the present invention on one or both surfaces of a resin film. The surface protective film of the present invention is a surface protective film formed by forming an adhesive layer formed by crosslinking the adhesive composition of the present invention on one surface of a resin film. The adhesive composition of the present invention has excellent antistatic properties because the components (a) to (I) are added in good balance, is excellent in balance of adhesion at a low peeling speed and a high peeling speed, and is also excellent in durability and reworkability (no transfer of contamination to an adherend of a polarizing plate having the acrylic protective film on its surface after drawing with a ballpoint pen via the adhesive layer on the surface protective film). Therefore, the present invention can be applied to a surface protective film of a polarizing plate having an acrylic protective film on the surface.
As the base film of the adhesive layer and a release film (separator) for protecting the adhesive surface, a resin film such as a polyester film can be used.
For the base film, an anti-fouling treatment such as a release agent or a coating agent for silicone and fluorine, silica particles, and an antistatic treatment such as application and kneading of an antistatic agent may be performed on the opposite surface of the resin film to the side where the adhesive layer is formed.
The release film may be subjected to a release treatment such as a silicone-based or fluorine-based release agent on the surface on the side of the adhesive surface of the adhesive layer.
Examples
The present invention will be specifically described below by way of examples.
< preparation of acrylic copolymer >
Example 1
Nitrogen was introduced into a reaction apparatus having a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and the air in the reaction apparatus was replaced with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 6.0 parts by weight of 8-hydroxyoctyl acrylate, 0.1 part by weight of acrylic acid, 10 parts by weight of polypropylene glycol monoacrylate (average repeating unit number of alkyleneoxy groups constituting the polyalkylene glycol chain n=12, diester component in the monomer was 0.1%, solubility to water was 0.8% of haze value in 20% aqueous solution state, moisture content was 0.05%), 2 parts by weight of N-vinylpyrrolidone, and 60 parts by weight of solvent (ethyl acetate) were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was dropped over 2 hours, and reacted at 65℃for 6 hours to obtain an acrylic copolymer solution having a weight average molecular weight of 50 ten thousand for example 1. A part of the acrylic copolymer was used as a sample for measuring an acid value described later.
Examples 2 to 8 and comparative examples 1 to 4
The acrylic copolymer solutions used in examples 2 to 8 and comparative examples 1 to 4 were obtained in the same manner as the acrylic copolymer solution used in example 1 described above, except that the compositions of the monomers were as shown in (A) to (E) and (I-2) of Table 1, respectively.
< preparation of adhesive composition and surface protective film >
Example 1
To the acrylic copolymer solution of example 1 prepared as described above, 1.0 part by weight of 1-octylpyridinium hexafluorophosphate and 8.5 parts by weight of acetylacetone were added and stirred, and then 3.0 parts by weight of Coronate HX (isocyanurate body of hexamethylene diisocyanate) and 0.1 part by weight of titanium triacetylacetone were added and stirred and mixed to obtain an adhesive composition of example 1. The 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 an adhesive sheet having an adhesive layer thickness of 25 μm.
Then, an adhesive sheet was transferred onto the opposite side of the antistatic and antifouling treated polyethylene terephthalate (PET) film on one side, to obtain the surface protective film of example 1 having a laminated structure of "antistatic and antifouling treated PET film/adhesive layer/release film (silicone resin coated PET film)".
Examples 2 to 8 and comparative examples 1 to 4
The surface protective films of examples 2 to 8 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 compositions of the additives were as shown in (F) to (J) of table 2, respectively.
In tables 1 and 2, the blending ratio of each component is shown in parentheses as a numerical value of parts by weight obtained by taking the total amount of group (a) as 100 parts by weight. Of the (I) antistatic agents, (I-2) acryl-containing ionic compounds copolymerized in the copolymer are shown in Table 1, and (I) antistatic agents added after copolymerization are shown in different columns.
The compound names of the components used in tables 1 and 2, in which the symbols are omitted, are shown in tables 3 and 4. In addition, coronate (registered trademark) HX, coronate HL, coronate L are trade names of Japanese polyurethane Industrial Co., ltd, and Takenate (registered trademark) D-140N, D-127N, D-110N, D-120N is a trade name of Mitsui chemical Co., ltd. For group (D) of Table 3, the number of "n" is the average number of repeating units of the alkyleneoxy groups constituting the polyalkylene glycol chain. The "diester" has a value of the diester component (%) in the monomer. The value of "moisture" is the moisture content (%). The value of "haze" is a haze value (%) in a 20% aqueous solution state. In addition, the value of "(H)/(G)" in Table 2 represents the weight ratio.
TABLE 1
Figure BDA0003955416450000261
TABLE 2
Figure BDA0003955416450000262
TABLE 3
Figure BDA0003955416450000271
TABLE 4
Figure BDA0003955416450000281
< test method and evaluation >
The surface protective films of examples 1 to 8 and comparative examples 1 to 4 were cured at 23℃under 50% RH for 7 days, and then the release film (silicone resin-coated PET film) was peeled off to expose the adhesive layer, and the adhesive layer was used as a sample for measuring gel fraction and surface resistivity.
Further, the surface protective film with the adhesive layer exposed was adhered to the surface of the polarizing plate adhered to the liquid crystal cell via the adhesive layer, and after leaving for 1 day, the film was subjected to autoclave treatment at 50℃under 5 atmospheres for 20 minutes, and left at room temperature for 12 hours, to be used as a test piece for measuring the adhesion, peeling static voltage, reworkability and durability. The polarizing plate of the adherend is a polarizing plate having an acrylic protective film on the surface.
< gel fraction >
The mass of the adhesive layer separated from the measurement sample after the completion of curing and before the lamination to the polarizing plate was accurately measured, and after immersing in toluene for 24 hours, the mixture was filtered through a 200-mesh metal mesh. Then, the filtrate was dried at 100℃for 1 hour, and the mass of the residue was accurately measured, whereby the gel fraction of the adhesive layer (crosslinked adhesive layer) was calculated from the following formula.
Gel fraction (%) =mass of insoluble fraction (g)/mass of adhesive layer (g) ×100
< adhesion force >
The measurement sample obtained above (obtained by bonding a 25mm wide surface protective film to the surface of a polarizing plate having an acrylic protective film on the surface) was peeled off with a low peeling speed (0.3 m/min) and a high peeling speed (30 m/min) in the direction of 180 ° by a tensile tester, and the measured peeling strength was taken as an adhesive force (N/25 mm).
< surface resistivity >
After curing and before bonding to the 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 by using a resistivity meter HIRESTA UP-HT450 (manufactured by mitsubishi chemical analysis).
< stripping static Voltage >
When 180 ° peeling was performed on the measurement sample obtained as described above at a stretching speed of 30 m/min, the polarizing plate having the acrylic protective film on the surface thereof was electrostatically charged to generate a voltage (electrostatic voltage) by high-precision electrostatic sensors SK-035 and SK-200 (manufactured by Keyence corporation), and the maximum value of the measured values was the peeling electrostatic voltage (kV).
< re-operability >
After drawing with a ballpoint pen (load 500g,3 rounds) on the surface protective film of the measurement sample obtained above, the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed to confirm that there was no contamination transfer to the polarizing plate. The evaluation target criteria were that the case where there was no contamination transfer to the polarizing plate was evaluated as "o", the case where at least a part of the contamination transfer was observed along the track drawn by the ballpoint pen was evaluated as "Δ", the case where the contamination transfer was observed along the track drawn by the ballpoint pen, and the case where the adhesive was peeled off from the adhesive surface was also observed as "x".
< durability >
After the measurement sample obtained above was left at 60℃for 250 hours under 90% RH atmosphere, the sample was taken out and left at room temperature, and after the sample was left for 12 hours, the adhesion was measured, and no significant increase in the adhesion was observed as compared with the initial adhesion. The evaluation target criteria were that the adhesion after the test was 1.5 times or less of the initial adhesion, and that it was "o" and that it was "x" when it was more than 1.5 times.
The evaluation results are shown in table 5. In addition, in the surface resistivity, "m×10 +n "is described as" mE+n "(where m is an arbitrary real number and n is a positive integer).
TABLE 5
Figure BDA0003955416450000301
In example 1 to8, wherein the adhesive force of the surface protective film of 0.04 to 0.2N/25mm at a low peeling speed of 0.3 m/min and the adhesive force of the surface protective film of 2.0N/25mm or less at a high peeling speed of 30 m/min is 9.0X10 g 10 in the adherend having the acrylic protective film on the surface +11 Omega/≡is less than or equal to + -0-1.0 kV, and the durability is excellent when the film is left under an atmosphere of 60 ℃ and 90% RH for 250 hours without transferring contamination to an adherend after drawing with a ballpoint pen on a surface protective film through an adhesive layer.
That is, all of the required properties of (1) obtaining a balance of the adhesive in the peeling speed of low speed and the peeling speed of high speed, (2) preventing the occurrence of the residual glue, (3) excellent antistatic property, and (4) reworkability are satisfied at the same time.
In the surface protective film of comparative example 1, (C) the carboxyl group-containing copolymerizable monomer is excessive, and there is a possibility that the adhesion at a low peeling speed of 0.3 m/min and a high peeling speed of 30 m/min is excessive due to the absence of (D) a polyalkylene glycol mono (meth) acrylate monomer, (G) a crosslinking catalyst, (H) a keto-enol tautomer compound, and the reworkability is poor.
In the surface protective film of comparative example 2, (C) the carboxyl group-containing copolymerizable monomer is too small, and (D) the diester component in the polyalkylene glycol mono (meth) acrylate monomer is too large, and the water content is high, and the solubility to water is low, so that the adhesion at a low peeling speed of 0.3 m/min and a high peeling speed of 30 m/min is too large, the surface resistivity and peeling static electricity pressure are high, and the durability is poor.
In the surface protective film of comparative example 3, the hydroxyl group-containing copolymerizable monomer (B) is not contained, (C) the carboxyl group-containing copolymerizable monomer is too much, (D) the diester component in the polyalkylene glycol mono (meth) acrylate monomer is large, the water content is high, the solubility to water is low, (H) the keto-enol tautomer compound is too small, and the weight ratio of (H)/(G) is small, so that the pot life becomes too short, gelation before coating is difficult, and coating cannot be performed.
In the surface protective film of comparative example 4, the average number of repeating units of alkyleneoxy groups constituting the polyalkylene glycol chain in the (D) polyalkylene glycol mono (meth) acrylate monomer is large, the diester component is large, the moisture content is high, the solubility to water is low, and the content thereof is too large, so that the adhesion at a low peeling rate of 0.3 m/min is too small, and the re-workability and durability are poor.
Therefore, in the surface protective films of comparative examples 1 to 4, all of the required properties of (1) obtaining a balance of the adhesive in the peeling speed at a low speed and the peeling speed at a high speed, (2) preventing the generation of the residual glue, (3) excellent antistatic property, and (4) re-operability could not be satisfied at the same time.

Claims (7)

1. An adhesive composition for a surface protective film of a polarizing plate having an acrylic protective film on the surface, comprising an acrylic polymer, characterized in that,
the acrylic polymer is a copolymer of (A) a C4-C18 (meth) acrylate monomer having an alkyl group, as a copolymerizable monomer group, (B) a hydroxyl group-containing copolymerizable monomer and (C) a carboxyl group-containing copolymerizable monomer and (D) a polyalkylene glycol mono (meth) acrylate monomer, and (E) at least one of a nitrogen-containing vinyl monomer having no hydroxyl group or an alkoxy group-containing alkyl (meth) acrylate monomer,
With respect to 100 parts by weight of the total amount of acrylic polymer of the copolymer,
the acrylic polymer contains:
70 to 90 parts by weight of (meth) acrylate monomers having C4 to C18 alkyl groups;
2 to 6 parts by weight of the (B) hydroxyl group-containing copolymerizable monomer;
0.05 to 0.5 part by weight of the (C) carboxyl group-containing copolymerizable monomer;
5 to 30 parts by weight of the (D) polyalkylene glycol mono (meth) acrylate monomer; and
0.3 to 8 parts by weight of the (E) hydroxyl group-free nitrogen-containing vinyl monomer or alkoxy group-containing alkyl (meth) acrylate monomer,
the adhesive composition further contains (F) a 3-functional isocyanate compound, (G) a crosslinking catalyst, (H) a keto-enol tautomer compound, and (I) an ionic compound and/or an acryl-containing ionic compound having a melting point of 25 to 50 ℃ as an antistatic agent, and does not contain a polyether-modified siloxane compound.
2. The adhesive composition according to claim 1, wherein,
the adhesive composition contains:
0.1 to 10 parts by weight of the (F) 3 functional isocyanate compound;
0.001 to 0.5 part by weight of the (G) crosslinking catalyst; and
0.1 to 300 parts by weight of the (H) keto-enol tautomer compound,
Further, as the (I) antistatic agent, an antistatic agent contained in the adhesive composition and an antistatic agent copolymerized in the copolymer together contain 0.01 to 5.0 parts by weight,
the diester component in the monomer of the (D) polyalkylene glycol mono (meth) acrylate monomer is 0.3% or less, the moisture content is 0.1% or less, the average number of repeating units of alkylene oxide groups constituting the polyalkylene glycol chain is 3 to 14, and the solubility in water is such that the haze value in a 20% aqueous solution is 2% or less.
3. The adhesive composition according to claim 1 or 2, wherein the (G) crosslinking catalyst is one or more selected from the group of compounds consisting of tris (2, 4-pentanedione) iron (III), iron triacetylacetonate, titanium triacetylacetonate, ruthenium triacetylacetonate, zinc diacetylacetonate, aluminum triacetylacetonate, zirconium tetra-acetylacetonate, tris (2, 4-hexanedione) iron (III), bis (2, 4-hexanedione) zinc, tris (2, 4-hexanedione) titanium, tris (2, 4-hexanedione) aluminum, and zirconium tetra (2, 4-hexanedione).
4. The adhesive composition according to claim 1 or 2, wherein the (B) hydroxyl group-containing copolymerizable monomer 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, N-hydroxyethyl (meth) acrylamide,
The (C) carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid,
the polyalkylene glycol mono (meth) acrylate monomer (D) is at least one 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 (I) antistatic agent contains 0.01 to 5.0 parts by weight of an ionic compound having a melting point of 25 to 50 ℃ contained in the copolymer and/or 0.01 to 5.0 parts by weight of an acryl-containing ionic compound copolymerized in the copolymer, relative to 100 parts by weight of the copolymer.
6. The adhesive composition according to claim 1 or 2, wherein the (H)/(G) weight ratio is 70 to 1000 comprising 1.0 to 30.0 parts by weight of the (H) keto-enol tautomer compound per 100 parts by weight of the copolymer.
7. An adhesive film, characterized in that the adhesive film is formed by forming an adhesive layer formed by crosslinking the adhesive composition according to any one of claims 1 to 6 on one or both surfaces of a resin film.
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