CN104419358A - Bonding Agent Composition, Bonding Film And Surface Protection Film - Google Patents

Bonding Agent Composition, Bonding Film And Surface Protection Film Download PDF

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Publication number
CN104419358A
CN104419358A CN201410410652.2A CN201410410652A CN104419358A CN 104419358 A CN104419358 A CN 104419358A CN 201410410652 A CN201410410652 A CN 201410410652A CN 104419358 A CN104419358 A CN 104419358A
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methyl
acrylate
alkyl
acid
film
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CN104419358B (en
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长仓毅
岛口龙介
长谷川良
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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
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Inorganic Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

The invention provides a bonding agent having good anti-static performance, good bonding force balance, durability and reprocessing performance at high-speed area and low-speed area stripping areas and capable of preventing defects due to cracks caused by external stress. The bonding agent comprises, by the use level of 100 parts by weight of (methyl) crylic acid polymer, the bonding agent composition contains 100 parts of (methyl) crylic acid polymer whose acid value is 0.01 to 8.0 and 0.1 to 5 parts of crosslinking agents. The (methyl) crylic acid polymer is composed of 55 to 97.5 parts by weight of (methyl) crylic acid alkyl ester having alkyl whose carbon atom number is 4 to 10, 1 to 30 parts of (methyl) crylic acid alkyl ester having alkyl whose carbon atom number is 14 to 18, 0.1 to 15 parts of hydroxyl-contained polymerism monometer and 0.1 to 2 parts of carboxyl-contained polymerism monometer. The anti-static agent is ion compound whose melting point is 30 to 50 DEG C.

Description

Adhesive composition, adhesive film and surface protection film
Technical field
The present invention relates to a kind of adhesive composition with antistatic property and the adhesive film and the surface protection film that adopt this adhesive composition at least one side of resin molding, define the adhesive layer with antistatic property.
In addition, the present invention relates to a kind of for the surface protection film in the manufacturing process of liquid-crystal display.More specifically; the present invention relates to and a kind ofly form the surface of the optics such as Polarizer, polarizer, antireflection film of liquid-crystal display and the surface protection film adhesive composition on the surface for the protection of opticses such as Polarizer, polarizer, antireflection films by being pasted onto, and employ the surface protection film of this adhesive composition.
Background technology
All the time, in the manufacturing process of the optics such as Polarizer, polarizer, antireflection film of the parts as formation liquid-crystal display, paste the surface protection film on the surface being used for temporary protection optics.This surface protection film only uses in the operation manufacturing optics, when optics is assembled into liquid-crystal display, it is peeled off from optics and removes.Because this surface protection film for the protection of optical component surfaces only uses in manufacturing process, therefore, be usually also referred to as " operation film ".
For so manufacturing the surface protection film used in the operation of optics; the one side of polyethylene terephthalate (PET) resin molding with optical transparence is formed with adhesive layer; but the stripping film be fitted with on adhesive layer through lift-off processing, to protect this adhesive layer until fit on optics.
In addition; for opticses such as Polarizer, polarizer, antireflection films; owing to carrying out the examination and test of products being mixed into etc. optical assessment with the display capabilities of LCD panel, tone, contrast gradient, impurity under the state of fitting surface protection film; so; as the performance requriements of effects on surface protective membrane, require in adhesive layer without bubble, impurity.
In addition; in recent years; from the opticses such as Polarizer, polarizer, antireflection film during stripper surface protective membrane; along with the stripping electrostatic that the electrostatic occurred when adherend peels off adhesive layer produces; likely can have influence on the fault of the electric control circuit of liquid-crystal display; therefore, require that adhesive layer has excellent antistatic property.
In addition; on the opticses such as Polarizer, polarizer, antireflection film during coating surface protective membrane; due to a variety of causes; the situation of adhesive surface protective membrane again again to be there is after temporary transient stripper surface protective membrane, now requires easily to peel off (re-workability) from the optics as adherend.
In addition, now, require not pollute adherend, namely require the phenomenon that so-called glue residue does not occur.
In addition, time finally from optics stripper surface protective membranes such as Polarizer, polarizer, antireflection films, requirement can be peeled off rapidly.That is, require cohesive force because of the change of peeling rate little, even if also can peel off rapidly when peeling off at a high speed.
So, in recent years, from maneuverable viewpoint during use surface protection film, require that forming the adhesive layer of surface protection film has following performance: (1), under the peeling rate of low-speed region and high-speed region, obtains the balance of cohesive force; (2) generation of glue residue is prevented; (3) there is excellent antistatic property; And (4) have reprocessing (ReWork) performance.
But; namely allow to meet the performance requriements to the adhesive layer forming surface protection film respectively; namely; namely allow to meet the indivedual performance requriementss in above-mentioned (1) ~ (4) respectively; but the over-all properties requirement of (1) that the adhesive layer of the surface protection film that meets the demands has ~ (4) is very difficult problem simultaneously.
In this manual, " low-speed region " refers to the region of peeling rate near 0.3m/min; " high-speed region " refers to the region of peeling rate near 30m/min.
Such as, under the peeling rate of low-speed region and high-speed region, obtain about (1) generation that the balance of cohesive force and (2) prevent glue residue, there will be a known suggestion as described below.
At (methyl) alkyl acrylate of the alkyl to have carbonatoms less than 7 and the multipolymer of carboxylic copolymerization compound as main component, and in the acrylic adhesive layer with linking agent, crosslinking Treatment being carried out to it and make, when through bonding for a long time, there is binding agent move to adherend side and be attached to adherend, and to the bonding force of adherend through time ascending large problem.In order to avoid this problem, there will be a known a kind of technical scheme being provided with following adhesive layer, described adhesive layer is the multipolymer using (methyl) alkyl acrylate with the alkyl of carbonatoms 8 ~ 10 and the copolymerization compound with alcoholic extract hydroxyl group, and with linking agent, it is carried out to the adhesive layer (patent documentation 1) of crosslinking Treatment.
In addition, also proposed a kind of technical scheme being provided with following adhesive layer, described adhesive layer is by multipolymer same as described above, coordinate the multipolymer of a small amount of (methyl) alkyl acrylate and carboxylic copolymerization compound, and with linking agent, it is carried out to the adhesive layer of crosslinking Treatment.But; when using it for surface tension and be low and in the surface protection of ganoid plastic plate etc.; produced problem is: produce the peelings such as separation because of heating when adding man-hour or preserve, and when peeling off under high speed in field hand-manipulated, releasable is poor.
In order to address these problems, propose a kind of adhesive composition, described adhesive composition is: a) to have (methyl) alkyl acrylate of the alkyl of carbonatoms 8 ~ 10 as in (methyl) alkyl acrylate 100 weight part of main component, add the carboxylic copolymerizable compound of b) 1 ~ 15 weight part, and c) aliphatic carboxylic acid of the carbonatoms 1 ~ 5 of 3 ~ 100 weight parts vinyl ester and obtain the multipolymer of monomer mixture, and in this multipolymer, coordinate the adhesive composition (patent documentation 2) of the linking agent of more than the equivalent of the carboxyl of above-mentioned b) composition.
In the adhesive composition that patent documentation 2 is recorded, the peeling of separation etc. can not be produced when adding man-hour or preserving, and, bonding force not through time significantly rising, thus releasable is excellent.In addition, preserve even long-term, particularly preserve for a long time in high temperature environments, also can peel off again with little strength, now not remaining binder in adherend, even and if also can peel off again with little strength when peeling off at a high speed.
In addition, the antistatic property excellent for (3), as the method for giving static resistance for effects on surface protective membrane, proposes the method etc. being mixed into static inhibitor in base material film.As static inhibitor, such as, disclose (a) quaternary ammonium salt, pyridinium salt, there are the various cationic antistatic agents of the cation radicals such as primary ~ uncle is amino; B () has the anionic antistatic agents of the anion-radicals of sulphonate-base, sulfuric ester alkali, phosphoric acid ester alkali, phosphonic acids alkali etc.; The both sexes static inhibitor of (c) amino acids, amidosulphuric acid ester class etc.; The non-ionic antistatic agent of (d) alkamine, glycerols, polyethylene glycols etc.; E () is carried out polymer to static inhibitor as above and is quantized (patent documentations 3) such as the Polymer Antistatic Agents obtained.
In addition, propose in recent years and static inhibitor so is directly contained in adhesive layer, instead of be contained in base material film or coat the scheme on base material film surface.
In addition, about (4) re-workability, such as, propose a kind of adhesive composition, described adhesive composition is: relative to 100 parts by weight propylene acid resins, coordinates the solidifying agent of isocyanate ester compound of 0.0001 ~ 10 weight part and specific silicate oligomer and obtains (patent documentation 4).
In patent documentation 4, record: using the carbonatoms of alkyl be the alkyl acrylate of about 2 ~ 12, the carbonatoms of alkyl be the alkyl methacrylate of about 4 ~ 12 etc. as main monomer component, and can containing the monomer component containing other functional group such as such as carboxylic monomer.Typically, preferably contain the above-mentioned principal monomer of more than 50 % by weight, and the content of wishing the monomer component containing functional group is 0.001 ~ 50 % by weight, is preferably 0.001 ~ 25 % by weight, is more preferably 0.01 ~ 25 % by weight.The adhesive composition that this patent documentation 4 is recorded, though at high temperature or hot and humid under, the rheological parameters' change with time of its cohesive force and bonding force is also little, and also demonstrates excellent effect to the bonding force of curved surface, therefore has re-workability.
Usually, if adhesive layer is soft proterties, then easily produces glue residue, re-workability also easily reduces.That is, after mistake laminating, peel off difficulty, and be difficult to again paste.From this viewpoint, in order to make it have re-workability, need by there is the functional groups such as carboxyl monomer crosslinked in host to make adhesive layer have certain hardness.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-225677 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-256111 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-070629 publication
Patent documentation 4: Japanese Unexamined Patent Publication 8-199130 publication
Summary of the invention
The problem that invention will solve
In technology in the past, require that forming the adhesive layer of surface protection film has following performance: (1), under the peeling rate of low-speed region and high-speed region, obtains the balance of cohesive force; (2) generation of glue residue is prevented; (3) there is excellent antistatic property; And (4) have reprocessing (ReWork) performance.But, namely allow to the performance requriements meeting individual term in above-mentioned (1) ~ (4) respectively, also cannot meet the over-all properties requirement required by adhering agent layer of surface protection film.
Further, in recent years, after adhesive-coated is formed adhesive layer on resin molding, there will be the problem that this adhesive layer produces the shortcomings such as indenture under outside stress.Thus, as the performance requriements for adhesive layer, except above-mentioned four, also require that (5) prevent because of shortcomings such as the indentures that external stress causes.
The present invention completes in view of the foregoing; its problem is, provide a kind of have excellent antistatic property, cohesive force under the peeling rate of low-speed region and high-speed region balance excellent and endurance quality and cycling processability also excellent, can prevent because of the adhesive composition of the defects such as the indenture that external stress causes, adhesive film and surface protection film.
Solve the method for problem
In order to solve above-mentioned problem, the invention provides a kind of adhesive composition, it is the adhesive composition containing static inhibitor and (methyl) acrylic polymers, wherein,
With the cooperation gauge of aforementioned (methyl) acrylic polymers relative to 100 weight parts, described (methyl) acrylic polymers be make 55 ~ 97.5 weight parts have (methyl) alkyl acrylate that carbonatoms is the alkyl of 4 ~ 10,1 ~ 30 weight part have that carbonatoms is (methyl) alkyl acrylate of the alkyl of 14 ~ 18, the copolymerization monomer of the hydroxyl of 0.1 ~ 15 weight part and the carboxylic copolymerization monomer of 0.1 ~ 2 weight part carry out copolymerization and form; Relative to aforementioned (methyl) acrylic polymers of 100 weight parts, the linking agent of described adhesive composition also containing 0.1 ~ 5 weight part; The acid number of described (methyl) acrylic polymers is 0.01 ~ 8.0; Described static inhibitor to be fusing point the be ionic compound of 30 ~ 50 DEG C.
In addition, it is aforementioned that to have carbonatoms be that (methyl) alkyl acrylate of the alkyl of 4 ~ 10 is preferably selected from by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, one or more in the compound group that (methyl) isodecyl acrylate forms, aforementioned (methyl) alkyl acrylate with the alkyl that carbonatoms is 14 ~ 18 be preferably selected from the compound group be made up of the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid isocetyl ester, (methyl) vinylformic acid isooctadecane base ester, (methyl) vinylformic acid tetradecyl ester, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate one or more.
Further, preferably containing the polyether modified siloxane compound that the HLB value as antistatic auxiliary is 7 ~ 15.
In addition, for the copolymerization monomer of aforementioned hydroxyl, be preferably selected from more than at least one in the compound group be made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
In addition, aforementioned carboxylic copolymerization monomer, be selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
Further, preferably containing be 7 ~ 15 as the HLB value of antistatic auxiliary and molecular weight be less than 10000 polyether modified siloxane compound.
In addition, preferred aforementioned crosslinking agent is the isocyanate compound of more than trifunctional.
Further, the invention provides a kind of adhesive film, it is characterized in that, the one side of resin molding is formed with adhesive layer, described adhesive layer foregoing adhesives composition is cross-linked form.
In addition, the invention provides a kind of surface protection film, it use aforementioned adhesive film.
In addition, the invention provides a kind of Polarizer surface protection film, it use aforementioned adhesive film.
In addition, the invention provides a kind of optics surface protection film, it use aforementioned adhesive film.
In addition, the invention provides a kind of Polarizer and display panel laminating adhesive film, it use aforementioned adhesive film.
In addition, the invention provides a kind of optical film material laminating adhesive film forming Polarizer, it use aforementioned adhesive film.
In addition, the invention provides a kind of touch panel blooming, it use aforementioned adhesive film.
In addition, the invention provides a kind of Electronic Paper blooming, it use aforementioned adhesive film.
Invention effect
Based on the present invention, the over-all properties required by adhesive layer of insurmountable effects on surface protective membrane in the prior art can be met, and excellent antistatic property can be obtained, the generation of glue residue phenomenon can be prevented.
Embodiment
Below, based on preferred embodiment the present invention being described.
Adhesive composition of the present invention is the adhesive composition containing static inhibitor and (methyl) acrylic polymers, wherein, preferably:
With the cooperation gauge of aforementioned (methyl) acrylic polymers relative to 100 weight parts, should (methyl) acrylic polymers be by 55 ~ 97.5 weight parts have (methyl) alkyl acrylate that carbonatoms is the alkyl of 4 ~ 10,1 ~ 30 weight part have that carbonatoms is (methyl) alkyl acrylate of the alkyl of 14 ~ 18, the copolymerization monomer of the hydroxyl of 0.1 ~ 15 weight part, the carboxylic copolymerization monomer of 0.1 ~ 2 weight part carry out copolymerization and form; Relative to aforementioned (methyl) acrylic polymers of 100 weight parts, foregoing adhesives composition also comprises the linking agent of 0.1 ~ 5 weight part, and, the acid number of aforementioned (methyl) acrylic polymers is 0.01 ~ 8.0, foregoing antistatic agents to be fusing point the be ionic compound of 30 ~ 50 DEG C.
As having (methyl) alkyl acrylate that carbonatoms is the alkyl of 4 ~ 10, preferably be selected from by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, one or more in the compound group that (methyl) isodecyl acrylate forms.
For (methyl) acrylic polymers of 100 weight parts, what preferably comprise 55 ~ 97.5 weight parts has (methyl) alkyl acrylate that carbonatoms is the alkyl of 4 ~ 10.
As having (methyl) alkyl acrylate that carbonatoms is the alkyl of 14 ~ 18, preferably be selected from by the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid isocetyl ester, (methyl) vinylformic acid isooctadecane base ester, (methyl) myristyl ester, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, one or more in the compound group that (methyl) octadecyl acrylate forms.Can enumerate: carbonatoms be 14 ~ 18 alkyl be (methyl) alkyl acrylate of branched-chain alkyl (methyl) alkyl acrylate or straight chained alkyl.
For (methyl) acrylic polymers of 100 weight parts, what preferably comprise 1 ~ 30 weight part has (methyl) alkyl acrylate that carbonatoms is the alkyl of 14 ~ 18.
When (methyl) alkyl acrylate monomer (carbonatoms is 4 ~ 10) that only adopt carbonatoms larger when considering the wettability of binding agent to adherend (wettability), only can make binding agent deliquescing simply.No matter when when (methyl) alkyl acrylate contains straight chained alkyl or containing branched-chain alkyl, when carbonatoms is about 6 ~ 8, the glass transition point (Tg) of homopolymer is minimum, when carbonatoms is greater than more than it, though then there is the tendency that Tg uprises, flexibility is maintained.Therefore, by making that there is (methyl) alkyl acrylate copolymer that carbonatoms is the alkyl of 14 ~ 18, the shortcomings such as indenture can be eliminated while keeping the wettability to adherend.
As the copolymerization monomer of hydroxyl, can enumerate: (methyl) acrylic amide etc. of (methyl) hydroxyalkyl acrylates class, hydroxyl.
The copolymerization monomer of preferred above-mentioned hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
For aforementioned (methyl) acrylic polymers of 100 weight parts, the content of the copolymerization monomer of preferred hydroxyl is 0.1 ~ 15 weight part.
As carboxylic copolymerization monomer, preferably be selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
For aforementioned (methyl) acrylic polymers of 100 weight parts, the content of preferred carboxylic copolymerization monomer is 0.1 ~ 2 weight part.
For adhesive composition of the present invention, preferably when forming adhesive layer, binder polymer is cross-linked.As the method for carrying out crosslinking reaction, also can be cross-linked by the photo-crosslinking of ultraviolet (UV) etc., but preferred binder composition contains linking agent.
As linking agent, can enumerate: more than more than more than two senses or trifunctional isocyanate compound, two senses or trifunctional epoxy compounds, two senses or trifunctional acrylic compound, metallo-chelate etc.Wherein, be preferably polyisocyanate compounds (isocyanate compound more than two senses or trifunctional), be more preferably the isocyanate compound of more than trifunctional.
For aforementioned (methyl) acrylic polymers of 100 weight parts, the content of preferred linking agent is 0.1 ~ 5 weight part.
As isocyanate compound more than trifunctional, as long as at least have the polyisocyanate compounds of isocyanic ester (NCO) base of more than three in a part.Polyisocyanate compounds comprises the classification such as aliphatic category isocyanic ester, aromatic series kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate, and the present invention can be any kind wherein.As the object lesson of polyisocyanate compounds, can enumerate: the aliphatic category isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI); The aromatic series kind isocyanate compounds such as diphenylmethanediisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenated xylylene vulcabond (H6XDI), dimethyl diphenylene vulcabond (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, can enumerate: the biuret modified body of diisocyanates (there is the compound of two NCO bases in a part) or isocyanurate-modified body, with the affixture (polyalcohol modified body) etc. of polyvalent alcohol (at least there is the compound of more than three OH bases in a part) more than the trivalents such as TriMethylolPropane(TMP) (TMP) or glycerine.
In order to give static resistance, preferred adhesive composition of the present invention contains static inhibitor.For static inhibitor, be preferably solid under normal temperature (such as 30 DEG C).More specifically, preferred static inhibitor to be fusing point the be ionic compound of 30 ~ 50 DEG C.Static inhibitor can be the quaternary ionic compound containing acryl.
Fusing point due to these static inhibitor is low and have the cause of chain alkyl, infers that they are high with the affinity of (methyl) acrylic polymers.
It is the static inhibitor of the ionic compound of 30 ~ 50 DEG C as fusing point, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is cationic nitrogenous or phosphorus positively charged ion, the sulphur positively charged ion etc. of pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium cation etc., and negatively charged ion is phosphorus hexafluoride acid group (PF 6 -), thiocyanate ion (SCN -), benzene sulfonamide acid group (RC 6h 4sO 3 -), perchlorate (ClO 4 -), tetrafluoride borate (BF 4 -) etc. the compound of inorganic or organic anion.By selecting the chain length, substituent position, number etc. of alkyl, the compound that fusing point is 30 ~ 50 DEG C can be obtained.Preferred cationic is quaternary nitrogen positively charged ion, can enumerate: the quaternary ammonium cation etc. of the season glyoxaline cation, tetra-allkylammonium etc. of the season pyridylium, 1,3-dialkylimidazolium (carbon atom of 2,4,5 both can have substituting group and also can not have substituting group) etc. of 1-alkyl pyridine (carbon atom of 2 ~ 6 both can have substituting group and also can not have substituting group) etc.
Relative to aforementioned (methyl) acrylic polymers of 100 weight parts, be that the content of the static inhibitor of the ionic compound of 30 ~ 50 DEG C is preferably 0.1 ~ 5.0 weight part as fusing point.
As the aforementioned quaternary ionic compound containing acryl, be the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is (methyl) acryloxyalkyl trialkyl ammonium (R 3n +-C nh 2n-OCOCQ=CH 2, wherein, Q=H or CH 3, R=alkyl) etc. containing the quaternary ammonium of (methyl) acryl, negatively charged ion is phosphorus hexafluoride acid group (PF 6 -), thiocyanate ion (SCN -), organic sulfonic acid root (RSO 3 -), perchlorate (ClO 4 -), tetrafluoride borate (BF 4 -), containing the imide root (R of F f 2n -) etc. the compound of inorganic or organic anion.As the imide root (R containing F f 2n -) R f, perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc. can be enumerated.As the imide root containing F, two (fluorosulfonyl) imide root ((FSO can be enumerated 2) 2n -), two (trifyl) imide root ((CF 3sO 2) 2n -), two (five fluorine ethylsulfonyls) imide root ((C 2f 5sO 2) 2n -) etc. two alkylsulfonyl imide roots.
Preferably aforementioned quaternary ionic compound copolymerization in aforementioned (methyl) acrylic polymers containing acryl has 0.1 ~ 5.0 % by weight.
As the object lesson of static inhibitor, be not particularly limited, but be the object lesson of the ionic compound of 30 ~ 50 DEG C as aforementioned fusing point, 1-octylpyridinium dodecylbenzene sulfonate, 1-dococylpyridinium thiocyanate-, 3-methyl isophthalic acid-dococylpyridinium hexafluorophosphate, 1-dococylpyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octylpyridinium hexafluorophosphate etc. can be enumerated.
In addition, as the object lesson of the aforementioned quaternary ionic compound containing acryl, dimethylaminomethyl (methyl) acrylate phosphofluoric acid methyl salt ((CH can be enumerated 3) 3n +cH 2oCOCQ=CH 2pF 6 -, wherein, Q=H or CH 3), two (trifyl) imide methyl salt ((CH of dimethyl aminoethyl (methyl) acrylate 3) 3n +(CH 2) 2oCOCQ=CH 2(CF 3sO 2) 2n -, wherein, Q=H or CH 3), two (fluorosulfonyl) imide methyl salt ((CH of dimethylaminomethyl (methyl) acrylate 3) 3n +cH 2oCOCQ=CH 2(FSO 2) 2n -, wherein, Q=H or CH 3) etc.
Adhesive composition of the present invention is preferably the polyether modified siloxane compound of 7 ~ 15 containing HLB value.Polyether modified siloxane compound is the silicone compounds with polyether-based, except common siloxane unit (-SiR 1 2-O-) outside, also comprise the siloxane unit (-SiR with polyether-based 1(R 2o (R 3o) nr 4)-O-).At this, R 1represent one or more alkyl or aryl, R 2and R 3represent one or more alkylidene group, R 4represent (terminal group) such as one or more alkyl, acyl groups.Can enumerate as polyether-based: polyethylene oxide base ((C 2h 4o) n) or polyoxytrimethylene base ((C 3h 6o) n) etc. polyoxyalkylene.
The molecular weight of foregoing polyethers modified silicone com preferably counts less than 10000 with weight-average molecular weight (Mw).From the view point of the intermiscibility to acrylic adhesive, HLB is low and intermiscibility that the is low person of molecular weight is good, if but the polyether modified siloxane compound that molecular weight is low, even if then HLB is higher (slightly low to the intermiscibility of binding agent), also excellent static resistance can be obtained.
In addition, foregoing polyethers modified silicone com is preferably 0.01 ~ 0.5 weight part relative to the content of aforementioned (methyl) acrylic polymers of 100 weight parts.
HLB refers to the hydrophilic-lipophilic balance (wetting ability and oil loving ratio) of the middle regulations such as such as JIS K3211 (tensio-active agent term).
Polyether modified siloxane compound, such as, obtains by following method: by hydrosilylation reactions, makes the organic compound with unsaturated link(age) and polyoxyalkylene be grafted on the main chain of the organopolysiloxane with silylation and obtain.Specifically, can enumerate: dimethyl siloxane-methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxytrimethylene) silicone copolymers etc.
By foregoing polyethers modified silicone com is matched with adhesive composition, cohesive force and the cycling processability of binding agent can be improved.
In addition, foregoing polyethers modified silicone com by with as fusing point be the static inhibitor of ionic compound of 30 ~ 50 DEG C and use, play the function as antistatic auxiliary.
Adhesive composition of the present invention can contain cross-linked inhibitor.As cross-linked inhibitor, can enumerate: the 'beta '-ketoester of methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid oil base ester, lauryl acetoacetate, etheric acid stearyl ester etc., the beta-diketon of methyl ethyl diketone, 2,4-hexanediones, benzoyl acetone etc.These are keto-enol tautomerism compounds, using polyisocyanate compounds as in the adhesive composition of linking agent, closed by the isocyanate group that linking agent is had, can suppress to coordinate the excessive rising of adhesive composition viscosity or the phenomenon of gelation after linking agent, the storage period of adhesive composition can be extended.
Preferred aforementioned cross-linked inhibitor is keto-enol tautomerism compound, is particularly preferably and is selected from methyl ethyl diketone, be more than at least one in compound group that methyl aceto acetate forms.
When adding aforementioned cross-linked inhibitor, aforementioned cross-linked inhibitor is preferably 1.0 ~ 5.0 weight parts relative to the content of aforementioned (methyl) acrylic polymers of 100 weight parts.
Adhesive composition of the present invention can contain crosslinking catalyst.When using polyisocyanate compounds as linking agent, as long as crosslinking catalyst plays the material of function to the reaction (crosslinking reaction) of aforementioned (methyl) acrylic polymers and linking agent as catalyzer, can enumerate: the organometallic compound etc. such as aminated compounds, organo-tin compound, organo-lead compound, organic zinc compound of tertiary amine etc.
Can enumerate as tertiary amine: trialkylamine, N, N, N', N'-tetra, N, N-dialkyl amido alcohol, triethylene diamine, morpholine derivative, bridged piperazine derivatives etc.
As organo-tin compound, can enumerate: the soap of dialkyl tin oxide, dialkyl tin, the soap etc. of sub-tin.
Preferred aforementioned crosslinking catalyst is organo-tin compound, is particularly preferably more than at least one in the compound group being selected from and being made up of di-n-octyltin oxide, tin dilaurate dioctyl tin.
When adding aforementioned crosslinking catalyst, relative to aforementioned (methyl) acrylic polymers of 100 weight parts, the content of aforementioned crosslinking catalyst is preferably 0.01 ~ 0.5 weight part.
Adhesive composition of the present invention can contain polyether compound.As polyether compound, be the compound with polyalkylene oxide base (polyalkylene oxide base, poly alkylene oxide), the polyether glycols such as polyalkylene glycol and their derivative can be enumerated.As the alkylidene group had in polyalkylene glycol and polyalkylene oxide base, ethylidene, propylidene, butylidene etc. can be enumerated, but be not limited to these.Polyalkylene glycol also can be the multipolymer of the two or more polyalkylene glycol in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.As the multipolymer of polyalkylene glycol, can enumerate polyethylene glycol-propylene glycol, polyethylene glycol-butyleneglycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol-propylene glycol-polytetramethylene glycol etc., this multipolymer can be segmented copolymer, random copolymers.
As the derivative of polyalkylene glycol, can enumerate: polyoxyalkylene monoalky lether, the polyoxyalkylene alkyl ether such as polyoxyalkylene dialkyl ether, polyoxyalkylene mono alkenyl ether, the polyoxyalkylene alkene ethers such as polyoxyalkylene dialkylene ether, polyoxyalkylene list aryl ethers, the polyoxyalkylene aryl ethers such as polyoxyalkylene diaryl ether, polyoxyalkylene alkylamine phenyl ether, polyoxyalkylene glycol mono fatty acid ester, the polyoxyalkylene glycol fatty acid esters such as polyoxyalkylene glycol di fatty acid ester, polyoxyalkylene sorbitan-fatty acid ester, polyoxyalkylene alkylamine amine, polyoxyalkylene diamines etc.
At this, as the alkyl oxide in polylalkylene glycol derivatives, can enumerate: the lower alkyl ether such as methyl ether, ether, the senior alkyl oxides such as lauryl ether, octadecyl ether.As the alkene ether in polylalkylene glycol derivatives, vinyl ether, allyl ethers, oleyl ether etc. can be enumerated.In addition, as the fatty acid ester in polylalkylene glycol derivatives, can enumerate: the polyunsaturated fatty acid ester such as acetic ester, stearate, unsaturated fatty acid ester such as (methyl) acrylate, oleic acid ester etc.
Preferred, polyethers compound is the compound containing oxyethylene group (ethylene oxide), the compound more preferably containing polyethylene oxide base.
When polyether compound has polymerizable functional group, itself and (methyl) acrylic polymers also can be made to carry out copolymerization.As polymerizable functional group, be preferably the ethene functional groups such as (methyl) propenyl, vinyl, allyl group.As the polyether compound with polymerizable functional group, can enumerate: polyalkylene glycol mono (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, alkoxy polyalkyleneglycol (methyl) acrylate, polyalkylene glycol mono allyl ethers, polyalkylene glycol diallyl ether, alkoxy polyalkyleneglycol allyl ethers, polyalkylene glycol mono vinyl ether, polyalkylene glycol divinyl ether, alkoxy polyalkyleneglycol vinyl ether etc.
And, as other composition, can suitably coordinate containing alkylene oxide (alkylene oxide) can the known additive such as (methyl) Acrylic Acid Monomer, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, tensio-active agent, curing catalyst, softening agent, weighting agent, curing inhibitors, processing aid, antiaging agent, antioxidant of copolymerization.These both may be used singly or in combination of two or more use.
By being that (methyl) alkyl acrylate of the alkyl of 4 ~ 10 and the copolymerization monomer of hydroxyl and the copolymerization monomer containing carboxyl carry out copolymerization by having carbonatoms, (methyl) acrylic polymers of the host as adhesive composition of the present invention can be synthesized.To the polymerization process of (methyl) acrylic polymers, there is no particular limitation, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.
In (methyl) acrylic polymers, also can make polyalkylene glycol mono (methyl) acrylate monomer, not hydroxyl and other monomers such as nitrogenous vinyl monomer, (methyl) alkyl acrylate monomer containing alkoxyl group, the quaternary ionic compound containing acryl carry out copolymerization.
Adhesive composition of the present invention, by coordinating linking agent, static inhibitor, also having suitable any additive to prepare in above-mentioned (methyl) acrylic polymers.
In addition, preferably the acid number of (methyl) acrylic polymers is 0.01 ~ 8.0.Thereby, it is possible to improve contaminative and improve the performance preventing glue residue phenomenon from occurring.
At this, " acid number " is one of index representing acid content, be with in and 1g contain carboxyl polymkeric substance required for the mg number of potassium hydroxide represent.
The cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked under the peeling rate 0.3m/min of low-speed region is 0.05 ~ 0.1N/25mm, and the cohesive force under the peeling rate 30m/min of high-speed region is below 1.0N/25mm.Thereby, it is possible to obtain cohesive force with the little performance of the change of peeling rate, even also can peel off rapidly when peeling off at a high speed.Further, even if in order to again paste during temporary transient stripper surface protective membrane, also without the need to excessive strength, be easy to peel off from adherend.
Foregoing adhesives composition is preferably made to carry out the surface resistivity of crosslinked adhesive layer 5.0 × 10 + 11Ω/below, stripping static voltage is ± 0 ~ 0.5kV.In addition, in the present invention, the meaning of so-called " ± 0 ~ 0.5kV " refers to " 0 ~-0.5kV " and " 0 ~+0.5kV ", namely means "-0.5 ~+0.5kV ".If surface resistivity is large, then to the poor performance that the electrostatic produced because of charged when peeling off discharges, therefore, by making surface resistivity enough little, the stripping static voltage produced with the electrostatic that occurs when peeling off adhesive layer from adherend can be reduced, the impact on the electric control circuit of adherend etc. can be suppressed.
The gel fraction of the adhesive layer (binding agent after crosslinked) preferably making adhesive composition of the present invention be cross-linked is 95 ~ 100%.Because gel fraction is so high, under the peeling rate of low-speed region, cohesive force can not become excessive, reduce the phenomenon of stripping unconverted monomer or oligomer from (methyl) acrylic polymers, thus the weather resistance can improved under re-workability, high temperature/high humidity, and suppress the pollution of adherend.
Adhesive film of the present invention forms adhesive layer at the single or double of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In addition, surface protection film of the present invention forms adhesive layer at the one side of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In adhesive composition of the present invention; owing to being combined with each composition with good balance; so have excellent antistatic property; the balance of the cohesive force under the peeling rate of low-speed region and high-speed region is excellent; and endurance quality and cycling processability (with ballpoint pen after adhesive layer is described on surface protection film, transferring the pollution to adherend) are also excellent.Therefore, can preferably be used as the surface protection film purposes of Polarizer, polarizer, antireflection film.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, the resin moldings etc. such as polyester film can be used.
For base material film, can on the face contrary with being formed with adhesive layer side of resin molding, implement the antifouling process undertaken by releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of silicone, fluorine class, the antistatic treatment of being undertaken by the coating of static inhibitor or be mixed into etc. can be implemented.
For stripping film, carry out fitting on the face of side at the adhesive surface with adhesive layer, implement the demoulding process undertaken by the releasing agent etc. of silicone, fluorine class.
For for various to Polarizer, phase retardation film etc. blooming is fitted in the opticses such as liquid crystal cells and other blooming, for the adhesive layer of adhesive film, preferably there is the sufficient transparency.In addition, if the optics surface protection film of Polarizer surface protection film etc., then preferred substrates film and adhesive layer have the sufficient transparency.
When adhesive film has base material film, adhesive film of the present invention can be suitably used in such as surface protection film, Polarizer surface protection film, optics surface protection film, the blooming with binding agent, the Polarizer with binding agent etc.
When adhesive film does not have base material film, by the face implementing demoulding process of the two-sided mold release film of fitting respectively at an adhesive layer, the formation of " mold release film/adhesive layer/mold release film " can be formed.In addition, also can form adhesive layer on the one side of mold release film and form the formation of " mold release film/adhesive layer ".In the case, by by the mold release film of both sides successively or peel off and expose adhesive surface simultaneously, can with the optical member adherings such as blooming.As blooming, light polarizing film, phase retardation film, antireflection film, anti-dazzle (anti-glare) film, ultraviolet-absorbing film, infrared absorbing film, optical compensation films, brightness enhancement film etc. can be enumerated.
Now, adhesive film of the present invention can be used in the laminating of Polarizer and display panel.Liquid crystal indicator, organic EL (Organic Electro-Luminescence:OEL) etc. can be enumerated as display panel, but be not limited to these.
In addition, adhesive film of the present invention can be used for forming in the various blooming of peripheral components, touch panel film, Electronic Paper film, organic EL film etc. of the material laminating adhesive film of Polarizer, the liquid-crystal display based on Polarizer.
In addition, can adhesive layer be stated at least one side upper strata prestack of these bloomings and prepare the blooming with adhesive layer.Particularly, the formation of " blooming/adhesive layer/blooming ", " blooming/adhesive layer/mold release film ", " blooming/adhesive layer ", " blooming/adhesive layer/blooming/adhesive layer/blooming ", " blooming/adhesive layer/blooming/adhesive layer/mold release film ", " mold release film/adhesive layer/blooming/adhesive layer/mold release film " etc. can be enumerated.
Such as; have when carrying out with mold release film the adhesive layer protected as " blooming/adhesive layer/mold release film "; peel mold release film off and expose the adhesive layer as " blooming/adhesive layer "; and fit with other blooming, the formation as " blooming/adhesive layer/blooming " adhesive layer being used for interlayer laminating can be obtained thus.
Embodiment
Below, the present invention is illustrated based on embodiment.
The manufacture > of < (methyl) acrylic polymers
[embodiment 1]
Nitrogen is imported in the reaction unit being furnished with agitator, thermometer, reflux exchanger and nitrogen ingress pipe, thus the air with nitrogen replacement in reaction unit.Then, in reaction unit, add the 2-EHA of 80 weight parts, the different tetradecyl ester of vinylformic acid of 10 weight parts, the vinylformic acid 8-hydroxyl monooctyl ester of 8.5 weight parts, the vinylformic acid of 1.5 weight parts, and add the solvent (ethyl acetate) of 60 weight parts simultaneously.Then, through the Diisopropyl azodicarboxylate as polymerization starter of 2 hours instillation 0.1 weight parts, at 65 DEG C, make it react 6 hours, obtain weight-average molecular weight be 500,000, for (methyl) acrylic polymer solution 1 of embodiment 1.Get a part for (methyl) acrylic polymers, as determination of acid value sample described later.
[embodiment 2 ~ 6 and comparative example 1 ~ 3]
Except have adjusted the composition of each monomer respectively as described in (A) in table 1,2 ~ (D) except, operate in the same manner as above-mentioned (methyl) acrylic polymer solution 1 for embodiment 1, obtain for (methyl) acrylic polymer solution in embodiment 2 ~ 6 and comparative example 1 ~ 3.
In addition, in table 1, table 2, (A) be there is (methyl) alkyl acrylate that carbonatoms is the alkyl of 4 ~ 10, (B) be there is (methyl) alkyl acrylate that carbonatoms is the alkyl of 14 ~ 18, (C) be the copolymerization monomer of hydroxyl, (D) is carboxylic copolymerization monomer.
Table 1
The manufacture > of < adhesive composition and surface protection film
[embodiment 1]
To (methyl) acrylic polymer solution 1 according to the embodiment 1 manufactured as mentioned above, add the 1-octylpyridinium dodecylbenzene sulfonate of 2.0 weight parts, the HLB of 0.1 weight part be 7 polyether modified siloxane compound (weight-average molecular weight Mw is 10000) and after stirring, add Coronate HX (the コ ロ ネ ー ト HX of 1.0 weight parts, the isocyanuric acid ester of hexamethylene diisocyanate compound) after be uniformly mixed, obtain the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film be made up of the polyethylene terephthalate scribbling silicone resin (PET) film, then at 90 DEG C, carries out drying and remove solvent, obtain the bonding sheet that adhesive layer thickness is 25 μm.
Then; prepare polyethylene terephthalate (PET) film face implementing antistatic treatment and antifouling process; and bonding sheet is transferred on the face contrary with the face implementing antistatic treatment and antifouling process of this polyethylene terephthalate (PET) film, obtain the surface protection film of the embodiment 1 of the stacked formation with " PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) implementing antistatic treatment and antifouling process ".
[embodiment 2 ~ 6 and comparative example 1 ~ 3]
Except as table 1,2 (E) ~ (G) as described in have adjusted each additive respectively composition except, operate in the same manner as the surface protection film of above-described embodiment 1, obtain embodiment 2 ~ 6 and compare 1 ~ 3 surface protection film.
In addition, in table 1,2, (E) is linking agent, and (F) is static inhibitor, and (G) is polyether modified siloxane compound.
Table 2
Numerical value in the bracket of table 1, all represents that the total total amount organized with (A) ~ (D) is set to 100 weight parts and the numerical value of the weight part obtained.
In addition, the compound title corresponding with the abbreviation of each composition used in table 1 is shown in Table 2.In addition, Coronate (コ ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L is Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) trade name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N are the trade names of Mitsui Chemicals, Inc.
< test method and evaluation >
23 DEG C, under the environment of 50%RH, the surface protection film of embodiment 1 ~ 6 and comparative example 1 ~ 3, after aging 7 days, is peeled off stripping film (scribbling the PET film of silicone resin), thus adhesive layer is exposed, and as the sample of chart surface resistivity.
And then; by the surface protection film that this adhesive layer exposes; the surface of the Polarizer pasted on liquid crystal cell is fitted in by adhesive layer; place and under 50 DEG C, 5 normal atmosphere, carry out pressure kettle process 20 minutes after 1 day; at room temperature place further after 12 hours, as measuring cohesive force, peeling off the sample of static voltage, re-workability and weather resistance.
< acid number >
The acid number of (methyl) acrylic polymers: by sample dissolution in solvent (diethyl ether and ethanol being carried out the solvent mixed with volume ratio 2:1), adopt potential difference automatic titration device (AT-610, capital of a country electronic industry Co., Ltd. manufactures), the potassium hydroxide-ethanol solution being about 0.1mol/L by concentration carries out potential difference titration, determine in and the amount of potassium hydroxide-ethanol solution needed for sample.Then, acid number is obtained according to following formula.
Acid number=(B × f × 5.611)/S
The amount (mL) of the 0.1mol/L potassium hydroxide-ethanol solution used in B=titration
The coefficient (factor) of f=0.1mol/L potassium hydroxide-ethanol solution
The quality (g) of the solids component of S=sample
< cohesive force >
Adopt tensile testing machine; with the peeling rate (30m/min) of the peeling rate of low-speed region (0.3m/min) and high-speed region; above-mentioned obtained mensuration sample (surface protection film wide for 25mm being fitted in the sample on Polarizer surface) is peeled off to 180 ° of directions; determine stripping strength, and using this stripping strength as cohesive force.
< surface resistivity >
After weathering, before laminating Polarizer, peel stripping film (scribbling the PET film of silicone resin) off and adhesive layer is exposed, adopt resistivity meter HirestaUP-HT450 (Ha イ レ ス タ UP-HT450, Mitsubishi of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture), determine the surface resistivity of adhesive layer.
< peels off static voltage >
Adopt high precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (KeyenceCorporation) manufacture), measure when to above-mentioned obtained mensuration sample with the draw speed of 30m/min carry out 180 ° peel off time Polarizer charged and produce voltage (static voltage), using the maximum value of measured value as peel off static voltage.
< re-workability >
After carrying out describing (load be 500g, 3 times back and forth) with ballpoint pen on the surface protection film of mensuration sample obtained above, from Polarizer stripper surface protective membrane, observe the surface of Polarizer, be confirmed whether to displaced pollution to Polarizer.Evaluation objective benchmark: be evaluated as "○" when not transferring the pollution to Polarizer; Be evaluated as " △ " when confirming that the track described along ballpoint pen at least displaced pollution to local; "×" is evaluated as when confirming that the track described along ballpoint pen has pollution transportation and also confirms from adhesive surface the disengaging having binding agent.
< weather resistance >
60 DEG C, 90%RH environment transfers to be set up and states obtained mensuration sample after 250 hours, taken out under being placed in room temperature and places 12 hours further, then measure cohesive force, confirms whether there has been obvious increase compared with initial stage cohesive force.Evaluation objective benchmark: is "○" when the cohesive force after test is the average evaluation of less than 1.5 times of initial stage cohesive force, average evaluation more than 1.5 times is "×".
< wettability >
The surface of the Polarizer that anti-dazzle (Anti Glare) processes has been applied with on surface, only contact one end of the mensuration sample of 2.5cm width × 5cm length, determine and measure sample uniform wet and be bonded in time needed for surface of Polarizer on the whole.Evaluation objective benchmark: when the time on the whole needed for uniform wet lower than 15 seconds time, be evaluated as "○"; When the time on the whole needed for uniform wet be more than 15 seconds and lower than 30 seconds time, be evaluated as " △ "; When the time on the whole needed for uniform wet is more than 30 seconds, be evaluated as "×".
< indenture test (dent test) >
On the surface measuring sample, be placed in 5cm × 5cm the indenture test fixture (jig) having 100 projections, and after the load applying 1kg places 1 day, the mensuration sample of 5cm × 5cm being fitted on Polarizer, determining the number of the bad shortcoming (bubble) of the laminating caused because measuring the indenture on the surface of sample after fitting.Evaluation objective benchmark: when the number of shortcoming is 0 ~ 5, be evaluated as "○"; When the number of shortcoming is 6 ~ 10, be evaluated as " △ "; When the number of shortcoming is more than 11, be evaluated as "×".
Evaluation result is shown in Table 3.In addition, in surface resistivity, represent " m × 10 by " mE+n " + n" (wherein, m is arbitrary real number, and n is positive integer).
Table 3
For the surface protection film of embodiment 1 ~ 6, the cohesive force under the peeling rate 0.3m/min of low-speed region is 0.05 ~ 0.1N/25mm, and the cohesive force under the peeling rate 30m/min of high-speed region is below 1.0N/25mm, and surface resistivity is 5.0 × 10 + 11Ω/below, stripping static voltage is ± 0 ~ 0.5kV.Further, use ballpoint pen across adhesive layer after surface protection film is described, do not transfer the pollution to adherend, and 60 DEG C, place 250 hours under the environment of 90%RH after weather resistance be also excellent.
That is, surface protection film of the present invention, meets simultaneously and is required by following 5 over-all propertiess for adhesive layer formed: (1) obtains the balance of the cohesive force under the peeling rate of low-speed region and high-speed region; (2) generation of glue residue is prevented; (3) there is excellent antistatic property; (4) there is cycling processability; And (5) prevent because of shortcomings such as the indentures that external stress causes.
For the surface protection film of comparative example 1; may be due to not containing have (methyl) alkyl acrylate that carbonatoms is the alkyl of 14 ~ 18, hydroxyl copolymerization monomer too much and not containing the cause of copolymerization monomer with carboxyl; cohesive force under the peeling rate 0.3m/min in its lower velocity region is little; surface resistivity is high with stripping static voltage, poor durability.And it is also slightly poor that its wettability and indenture are tested.
For the surface protection film of comparative example 2, owing to not containing static inhibitor, therefore surface resistivity is high with stripping static voltage.In addition, may be due to not containing having (methyl) alkyl acrylate that carbonatoms is the alkyl of 14 ~ 18 and the too much cause of the copolymerization monomer of hydroxyl, its weather resistance be slightly poor.Further, the result of wettability and indenture test is poor.
For the surface protection film of comparative example 3; may be due to not containing having (methyl) alkyl acrylate that carbonatoms is the alkyl of 14 ~ 18, not containing the cause of copolymerization monomer with carboxyl, its surface resistivity and peel off that static voltage is high, re-workability is slightly poor.In addition, the result of indenture test is poor.
As mentioned above, for the surface protection film of comparative example 1 ~ 3, can not meet simultaneously and be required by following 5 over-all propertiess for adhesive layer formed: (1) obtains the balance of the cohesive force under the peeling rate of low-speed region and high-speed region; (2) generation of glue residue is prevented; (3) there is excellent antistatic property; (4) there is cycling processability; And (5) prevent because of shortcomings such as the impressions that external stress causes.
Industrial applicibility
At surface protection film of the present invention, there is antistatic property; the balance of the cohesive force under the peeling rate of low-speed region and high-speed region is excellent; and endurance quality and cycling processability (with ballpoint pen after adhesive layer is described on surface protection film, transferring the pollution to adherend) are also excellent.Therefore, can preferably be used as the surface protection film purposes of Polarizer, polarizer, antireflection film, practical value is industrially large.

Claims (15)

1. an adhesive composition, containing static inhibitor and (methyl) acrylic polymers, wherein,
With the cooperation gauge relative to (methyl) acrylic polymers described in 100 weight parts, should (methyl) acrylic polymers be make 55 ~ 97.5 weight parts have (methyl) alkyl acrylate that carbonatoms is the alkyl of 4 ~ 10,1 ~ 30 weight part have that carbonatoms is (methyl) alkyl acrylate of the alkyl of 14 ~ 18, the copolymerization monomer of the hydroxyl of 0.1 ~ 15 weight part and the carboxylic copolymerization monomer of 0.1 ~ 2 weight part carry out copolymerization and form
Relative to (methyl) acrylic polymers described in 100 weight parts, the linking agent of described adhesive composition also containing 0.1 ~ 5 weight part,
The acid number of described (methyl) acrylic polymers is 0.01 ~ 8.0,
Described static inhibitor to be fusing point the be ionic compound of 30 ~ 50 DEG C.
2. adhesive composition as claimed in claim 1, wherein,
It is described that to have carbonatoms be (methyl) alkyl acrylate of the alkyl of 4 ~ 10 is be selected from by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, one or more in the compound group that (methyl) isodecyl acrylate forms,
Described (methyl) alkyl acrylate with the alkyl that carbonatoms is 14 ~ 18 be selected from the compound group that is made up of the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid isocetyl ester, (methyl) vinylformic acid isooctadecane base ester, (methyl) vinylformic acid tetradecyl ester, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate one or more.
3. adhesive composition as claimed in claim 1 or 2 wherein, is also the polyether modified siloxane compound of 7 ~ 15 containing the HLB as antistatic auxiliary.
4. the adhesive composition according to any one of claims 1 to 3, wherein, the copolymerization monomer of described hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
5. the adhesive composition according to any one of Claims 1 to 4, wherein, described carboxylic copolymerization monomer is selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
6. the adhesive composition according to any one of Claims 1 to 5, wherein, also containing be 7 ~ 15 as the HLB value of antistatic auxiliary and molecular weight be less than 10000 polyether modified siloxane compound.
7. the adhesive composition according to any one of claim 1 ~ 6, wherein, described linking agent is the isocyanate compound of more than trifunctional.
8. an adhesive film, it on the one side of resin molding, forms adhesive layer form, and described adhesive layer the adhesive composition according to any one of claim 1 ~ 7 is cross-linked form.
9. a surface protection film, it uses adhesive film according to claim 8.
10. a Polarizer surface protection film, it uses adhesive film according to claim 8.
11. 1 kinds of optics surface protection films, it use adhesive film according to claim 8.
12. 1 kinds of Polarizers and display panel laminating adhesive film, it use adhesive film according to claim 8.
13. 1 kinds of optical film material laminating adhesive films forming Polarizer, it use adhesive film according to claim 8.
14. 1 kinds of touch panel bloomings, it use adhesive film according to claim 8.
15. 1 kinds of Electronic Paper bloomings, it use adhesive film according to claim 8.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107868635A (en) * 2016-09-28 2018-04-03 藤森工业株式会社 Adhesion agent composition and adhesive film
CN109826021A (en) * 2019-03-21 2019-05-31 苏州宏裕千智能设备科技有限公司 A kind of antistatic silicone synthetic leather and preparation method thereof
CN115991967A (en) * 2023-01-12 2023-04-21 京东方科技集团股份有限公司 Glue forming composition, glue and flexible display device

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6310271B2 (en) * 2014-02-18 2018-04-11 綜研化学株式会社 Optical pressure-sensitive adhesive composition, optical pressure-sensitive adhesive sheet, and image display device
TWI620804B (en) * 2015-04-10 2018-04-11 Mitsubishi Chemical Corporation Adhesive composition and adhesive using the adhesive composition and adhesive for polarizing plate
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JP6848387B2 (en) * 2016-11-21 2021-03-24 三菱ケミカル株式会社 Polarizer protective film
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JP7107804B2 (en) * 2018-09-27 2022-07-27 藤森工業株式会社 Adhesive composition, and adhesive film and surface protective film using the same
WO2020116951A1 (en) * 2018-12-05 2020-06-11 주식회사 엘지화학 Adhesive agent composition, surface protection film, and method of manufacturing organic light-emitting electronic device
KR20200069799A (en) 2018-12-07 2020-06-17 엘지디스플레이 주식회사 Fordable display device
JP6776417B2 (en) * 2019-08-05 2020-10-28 藤森工業株式会社 Surface protective film
JP7321239B2 (en) * 2020-10-06 2023-08-04 藤森工業株式会社 surface protection film
JP6992140B2 (en) * 2020-10-06 2022-01-13 藤森工業株式会社 Surface protective film

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683464A (en) * 2004-04-15 2005-10-19 日东电工株式会社 Adhesive composition for optical member, adhesive layer for optical member and its producing method, optical member with adhesive, and image display device
JP2008308633A (en) * 2007-06-18 2008-12-25 Nitto Denko Corp Self-adhesive composition for optical member
CN102333834A (en) * 2009-02-26 2012-01-25 日东电工株式会社 Adhesive composition for use in surface protective film and use thereof
CN103131356A (en) * 2011-11-22 2013-06-05 三星显示有限公司 Acrylate based ashesive composition for optical use, acrylate based adhesive sheet for optical use, and method for sepaeating optical component
CN103131362A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition, and surface protection film
CN103131357A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition and surface-protective adhesive film
CN103242781A (en) * 2012-02-13 2013-08-14 藤森工业株式会社 Adhesive composition, adhesive film and surface-protective adhesive film

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63202682A (en) * 1987-02-18 1988-08-22 Nitto Electric Ind Co Ltd Pressure-sensitive adhesive
JPS63225677A (en) 1987-03-13 1988-09-20 Nitto Electric Ind Co Ltd Pressure-sensitive adhesive
JP3487940B2 (en) 1995-01-24 2004-01-19 日本合成化学工業株式会社 Adhesive composition
JP4106749B2 (en) 1997-06-25 2008-06-25 三菱化学ポリエステルフィルム株式会社 LCD panel surface protective film
JP3923643B2 (en) 1998-03-11 2007-06-06 日東電工株式会社 Surface protective film adhesive and surface protective film
JP4824154B2 (en) * 2000-05-16 2011-11-30 日東電工株式会社 Adhesive and surface protective film for optical member using the adhesive
US20090110849A1 (en) * 2005-09-20 2009-04-30 Soken Chemical & Engineering Co., Ltd. Adhesive Composition for Polarizing Plate and Polarizing Plate with Adhesive Layer
JP4755876B2 (en) * 2005-10-06 2011-08-24 日本合成化学工業株式会社 Method for producing functional group-containing acrylic copolymer and method for producing pressure-sensitive adhesive composition
JP2009149834A (en) * 2007-11-28 2009-07-09 Toyo Ink Mfg Co Ltd Antistatic acrylic resin composition, antistatic acrylic adhesive composition, and protective film for optical member
WO2010018794A1 (en) * 2008-08-11 2010-02-18 住友化学株式会社 Optical film with adhesive and optical laminate using same
JP5393393B2 (en) * 2008-10-21 2014-01-22 日本合成化学工業株式会社 Adhesive composition and pressure-sensitive adhesive, and pressure-sensitive adhesive for optical members, and optical member with a pressure-sensitive adhesive layer obtained using the same
JP2010185016A (en) * 2009-02-12 2010-08-26 Nippon Shokubai Co Ltd Solvent type repeelable adhesive composition and repeelable adhesive product
TW201107437A (en) * 2009-06-09 2011-03-01 Nippon Synthetic Chem Ind Adhesive compositions and adhesive, adhesive for optical members and optical member with adhesive layer using it
KR101832702B1 (en) * 2011-04-21 2018-02-27 동우 화인켐 주식회사 Adhesive composition, polarizing plate and liquid crystal display device comprising the same
TW201336954A (en) * 2012-02-10 2013-09-16 Sumitomo Chemical Co Adhesive sheet, optical film with adhesive, optical laminate, and method for producing adhesive sheet

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683464A (en) * 2004-04-15 2005-10-19 日东电工株式会社 Adhesive composition for optical member, adhesive layer for optical member and its producing method, optical member with adhesive, and image display device
JP2008308633A (en) * 2007-06-18 2008-12-25 Nitto Denko Corp Self-adhesive composition for optical member
CN102333834A (en) * 2009-02-26 2012-01-25 日东电工株式会社 Adhesive composition for use in surface protective film and use thereof
CN103131362A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition, and surface protection film
CN103131357A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition and surface-protective adhesive film
CN103131356A (en) * 2011-11-22 2013-06-05 三星显示有限公司 Acrylate based ashesive composition for optical use, acrylate based adhesive sheet for optical use, and method for sepaeating optical component
CN103242781A (en) * 2012-02-13 2013-08-14 藤森工业株式会社 Adhesive composition, adhesive film and surface-protective adhesive film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107868635A (en) * 2016-09-28 2018-04-03 藤森工业株式会社 Adhesion agent composition and adhesive film
CN107868635B (en) * 2016-09-28 2022-03-01 藤森工业株式会社 Adhesive composition and adhesive film
CN109826021A (en) * 2019-03-21 2019-05-31 苏州宏裕千智能设备科技有限公司 A kind of antistatic silicone synthetic leather and preparation method thereof
CN115991967A (en) * 2023-01-12 2023-04-21 京东方科技集团股份有限公司 Glue forming composition, glue and flexible display device

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