CN104419358B - Adhesive composition, adhesive film and surface protection film - Google Patents

Adhesive composition, adhesive film and surface protection film Download PDF

Info

Publication number
CN104419358B
CN104419358B CN201410410652.2A CN201410410652A CN104419358B CN 104419358 B CN104419358 B CN 104419358B CN 201410410652 A CN201410410652 A CN 201410410652A CN 104419358 B CN104419358 B CN 104419358B
Authority
CN
China
Prior art keywords
methyl
acrylate
film
weight
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410410652.2A
Other languages
Chinese (zh)
Other versions
CN104419358A (en
Inventor
长仓毅
岛口龙介
长谷川良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujimori Kogyo Co Ltd
Original Assignee
Fujimori Kogyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujimori Kogyo Co Ltd filed Critical Fujimori Kogyo Co Ltd
Publication of CN104419358A publication Critical patent/CN104419358A/en
Application granted granted Critical
Publication of CN104419358B publication Critical patent/CN104419358B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Inorganic Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provide with excellent antistatic behaviour, cohesive force balance is excellent under the peeling rate of low speed and high-speed region, durability and re-workability are also excellent, can prevent because of impression caused by external stress the defects of adhesive composition.With relative to the cooperation gauge of 100 parts by weight (methyl) acrylic polymer, the adhesive composition contains (methyl) acrylic polymer and 0.1~5 parts by weight of crosslinking agent that 100 parts by weight acid numbers are 0.01~8.0, (methyl) acrylic polymer is had (methyl) alkyl acrylate of the alkyl of carbon number 4~10 by 55~97.5 parts by weight, 1~30 parts by weight have (methyl) alkyl acrylate of the alkyl of carbon number 14~18, 0.1~15 parts by weight hydroxyl combined polymerization monomer and 0.1~2 parts by weight combined polymerization containing carboxyl monomer copolymerization form；Antistatic additive is the ionic compound of 30~50 DEG C of fusing point.

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 using the adhesive composition in resin The adhesive film and surface protection film that the adhesive layer with antistatic property is at least formd on one side of film.
A kind of moreover, it relates to surface protection film in manufacturing process for liquid crystal display.More specifically, The present invention relates to a kind of by being pasted onto the optical components such as the Polarizer for forming liquid crystal display, polarizer, antireflection film Surface and be used for the surface protection film binding agent group for protecting the surface of the optical components such as Polarizer, polarizer, antireflection film Compound, and used the surface protection film of the adhesive composition.
Background technology
All the time, in optical sections such as the Polarizers, polarizer, antireflection film as the part for forming liquid crystal display In the manufacturing process of part, the surface protection film on the surface for temporary protection optical component is pasted.This surface protection film only exists Manufacture optical component process in use, when optical component is assembled into liquid crystal display, by its from optical component peel off and Remove.Due to it is this be used for protect the surface protection film of optical component surfaces only to be used in manufacturing process, therefore, generally also by Referred to as " process film ".
For the surface protection film used in so process of manufacture optical component, poly- with optical transparence Formed with adhesive layer on the one side of ethylene glycol terephthalate (PET) resin film, but be fitted with adhesive layer by The stripping film of lift-off processing, to protect the adhesive layer until fitting on optical component.
In addition, for the optical components such as Polarizer, polarizer, antireflection film, due to being bonded surface protection film In the state of be mixed into etc. with display capabilities, tone, contrast, the impurity of LCD panel the product inspection of optical assessment Test, so, as the performance requirement to surface protection film, it is desirable to without bubble, impurity in adhesive layer.
In addition, in recent years, when surface protection film is peeled off from the optical components such as Polarizer, polarizer, antireflection film, companion Electrostatic is peeled off with caused by the electrostatic occurred when peeling off adhesive layer from adherend, it is possible to influences whether liquid crystal display The failure of the electric control circuit of device, it is therefore desirable to which adhesive layer has excellent antistatic property.
In addition, in coating surface diaphragm on the optical components such as Polarizer, polarizer, antireflection film, due to various Reason, can there is a situation where to re-paste surface protection film again after temporarily peeling off surface protection film, now require easily from work To peel off (re-workability) on the optical component of adherend.
In addition, now, it is desirable to do not pollute adherend, that is, require that the phenomenon of so-called glue residue does not occur.
In addition, when finally peeling off surface protection film from optical components such as Polarizer, polarizer, antireflection films, it is desirable to energy It is enough rapidly to peel off.I.e., it is desirable to which cohesive force is because the change of peeling rate is small, also can in the case of high speed stripping Rapidly peel off.
Maneuverable viewpoint when so, in recent years, from using surface protection film, it is desirable to form surface protection film Adhesive layer there is following performance：(1) under the peeling rate of low-speed region and high-speed region, the balance of cohesive force is obtained； (2) generation of glue residue is prevented；(3) there is excellent antistatic property；And (4) have reprocessing (ReWork) property Energy.
But allow to meet respectively the performance requirement of the adhesive layer to forming surface protection film, i.e. allow to Meet indivedual performance requirements in above-mentioned (1)~(4) respectively, but satisfaction requires what the adhesive layer of surface protection film had simultaneously (1) the over-all properties requirement of~(4), is extremely difficult problem.
In this manual, " low-speed region " refers to region of the peeling rate near 0.3m/min；" high-speed region " is Refer to region of the peeling rate near 30m/min.
For example, balance and (2) of cohesive force are obtained under the peeling rate of low-speed region and high-speed region on (1) Prevent the generation of glue residue, it is known to suggestion as described below.
With (methyl) alkyl acrylate of the alkyl with carbon number below 7 and carboxylic combined polymerization chemical combination The copolymer of thing as main component, and with crosslinking agent crosslinking Treatment is carried out to it and manufactured acrylic adhesive layer In, in the case of by being bonded for a long time, binding agent be present and be attached to adherend to the movement of adherend side, and To the bonding force of adherend through when it is ascending big the problem of.In order to avoid the problem, it is known to which one kind is provided with following viscous The technical scheme of oxidant layer is tied, the adhesive layer is (methyl) acrylic acid alkyl for using the alkyl with carbon number 8~10 Ester and the copolymer of the combined polymerization compound with alcoholic extract hydroxyl group, and the bonding that crosslinking Treatment forms is carried out to it with crosslinking agent Oxidant layer (patent document 1).
In addition, it is also proposed that a kind of technical scheme for being provided with following adhesive layers, the adhesive layer be by with In above-mentioned identical copolymer, coordinate the copolymerization of a small amount of (methyl) alkyl acrylate and carboxylic combined polymerization compound Thing, and the adhesive layer that crosslinking Treatment forms is carried out to it with crosslinking agent.But when using it for, surface tension is low and surface light When in the surface protection of sliding plastic plate etc., problem appear to is that：Because processing when or preserve when heating produce separation etc. stripping From phenomenon, and releasable is poor when being peeled off under high speed in field hand-manipulated.
In order to solve these problems, it is proposed that a kind of adhesive composition, the adhesive composition are：A) with (methyl) alkyl acrylate 100 weight of (methyl) alkyl acrylate of the alkyl of carbon number 8~10 as main component Measure in part, add b) the carboxylic copolymerizable compound of 1~15 parts by weight and c) carbon number 1 of 3~100 parts by weight The vinyl esters of~5 aliphatic carboxylic acid and obtain the copolymer of monomer mixture, and coordinate into the copolymer it is above-mentioned b) The adhesive composition (patent document 2) that the crosslinking agent more than equivalent of the carboxyl of composition forms.
In the adhesive composition that patent document 2 is recorded, in processing or the when of preservation, will not produce the stripping of separation etc. Phenomenon, also, bonding force not through when be substantially increased, so as to releasable it is excellent.In addition, even long-term preserve, especially It is to preserve for a long time in high temperature environments, also can be again peeled off with small strength, not remain bonding in adherend now Agent, and can also be peeled off again with small strength in the case that high speed is peeled off.
In addition, for the antistatic property excellent to (3), as the side for assigning antistatic behaviour to surface protection film Method, it is proposed that method that antistatic additive is mixed into base material film etc..As antistatic additive, such as disclose (a) quaternary ammonium salt, pyridine Salt, the various cationic antistatic agents with cation bases such as primary~tertiary aminos；(b) have sulphonate-base, sulfuric ester alkali, The anionic antistatic agents of the anion base of phosphate alkali, phosphonic acids alkali etc.；(c) amino acids, amidosulphuric acid esters etc. Both sexes antistatic additive；(d) non-ionic antistatic agent of alkamine, glycerols, polyethylene glycols etc.；(e) to as described above Antistatic additive is carried out (patent documents 3) such as the Polymer Antistatic Agents that molecular weight obtains.
Antistatic additive so is directly contained in adhesive layer in addition, proposing in recent years, without being contained within base Material film or the scheme for being coated on base material film surface.
In addition, on (4) re-workability, such as, it is proposed that a kind of adhesive composition, the adhesive composition are： Relative to 100 parts by weight propylene acid resins, coordinate the isocyanate ester compound of 0.0001~10 parts by weight curing agent and Specific silicate oligomer and obtain (patent document 4).
In patent document 4, record：Alkyl acrylate, alkyl using the carbon number of alkyl as 2~12 or so Carbon number is that 4~12 or so alkyl methacrylate etc. is used as main monomer component, and can be contained for example carboxylic The monomer component containing other functional groups such as monomer.Typically, above-mentioned principal monomers more than 50 weight % is preferably comprised, and is wished The content for hoping the monomer component containing functional group is 0.001~50 weight %, preferably 0.001~25 weight %, is more preferably 0.01~25 weight %.The adhesive composition that this patent document 4 is recorded, though at high temperature or it is hot and humid under, its The rheological parameters' change with time of cohesiveness and bonding force is also small, and also shows that excellent effect to the bonding force of curved surface, therefore has and add again Work.
Generally, if adhesive layer is soft character, easily glue residue is produced, re-workability is also easily reduced.That is, Difficulty is peeled off after mistake is bonded, and is difficult to re-paste.From this viewpoint, in order to make it have re-workability, it is necessary to By with functional groups such as carboxyls it is monomer crosslinked in host so that adhesive layer is with certain hardness.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 63-225677 publications
Patent document 2：Japanese Unexamined Patent Publication 11-256111 publications
Patent document 3：Japanese Unexamined Patent Publication 11-070629 publications
Patent document 4：Japanese Unexamined Patent Publication 8-199130 publications
The content of the invention
The invention problem to be solved
In conventional technology, it is desirable to which forming the adhesive layer of surface protection film has following performance：(1) in low-speed region Under the peeling rate of high-speed region, the balance of cohesive force is obtained；(2) generation of glue residue is prevented；(3) have excellent Antistatic property；And (4) have reprocessing (ReWork) performance.But allow to respectively meet in above-mentioned (1)~(4) The performance requirement of individual term, it can not also meet the over-all properties requirement required by the adhering agent layer of surface protection film.
Also, in recent years, by adhesive-coated on resin film and after forming adhesive layer, it may appear that the adhesive layer The problem of the shortcomings of indenture is produced under outside stress.Thus, as the performance requirement for adhesive layer, except above-mentioned Beyond four, (5) are claimed as well and prevent because of the indenture caused by external stress the shortcomings of.
The present invention is to complete in view of the foregoing, and its problem is, there is provided it is a kind of have excellent antistatic property, The balance of cohesive force under the peeling rate of low-speed region and high-speed region is excellent and endurance quality and cycling processability Also it is excellent, adhesive composition, adhesive film and surface protection because of the indenture caused by external stress the defects of can be prevented Film.
The method for solving problem
In order to solve above-mentioned problem, the present invention provides a kind of adhesive composition, and it is containing antistatic additive and (methyl) The adhesive composition of acrylic polymer, wherein,
With relative to the cooperation gauge of foregoing (methyl) acrylic polymer of 100 parts by weight, (methyl) propylene Acids polymers be make 55~97.5 parts by weight have carbon number be 4~10 alkyl (methyl) alkyl acrylate, 1 ~30 parts by weight have containing for (methyl) alkyl acrylate of alkyl, 0.1~15 parts by weight that carbon number is 14~18 The combined polymerization monomer of hydroxyl and the carboxylic combined polymerization monomer of 0.1~2 parts by weight carry out copolymerization and formed；Relative to 100 Foregoing (methyl) acrylic polymer of parts by weight, crosslinking agent of the adhesive composition also containing 0.1~5 parts by weight； The acid number of (methyl) acrylic polymer is 0.01~8.0；The antistatic additive is the ion that fusing point is 30~50 DEG C Property compound.
In addition, it is foregoing with carbon number be 4~10 alkyl (methyl) alkyl acrylate be preferably selected from by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) Heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) The chemical combination that acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate are formed It is more than one or both of thing group；Foregoing (methyl) alkyl acrylate with the alkyl that carbon number is 14~18 is preferred For selected from by the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid isohexadecane base ester, (methyl) acrylic acid different ten Eight Arrcostabs, (methyl) acrylic acid tetradecane base ester, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate It is more than one or both of compound group formed.
Also, preferably comprise the polyether modified siloxane compound for being 7~15 as the HLB value of antistatic adjuvant.
In addition, for combined polymerization monomer to foregoing hydroxyl, it is preferably selected from by (methyl) acrylic acid 8- hydroxyls Monooctyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- The chemical combination that hydroxyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed It is more than at least one of thing group.
In addition, foregoing carboxylic combined polymerization monomer, is selected from by (methyl) acrylic acid, (methyl) acrylic acid carboxylic second Ester, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxy Propyl group hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Amber acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl One or more of compound group that epoxide ethyl tetrahydrophthalic acid is formed.
Also, the polyethers that it is 7~15 to preferably comprise as the HLB value of antistatic adjuvant and molecular weight is less than 10000 Modified silicone com.
Additionally, it is preferred that aforementioned crosslinking agent is isocyanate compound more than trifunctional.
Also, the present invention provides a kind of adhesive film, it is characterised in that formed with adhesive layer on the one side of resin film, The adhesive layer is to form the crosslinking of foregoing adhesives composition.
In addition, the present invention provides a kind of surface protection film, foregoing adhesive film is it used.
In addition, the present invention provides a kind of Polarizer surface protection film, foregoing adhesive film is it used.
In addition, the present invention provides a kind of optics surface protection film, foregoing adhesive film is it used.
In addition, the present invention provides a kind of Polarizer and display panel fitting adhesive film, foregoing adhesive film is it used.
In addition, the present invention provides a kind of optical film material fitting adhesive film for forming Polarizer, it use foregoing viscous Conjunctiva.
In addition, the present invention provides a kind of touch panel optical film, foregoing adhesive film is it used.
In addition, the present invention provides a kind of Electronic Paper optical film, foregoing adhesive film is it used.
Invention effect
Based on the present invention, required by disclosure satisfy that the insurmountable adhesive layer to surface protection film in the prior art Over-all properties, and excellent antistatic property can be obtained, the generation of glue residue phenomenon can be prevented.
Embodiment
Below, the present invention is illustrated based on preferred embodiment.
The adhesive composition of the present invention, it is that the binding agent containing antistatic additive and (methyl) acrylic polymer combines Thing, wherein, preferably：
Relative to the cooperation gauge of foregoing (methyl) acrylic polymer of 100 parts by weight, to be somebody's turn to do (methyl) acrylic acid Compound of birdsing of the same feather flock together be by 55~97.5 parts by weight have carbon number be 4~10 alkyl (methyl) alkyl acrylate, 1~ 30 parts by weight there is (methyl) alkyl acrylate of alkyl, 0.1~15 parts by weight that carbon number is 14~18 contain hydroxyl The combined polymerization monomer of base, the carboxylic combined polymerization monomer of 0.1~2 parts by weight carry out copolymerization and formed；Relative to 100 weight Foregoing (methyl) acrylic polymer of part, foregoing adhesives composition also include the crosslinking agent of 0.1~5 parts by weight, also, The acid number of foregoing (methyl) acrylic polymer is 0.01~8.0, and foregoing antistatic agents are the ions that fusing point is 30~50 DEG C Property compound.
As (methyl) alkyl acrylate for the alkyl for carbon number being 4~10, it is preferably selected from by (first Base) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) propylene Heptyl heptylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) propylene The compound group that sour nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate are formed One or both of more than.
For (methyl) acrylic polymer of 100 parts by weight, the tool of 55~97.5 parts by weight is preferably comprised There is (methyl) alkyl acrylate for the alkyl that carbon number is 4~10.
As (methyl) alkyl acrylate with the alkyl that carbon number is 14~18, it is preferably selected from by (first Base) the different tetradecane base ester of acrylic acid, (methyl) acrylic acid isohexadecane base ester, (methyl) acrylic acid isooctadecane base ester, (first Base) myristyl ester, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate acyl ester, (methyl) acrylic acid tetradecane Base ester, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (first Base) it is more than one or both of the compound group that is formed of octadecyl acrylate.It can enumerate：Carbon number be 14~ 18 alkyl is (methyl) alkyl acrylate of branched alkyl (methyl) alkyl acrylate or straight chained alkyl.
For (methyl) acrylic polymer of 100 parts by weight, preferably comprise 1~30 parts by weight has carbon Atomicity is (methyl) alkyl acrylate of 14~18 alkyl.
When in view of binding agent to the wettability (wetability) of adherend and only with the bigger (first of carbon number Base) in the case of alkyl acrylate monomer (carbon number be 4~10), only simply binding agent can be made to soften.No matter (first Base) alkyl acrylate contains in the case of straight chained alkyl or containing in the case of branched alkyl, when carbon number is 6~8 During left and right, the glass transition point (Tg) of homopolymer is minimum, when more than carbon number is more than it, though then there is what Tg uprised to incline To, but flexibility is maintained.Therefore, (methyl) alkyl acrylate of the alkyl by making there is carbon number to be 14~18 is common It is poly-, can be while the wettability to adherend be kept the shortcomings of elimination indenture.
As the combined polymerization monomer of hydroxyl, can enumerate：(methyl) hydroxyalkyl acrylates classes, hydroxyl (methyl) acrylic amide etc..
It is preferred that the combined polymerization monomer of above-mentioned hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) third The own ester of olefin(e) acid 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) propylene At least one in the compound group that acid amides, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed More than kind.
For foregoing (methyl) acrylic polymer of 100 parts by weight, the preferred combined polymerization list of hydroxyl The content of body is 0.1~15 parts by weight.
As carboxylic combined polymerization monomer, it is preferably selected from by (methyl) acrylic acid, (methyl) acrylic acid carboxylic second Ester, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxy Propyl group hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Amber acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl One or more of compound group that epoxide ethyl tetrahydrophthalic acid is formed.
For foregoing (methyl) acrylic polymer of 100 parts by weight, preferably carboxylic combined polymerization list The content of body is 0.1~2 parts by weight.
For the adhesive composition of the present invention, preferably handed over binder polymer when forming adhesive layer Connection.As the method for carrying out cross-linking reaction, can also be crosslinked by the photo-crosslinking of ultraviolet (UV) etc., but preferred binder Composition contains crosslinking agent.
As crosslinking agent, can enumerate：More than two functions or trifunctional isocyanate compound, two functions or trifunctional More than epoxide above, two functions or trifunctional acrylate compounds, metallo-chelate etc..Wherein, it is preferably Polyisocyanate compounds (isocyanate compounds more than two functions or trifunctional), the isocyanide more preferably more than trifunctional Ester compound.
For foregoing (methyl) acrylic polymer of 100 parts by weight, preferably the content of crosslinking agent be 0.1~ 5 parts by weight.
As isocyanate compound more than trifunctional, as long as at least there is the isocyanide of more than three in a molecule The polyisocyanate compounds of acid esters (NCO) base.Polyisocyanate compounds include aliphatic category isocyanates, aromatic series Kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate etc. are classified, and the present invention can be therein any number of Class.As the specific example of polyisocyanate compounds, can enumerate：Hexamethylene diisocyanate (HDI), isophorone two The aliphatic category isocyanate compounds such as isocyanates (IPDI), trimethyl hexamethylene diisocyanate (TMDI)；Diphenyl Methane diisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), two The aromatic series kind isocyanate compounds such as methyl diphenylene diisocyanate (TOID), toluene di-isocyanate(TDI) (TDI).
As isocyanate compound more than trifunctional, can enumerate：Diisocyanates (have two in a molecule The compound of individual NCO bases) biuret modified body or isocyanurate-modified body, with trimethylolpropane (TMP) or glycerine etc. The addition product of polyalcohol (compound at least in a molecule with more than three OH bases) more than trivalent is (polyalcohol modified Body) etc..
In order to assign antistatic behaviour, preferably adhesive composition of the invention contains antistatic additive.For antistatic additive, It is preferred that it is solid under normal temperature (such as 30 DEG C).More specifically, preferably antistatic additive is that fusing point is 30~50 DEG C ionic Compound.Antistatic additive can be the quaternary ionic compound containing acryloyl group.
Because the fusing point of these antistatic additive is low and has the reason of chain alkyl, thus it is speculated that them and (methyl) acrylic compounds The compatibility of polymer is high.
It is the antistatic additive of 30~50 DEG C of ionic compound as fusing point, is the ion with cation and anion Property compound, can be enumerated：Cation be pyridylium, glyoxaline cation, pyrimidine cation, pyrazoles sun from Cationic nitrogenous or phosphorus cation, sulphur cation of son, pyrroles's cation, ammonium cation etc. etc., anion is Phosphorus hexafluoride acid group (PF6 -), thiocyanate radical (SCN-), benzene sulfonamide acid group (RC6H4SO3 -), perchlorate (ClO4 -), tetrafluoride Borate (BF4 -) etc. inorganic or organic anion compound.By selecting the chain length of alkyl, the position of substituent, number Deng it is 30~50 DEG C of compound that can obtain fusing point.Preferred cationic is quaternary nitrogen cation, can be enumerated：1- alkylated pyrazoles Pyridine (carbon atom of 2~6 can have substituent or not have a substituent) etc. season pyridylium, 1,3- The season imidazoles sun of dialkylimidazolium (carbon atom of 2,4,5 can have substituent or not have substituent) etc. Quaternary ammonium cation of ion, tetra-allkylammonium etc. etc..
It is 30~50 DEG C ionic as fusing point relative to foregoing (methyl) acrylic polymer of 100 parts by weight The content of the antistatic additive of compound is preferably 0.1~5.0 parts by weight.
It is the ion with cation and anion as the foregoing quaternary ionic compound containing acryloyl group Property compound, can be enumerated：Cation is (methyl) acryloxyalkyl trialkyl ammonium (R3N+-CnH2n- OCOCQ=CH2, its In, Q=H or CH3, R=alkyl) etc. the quaternary ammonium containing (methyl) acryloyl group, anion is phosphorus hexafluoride acid group (PF6 -)、 Thiocyanate radical (SCN-), organic sulfonic acid root (RSO3 -), perchlorate (ClO4 -), tetrafluoride borate (BF4 -), the acid imide containing F Root (RF 2N-) etc. inorganic or organic anion compound.As the acid imide root (R containing FF 2N-) RF, trifluoro can be enumerated Perfluoroalkyl group sulfonyl, the fluorosulfonyl of mesyl, five fluorine ethylsulfonyls etc..As the acid imide root containing F, can enumerate double (fluorosulfonyl) acid imide root ((FSO2)2N-), double (trifyl) acid imide root ((CF3SO2)2N-), double (five fluorine second sulphurs Acyl group) acid imide root ((C2F5SO2)2N-) etc. double sulfonyl acid imide roots.
It is preferred that the foregoing quaternary ionic compound containing acryloyl group is in foregoing (methyl) acrylic polymer Middle copolymerization has 0.1~5.0 weight %.
As the specific example of antistatic additive, it is not particularly limited, but is 30~50 DEG C ionic as foregoing fusing point The specific example of compound, 1- octylpyridiniums dodecyl benzene sulfonate, 1- dococylpyridinium thiocyanic acids can be enumerated Salt, 3- methyl isophthalic acids-dococylpyridinium hexafluorophosphate, 1- dococylpyridiniums dodecyl benzene sulfonate, 4- methyl- 1- octylpyridinium hexafluorophosphates etc..
In addition, the specific example as the foregoing quaternary ionic compound containing acryloyl group, can enumerate two Methylaminomethyl (methyl) acrylate hexafluorophosphoric acid methyl salt ((CH3)3N+CH2OCOCQ=CH2·PF6 -, wherein, Q=H Or CH3), double (trifyl) acid imide methyl salt ((CH of dimethyl aminoethyl (methyl) acrylate3)3N+(CH2)2OCOCQ=CH2·(CF3SO2)2N-, wherein, Q=H or CH3), double (the fluorine sulphonyl of dimethylaminomethyl (methyl) acrylate Base) acid imide methyl salt ((CH3)3N+CH2OCOCQ=CH2·(FSO2)2N-, wherein, Q=H or CH3) etc..
The adhesive composition of the present invention preferably comprises the polyether modified siloxane compound that HLB value is 7~15.Polyethers changes Property silicone compounds are the silicone compounds for having polyether-based, except common siloxane unit (- SiR1 2- O-) outside, Also include the siloxane unit (- SiR with polyether-based1(R2O(R3O)nR4)-O-).Here, R1Represent one or more Alkyl or aryl, R2And R3Represent alkylidene, the R of one or more4Represent alkyl, acyl group of one or more etc. (terminal groups).It can be enumerated as polyether-based：Polyethylene oxide base ((C2H4O)n) or PPOX base ((C3H6O)n) etc. it is poly- Alkylidene oxide.
The molecular weight of foregoing polyether modified siloxane compound is preferably calculated as less than 10000 with weight average molecular weight (Mw).From From the viewpoint of the intermiscibility of acrylic adhesive, HLB is low and the intermiscibility of the low person of molecular weight is good, but if molecular weight Low polyether modified siloxane compound, even if then HLB is higher (slightly lower to the intermiscibility of binding agent), it can also obtain excellent Antistatic behaviour.
In addition, foregoing (methyl) acrylic of the foregoing polyether modified siloxane compound phase for 100 parts by weight The content of thing is preferably 0.01~0.5 parts by weight.
HLB refers to hydrophile-lipophile balance (hydrophily and the parent such as specified in JIS K3211 (surfactant term) The ratio of oiliness).
Polyether modified siloxane compound, for example, can obtain by the following method：By hydrosilylation reactions, make tool The organic compound for having unsaturated bond and polyoxyalkylene is grafted on the main chain with the polysiloxane of silylation and obtained .Specifically, can enumerate：Dimethyl siloxane-methyl (polyethylene glycol oxide) silicone copolymers, dimethyl siloxane- Methyl (polyethylene glycol oxide) siloxane-methyl (PPOX) silicone copolymers, dimethyl siloxane-methyl (polyoxygenated Propylene) silicone copolymers etc..
By the way that foregoing polyether modified siloxane compound is matched with into adhesive composition, the bonding of binding agent can be improved Power and cycling processability.
In addition, foregoing polyether modified siloxane compound passes through with being used as fusing point for 30~50 DEG C of ionic compound Antistatic additive is used in combination, to play the function as antistatic adjuvant.
The adhesive composition of the present invention can contain cross-linked inhibitor.As cross-linked inhibitor, can enumerate：Acetyl second Sour methyl esters, ethyl acetoacetate, acetoacetate monooctyl ester, acetoacetate oil base ester, lauryl acetoacetate, acetoacetate stearoyl The beta-diketon of the 'beta '-ketoester of ester etc., acetylacetone,2,4-pentanedione, 2,4- acetyl butyryls, benzoyl acetone etc..These are keto-enol tautomerisms Compound, in the adhesive composition using polyisocyanate compounds as crosslinking agent, by by isocyanide possessed by crosslinking agent Perester radical is closed, can suppress coordinate crosslinking agent after adhesive composition viscosity excessive rising or gelation phenomenon, The storage period of adhesive composition can be extended.
It is preferred that foregoing cross-linked inhibitor is keto-enol tautomerism compound, particularly preferably selected from acetylacetone,2,4-pentanedione, acetyl It is more than at least one of compound group that ethyl acetate is formed.
In the case where adding foregoing cross-linked inhibitor, foregoing cross-linked inhibitor relative to 100 parts by weight foregoing (first Base) content of acrylic polymer is preferably 1.0~5.0 parts by weight.
The adhesive composition of the present invention can contain crosslinking catalyst.Crosslinking agent is being used as using polyisocyanate compounds In the case of, as long as crosslinking catalyst is as catalyst and to the reaction of foregoing (methyl) acrylic polymer and crosslinking agent (cross-linking reaction) plays the material of function, can enumerate：Aminated compounds, organo-tin compound, the Organic leadP of tertiary amine etc. Organo-metallic compounds such as compound, organic zinc compound etc..
It can be enumerated as tertiary amine：Trialkylamine, N, N, N', N'- tetras, N, N- dialkyl amidos alcohol, three second Alkene diamines, morpholine derivative, bridged piperazine derivatives etc..
As organo-tin compound, can enumerate：Dialkyl tin oxide, the soap of dialkyl tin, the fat of stannous Fat hydrochlorate etc..
It is preferred that foregoing crosslinking catalyst is organo-tin compound, particularly preferably it is selected from by di-n-octyltin oxide, February It is more than at least one of compound group that cinnamic acid dioctyl tin is formed.
It is foregoing relative to foregoing (methyl) acrylic polymer of 100 parts by weight when adding foregoing crosslinking catalyst The content of crosslinking catalyst is preferably 0.01~0.5 parts by weight.
The adhesive composition of the present invention can contain polyether compound.It is with polyalkylene as polyether compound The compound of epoxide (polyoxyalkylene epoxide, poly alkylene oxide), can enumerate the PPGs such as PAG And their derivative.As the alkylidene having in PAG and polyalkylene epoxide, can enumerate ethylidene, Propylidene, butylidene etc., but it is not limited to these.PAG can also be polyethylene glycol, polypropylene glycol, polybutadiene The copolymer of two or more PAGs in alcohol etc..As the copolymer of PAG, poly- second can be enumerated Glycol-polypropylene glycol, polyethylene glycol butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propane diols-polytetramethylene glycol Deng the copolymer can be block copolymer, random copolymer.
As the derivative of PAG, can enumerate：Polyoxyalkylene monoalky lether, polyoxyalkylene two The polyoxygenated such as the polyoxyalkylene alkyl ethers such as alkyl ether, polyoxyalkylene mono alkenyl ether, polyoxyalkylene dialkylene ether The polyoxyalkylene aryl ether such as alkylidene alkene ether, polyoxyalkylene list aryl ether, polyoxyalkylene diaryl ether, gather Alkylidene oxide alkyl phenyl ether, polyoxyalkylene glycol mono fatty acid ester, polyoxyalkylene glycol di fatty acid ester etc. Polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine amine, gather Alkylidene oxide diamines etc..
Here, as the alkyl ether in polylalkylene glycol derivatives, can enumerate：The lower alkyl ethers such as methyl ether, ether, The advanced alkyl ether such as lauryl ether, octadecyl ether.As the alkene ether in polylalkylene glycol derivatives, second can be enumerated Alkene ether, allyl ether, oleyl ether etc..In addition, as the fatty acid ester in polylalkylene glycol derivatives, can enumerate： The unsaturated fatty acid ester such as the polyunsaturated fatty acid esters such as acetate, stearate, (methyl) acrylate, oleate.
Preferred, polyethers compound is the compound containing oxyethylene group (ethylene oxide), further preferably polyoxy Change the compound of vinyl.
When polyether compound has polymerizable functional group, it can also be made to be total to (methyl) acrylic polymer It is poly-.It is preferably the ethene functional groups such as (methyl) acrylic, vinyl, pi-allyl as polymerizable functional group.As with poly- The polyether compound of He Xing functional groups, it can enumerate：Polyalkylene glycol mono (methyl) acrylate, PAG two (methyl) acrylate, alkoxy polyalkyleneglycol (methyl) acrylate, polyalkylene glycol mono allyl ether, poly- alkylene Base glycol diallyl ether, alkoxy polyalkyleneglycol allyl ether, polyalkylene glycol mono vinyl ethers, polyalkylene two Alcohol divinyl ether, alkoxy polyalkyleneglycol vinyl ethers etc..
Also, as other compositions, the copolymerizable (first containing alkylene oxide (alkylene oxide) can be mated properly into Base) acrylic monomers, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, surfactant, solidification promote Additive known to agent, plasticizer, filler, curing inhibitors, processing aid, age resister, antioxidant etc..These both may be used To be used alone, can also be used in combination of two or more.
By by with (methyl) alkyl acrylate of alkyl and the combined polymerization of hydroxyl that carbon number is 4~10 Monomer and combined polymerization monomer containing carboxyl are copolymerized, and can synthesize the host as adhesive composition of the present invention (methyl) acrylic polymer.To the polymerization of (methyl) acrylic polymer, there is no particular limitation, can use The appropriate polymerization such as polymerisation in solution, emulsion polymerization.
In (methyl) acrylic polymer, polyalkylene glycol mono (methyl) acrylate monomer, no can also be made Hydroxyl and nitrogenous vinyl monomer, (methyl) alkyl acrylate monomer containing alkoxy, the season containing acryloyl group Other monomers such as ammonium salt type ionic compound are copolymerized.
The adhesive composition of the present invention, can be by coordinating crosslinking agent, resisting in above-mentioned (methyl) acrylic polymer Electrostatic agent, there is appropriate any additive to be prepared.
Additionally, it is preferred that the acid number of (methyl) acrylic polymer is 0.01~8.0.Thereby, it is possible to improve contaminative simultaneously And improve the performance for preventing that glue residue phenomenon from occurring.
It is to neutralize required for 1g contains the polymer of carboxyl here, " acid number " is to represent one of index of acid content The mg numbers of potassium hydroxide represent.
It is preferred that make the adhesive layer that the crosslinking of foregoing adhesives composition forms in the peeling rate 0.3m/min of low-speed region Under cohesive force be 0.05~0.1N/25mm, the cohesive force under the peeling rate 30m/min of high-speed region is 1.0N/25mm Below.Thereby, it is possible to obtain cohesive force with the small performance of the change of peeling rate, even also may be used in the case where high speed is peeled off To peel off rapidly.Also, even if when temporarily peeling off surface protection film to re-paste, without excessive strength, it is easy to Peeled off from adherend.
It is preferred that foregoing adhesives composition is set to carry out the surface resistivity for the adhesive layer that crosslinking forms 5.0 × 10+11 Ω/below, stripping electrostatic pressure are ± 0~0.5kV.In addition, in the present invention, so-called " ± 0~0.5kV's " is meant that " 0~-0.5kV " and " 0~+0.5kV ", mean " -0.5~+0.5kV ".If surface resistivity is big, to peel off when because The poor performance that powered and caused electrostatic is discharged, therefore, by making surface resistivity sufficiently small, it can reduce adjoint from quilt Adherend, which is peeled off, peels off electrostatic pressure caused by the electrostatic occurred during adhesive layer, can suppress the electric control electricity to adherend The influence on road etc..
It is preferred that the adhesive composition of the present invention is set to be crosslinked the gel point of the adhesive layer (binding agent after crosslinking) formed Number is 95~100%.Because gel fraction is so high, cohesive force will not become too much under the peeling rate of low-speed region, drop The low phenomenon of dissolution unconverted monomer or oligomer from (methyl) acrylic polymer, so as to improve reprocessing Durability under property, high temperature/high humidity, and suppress the pollution of adherend.
The present invention adhesive film be resin film single or double formed adhesive layer form, the adhesive layer is to make The adhesive composition crosslinking of the present invention forms.In addition, the surface protection film of the present invention is to form bonding in the one side of resin film Oxidant layer forms, and the adhesive layer is that the adhesive composition crosslinking for making the present invention forms.In the adhesive composition of the present invention In, due to being combined with each composition with good balance, so with excellent antistatic property, in low-speed region and high velocity The balance of cohesive force under the peeling rate in domain is excellent, and endurance quality and cycling processability are (with ball pen across viscous After knot oxidant layer is described on surface protection film, do not transferred the pollution to adherend) it is also excellent.Thus, it may be preferable to conduct Polarizer, polarizer, the surface protection film purposes of antireflection film are used.
Base material film, the stripping film (barrier film) of protection adhesive surface as adhesive layer, can use the resin films such as polyester film Deng.
For base material film, it can implement to pass through silicone on the face opposite with formed with adhesive layer side of resin film The antifouling process of the progress such as class, the releasing agent of fluorine class or coating agent, silicon dioxide microparticle, can implement the coating by antistatic additive Or the antistatic treatment of progress such as it is mixed into.
For stripping film, with the adhesive surface of adhesive layer be bonded on the face of side, implementing by silicone, fluorine The demoulding processing of the progress such as releasing agent of class.
For for the various optical films such as Polarizer, phase retardation film to be fitted in into the optical components such as liquid crystal cells and other light For adhesive layer that learn film, adhesive film, preferably there is the sufficiently transparency.In addition, if Polarizer surface protection film Deng optics surface protection film, then preferred substrates film and adhesive layer have the sufficiently transparency.
When adhesive film has base material film, adhesive film of the invention can be suitably used for such as surface protection film, polarisation In plate surface protection film, optics surface protection film, the optical film with binding agent, Polarizer with binding agent etc..
When adhesive film does not have base material film, by being bonded implementing for mold release film respectively in the two-sided of adhesive layer The face of processing is stripped, the composition of " mold release film/adhesive layer/mold release film " can be formed.Alternatively, it is also possible in the one side of mold release film It is upper to form adhesive layer and form the composition of " mold release film/adhesive layer ".In the case, by by the mold release film of both sides successively Or peel off simultaneously and expose adhesive surface, can be with the optical member adhering such as optical film.As optical film, can enumerate light polarizing film, Phase retardation film, antireflection film, anti-dazzle (anti-glare) film, ultraviolet-absorbing film, infrared absorbing film, optical compensation films, increasing Bright film etc..
Now, adhesive film of the invention can be used in the fitting of Polarizer and display panel.Can be with as display panel Enumerate liquid crystal display device, organic EL (Organic Electro-Luminescence:OEL) etc., but it is not limited to these.
In addition, the adhesive film of the present invention can be used for the material fitting adhesive film of composition Polarizer, based on Polarizer The peripheral components of liquid crystal display are with various optical films, touch panel film, Electronic Paper film, organic EL films etc..
In addition, adhesive layer can be stated at least one side upper strata prestack of these optical films and prepare the light with adhesive layer Learn film.Specifically, " optical film/adhesive layer/optical film ", " optical film/adhesive layer/mold release film ", " optics can be enumerated Film/adhesive layer ", " optical film/adhesive layer/optical film/adhesive layer/optical film ", " optical film/adhesive layer/optics The composition of film/adhesive layer/mold release film ", " mold release film/adhesive layer/optical film/adhesive layer/mold release film " etc..
For example, there are the feelings for the adhesive layer protected with mold release film as " optical film/adhesive layer/mold release film " Under condition, peel mold release film off and expose the adhesive layer as " optical film/adhesive layer ", and pasted with other optical films Close, thus, it is possible to obtain adhesive layer for interlayer fitting such as the composition of " optical film/adhesive layer/optical film ".
Embodiment
Below, the present invention is illustrated based on embodiment.
<The manufacture of (methyl) acrylic polymer>
[embodiment 1]
Nitrogen is imported into the reaction unit equipped with agitator, thermometer, reflux condenser and nitrogen ingress pipe, so as to use nitrogen Gas has replaced the air in reaction unit.Then, added into reaction unit 80 parts by weight 2-EHA, 10 The different tetradecane base ester of acrylic acid of parts by weight, acrylic acid 8- hydroxyls monooctyl ester, the acrylic acid of 1.5 parts by weight of 8.5 parts by weight, and together When add the solvents (ethyl acetate) of 60 parts by weight.Then, by 2 hours conduct polymerization initiators for instilling 0.1 parts by weight Azodiisobutyronitrile, make at 65 DEG C its react 6 hours, obtain weight average molecular weight be 500,000, it is for embodiment 1 (methyl) acrylic polymer solution 1.A part for (methyl) acrylic polymer is taken, is tried as acid value measuring described later Sample.
[embodiment 2~6 and comparative example 1~3]
Except (A) in such as table 1,2~(D) it is described have adjusted the composition of each monomer respectively in addition to, with it is above-mentioned be used for it is real (methyl) acrylic polymer solution 1 for applying example 1 is similarly operated, and is obtained for embodiment 2~6 and comparative example 1 (methyl) acrylic polymer solution in~3.
In addition, in table 1, table 2, (A) be the alkyl that there is carbon number to be 4~10 (methyl) alkyl acrylate, (B) it is that (methyl) alkyl acrylate, (C) of the alkyl that there is carbon number to be 14~18 are the combined polymerization lists of hydroxyl Body, (D) are carboxylic combined polymerization monomers.
Table 1
<The manufacture of adhesive composition and surface protection film>
[embodiment 1]
To (methyl) acrylic polymer solution 1 of the embodiment 1 manufactured as described above, 2.0 parts by weight are added 1- octylpyridiniums dodecyl benzene sulfonate, 0.1 parts by weight HLB be 7 polyether modified siloxane compound (divide equally again 10000) and after being stirred son amount Mw is, adds Coronate HX (U ロ ネ ー ト HX, the hexa-methylene two of 1.0 parts by weight The isocyanuric acid ester of isocyanate compound) after be stirred, obtain the adhesive composition of embodiment 1.This is glued Knot agent composition is coated on the stripping film being made up of polyethylene terephthalate (PET) film for scribbling silicone resin, so It is dried afterwards at 90 DEG C and removes solvent, obtains the bonding sheet that adhesive layer thickness is 25 μm.
Then, the polyethylene terephthalate of antistatic treatment and antifouling process is implemented with one face of preparation (PET) film, and bonding sheet is transferred to polyethylene terephthalate (PET) film with being implemented with antistatic treatment and anti- On the opposite face in face of dirt processing, had and " be implemented with PET film/adhesive layer/stripping of antistatic treatment and antifouling process From film (PET film for scribbling silicone resin) " stacking form embodiment 1 surface protection film.
[embodiment 2~6 and comparative example 1~3]
Except (E)~(G) of such as table 1,2 it is described have adjusted the composition of each additive respectively in addition to, with above-described embodiment 1 Surface protection film similarly operated, obtain embodiment 2~6 and compare 1~3 surface protection film.
In addition, in table 1,2, (E) is crosslinking agent, and (F) is antistatic additive, and (G) is polyether modified siloxane compound.
Table 2
Numerical value in the bracket of table 1, represent the weight for being set to 100 parts by weight with total total amount of (A)~(D) groups and obtaining Measure the numerical value of part.
In addition, the corresponding compound name of the abbreviation of each composition with being used in table 1 is shown in Table 2.In addition, Coronate (U ロ ネ ー ト, registration mark) HX, Coronate HL and Coronate L is Japanese polyurethane industry strain formula meeting The trade name of society (Nippon Polyurethane Industry Co., Ltd.s), Takenate (タ ケ ネ ー ト, registrar Mark) D-140N, D-127N, D-110N be Mitsui Chemicals, Inc trade name.
<Test method and evaluation>
In the environment of 23 DEG C, 50%RH, after the surface protection film aging 7 days of embodiment 1~6 and comparative example 1~3, Peel stripping film (PET film for scribbling silicone resin) off, so that adhesive layer is exposed, and as the examination of measure surface resistivity Sample.
And then by the exposed surface protection film of the adhesive layer, fitted in by adhesive layer and be pasted onto liquid crystal cells On Polarizer surface, place 1 day after under 50 DEG C, 5 atmospheric pressure carry out pressure cooker handle 20 minutes, further in room temperature After lower placement 12 hours, the sample as measure cohesive force, stripping electrostatic pressure, re-workability and durability.
<Acid number>
The acid number of (methyl) acrylic polymer：Sample is dissolved in solvent (by diethyl ether and ethanol with volume ratio 2:1 The solvent mixed) in, using potential difference automatic titration device (AT-610, the manufacture of capital of a country electronics industry Co., Ltd.), use Concentration about 0.1mol/L potassium hydroxide-ethanol solution carries out potential difference titration, determines for neutralizing the hydroxide needed for sample The amount of potassium ethanol solution.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 solutions used in B=titration
The coefficient (factor) of f=0.1mol/L potassium hydroxide-ethanol solutions
The quality (g) of the solid constituent of S=samples
<Cohesive force>
Using cupping machine, with the peeling rate (0.3m/min) of low-speed region and the peeling rate of high-speed region (30m/min), peel off above-mentioned resulting measure sample to 180 ° of directions and (the wide surface protection films of 25mm are fitted in into Polarizer The sample that surface forms), peel strength is determined, and using the peel strength as cohesive force.
<Surface resistivity>
After weathering, it is bonded before Polarizer, peels stripping film (PET film for scribbling silicone resin) off and make outside adhesive layer Dew, using resistivity meter HirestaUP-HT450 (Ha イ レ ス タ UP-HT450, Mitsubishi of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.s) manufactures), determine the surface resistivity of adhesive layer.
<Peel off electrostatic pressure>
Using high-precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (Keyence Corporation) Manufacture), it is powered to determine the Polarizer when carrying out 180 ° of strippings to above-mentioned resulting measure sample with 30m/min draw speed And caused voltage (electrostatic pressure), using the maximum of measured value as stripping electrostatic pressure.
<Re-workability>
Described (load 500g, back and forth 3 on the surface protection film of measure sample obtained above with ball pen It is secondary) after, surface protection film is peeled off from Polarizer, the surface of Polarizer is observed, is confirmed whether to displaced pollution to Polarizer.Evaluation Target fiducials："○" is evaluated as when not transferred the pollution to Polarizer；When confirm along ball pen describe track at least to It is evaluated as " △ " during local transfer pollution；When confirming there is pollution transportation and from binding agent table along the track that ball pen is described Face also confirms to be evaluated as "×" when having the disengaging of binding agent.
<Durability>
Above-mentioned resulting measure sample is placed under 60 DEG C, 90%RH environment after 250 hours, is drawn off being placed in room temperature Under further place 12 hours, then determine cohesive force, confirm whether there is obvious increase compared with initial stage cohesive force. Evaluate target fiducials：Cohesive force after experiment be initial stage less than 1.5 times of situation of cohesive force be evaluated as "○", more than 1.5 Situation again is evaluated as "×".
<Wetability>
The surface of the Polarizer of anti-dazzle (Anti Glare) processing has been applied with surface, only contact 2.5cm width × 5cm length measure sample one end, determine measure sample on the whole uniform wet and be bonded in needed for the surface of Polarizer Time.Evaluate target fiducials：When being less than 15 seconds the time needed for uniform wet on the whole, "○" is evaluated as；When on the whole Time needed for uniform wet for 15 seconds less than 30 seconds when, be evaluated as " △ "；When needed for uniform wet on the whole Between be more than 30 seconds when, be evaluated as "×".
<Indenture tests (dent test)>
On the surface of measure sample, the indenture test fixture (jig) for there are 100 projections in 5cm × 5cm is placed on, and After application 1kg load is placed 1 day, 5cm × 5cm measure sample is fitted on Polarizer, determined because being determined after fitting The number of the shortcomings that caused fitting of the indenture on the surface of sample is bad (bubble).Evaluate target fiducials：When the number of shortcoming For 0~5 when, be evaluated as "○"；When the number of shortcoming is 6~10, it is evaluated as " △ "；When shortcoming number for 11 with When upper, "×" was evaluated as.
Evaluation result is shown in Table 3.In addition, in surface resistivity, " m × 10 are represented by " mE+n "+n" (its In, 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, the cohesive force under the peeling rate 30m/min of high-speed region are below 1.0N/25mm, sheet resistance Rate is 5.0 × 10+11Ω/below, stripping electrostatic pressure are ± 0~0.5kV.Also, exist using ball pen across adhesive layer After surface protection film is described, do not transferred the pollution to adherend, and 250 are placed in the environment of 60 DEG C, 90%RH Durability after hour is also excellent.
That is, surface protection film of the invention, while meet by following 5 over-all properties for adhesive layer formed It is required that：(1) balance of the cohesive force under the peeling rate of low-speed region and high-speed region is obtained；(2) glue residue is prevented Generation；(3) there is excellent antistatic property；(4) there is cycling processability；And (5) are prevented because external stress draws The shortcomings of indenture risen.
For the surface protection film of comparative example 1, it may be possible to due to without with the alkyl that carbon number is 14~18 (methyl) alkyl acrylate, the combined polymerization monomer of hydroxyl are excessive and without the edge of the combined polymerization monomer with carboxyl Therefore the cohesive force under the peeling rate 0.3m/min in its low velocity region is small, surface resistivity and stripping electrostatic pressure are high, durability Difference.Moreover, its wetability and indenture experiment are also slightly worse.
For the surface protection film of comparative example 2, due to without antistatic additive, therefore surface resistivity and electrostatic pressure is peeled off It is high.Additionally, it is possible to it is due to be free of (methyl) alkyl acrylate and hydroxyl with the alkyl that carbon number is 14~18 The excessive reason of combined polymerization monomer, its durability is slightly worse.Also, wetability and the result of indenture experiment are poor.
For the surface protection film of comparative example 3, it may be possible to due to without with the alkyl that carbon number is 14~18 (methyl) alkyl acrylate, the reason without the combined polymerization monomer with carboxyl, its surface resistivity and stripping electrostatic pressure Height, re-workability are slightly worse.In addition, the result of indenture experiment is poor.
For the surface protection film of comparative example 1~3, have not been able to meet what is formed by following 5 simultaneously For the over-all properties requirement of adhesive layer：(1) the flat of the cohesive force under the peeling rate of low-speed region and high-speed region is obtained Weighing apparatus property；(2) generation of glue residue is prevented；(3) there is excellent antistatic property；(4) there is cycling processability；And (5) prevent because of the impression caused by external stress the shortcomings of.
Industrial applicibility
There is antistatic property in the surface protection film of the present invention, under the peeling rate of low-speed region and high-speed region The balance of cohesive force is excellent, and endurance quality and cycling processability are (with ball pen across adhesive layer in surface protection After being described on film, do not transferred the pollution to adherend) it is also excellent.Thus, it may be preferable to as Polarizer, polarizer, The surface protection film purposes of antireflection film is used, and practical value industrially is big.

Claims (14)

1. a kind of adhesive composition, containing antistatic additive and (methyl) acrylic polymer, wherein,
Relative to the cooperation gauge of (methyl) acrylic polymer described in 100 parts by weight, to be somebody's turn to do (methyl) acrylic polymer Compound is (methyl) alkyl acrylate, 1~30 weight with the alkyl that carbon number is 4~10 for making 55~97.5 parts by weight The hydroxyl with (methyl) alkyl acrylate of alkyl, 4~15 parts by weight that carbon number is 14~18 of amount part is total to Polymerizable monomer and the carboxylic combined polymerization monomer of 0.1~2 parts by weight carry out copolymerization and formed,
The combined polymerization monomer of the hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 6- hydroxyls The own ester of base, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acrylamide, N- It is more than at least one of compound group that methylol (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed,
(methyl) acrylic polymer does not contain polyalkylene glycol mono (methyl) acrylate monomer,
Relative to (methyl) acrylic polymer described in 100 parts by weight, the adhesive composition also contains 0.1~5 weight The crosslinking agent of part is measured,
The acid number of (methyl) acrylic polymer is 0.01~8.0,
The antistatic additive is the ionic compound that fusing point is 30~50 DEG C.
2. adhesive composition as claimed in claim 1, wherein,
Described (methyl) alkyl acrylate with the alkyl that carbon number is 4~10 is selected from by (methyl) acrylic acid fourth Ester, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (first Base) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (first Base) one kind in the compound group that is formed of the different nonyl ester of acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate or It is two or more,
Described (methyl) alkyl acrylate with the alkyl that carbon number is 14~18 is selected from by (methyl) acrylic acid Different tetradecane base ester, (methyl) acrylic acid isohexadecane base ester, (methyl) acrylic acid isooctadecane base ester, (methyl) acrylic acid ten One in the compound group that tetraalkyl ester, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate are formed Kind is two or more.
3. adhesive composition as claimed in claim 1 or 2, wherein, also contain as the HLB of antistatic adjuvant be 7~ 15 polyether modified siloxane compound.
4. adhesive composition as claimed in claim 1 or 2, wherein, the carboxylic combined polymerization monomer is to be selected from By (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyl six Hydrogen phthalic acid, 2- (methyl) acryloxypropyls hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl neighbour's benzene Dioctyl phthalate, 2- (methyl) acryloyl-oxyethyls butanedioic acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone In the compound group that single (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl tetrahydrophthalic acid are formed at least More than one.
5. adhesive composition as claimed in claim 1 or 2, wherein, it is 7 also to contain as the HLB value of antistatic adjuvant ~15 and molecular weight be less than 10000 polyether modified siloxane compound.
6. adhesive composition as claimed in claim 1 or 2, wherein, the crosslinking agent is isocyanates more than trifunctional Compound.
7. a kind of adhesive film, it is to form adhesive layer on the one side of resin film to form, and the adhesive layer is to make right will Ask the adhesive composition any one of 1~6 to be crosslinked to form.
8. a kind of surface protection film, it use the adhesive film described in claim 7.
9. a kind of Polarizer surface protection film, it uses the adhesive film described in claim 7.
10. a kind of optics surface protection film, it uses the adhesive film described in claim 7.
11. a kind of Polarizer and display panel fitting adhesive film, it use the adhesive film described in claim 7.
12. a kind of optical film material fitting adhesive film for forming Polarizer, it uses the adhesive film described in claim 7.
13. a kind of touch panel optical film, it uses the adhesive film described in claim 7.
14. a kind of Electronic Paper optical film, it uses the adhesive film described in claim 7.
CN201410410652.2A 2013-09-04 2014-08-20 Adhesive composition, adhesive film and surface protection film Active CN104419358B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-183360 2013-09-04
JP2013183360A JP5952242B2 (en) 2013-09-04 2013-09-04 Adhesive composition, adhesive film and surface protective film

Publications (2)

Publication Number Publication Date
CN104419358A CN104419358A (en) 2015-03-18
CN104419358B true CN104419358B (en) 2017-11-17

Family

ID=52698749

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410410652.2A Active CN104419358B (en) 2013-09-04 2014-08-20 Adhesive composition, adhesive film and surface protection film

Country Status (4)

Country Link
JP (1) JP5952242B2 (en)
KR (4) KR101697310B1 (en)
CN (1) CN104419358B (en)
TW (2) TWI621678B (en)

Families Citing this family (21)

* 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
CN106795408B (en) * 2015-04-10 2018-05-04 日本合成化学工业株式会社 Adhesive composition and use adhesive obtained from it and polarizer adhesive
CN106339116B (en) * 2015-07-11 2023-07-14 宸新科技(厦门)有限公司 Touch panel and manufacturing method thereof
JP6676311B2 (en) * 2015-08-26 2020-04-08 リンテック株式会社 Protective film and laminate
JP2017144608A (en) * 2016-02-16 2017-08-24 藤森工業株式会社 Surface protective film and optical component laminated with the same
JP6580540B2 (en) * 2016-09-28 2019-09-25 藤森工業株式会社 Adhesive composition and adhesive film
JP6848387B2 (en) * 2016-11-21 2021-03-24 三菱ケミカル株式会社 Polarizer protective film
JP6725448B2 (en) * 2017-04-07 2020-07-15 藤森工業株式会社 Adhesive composition and adhesive film
JP6677673B2 (en) * 2017-05-15 2020-04-08 藤森工業株式会社 Pressure-sensitive adhesive composition and surface protective film
JP6570612B2 (en) * 2017-12-25 2019-09-04 藤森工業株式会社 Surface protection film
JP2020003676A (en) * 2018-06-28 2020-01-09 日東電工株式会社 Surface protective film and optical film
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
JP7152234B2 (en) * 2018-09-27 2022-10-12 藤森工業株式会社 Adhesive composition, and adhesive film and surface protective film using the same
JP7193286B2 (en) * 2018-09-27 2022-12-20 藤森工業株式会社 surface protection film
JP7214296B2 (en) * 2018-12-05 2023-01-30 エルジー・ケム・リミテッド PSA COMPOSITION, SURFACE PROTECTIVE FILM AND METHOD FOR MANUFACTURING ORGANIC LIGHT-EMITTING ELECTRONIC DEVICE
KR20200069799A (en) 2018-12-07 2020-06-17 엘지디스플레이 주식회사 Fordable display device
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
JP6776417B2 (en) * 2019-08-05 2020-10-28 藤森工業株式会社 Surface protective film
JP6992140B2 (en) * 2020-10-06 2022-01-13 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
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

Citations (6)

* 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
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
CN103131357A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition and surface-protective adhesive film
CN103131362A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition, and surface protection 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 (16)

* 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
CN101268391B (en) * 2005-09-20 2010-06-16 综研化学株式会社 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
JP5204937B2 (en) * 2007-06-18 2013-06-05 日東電工株式会社 Adhesive composition for optical members
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
CN102119349B (en) * 2008-08-11 2014-07-09 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
JP2011016990A (en) * 2009-06-09 2011-01-27 Nippon Synthetic Chem Ind Co Ltd:The Adhesive composition and adhesive, and adhesive for optical member, adhesive layer-having optical member obtained therewith
KR101832702B1 (en) * 2011-04-21 2018-02-27 동우 화인켐 주식회사 Adhesive composition, polarizing plate and liquid crystal display device comprising the same
CN104105769B (en) * 2012-02-10 2016-06-15 住友化学株式会社 The manufacture method of the blooming of adhesive sheet, band tackiness agent, optical laminate and adhesive sheet

Patent Citations (6)

* 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
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
CN103131357A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition and surface-protective adhesive film
CN103131362A (en) * 2011-11-21 2013-06-05 藤森工业株式会社 Adhesive composition, and surface protection 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

Also Published As

Publication number Publication date
KR20150027688A (en) 2015-03-12
TW201629177A (en) 2016-08-16
KR101782524B1 (en) 2017-09-27
KR101697310B1 (en) 2017-01-17
JP5952242B2 (en) 2016-07-13
KR20180122585A (en) 2018-11-13
KR101917611B1 (en) 2018-11-12
KR20170110562A (en) 2017-10-11
CN104419358A (en) 2015-03-18
KR102017504B1 (en) 2019-09-03
JP2015048469A (en) 2015-03-16
TW201518453A (en) 2015-05-16
KR20170007716A (en) 2017-01-19
TWI537353B (en) 2016-06-11
TWI621678B (en) 2018-04-21

Similar Documents

Publication Publication Date Title
CN104419358B (en) Adhesive composition, adhesive film and surface protection film
CN103571400B (en) Adhesive composition and surface protection film
CN103509502B (en) Adhesive composition and surface protection film
CN103834328B (en) Adhesive composition, adhesive film and surface protection film
JP5879160B2 (en) Adhesive composition and surface protective film
JP5909137B2 (en) Adhesive composition and surface protective film
JP5683369B2 (en) Adhesive composition and surface protective film
CN103820058B (en) Adhesive composition, adhesive film, and surface-protective film
CN107216825A (en) Adhesive composition, bonding film and surface protection film
CN104650779A (en) Adhesive composition and surface protection film
CN104449481A (en) Adhesive composition and surface protection film
CN103820059A (en) Adhesive composition, adhesive film, and surface-protective film
CN104342072B (en) Adhesive composition, adhesive film and surface protection film
JP2019206709A (en) Surface protective film and optical member
JP6219482B2 (en) Adhesive composition and surface protective film
JP6039118B2 (en) Adhesive composition and surface protective film
JP6562485B2 (en) Surface protective film and optical member
JP6460549B2 (en) Surface protection film
JP6744385B2 (en) Surface protection film
JP6336662B2 (en) Surface protective film and optical member
JP6117397B2 (en) Adhesive composition, adhesive film and surface protective film
JP7416893B2 (en) surface protection film
JP6999735B2 (en) Surface protective film
JP6734335B2 (en) Surface protection film
JP6240275B2 (en) Surface protection film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant