CN108659748A - Adhesive composition and surface protection film - Google Patents

Adhesive composition and surface protection film Download PDF

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Publication number
CN108659748A
CN108659748A CN201810472273.4A CN201810472273A CN108659748A CN 108659748 A CN108659748 A CN 108659748A CN 201810472273 A CN201810472273 A CN 201810472273A CN 108659748 A CN108659748 A CN 108659748A
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compound
methyl
adhesive composition
weight
parts
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CN201810472273.4A
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CN108659748B (en
Inventor
长仓毅
岛口龙介
长谷川良
新见洋人
吉田弘幸
菱沼昌世
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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
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides that a kind of the balance of cohesive force is excellent with antistatic property, under low peeling rate and high peeling rate and storage period is long, durability and re-workability also excellent adhesive composition.The adhesive composition includes：(A) carbon atom number of alkyl is copolymer 1 00 parts by weight of at least one of (methyl) acrylate monomer of C4~C18 with the copolymerisable monomer of (B) hydroxyl as copolymerisable monomer group；(C) 0.1~10 parts by weight of isocyanate compound more than two functions；(D) 0.001~0.5 parts by weight of crosslinking catalyst of metallo-chelate；(E) 0.1~200 parts by weight of keto-enol tautomer compound；And 0.05~5 parts by weight of ionic compound that the fusing point as (F) antistatic agent is 25~50 DEG C, and the parts by weight ratio of (E)/(D) is 70~700.

Description

Adhesive composition and surface protection film
It is on February 02nd, 2015, entitled " bonding that the present invention, which is application No. is the 201510053170.0, applying date, The divisional application of agent composition and surface protection film ", the application was with the patent application in Japanese publication on the 24th in 04 month in 2014 It is claimed priority based on No. JP2014-090580.
Technical field
The present invention relates to a kind of adhesive composition and surface protection films.More specifically, a kind of the present invention relates to providing With antistatic property, under low peeling rate and high peeling rate, the balance of cohesive force is excellent, storage period is long, durability and The surface protection film adhesive composition and surface protection film of re-workability also excellent polarizer.
Background technology
For the binder of optical applications, from the viewpoint of excellent transparency, it is preferable to use with (methyl) acrylic acid Arrcostab as main component and with there is copolymer institute made of the acrylic monomers copolymerization of hydroxyl, carboxyl etc. as functional group The acrylic adhesive of composition.Furthermore, it is desirable to the binder suitably adjusted to the various physical properties such as cohesive force.Especially It is, in order to be suitable for the manufacturing process of plant produced, for binder of surface protection film etc., it is desirable that it is being fitted through Cohesive force balance under the low peeling rate and high peeling rate of automatic joint device fitting is excellent.In addition, it is desirable in addition to viscous It is long to tie storage period other than the balance of power, durability, re-workability and antistatic property also excellent binder.
For the various physical properties of this binder, it can be bonded by using with the acrylic compounds being made of copolymer The functional groups such as hydroxyl, carboxyl react contained in agent isocyanates crosslinking agent, epoxies crosslinking agent etc. are handed over Connection reaction, so as to adjust cohesive force, cohesiveness etc..
Back and forth, as the crosslinking agent of acrylic adhesive, generally use isocyanates crosslinking agent.In addition, In the cross-linking reaction for using isocyanates crosslinking agent, as the catalyst for promoting cross-linking reaction, metal chelating is mostly used Close object.
Typically, from the viewpoint of the reaction speed of cross-linking reaction is excellent, the catalyst as cross-linking reaction uses Organo-tin compound, that is, dibutyltin dilaurate etc., but since detrimental toxicities are presented in dibutyltin compound, exist at present It avoids using.
Therefore, it is necessary to one kind can with isocyanates crosslinking agent and use, can substitute dibutyltin compound, it is cheap and The excellent crosslinking catalyst of the reaction speed of cross-linking reaction, but be difficult to develop and acquire.
In view of the foregoing, patent document 1 discloses following the description：As can be with the friendship of isocyanates crosslinking agent Join catalyst, the preferred iron chelate in metallo-chelate；And since the catalytic activity that three (levulinic ketone groups) are coordinated iron is excellent, So particularly preferably.
However, the acrylic adhesive composition containing crosslinking catalyst, can delay during placing at normal temperatures Slow-motion row cross-linking reaction.Therefore, in the industrial production of binder, in order to after the raw material for having coordinated adhesive composition extremely Start to make cross-linking reaction stop in a period of cross-linking reaction, usually and has used crosslinking catalyst and reaction suppressor.
About being used in combination for the crosslinking catalyst and reaction suppressor, Patent Document 2 discloses a kind of systems of polyurethane Make method, wherein use comprising being formed and aforementioned metal by the mixture of at least one metal acetylacetonate and acetylacetone,2,4-pentanedione The weight ratio of acetylacetone,2,4-pentanedione and aforementioned acetylacetone,2,4-pentanedione is 2:The reaction polyurethane mixture of 1 antigravity system.
For adhesive composition recorded in patent document 1, although proposing metallic compound (cross-linking catalyst Agent) relative to using the additive amount of copolymer of (methyl) acrylate as monomeric unit is constituted and containing hydroxyl and carboxyl, but The additive amount of cross-linked inhibitor is not recorded.In addition, in patent document 1, being crosslinked as inhibiting to coordinate in adhesive composition The method of viscosity climbing after agent has enumerated the method using reaction suppressor, addition is inhibited molten to viscosity rising The method of agent, used blocked isocyanate etc. functional group closed (block) crosslinking agent method etc., but do not have Body explanation.
In addition, Patent Document 2 discloses a kind of polyurethane manufacturing methods, wherein the antigravity system utilized contains： It will not lead to premature cure and tool using the metal acetylacetonate catalyst of very high iron active at low temperature, copper etc. There are the metal acetylacetonate and acetylacetone,2,4-pentanedione of excellent stability and good catalytic activity.
But in method described in Patent Document 2, the weight ratio of metal acetylacetonate and acetylacetone,2,4-pentanedione is set as 2:1, But in the case of using the compounding ratio in the manufacturing process of acrylic adhesive, can not also cross-linking reaction be made temporarily to stop Only.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-001440 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2008-285681 bulletins
Invention content
The subject that the invention solves
The present invention is exactly to complete in view of the foregoing, and project is to provide one kind without using organo-tin compound In the case of have antistatic property and under low peeling rate and high peeling rate the balance of cohesive force it is excellent and store Phase is long, the surface protection film adhesive composition and surface protection film of durability and re-workability also excellent polarizer.
The method to solve the problem
In order to solve the above problems, the present invention provides a kind of adhesive composition, wherein
The adhesive composition includes：(A) in (methyl) acrylate monomer that the carbon atom number of alkyl is C4~C18 At least one 00 parts by weight of copolymer 1 with the copolymerisable monomer of (B) hydroxyl as copolymerisable monomer group；(C) two function Above 0.1~10 parts by weight of isocyanate compound；(D) 0.001~0.5 parts by weight of crosslinking catalyst of metallo-chelate； (E) 0.1~200 parts by weight of ketone-enol tautomers compound；And the fusing point as (F) antistatic agent is 25~50 DEG C 0.05~5 parts by weight of ionic compound, and the parts by weight ratio of (E)/(D) be 70~700.
Additionally, it is preferred that the copolymerisable monomer of aforementioned (B) hydroxyl be 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- hydroxyls The compound group that (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed At least one of more than.
In addition, as isocyanate compound more than aforementioned (C) two function, preferably as two functional isocyanate chemical combination Object is non-ring type aliphatic isocyanates compound and is that diisocyanate cpd is made to be reacted and be given birth to diol compound At compound.It is aliphatic diisocyanate as aforementioned diisocyanates compound, is preferably chosen from by tetramethylene two Isocyanates, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, relies ammonia at pentamethylene diisocyanate One kind in the compound group that sour diisocyanate is formed.In addition, as foregoing glycols compound, it is preferably selected from by 2- Methyl 1,3- propylene glycol, 2,2- dimethyl -1,3- propylene glycol, 2- methyl-2-propyl -1,3- propylene glycol, 2- ethyl -2- butyl - 1,3- propylene glycol, 3- methyl-1s, 5- pentanediols, polyethylene glycol, gather 2,2- dimethyl -1,3- propylene glycol monohydroxies pivalate One kind in the compound group that propylene glycol is formed.
In addition, as isocyanate compound more than aforementioned (C) two function, preferably as trifunctional isocyanates chemical combination Object selected from by the isocyanuric acid ester of hexamethylene diisocyanate compound, isophorone diisocyanate compound it is different Cyanurate, the addition product of hexamethylene diisocyanate compound, the addition product of isophorone diisocyanate compound, six The biuret of methylene diisocyanate compound, the biuret of isophorone diisocyanate compound, toluene diisocynate The isocyanuric acid ester of ester compounds, the isocyanuric acid ester of xylylene diisocyanate compound, two isocyanide of hydrogenated xylylene The isocyanuric acid ester of ester compound, the addition product of tolunediisocyanate compound, xylylene diisocyanate compound Addition product, hydrogenated xylylene diisocyanate compound at least one of the compound group that is formed of addition product with On.
In addition, the crosslinking catalyst in foregoing adhesives composition, be preferably selected from by aluminium chelate compound, titanium chelate, It is more than at least one of group that iron chelate is formed.
Additionally, it is preferred that aforementioned (F) antistatic agent is to contain 0.05~5.0 weight relative to the aforementioned copolymers of 100 parts by weight Amount part and the ionic compound of 25~50 DEG C of fusing point, and/or be copolymerization amount in aforementioned copolymer be 0.1~5.0 weight Measure % and the ionic compound containing acryloyl group.
It is preferred that aforementioned copolymer includes carboxylic monomer, not hydroxyl and nitrogenous second as other copolymerisable monomer groups More than at least one of alkenyl monomer, polyalkylene glycol mono (methyl) acrylate monomer, and/or as additive include Polyether silicone compound and other previous antioxidants etc..
Additionally, it is preferred that adhesive layer is at low peeling rate 0.3m/min made of so that foregoing adhesives composition is crosslinked Cohesive force is 0.05~0.1N/25mm, and the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less.
Additionally, it is preferred that the surface resistivity of adhesive layer is 9.0 × 10 made of so that foregoing adhesives composition is crosslinked+11 Ω/ is hereinafter, stripping electrostatic pressure is ± 0~0.5kV.
In addition, the present invention provides a kind of adhesive film, it is to form adhesive layer on the single or double of resin film to form, The adhesive layer is that foregoing adhesives composition is made to be crosslinked.
It is to form adhesive layer in the single side of resin film and form in addition, the present invention provides a kind of surface protection film, it is described Adhesive layer is that foregoing adhesives composition is made to be crosslinked, wherein uses ball pen across adhesive layer on surface protection film After being described, pollution is not transferred in adherend.
In addition, the surface protection film purposes that the surface protection film of the present invention can be used as polarizer is used.
In addition, the present invention surface protection film in, preferably aforementioned resin film be formed with the one of foregoing adhesives layer Side is implemented with antistatic and antifouling process on opposite face.
Invention effect
Based on the present invention, can meet without using organo-tin compound insurmountable in the prior art Over-all properties required by adhesive layer to surface protection film, and excellent antistatic property can be obtained, it can prevent from gluing Tie the generation of agent residual phenomena.Specifically, excellent antistatic property can not only be kept, but also can reduce antistatic The additive amount of agent can also improve the performance for preventing glue residue.
Specific implementation mode
In the following, illustrating the present invention based on preferred embodiment.
The present invention adhesive composition include：(A) carbon atom number of alkyl is (methyl) acrylate list of C4~C18 00 parts by weight of copolymer 1 of at least one of body and the copolymerisable monomer of (B) hydroxyl as copolymerisable monomer group；(C) 0.1~10 parts by weight of isocyanate compound more than two functions；(D) 0.001~0.5 weight of crosslinking catalyst of metallo-chelate Measure part；(E) 0.1~200 parts by weight of ketone-enol tautomers compound；And as (F) antistatic agent fusing point be 25~ 50 DEG C of ionic compound is 0.05~5 parts by weight, and the parts by weight ratio of (E)/(D) is 70~700.
Aforementioned copolymer may include carboxylic monomer, not hydroxyl and nitrogenous second as other copolymerisable monomer groups It is more than at least one of alkenyl monomer, polyalkylene glycol mono (methyl) acrylate monomer.
Aforementioned (F) antistatic agent can be relative to 100 parts by weight aforementioned copolymer contain 0.05~5.0 parts by weight and The ionic compound, and/or be the copolymerization amount in aforementioned copolymer for 0.1~5.0 weight % and contain that 25~50 DEG C of fusing point There is the ionic compound of acryloyl group.
In addition, the adhesive composition of the present invention, it may include polyether silicone compound and other previous as additive Antioxidant etc..
(methyl) acrylate monomer that carbon atom number as (A) alkyl is C4~C18, can enumerate：(methyl) third Olefin(e) acid butyl ester, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptan Ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl Ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane Base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (first Base) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (methyl) propylene Sour stearyl, (methyl) myristyl ester, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid spermaceti Ester, (methyl) acrylic acid isohexadecane base ester, (methyl) stearyl acrylate acyl ester, (methyl) acrylic acid isooctadecane base ester etc..
Relative to 100 parts by weight aforementioned copolymers, the preferably carbon atom number of (A) alkyl is (methyl) propylene of C4~C18 The content of acid ester monomer is 50~98 parts by weight.
As the copolymerisable monomer of (B) hydroxyl, can enumerate：(methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) propylene (methyl) dihydroxypropyls such as the own ester of sour 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates Alkyl esters；N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide etc. (methyl) acrylic amide containing hydroxyl etc..
It is preferred that the copolymerisable monomer of above-mentioned hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) propylene The own ester of sour 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acryloyl At least one of the compound group that amine, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed More than.
Relative to the aforementioned copolymer of 100 parts by weight, the content of the copolymerisable monomer of preferably aforementioned (B) hydroxyl is 0.1 ~10 parts by weight.
For aforementioned copolymer, be alternatively arranged as other copolymerisable monomer groups include carboxylic monomer, not hydroxyl and It is more than at least one of nitrogenous vinyl monomer, polyalkylene glycol mono (methyl) acrylate monomer.
It is preferred that aforementioned carboxylic monomer is selected from by (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) Carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxypropyl hexahydro Phthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyls succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloxy second It is more than at least one of compound group that base tetrahydrophthalic acid is formed.
When aforementioned copolymer includes carboxylic monomer as other copolymerisable monomer groups, relative to 100 parts by weight The content of aforementioned copolymer, preferably carboxylic monomer is 0.1~1.0 parts by weight.Aforementioned copolymer can not also contain aforementioned contain The monomer of carboxyl.
As aforementioned polyalkylene glycol mono (methyl) acrylate monomer, as long as more possessed by polyalkylene glycol A hydroxyl in a hydroxyl is esterified as the compound of (methyl) acrylate.It is poly- since (methyl) is acrylate-based Conjunction property base, therefore can be copolymerized with the copolymer of host agent.Other hydroxyls can both keep the state of OH, can also become The alkyl ether of methyl ether, ether etc., or saturated carboxylic acids esters such as acetate etc. can be become.
As alkylidene possessed by polyalkylene glycol, vinyl, acrylic, cyclobutenyl etc. can be enumerated, but not It is defined in these.Polyalkylene glycol can also be the two or more poly- alkylenes in polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. The copolymer of base glycol.As the copolymer of polyalkylene glycol, polyethylene glycol propylene glycol, polyethylene glycol can be enumerated Butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propylene glycol-polytetramethylene glycol etc., which can be block copolymerization Object, random copolymer.
It is preferred that constituting the alkylene oxide of polyalkylene glycol chain in aforementioned polyalkylene glycol mono (methyl) acrylate monomer Averaged repeating numbers be 3~14.So-called " averaged repeating numbers of alkylene oxide " refer to aforementioned polyalkylene glycol mono (methyl) propylene The average that alkylene oxide unit repeats in " polyalkylene glycol chain " part contained in the molecular structure of acid ester monomer.
As aforementioned polyalkylene glycol mono (methyl) acrylate monomer, it is preferably selected from polyalkylene glycol mono (first Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate At least one of more than.
More specifically, it can enumerate：Mono- (methyl) acrylate of polyethylene glycol-, mono- (methyl) acrylic acid of polypropylene glycol- Mono- (methyl) acrylate of ester, polytetramethylene glycol-, polyethylene glycol propylene glycol-mono- (methyl) acrylate, polyethylene glycol fourth Mono- (methyl) acrylate of glycol-, mono- (methyl) acrylate of polypropylene glycol-polytetramethylene glycol-, polyethylene glycol propylene glycol-are poly- Mono- (methyl) acrylate of butanediol-；Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) third Olefin(e) acid ester, methoxyl group polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-(methyl) acrylate, Methoxypolyethylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylic acid Ester, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate；Ethyoxyl polyethylene glycol-(methyl) propylene Acid esters, ethyoxyl polypropylene glycol-(methyl) acrylate, ethyoxyl polytetramethylene glycol-(methyl) acrylate, the poly- second of ethyoxyl- Glycol-polypropylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol butanediol-(methyl) acrylate, ethyoxyl- Polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol propylene glycol-polytetramethylene glycol-(methyl) propylene Acid esters etc..
Relative to the aforementioned copolymer of 100 parts by weight, preferably aforementioned polyalkylene glycol mono (methyl) acrylate monomer Content be 0~50 parts by weight.Aforementioned copolymer can not also include aforementioned polyalkylene glycol mono (methyl) acrylate list Body.
The nitrogenous vinyl monomer as aforementioned not hydroxyl, can enumerate：Vinyl monomer containing amido bond contains There are the vinyl monomer of amino, the vinyl monomer etc. with nitrogenous heterocycle structure.More specifically, it can enumerate：N- second Alkenyl -2-Pyrrolidone, n-vinyl pyrrolidone, methyl ethylene pyrrolidones, N- vinylpyridines, N- vinylpiperidines Ketone, N- vinyl pyrimidines, N- vinyl piperazine, N- vinylpyrazines, N- vinyl pyrroles, N- vinyl imidazoles, N- vinyl Replacing with N- vinyl for oxazole, N- polyvinyl morpholinones, N- caprolactams, N- vinyl lauric lactams etc. is miscellaneous The cyclic annular nitrogen vinyl compound of ring structure；N- (methyl) acryloyl morpholine, N- (methyl) acryloylpiperazines, N- (methyl) Propylene acyl group aziridine, N- (methyl) acryloyl groups azetidine, N- (methyl) acryloyl groups pyrrolidines, N- (methyl) acryloyl group Piperidines, N- (methyl) acryloyl groups azepan, N- (methyl) acryloyl group Azacyclooctane etc. have N- (methyl) third The cyclic annular nitrogen vinyl compound of the heterocycle structure of enoyl- substitution；N- N-cyclohexylmaleimides, N-phenylmaleimide Deng the cyclic annular nitrogen vinyl compound with the heterocycle structure containing nitrogen-atoms and vinyl-based unsaturated bond in ring；(methyl) Acrylamide, N- methyl (methyl) acrylamide, N- isopropyls (methyl) acrylamide, N- tertiary butyls (methyl) acrylamide etc. (methyl) acrylamide of unsubstituted or monoalkyl substitution；N, N- dimethyl (methyl) acrylamide, N, N- diethyl (first Base) acrylamide, N, N- dipropyl acrylamide, N, N- diisopropyls (methyl) acrylamide, N, N- dibutyl (methyl) third Acrylamide, N- ethyl-N-methyls (methyl) acrylamide, N- Methyl-N-propyls (methyl) acrylamide, N- methyl-N-isopropyls third The dialkyl group such as base (methyl) acrylamide replace (methyl) acrylamide；N, N- dimethylaminomethyl (methyl) acrylate, N, N- dimethyl aminoethyl (methyl) acrylate, N, N- dimethylaminopropyls (methyl) acrylate, N, N- dimethyl Amino isopropyl (methyl) acrylate, N, N- dimethrlaminobutyls (methyl) acrylate, N, N- diethylamino methyl (methyl) acrylate, N, N- diethylaminos ethyl (methyl) acrylate, N- ethyl-N-methylaminos ethyl (methyl) third Olefin(e) acid ester, N- methyl-N-propylaminos ethyl (methyl) acrylate, N- methyl-N-isoproylaminos ethyl (methyl) propylene Acid esters, N, the dialkyl aminos such as N- Dibutylaminoethyls (methyl) acrylate, t-butylamino ethyl (methyl) acrylate Base (methyl) acrylate；N, N- dimethylaminopropyl (methyl) acrylamide, N, N- diethyl amino propyls (methyl) third Acrylamide, N, N- dipropylaminos propyl (methyl) acrylamide, N, N- diisopropylaminoethyls propyl (methyl) acrylamide, N- Ethyl-N-methylamino propyl (methyl) acrylamide, N- methyl-N-propylaminos propyl (methyl) acrylamide, N- methyl- The N of N- isopropylaminopropyls (methyl) acrylamide etc., N- dialkyl group substituted-amino propyl (methyl) acrylamide；N- ethylene The N- vinylcarboxylic acid amide types such as base formamide, N- vinyl acetamides, N- vinyl-N-methylacetaniides；N- methoxy methyls Base (methyl) acrylamide, N- ethoxyethyl groups (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide, two acetone Acrylamide, N, (methyl) acrylic amide such as N- di-2-ethylhexylphosphine oxides (methyl) acrylamide；The unsaturation carboxylic such as (methyl) acrylonitrile Sour nitrile；Deng.
Relative to the aforementioned copolymer of 100 parts by weight, the content of preferably aforementioned not hydroxyl and nitrogenous vinyl monomer For 0~20 parts by weight.Aforementioned copolymer can not also comprising aforementioned not hydroxyl nitrogenous vinyl monomer.
As isocyanate compound more than (C) two function, as long as at least having two or more in a molecule At least one of polyisocyanate compounds of isocyanates (NCO) base or two or more.Polyisocyanate chemical combination Object includes aliphatic category isocyanates, aromatic isocyanates, non-ring type kind isocyanate, ester ring type kind isocyanate decile Class, the present invention can be any kinds therein.As the specific example of polyisocyanate compounds, can enumerate：Six methylenes The fat such as group diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI) Fat same clan isocyanate compound；Methyl diphenylene diisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenation of benzene Diformazan group diisocyanate (H6XDI), dimethyl diphenylene diisocyanate (TOID), toluene di-isocyanate(TDI) (TDI) etc. Aromatic isocyanate compound.
As isocyanate compound more than trifunctional, can enumerate：Two functional isocyanate compounds are (in a molecule Middle tool there are two NCO bases compound) biuret modified body or isocyanurate-modified body, with trimethylolpropane (TMP) Or the addition product of polyalcohols (at least there are three the compounds of the above OH bases for tool in a molecule) more than the trivalents such as glycerine is (polynary Alcohol modified body) etc..
As isocyanate compound more than (C) two function, can only with (C-1) trifunctional isocyanates compound, Or only with (C-2) two functional isocyanate compound.Alternatively, it is also possible to and with (C-1) trifunctional isocyanates compound (C-2) two functional isocyanate compound.
Also, (C-1) trifunctional isocyanates compound used in the present invention preferably includes to be selected from (C-1-1) At least one of first aliphatic category isocyanate compound group is above and is selected from (C-1-2) second aromatic isocyanates More than at least one of compound group, wherein (C-1-1) first aliphatic category isocyanate compound group is by six Asias The isocyanuric acid ester of methyl diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, six methylenes The addition product of group diisocyanate compound, the addition product of isophorone diisocyanate compound, hexa-methylene diisocyanate The biuret of ester compounds, the biuret of isophorone diisocyanate compound are formed；(C-1-2) second aromatic series Kind isocyanate compound group is isocyanuric acid ester, the xylylene diisocyanate chemical combination by tolunediisocyanate compound The isocyanuric acid ester of object, the isocyanuric acid ester of hydrogenated xylylene diisocyanate compound, tolunediisocyanate compound Addition product, xylylene diisocyanate compound addition product, hydrogenated xylylene diisocyanate compound addition Object is formed.(C-1-1) the first aliphatic category isocyanate compound group and (C-1-2) second aromatic isocyanide is preferably used in combination Ester compound group.In the present invention, the isocyanate compound as (C-1) trifunctional, by and with selected from (C-1-1) the At least one of one aliphatic category isocyanate compound group is above and is selected from (C-1-2) second aromatic isocyanation esterification At least one of object group or more is closed, the flat of low speed stripping area and the cohesive force in high speed stripping area can be further improved Weighing apparatus property.
Additionally, it is preferred that the isocyanate compound of (C-1) trifunctional includes different selected from aforementioned (C-1-1) the first aliphatic category At least one of cyanate esters group is above and in aforementioned (C-1-2) second aromatic isocyanate compound group At least one more than, and relative to the aforementioned copolymer of 100 parts by weight, isocyanates chemical combination that should be more than (C) trifunctional Total content of object is 0.5~5.0 parts by weight.In addition, as selected from (C-1-1) the first aliphatic category isocyanate compound group At least one of it is above with it is mixed more than at least one of (C-1-2) second aromatic isocyanate compound group Composition and division in a proportion rate, it is preferably (C-1-1) to be calculated with weight ratio:(C-1-2) 10%:90%~90%:In the range of 10%.
Also, (C-2) the two functional isocyanate compound used as the present invention, preferably non-ring type aliphatic isocyanide Ester compound and to be diisocyanate cpd react with diol compound and the compound that generates.
For example, when indicating diisocyanate chemical combination with general formula " O=C=N-X-N=C=O " (wherein, X is divalent group) Object, when indicating diol compound with general formula " HO-Y-OH " (wherein, Y be divalent group), as diisocyanate cpd and two Alcoholic compound reacts generated compound, for example, the compound that following general formula Z is indicated can be enumerated.
[general formula Z]
O=C=N-X- (NH-CO-O-Y-O-CO-NH-X)n- N=C=O
Here, the integer that n is 0 or more.When n is 0, general formula Z is expressed as " O=C=N-X-N=C=O ".As two officials The compound that the non-ring type aliphatic isocyanates compound of energy can also be 0 including n in general formula Z is (not relative to diol compound The diisocyanate cpd of reaction), preferably as must composition contain n be 1 or more integer compound.Two functions are acyclic Formula aliphatic isocyanates compound can also be the mixture being made of the different multiple compounds of n in general formula Z.
The diisocyanate cpd that general formula " O=C=N-X-N=C=O " indicates, is aliphatic diisocyanate.It is preferred that X is the aliphatic divalent group of non-ring type.As aforementioned aliphatic diisocyanate, it is preferably selected from different by tetramethylene two Cyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine One or more of the compound group that diisocyanate is formed.
The diol compound that general formula " HO-Y-OH " indicates is aliphatic diol.It is preferred that Y is the aliphatic divalent base of non-ring type Group.As foregoing glycols compound, preferably by selected from by 2- methyl 1,3-PD, 2,2- dimethyl -1,3- the third two Alcohol, 2- methyl-2-propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1s, 5- pentanediols, 2,2- bis- One or both of the compound group that methyl-1,3-propanediol monohydroxy pivalate, polyethylene glycol, polypropylene glycol are formed More than.
It is preferred that the weight ratio of aforementioned (C-1) trifunctional isocyanates compound and (C-2) two functional isocyanate compound (C-1/C-2) it is 1~90.Relative to 100 parts by weight aforementioned copolymers, isocyanation esterification more than preferably aforementioned (C) two function Conjunction object is 0.1~10 parts by weight.
Using polyisocyanate compounds as crosslinking agent, (D) if metallo-chelate crosslinking catalyst It is as catalyst and to the substance for reacting (cross-linking reaction) and functioning of aforementioned copolymer and crosslinking agent, Ke Yiju Go out：Aminated compounds, metallo-chelate, organo-tin compound, organo-lead compound, the organic zinc compound of tertiary amine etc. etc. are organic Metallic compound etc..Use metallo-chelate as crosslinking catalyst in the present invention.
It is that more than one multidentate ligand L is bonded to compound made of central metal atom M as metallo-chelate.Gold Belonging to chelate both can be with can not also be with the more than one monodentate ligand X being bonded on metallic atom M.For example, working as By the general formula of the metallic atom M metallo-chelates for being one with M (L)m(X)nWhen expression, m >=1, n >=0.When m is 2 or more, m A L is either identical ligand can also be different ligand.When n is 2 or more, n X are either identical match Body can also be different ligand.
As metallic atom M, Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn etc. can be enumerated.
As multidentate ligand L, can enumerate：Methyl acetoacetate, ethyl acetoacetate, acetoacetate monooctyl ester, acetyl second The 'beta '-ketoester of sour grease, lauryl acetoacetate, acetoacetate stearoyl ester etc.；Acetylacetone,2,4-pentanedione (alias：2,4- pentanediones), 2, The beta-diketon of 4- acetyl butyryls, benzoyl acetone etc..They are ketone-enol tautomers compounds, also may be used in multidentate ligand L To be that enol carries out enolate (for example, acetylacetonate) made of deprotonation.
As monodentate ligand X, the halogen atoms such as chlorine atom, bromine atom, valeryl, caproyl, 2- ethyl hexanoyls can be enumerated The acyloxy such as base, caprylyl, pelargonyl group, capryl, Lauroyl, stearyl, methoxyl group, ethyoxyl, positive propoxy, isopropyl Alkoxies such as oxygroup, butoxy etc..
As the specific example of metallo-chelate, can enumerate：Three (2,4- pentanediones) iron (III) (Tris (2,4- Pentanedionato) iron (III)), praseodynium iron, praseodynium titanium, praseodynium ruthenium, diacetyl acetone Zinc, praseodynium aluminium, four acetylacetone,2,4-pentanedione zirconiums, three (2,4- acetyl butyryls) iron (III), bis- (2,4- acetyl butyryls) zinc, three (2,4- oneself Diketone) titanium, three (2,4- acetyl butyryls) aluminium, four (2,4- acetyl butyryls) zirconiums etc..
As organo-tin compound, can enumerate：The fat of dialkyl tin oxide, the fatty acid salt of dialkyl tin, stannous Fat hydrochlorate etc..In the past, dibutyltin compound has in most cases been used, but the toxicity of organo-tin compound is asked in recent years Topic is noted, and especially tributyl tin contained in dibutyltin compound (TBT) is also to make us carrying on a shoulder pole as endocrine disruptors The heart.It sets out from a security point, preferably the chain alkyl tin compound of dioctyl tin compound etc..As specific organotin Compound can enumerate di-n-octyltin oxide, tin dilaurate dioctyl tin etc..Although Sn chemical combination can also be used temporarily Object, but in view of the trend for requiring the higher substance of safety in utilization in the future, it is preferable to use safe Al, Ti, F in Sne Deng metallo-chelate.
As the metallo-chelate in the adhesive composition of the present invention, preferably comprise selected from by aluminium chelate compound, titanium chela Close at least one of object, group that iron chelate is formed or more.
Relative to 100 parts by weight copolymers, the preferably content of the crosslinking catalyst of (D) metallo-chelate is 0.001~0.5 Parts by weight.
As (E) ketone-enol tautomers compound, can enumerate：Methyl acetoacetate, ethyl acetoacetate, second The 'beta '-ketoester of ethyl acetoacetic acid monooctyl ester, acetoacetate grease, lauryl acetoacetate, acetoacetate stearoyl ester etc.；Acetylacetone,2,4-pentanedione, 2, The beta-diketon of 4- acetyl butyryls, benzoyl acetone etc..They are in the binder combination using polyisocyanate compounds as crosslinking agent In object, by closing isocyanate group possessed by crosslinking agent, adhesive composition after cooperation crosslinking agent can be inhibited The phenomenon that excessive rising or gelation of viscosity, the storage period of adhesive composition can be extended.
Relative to the copolymer of 100 parts by weight, preferably the content of (E) ketone-enol tautomers compound be 0.1~ 200 parts by weight.
Crosslinking catalyst with (D) metallo-chelate is on the contrary, (E) ketone-enol tautomers compound has inhibition Crosslinked effect, it is therefore preferable that suitably setting friendship of (E) the ketone-enol tautomers compound relative to (D) metallo-chelate Join the ratio of catalyst.In order to extend the storage period of adhesive composition and improve storage stability, preferably (E) keto-enol is mutual Parts by weight ratio (E)/(D) of the crosslinking catalyst of tautomeric compound/(D) metallo-chelate is high level.It is preferred that (E)/(D) Value be 70~700 range, more preferably 70~300, most preferably 80~300.
As (F) antistatic agent, can enumerate in antistatic agent and aforementioned copolymer contained in adhesive composition The antistatic agent being copolymerized.Relative to 100 parts by weight copolymers, the preferably content of (F) antistatic agent is 0.05~5.0 weight Part.
It is preferred that (F) antistatic agent, which is the ionic compound that (F-1) fusing point is 25~50 DEG C, and/or (F-2), contains propylene The ionic compound of acyl group.
In the present invention, as (F) antistatic agent, the ionic compound that (F-1) fusing point is 25~50 DEG C is made an addition to It is copolymerized in copolymer in copolymer and/or by the ionic compound of (F-2) containing acryloyl group.Speculate due to these (F) The fusing point of antistatic agent is low and has chain alkyl, therefore, high with the compatibility of acrylic copolymer.
The ionic compound for being 25~50 DEG C as (F-1) fusing point is ionicization with cation and anion Object is closed, can be enumerated：Cation is pyridylium, glyoxaline cation, pyrimidine cation, pyrazoles cation, pyrrole The cationic nitrogenous , Huo person phosphonium cation, sulfonium cation etc. of cation, ammonium cation etc. are coughed up, anion is hexafluorophosphoric acid Root (PF6 -), thiocyanate radical (SCN-), benzene sulfonamide acid group (RC6H4SO3 -), perchlorate (ClO4 -), tetrafluoroborate (BF4 -)、 Bis- (fluorosulfonyl) acid imide roots (FSI), bis- (trifyl) acid imide roots (TFSI), trifluoromethanesulfonic acid root (TF) etc. Inorganic or organic anion compound.It is preferred that be solid under room temperature (such as 25 DEG C), and by selecting the chain length of alkyl, taking Position, number of Dai Ji etc. can obtain the compound that fusing point is 25~50 DEG C.Preferred cationic is quaternary nitrogen cation, can To enumerate：The season pyrrole of 1- alkyl pyridines (2~6 carbon atoms both can not also be with substituent group with substituent group) etc. Pyridine cation, 1,3- dialkylimidazoliums (2,4,5 carbon atoms both can have substituent group can not also with replace Base) etc. season glyoxaline cation, tetra-allkylammonium etc. quaternary ammonium cation etc..
Relative to the copolymer of 100 parts by weight, the content for the ionic compound that preferably (F-1) fusing point is 25~50 DEG C is 0.05~5 parts by weight.
It is the ionic chemical combination with cation and anion as the ionic compound of (F-2) containing acryloyl group Object can be enumerated：Cation is (methyl) acryloxyalkyl trialkyl ammonium (R3N+-CnH2n- OCOCQ=CH2, wherein Q= H or CH3, R=alkyl) etc. the cation containing (methyl) acryloyl group；Anion is hexafluoro-phosphate radical (PF6 -), thiocyanic acid Root (SCN-), organic sulfonic acid root (RSO3 -), perchlorate (ClO4 -), tetrafluoroborate (BF4 -), the acid imide root containing F (RF 2N-) etc. inorganic or organic anion compound.As the acid imide root (R containing FF 2N-) RF, fluoroform can be enumerated Perfluoroalkyl group sulfonyl, the fluorosulfonyl of sulfonyl, five fluorine ethylsulfonyls etc..As the acid imide root containing F, can enumerate double (fluorosulfonyl) acid imide root ((FSO2)2N-), bis- (trifyl) acid imide root ((CF3SO2)2N-), bis- (five fluorine second sulphurs Acyl group) acid imide root ((C2F5SO2)2N-) etc. double sulfonyl acid imide roots.
It is preferred that the copolymerization amount of the ionic compound of (F-2) containing acryloyl group in the copolymer is 0.1~5.0 weight Measure %.
As the specific example of (F) antistatic agent, be not particularly limited, but as (F-1) fusing point be 25~50 DEG C from The specific example of sub- property compound can enumerate 1- octylpyridiniums hexafluorophosphate, 1- nonylpyridines hexafluorophosphate, 2- Methyl-1-dococylpyridinium hexafluorophosphate, 1- octylpyridiniums dodecyl benzene sulfonate, 1- dococylpyridiniums Rhodanate, 1- dococylpyridiniums dodecyl benzene sulfonate, 4- methyl-1s-octylpyridinium hexafluorophosphate, trifluoro The quaternary ammonium salt etc. of methanesulfonic acid.In addition, the specific example as the ionic compound of (F-2) containing acryloyl group, can enumerate Dimethylaminomethyl (methyl) acrylate hexafluorophosphoric acid methyl salt ((CH3)3N+CH2OCOCQ=CH2·PF6 -, wherein, Q= H or CH3), bis- (trifyl) acid imide the methyl salt ((CH of dimethyl aminoethyl (methyl) acrylate3)3N+(CH2)2OCOCQ=CH2·(CF3SO2)2N-, wherein Q=H or CH3), bis- (fluorosulfonyl) acyls of dimethylamine methyl esters Formimino group salt ((CH3)3N+CH2OCOCQ=CH2·(FSO2)2N, wherein Q=H or CH3) etc..
The adhesive composition of the present invention, contains polyether silicone compound and other previous antioxygens as additive Agent etc..
Aforementioned polyether modified siloxane compound is the silicone compounds for having polyether-based, in addition to common siloxanes list Member (- SiR1 2- O-) except, also there is the siloxane unit (- SiR comprising polyether-based1(R2O(R3O)nR4)-O-).Here, R1Table Show one or more kinds of alkyl or aryls, R2And R3Indicate alkylidene, the R of one or more4Indicate one or two kinds of Above alkyl, acyl group etc. (terminal groups).It can be enumerated as polyether-based：Polyethylene oxide base ((C2H4O)n) or polyoxygenated third Alkenyl ((C3H6O)n) etc. polyoxyalkylenes.
It is preferred that aforementioned polyether modified siloxane compound is the polyether modified siloxane compound that HLB value is 7~15.Separately Outside, the content of the copolymer relative to 100 parts by weight, preferably aforementioned polyether modified siloxane compound is 0.01~1.0 weight Part, more preferably 0.1~0.5 parts by weight.
HLB refer to such as JIS K3211 (surfactant term) as defined in hydrophile-lipophile balance (hydrophily and oleophylic The ratio of property).
Aforementioned polyether modified siloxane compound, for example, can obtain by the following method：By hydrosilylation reactions, The organic compound with unsaturated bond and polyoxyalkylene is set to be grafted on the main chain of the polysiloxane with silylation And it obtains.Specifically, can enumerate：Dimethyl siloxane-methyl (polyethylene glycol oxide) silicone copolymers, dimethyl silica Alkane-methyl (polyethylene glycol oxide) siloxane-methyl (polypropylene oxide) silicone copolymers, dimethyl siloxane-methyl (polyoxy Change propylene) silicone copolymers etc..
By the way that aforementioned polyether modified siloxane compound is matched with adhesive composition, the bonding of binder can be improved Power and cycling processability.When adhesive composition is free of polyether modified siloxane compound, cost can be made lower.
As aforementioned antioxidant, hindered phenol anti-oxidants, polyphenolic substance, tocopherol compound can be enumerated Deng.Wherein, preferably tocopherol compound.Tocopherol compound is typically vitamin E, and from natural chemicals Matter.Few to the harmful effect of human body as a result, in use safe is conducive to environmental protection.In addition, due to having oil Dissolubility and be liquid at normal temperatures, thus it is excellent with the intermiscibility of adhesive composition and resistance to precipitation property is also excellent.By matching Cooperation is the tocopherol compound of aforementioned antioxidant, can improve the storage stability of binder, therefore can improve cooperation The storage period of the adhesive composition of curing agent.
As the tocopherol compound that the present invention uses, from being matched in adhesive composition, use (will not be in human body It is interior such to receive metabolism) from the perspective of, preferably the phenolic hydroxyl group of tocopherol does not become ester etc. and the compound containing phenolic hydroxyl group. For example, tocopherol, tocotrienols can be enumerated.It is known that there are natural type compound (d- in tocopherol, tocotrienols Body), non-natural type compound (l- bodies), their equal amount of mixture raceme (dl- bodies) etc. difference.Natural type compound (d- bodies) and raceme (dl- bodies) are the substances that also can be used as food additives etc. and use, therefore preferably.
As specific tocopherol compound, can enumerate selected from by d-αTocopherol, dl-αTocopherol, d- β-life Educate phenol, dl- betatocopherols, d- Gamma-Tocopherols, dl- Gamma-Tocopherols, d- Delta-Tocopherols, dl- Delta-Tocopherols, d- α-fertility triolefin Phenol, dl- alpha-tocotrienols, d- β-tocotrienols, dl- β-tocotrienols, d- γ-tocotrienols, dl- γ-fertility At least one of the compound group that trienol, d- δ-tocotrienols, dl- δ-tocotrienols are formed.It can also be used in combination Two or more tocopherol compounds.As food additives, it is referred to as " mixed tocopherol (mixed tocopherol) " Be that mixture as main component is made with d- alpha-tocopherols, d- betatocopherols, d- Gamma-Tocopherols and d- Delta-Tocopherols；Claimed What it is for " tocotrienols " is with d- alpha-tocotrienols, d- β-tocotrienols, d- γ-tocotrienols and d- δ-fertility three Alkene phenol makees mixture as main component.
When the adhesive composition of the present invention contains tocopherol compound, relative to 100 parts by weight copolymers, preferably The content of tocopherol compound is 0.01~5 parts by weight.
Also, as other ingredients, 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 catalysis Additive well 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.
The copolymer of host agent used in adhesive composition as the present invention, can be by being by the carbon atom number of (A) alkyl It is at least one of (methyl) acrylate monomer of C4~C18, copolymerizable with (B) hydroxyl as copolymerisable monomer group Monomer is copolymerized to synthesize.To the polymerization of copolymer, there is no particular limitation, can use polymerisation in solution, emulsion polymerization Etc. polymerization appropriate.
When using (F-2) ionic compound containing acryloyl group as (F) antistatic agent, binder group of the invention The copolymer of the host agent used in object is closed, (methyl) acrylate monomer by the carbon atom number of (A) alkyl for C4~C18 can be passed through At least one of, with as copolymerisable monomer group (B) hydroxyl copolymerisable monomer and (F-2) containing acryloyl group Ionic compound is copolymerized to synthesize.
In addition, for aforementioned copolymer, it may include carboxylic monomer, not hydroxyl as other copolymerisable monomer groups And more than at least one of nitrogenous vinyl monomer, polyalkylene glycol mono (methyl) acrylate monomer.
The adhesive composition of the present invention can pass through the isocyanates in above-mentioned copolymer more than cooperation (C) two function Compound, the crosslinking catalyst of (D) metallo-chelate, (E) ketone-enol tautomers compound, as (F) antistatic agent (F-1) fusing point for 25~50 DEG C ionic compound, also have arbitrary additive appropriate to be prepared.If in addition, In the case that (F-2) ionic compound containing acryloyl group is polymerize in host agent copolymer, both can to copolymer into The ionic compound that it is 25~50 DEG C as (F-1) fusing point of (F) antistatic agent that one step, which is added, can not also add conduct (F) ionic compound that (F-1) fusing point of antistatic agent is 25~50 DEG C.
It is preferred that aforementioned copolymer is acrylic polymer, (methyl) acrylate of 50~100 weight % is preferably comprised The acrylic monomers such as monomer or (methyl) acrylic acid, (methyl) acrylic amide.
Additionally, it is preferred that the acid value of aforementioned copolymer is 0.01~8.0.Thereby, it is possible to improve pollution and improve to prevent The performance that glue residue phenomenon occurs.
Here, " acid value " is to indicate one of index of acid content, it is required to neutralize the polymer that 1g contains carboxyl The mg numbers of potassium hydroxide indicate.
It is preferred that bonding of the adhesive layer at low peeling rate 0.3m/min made of making foregoing adhesives composition be crosslinked Power is 0.05~0.1N/25mm, and the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less.Thereby, it is possible to obtain Cohesive force is obtained with the small performance of the variation of peeling rate, even can also be removed rapidly in the case where high speed is removed.Also, Even if temporarily remove surface protection film to re-paste, without excessive strength, it is easy to remove from adherend.
It is preferred that the surface resistivity of adhesive layer is 9.0 × 10 made of so that foregoing adhesives composition is crosslinked+11Ω/□ Hereinafter, stripping electrostatic pressure is ± 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 ", i.e. " -0.5~+0.5kV ".If surface resistivity is big, produced because of electrification when to stripping Therefore the poor performance that raw electrostatic is discharged by keeping surface resistivity sufficiently small, can be reduced and be shelled with from adherend Electrostatic pressure is removed caused by the electrostatic occurred when from adhesive layer, the shadow to the electric control circuit of adherend etc. can be inhibited It rings.
It is preferred that making the gel point of adhesive layer (binder after crosslinking) made of the adhesive composition crosslinking of the present invention Number is 95~100%.Since gel fraction is so high, cohesive force will not become too much in the case of low peeling rate, reduce The phenomenon that unconverted monomer or oligomer are dissolved out from copolymer, it is so as to improve resistance under re-workability, high temperature/high humidity Long property, and inhibit 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 of the present invention is crosslinked.In addition, the surface protection film of the present invention is to form bonding in the single side of resin film Oxidant layer forms, and the adhesive layer is that the adhesive composition of the present invention is made to be crosslinked.In the adhesive composition of the present invention In, due to being combined with each ingredient of above-mentioned (A)~(F) with good balance, so there is excellent antistatic property, low The balance of peeling rate and the cohesive force under high peeling rate is excellent, and endurance quality and cycling processability (use ball Pen is not transferred the pollution to adherend after adhesive layer is described on surface protection film) it is also excellent.Therefore, may be used It is used preferably as the surface protection film purposes of polarizer.
In the adhesive film and surface protection film of the present invention, as resin film or the stripping film (diaphragm) of protection adhesive layer Base material, polyester film etc. can be used.
In addition, for resin film, can implement to pass through on the face opposite with adhesive layer side is formed with of resin film The antifouling process of the progress such as silicone, the releasing agent of fluorine class or coating agent, silicon dioxide microparticle, can implement through antistatic agent The antistatic treatment of progress such as it is coated with or is mixed into.
In addition, for stripping film, with the adhesive surface of adhesive layer be bonded on the face of side, implementation passes through silicone The demoulding of the progress such as releasing agent of class, fluorine class is handled.
Embodiment
In the following, illustrating the present invention based on embodiment.
<The manufacture of acrylic copolymer>
[embodiment 1]
Nitrogen is imported into the reaction unit equipped with blender, thermometer, reflux condenser and nitrogen ingress pipe, to use nitrogen Gas has replaced the air in reaction unit.Then, added into reaction unit 100 parts by weight 2-EHA, The acrylic acid 8- hydroxyl monooctyl esters of 3.5 parts by weight.Then, azo two of 0.1 parts by weight as polymerization initiator was instilled by 2 hours Isobutyronitrile makes it react 6 hours at 65 DEG C, obtain weight average molecular weight be 500,000, acrylic acid copolymer for embodiment 1 Object solution 1.A part for acrylic copolymer is taken, aftermentioned acid value measuring sample is used as.
[embodiment 2~6 and comparative example 1~3]
In addition to (A), (B), (I) and (F-2) in such as table 1 it is described adjusted separately the composition of each monomer other than, and it is upper It states and is carried out similarly operation for the acrylic acid copolymer soln 1 of embodiment 1, obtain for embodiment 2~6 and comparative example 1 Acrylic acid copolymer soln in~3.
Table 1
<The manufacture of adhesive composition and surface protection film>
[embodiment 1]
1.5 parts by weight 1- octyl pyrroles are added in acrylic acid copolymer soln 1 to the embodiment 1 manufactured as described above Pyridine hexafluorophosphate, 4.0 parts by weight acetylacetone,2,4-pentanediones and after being stirred, are added 1.5 parts by weight Coronate HX (U ロ ネ The isocyanuric acid ester of ー ト HX, hexamethylene diisocyanate compound), three (2,4- pentanediones) iron (III) of 0.05 parts by weight After be stirred, obtain the adhesive composition of embodiment 1.The adhesive composition is coated on by being coated with silicone resin It on the stripping film that polyethylene terephthalate (PET) film is constituted, is then dried at 90 DEG C and removes solvent, obtained The bonding sheet that adhesive layer thickness is 25 μm.
Then, prepare the polyethylene terephthalate that antistatic treatment and antifouling process are implemented on a face (PET) film, and bonding sheet is transferred to polyethylene terephthalate (PET) film be implemented with antistatic treatment and anti- On the opposite face in the dirty face handled, is had and " be implemented with PET film/adhesive layer/stripping of antistatic treatment and antifouling process From film (PET film for being coated with silicone resin) " stacking constitute embodiment 1 surface protection film.
[embodiment 2~6 and comparative example 1~3]
In addition to (C) of such as table 2~(F) and (J) it is described adjusted separately the composition of each additive other than, with above-mentioned implementation The surface protection film of example 1 is carried out similarly operation, obtains the surface protection film of embodiment 2~6 and comparative example 1~3.
Table 2
Tables 1 and 2 be by indicate each components matching than whole table be divided into the tables of two parts, the equal table of numerical value in bracket Show the numerical value for each Parts by Ingredients that the total amount organized with (A) is set as 100 parts by weight and finds out.In addition, by the ratio of (E)/(D) It is shown in Table 3.In addition, compound name corresponding with the abbreviation of each ingredient used in Tables 1 and 2 is shown in table 4 and table 5 In.In addition, Coronate (U ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L is Japanese polyurethane work The trade name of industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.s), Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N be Mitsui Chemicals, Inc trade name, Desmodur (デ ス モ ジ ュ ー Le, registered trademark) N3400 be Sumika Bayer Urethane Co., Ltd. (firmly change バ イ エ Le ウ レ タ Application strains Formula commercial firm) trade name.
In table 1, by the ionic compound of (F-2) containing acryloyl group of the copolymerization in (F) antistatic agent in copolymer (F) antistatic agent with being added after polymerization, is recorded in respectively in different columns.Table 3
(E)/(D)
Embodiment 1 80
Embodiment 2 85
Embodiment 3 267
Embodiment 4 120
Embodiment 5 333
Embodiment 6 500
Comparative example 1 -
Comparative example 2 12
Comparative example 3 3
Table 4
Table 5
The synthesis ＞ of bis- functional isocyanate compounds of ＜
Two functional isocyanate compounds of synthesis example 1 and 2 are synthesized using following methods.That is, as shown in table 6 and table 7, it will Diisocyanate and diol compound are mixed with the ratio of molar ratio NCO/OH=16, are reacted 3 hours at 120 DEG C, then, are adopted It removes unreacted diisocyanate under reduced pressure with thin film evaporation unit, obtains desired two functional isocyanates chemical combination Object.
Table 6
Synthesis example 1G-1 Synthesis example 2G-2
Diisocyanate cpd HDI HDI
Diol compound H-1 H-2
Table 7
<Test method and evaluation>
In the environment of 23 DEG C, 50%RH, after the surface protection film aging 7 days of Examples 1 to 6 and comparative example 1~3, Stripping film (PET film for being coated with silicone resin) is peeled off, to keep adhesive layer exposed, and as the examination for measuring surface resistivity Sample.
In turn, it by the exposed surface protection film of the adhesive layer, is fitted in by adhesive layer and has been 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, it is used as the sample for measuring cohesive force, removing electrostatic pressure, re-workability and durability.
<Cohesive force>
Using cupping machine, with low peeling rate (0.3m/min) and high peeling rate (30m/min), to 180 ° of directions Above-mentioned obtained measurement sample (surface protection film of 25mm wide is fitted in into sample made of polarisation plate surface) is removed, is measured Peel strength, and using the peel strength as cohesive force.
<Surface resistivity>
After weathering, it fits in before polarizer, peels stripping film (PET film for being coated with silicone resin) off and make adhesive layer It is exposed, 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.
<Remove electrostatic pressure>
Using high-precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (Keyence Corporation) Manufacture), it measures when to the above-mentioned obtained tensile speed 180 ° of strippings of progress for measuring sample with 30m/min, polarizer band Electric and generation voltage (electrostatic pressure), using the maximum value of measured value as stripping electrostatic pressure.
<Re-workability>
Described (load 500g, back and forth 3 on the surface protection film obtained above for measuring sample with ball pen It is secondary) after, surface protection film is removed from polarizer, the surface of polarizer is observed, is confirmed whether to transfer the pollution to polarizer.Evaluate mesh Mark benchmark："○" is evaluated as when not transferring the pollution to polarizer；When the track that confirmation is described along ball pen is at least to office Portion is evaluated as " △ " when displaced pollution；When confirming that there is pollution transportation in the track described along ball pen and from adhesive surface Also confirm that the when of having the disengaging of binder is evaluated as "×".
＜ storage period ＞
The additive of (C)~(F) and (J) is coordinated to measure the viscosities il of adhesive composition at once later0(initial viscosity), And then 23 DEG C × 8 hours viscosities ils that adhesive composition is determined after placement adhesive composition under air-tight state1(8 hours Viscosity afterwards).As the index of storage period, find out with η0η when being 1.01Value, i.e. η1/η0The ratio between.Evaluation goal benchmark It is as follows：Viscosity after 8 hours is evaluated as "○" when being less than 1.25 times of initial viscosity, at 1.25 times less than 1.50 times When be evaluated as " △ ", place at 1.50 times or more or by 8 hours and be evaluated as "×" when gelation occurs.
<Durability>
Above-mentioned obtained measurement 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 measure cohesive force, whether confirmation has apparent increase compared with initial stage cohesive force.It comments Valence target fiducials：Cohesive force after experiment is that 1.5 times of initial stage cohesive force or less of situation is evaluated as "○", more than 1.5 times The case where be evaluated as "×".
It will be evaluation result is shown in table in 8.In addition, in surface resistivity, " m × 10 are indicated by " mE+n "+n" (its In, m is arbitrary real number, and n is positive integer).
Table 8
For the surface protection film of Examples 1 to 6, the cohesive force at low peeling rate 0.3m/min is 0.05~ 0.1N/25mm, the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less；Surface resistivity is 9.0 × 10+11 Ω/ is hereinafter, stripping electrostatic pressure is ± 0~0.5kV；Also, using ball pen across adhesive layer surface protection film into After row is described, do not transfer the pollution to adherend, storage period length and after being placed 250 hours in the environment of 60 DEG C, 90%RH Durability be also excellent.
That is, with excellent antistatic property, under low peeling rate and high peeling rate the balance of cohesive force it is excellent, And storage period length, durability and re-workability are also excellent.
In addition, for the surface protection film of Examples 1 to 6, due to being free of organo-tin compound in adhesive composition, Therefore safe.
For the surface protection film of comparative example 1, it may be possible to more than without containing (C) two function as crosslinking agent The reason of isocyanate compound, the cohesive force at low peeling rate 0.3m/min and high peeling rate 30m/min is excessive, Surface resistivity and stripping electrostatic pressure are high, and re-workability and durability are poor.
For the surface protection film of comparative example 2, it may be possible to due to (E) ketone-enol tautomers compound relative to (D) the small reason of the ratio of the crosslinking catalyst of metallo-chelate, stripping electrostatic pressure is high, and storage period is short, and durability is poor.
The surface protection film of comparative example 3, it may be possible to since (E) ketone-enol tautomers compound is relative to (D) metal The small reason of the ratio of the crosslinking catalyst of chelate, storage period becomes too short, due to having been carried out crosslinking before coating, because This can not be coated.
So, for the surface protection film of comparative example 1~3, can not meet simultaneously with excellent antistatic property, The balance of cohesive force is excellent under low peeling rate and high peeling rate, and storage period is long, durability and re-workability Excellent equal whole performance requirement.

Claims (12)

1. a kind of adhesive composition, wherein including：
(A) at least one of (methyl) acrylate monomer that the carbon atom number of alkyl is C4~C18 with as copolymerizable list 00 parts by weight of copolymer 1 of the copolymerisable monomer of (B) hydroxyl of body group；
(C) 0.1~10 parts by weight of isocyanate compound more than two functions；
(D) 0.001~0.5 parts by weight of crosslinking catalyst of metallo-chelate；
(E) 0.1~200 parts by weight of ketone-enol tautomers compound；And
0.05~5 parts by weight of ionic compound that fusing point as (F) antistatic agent is 25~50 DEG C,
And the parts by weight ratio of (E)/(D) is 80~300,
And the adhesive composition does not include polyether modified siloxane compound.
2. adhesive composition as described in claim 1, wherein the copolymerisable monomer of (B) hydroxyl be 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) third Olefin(e) acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) propylene It is more than at least one of compound group that amide is formed.
3. adhesive composition as claimed in claim 1 or 2, wherein
For isocyanate compound more than (C) two function,
It is non-ring type aliphatic isocyanates compound as two functional isocyanate compounds and is to make diisocyanate chemical combination Object is reacted with diol compound and the compound that generates；
The diisocyanate cpd is aliphatic diisocyanate, is selected from by tetramethylene diisocyanate, five Asias Methyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate institute One kind in the compound group of composition,
The diol compound is selected from by 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- propylene glycol, 2- methyl -2- Propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1s, 5- pentanediols, 2,2- dimethyl -1,3- third One kind in the compound group that glycol monohydroxy pivalate, polyethylene glycol, polypropylene glycol are formed,
It is isocyanuric acid ester, the isophorone two of hexamethylene diisocyanate compound as trifunctional isocyanates compound The isocyanuric acid ester of isocyanate compound, the addition product of hexamethylene diisocyanate compound, isophorone diisocyanate The addition product of ester compounds, the biuret of hexamethylene diisocyanate compound, isophorone diisocyanate compound Biuret, the isocyanuric acid ester of tolunediisocyanate compound, xylylene diisocyanate compound isocyanuric acid ester, The isocyanuric acid ester of hydrogenated xylylene diisocyanate compound, the addition product of tolunediisocyanate compound, benzene diformazan The addition product of group diisocyanate compound, the addition product of hydrogenated xylylene diisocyanate compound.
4. adhesive composition as claimed in claim 1 or 2, wherein the crosslinking catalyst in the adhesive composition is More than at least one of group being made of aluminium chelate compound, titanium chelate, iron chelate.
5. adhesive composition as claimed in claim 1 or 2, wherein (F) antistatic agent is relative to 100 parts by weight The copolymer contain the ionic compound and/or be described total that 0.05~5.0 parts by weight and fusing point are 25~50 DEG C Copolymerization amount in polymers is 0.1~5.0 weight % and the ionic compound containing acryloyl group.
6. adhesive composition as claimed in claim 1 or 2, wherein the copolymer is as other copolymerisable monomer group packets Include carboxylic monomer, not hydroxyl and in nitrogenous vinyl monomer, polyalkylene glycol mono (methyl) acrylate monomer At least one more than.
7. adhesive composition as claimed in claim 1 or 2, wherein bonded made of so that the adhesive composition is crosslinked Cohesive force of the oxidant layer at low peeling rate 0.3m/min is 0.05~0.1N/25mm, viscous at high peeling rate 30m/min Knot power is 1.0N/25mm or less.
8. adhesive composition as claimed in claim 1 or 2, wherein bonded made of so that the adhesive composition is crosslinked The surface resistivity of oxidant layer is 9.0 × 10+11Ω/ is hereinafter, stripping electrostatic pressure is ± 0~0.5kV.
9. it is to form adhesive layer in the single or double of resin film and form, the adhesive layer is to make power a kind of adhesive film Profit requires the adhesive composition described in any one of 1~8 to be crosslinked.
10. a kind of surface protection film forms adhesive layer in the single side of resin film and forms, the adhesive layer is that right is made to want The adhesive composition described in any one of 1~8 is asked to be crosslinked, wherein with ball pen across the adhesive layer on surface After being described on protective film, do not transfer the pollution to adherend.
11. surface protection film as claimed in claim 10, the surface protection film purposes as polarizer is used.
12. surface protection film as claimed in claim 11, wherein the resin film be formed with the adhesive layer On the opposite face in side, it is implemented with antistatic and antifouling process.
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