CN104861905A - Adhesive Composition And Surface Protection Film - Google Patents

Adhesive Composition And Surface Protection Film Download PDF

Info

Publication number
CN104861905A
CN104861905A CN201510025694.9A CN201510025694A CN104861905A CN 104861905 A CN104861905 A CN 104861905A CN 201510025694 A CN201510025694 A CN 201510025694A CN 104861905 A CN104861905 A CN 104861905A
Authority
CN
China
Prior art keywords
methyl
compound
adhesive composition
monomer
acrylate
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.)
Granted
Application number
CN201510025694.9A
Other languages
Chinese (zh)
Other versions
CN104861905B (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
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 CN104861905A publication Critical patent/CN104861905A/en
Application granted granted Critical
Publication of CN104861905B publication Critical patent/CN104861905B/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides an adhesive composition which possesses an anti-static performance, is excellent in binding force balance at low peel-away speed and high peel-away speed, is long in storage period, and is also excellent in durability and reprocessability. The adhesive composition of the present invention comprises (A) a (meth) acrylate monomer of which the carbon number of alkyl is C4-C18, (B) a copolymerizable monomer having hydroxide radical, (C) a copolymerizable monomer having carboxyl, (D) a poly alkylene glycol single (meth) acrylate monomer, (E) a vinyl monomer having nitrogen instead of hydroxy or alkyl(meth)acrylates having alkoxy, acrylic copolymer of copolymer of which the acid value is 0.01-8.0, (F) a bifunctional isocyanate compound, (G) a crosslinking catalyst of a metallo-chelate, (H) a ketone-enol tautomer compound, (I) an antistatic agent, (J) a polyether modified silicone compound, and (K) an antioxidant.

Description

Adhesive composition and surface protection film
Technical field
The present invention relates to a kind of adhesive composition and surface protection film.More specifically, the present invention relates to provide a kind of there is antistatic property, under low peeling rate and high peeling rate, the balance of cohesive force is excellent and storage period long, the surface protection film adhesive composition of weather resistance and the also excellent Polarizer of re-workability and surface protection film.
Background technology
For the binding agent of optical applications, from the view point of excellent transparency, preferably use using (methyl) alkyl acrylate as main component and the acrylic adhesive formed with the multipolymer of the Acrylic Acid Monomer copolymerization as functional group with hydroxyl, carboxyl etc.Further, the binding agent various physical propertiess such as cohesive force being carried out to suitably adjustment is needed.Particularly, in order to be suitable for the manufacturing process of plant produced, the binding agent etc. of effects on surface protective membrane, requires that it is to be applicable to the cohesive force balance under the low peeling rate of being fitted by automatic joint device and high peeling rate excellent.And, need storage period except the balance of cohesive force long, the binding agent that weather resistance, re-workability and static resistance are also excellent.
For the various physical propertiess of this binding agent, by adopting the isocyanates linking agent, epoxies linking agent etc. reacted with the contained functional group such as hydroxyl, carboxyl in the acrylic adhesive to be made up of multipolymer to carry out crosslinking reaction, thus adjustment cohesive force, cohesive force etc.
Since in the past, as the linking agent of acrylic adhesive, usually adopt isocyanates linking agent.In addition, in the crosslinking reaction that have employed isocyanates linking agent, as the catalyzer for promoting crosslinking reaction, adopt metallo-chelate more.
Typically, excellent from the view point of the speed of response of crosslinking reaction, the catalyzer as crosslinking reaction employs organo-tin compound and dibutyltin dilaurate etc., but presents detrimental toxicities due to dibutyltin compound, is avoiding using at present.
Therefore, need a kind of can with isocyanates linking agent and, as the cheapness of the substitute of dibutyltin compound and the excellent crosslinking catalyst of the speed of response of crosslinking reaction, but be difficult to exploitation and acquire.
In this case, patent documentation 1 discloses following content: as can with isocyanates linking agent and crosslinking catalyst, preferred iron chelate in metallo-chelate, and due to the catalytic activity of three (acetylacetone based) coordination iron excellent, so particularly preferably.
But the acrylic adhesive composition containing crosslinking catalyst, even if also slowly can carry out crosslinking reaction between resting period at normal temperatures.Therefore, in the industrial production of binding agent, in order to make crosslinking reaction stop to the period usually starting crosslinking reaction after the raw material coordinating adhesive composition, and crosslinking catalyst and reaction suppressor have been used.
About this crosslinking catalyst and reaction suppressor and use, Patent Document 2 discloses a kind of manufacture method of urethane, wherein, have employed to comprise and to be formed by the mixture of at least one metal acetylacetonate and methyl ethyl diketone and the weight ratio of aforementioned metal methyl ethyl diketone and aforementioned methyl ethyl diketone is the reaction polyurethane mixture of the catalyst system of 2:1.
For adhesive composition described in patent documentation 1, although propose metallic compound (crosslinking catalyst) relative to using (methyl) acrylate as being formed monomeric unit and the addition of multipolymer containing hydroxyl and carboxyl, do not record the addition of cross-linked inhibitor.In addition, in patent documentation 1, as suppressing the method coordinating the viscosity rate of rise after linking agent in adhesive composition, enumerated and used the method for reaction suppressor, add to viscosity rise the solvent that suppresses method, employ the method etc. to the linking agent that functional group closes such as blocked isocyanate, but not illustrate.
In addition, Patent Document 2 discloses a kind of polyurethane making method, the catalyst system wherein used contains: even if adopt the metal acetylacetonate catalyzer of active at low temperatures very high iron, copper etc. also can not cause premature curing and have metal acetylacetonate and the methyl ethyl diketone of excellent stability and good catalytic activity.
But, in the method that patent documentation 2 is recorded, the weight ratio of metal acetylacetonate and methyl ethyl diketone is set to 2:1, but when using this compounding ratio in the manufacturing process of acrylic adhesive, crosslinking reaction also cannot be made temporarily to stop.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-001440 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-285681 publication
Summary of the invention
The problem that invention will solve
The present invention completes in view of the foregoing; its problem is that providing a kind of has antistatic property when not using organo-tin compound; and the balance of cohesive force is excellent under low peeling rate and high peeling rate; and storage period is long, the adhesive composition of the surface protection film of the Polarizer that weather resistance and re-workability are also excellent and surface protection film.
Solve the method for problem
In order to solve above-mentioned problem, the invention provides a kind of adhesive composition, wherein,
This adhesive composition comprises: the carbonatoms containing (A) alkyl is at least one in (methyl) acrylate monomer of C4 ~ C18, and be selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) acrylic polymers of the multipolymer of the acid number 0.01 ~ 8.0 of polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one not in hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group,
Further, the crosslinking catalyst also containing (F) two isocyanate compound more than sense, (G) metallo-chelate, (H) keto-enol tautomerism body compound, (I) ionic compound as the fusing point 25 ~ 50 DEG C of static inhibitor and/or the ionic compound containing acryl, (J) polyether modified siloxane compound and (K) antioxidant.
In addition, relative to the total amount of the acrylic polymers of 100 weight part aforementioned copolymer, preferred foregoing acrylic polymkeric substance contains: the carbonatoms of 50 ~ 95 weight parts aforementioned (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, the copolymerisable monomer of 0.1 ~ 10 weight part aforementioned (B) hydroxyl, 0.1 ~ 1.0 weight part aforementioned (C) copolymerisable monomer containing carboxyl, 0 ~ 50 weight part aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer, and 0 ~ 20 weight part aforementioned (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group,
And, foregoing adhesives composition contains: isocyanate compound more than 0.1 ~ 10 weight part aforementioned (F) two sense, the crosslinking catalyst of 0.001 ~ 0.5 weight part aforementioned (G) metallo-chelate and 0.1 ~ 200 weight part aforementioned (H) keto-enol tautomerism body compound, further, weight part ratio (H)/(G) of the crosslinking catalyst of aforementioned (H) keto-enol tautomerism body compound/(G) metallo-chelate is 1 ~ 700;
And then also contain: as the static inhibitor of institute's copolymerization in contained static inhibitor in aforementioned (I) static inhibitor total amount foregoing adhesives composition that is 0.05 ~ 5.0 weight part and aforementioned copolymer, 0.01 ~ 1.0 weight part aforementioned (J) polyether modified siloxane compound and 0.01 ~ 5 weight part tocopherols antioxidant as aforementioned (K) antioxidant.
In addition, preferably the copolymerisable monomer of aforementioned (B) hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
In addition, preferably aforementioned (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
In addition, preferably (D) polyalkylene glycol mono (methyl) acrylate monomer is that the averaged repeating numbers of the alkylene oxide forming polyalkylene glycol chain is 3 ~ 14 and is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
In addition, preferred foregoing acrylic polymkeric substance contains aforementioned (E) not hydroxyl and nitrogenous vinyl monomer or containing more than at least one in (methyl) alkyl acrylate monomer of alkoxyl group as aforementioned copolymerisable monomer group.
In addition, as aforementioned (F) two isocyanate compound more than sense, preferably as the non-ring type aliphatic isocyanates compound of two functional isocyanate compounds and diisocyanate cpd and the diol compound compound that reacts and generate.As aforementioned diisocyanates compound, be aliphatic diisocyanate, form preferably by the one be selected from the compound group that is made up of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate.In addition, as foregoing glycols compound, preferably by being selected from by 2-methyl 1,3-PD, 2,2-dimethyl-1, ammediol, 2-methyl-2-propyl-1, ammediol, 2-ethyl-2-butyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2, one in the compound group that 2-dimethyl-1,3-propylene glycol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol form is formed.
In addition, as aforementioned (F) two isocyanate compound more than sense, be selected from by the isocyanuric acid ester of hexamethylene diisocyanate compound preferably as trifunctional isocyanates compound, the isocyanuric acid ester of isophorone diisocyanate compound, the affixture of hexamethylene diisocyanate compound, the affixture of isophorone diisocyanate compound, the biuret of hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound, the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, in the compound group that the affixture of hydrogenated xylylene diisocyanate cpd forms more than at least one.
In addition, preferably aforementioned (I) static inhibitor be contain 0.1 ~ 5.0 weight part relative to the aforementioned copolymer of 100 weight parts and the ionic compound of fusing point 25 ~ 50 DEG C and/or the copolymerization amount in aforementioned copolymer be 0.1 ~ 5.0 % by weight containing the ionic compound of acryl.
In addition, preferably the HLB value of aforementioned (J) polyether modified siloxane compound is 7 ~ 15.
In addition, the crosslinking catalyst in preferred foregoing adhesives composition does not include machine tin compound.
In addition, as the tocopherol compound of aforementioned antioxidant, be preferably selected from least one in the compound group be made up of d-alpha-tocopherol, dl-alpha-tocopherol, d-5,8-dimethyl tocol, dl-5,8-dimethyl tocol, d-Gamma-Tocopherol, dl-Gamma-Tocopherol, d-Delta-Tocopherol, dl-Delta-Tocopherol, d-alpha-tocotrienol, dl-alpha-tocotrienol, d-β-tocotrienols, dl-β-tocotrienols, d-γ-tocotrienols, dl-γ-tocotrienols, d-δ-tocotrienols, dl-δ-tocotrienols.
In addition, the cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.
In addition, the surface resistivity of the adhesive layer preferably making foregoing adhesives composition be cross-linked is 9.0 × 10 + 11Ω/below, stripping static voltage is ± 0 ~ 0.5kV.
In addition, the invention provides a kind of adhesive film, it is characterized in that, the single or double of resin molding forms adhesive layer and forms, described adhesive layer foregoing adhesives composition is cross-linked form.
In addition; the invention provides a kind of surface protection film; it forms adhesive layer at the one side of resin molding to form; described adhesive layer foregoing adhesives composition is cross-linked form; it is characterized in that; with ballpoint pen after adhesive layer is described on surface protection film, pollute and be not transferred in adherend.
In addition, the purposes that surface protection film of the present invention can be used as the surface protection film of Polarizer is used.
In addition, in surface protection film of the present invention, preferably on the face contrary with the side being formed with foregoing adhesives layer of aforementioned resin film, implement antistatic and antifouling process.
Invention effect
Based on the present invention; the over-all properties required by adhesive layer of insurmountable effects on surface protective membrane in the prior art can be met when not using organo-tin compound; and excellent antistatic property can be obtained, the generation of glue residue phenomenon can be prevented.Specifically, excellent antistatic property can not only be kept, but also the addition of static inhibitor can be reduced, also can improve the performance preventing glue residue.
Embodiment
Below, based on preferred embodiment the present invention being described.
Adhesive composition of the present invention, it is characterized in that, its host is at least one in (methyl) acrylate monomer of C4 ~ C18 by the carbonatoms containing (A) alkyl, and be selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one not in hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group, acid number is that the acrylic polymers of the multipolymer of 0.01 ~ 8.0 is formed,
Further, the crosslinking catalyst also containing (F) two isocyanate compound more than sense, (G) metallo-chelate, (H) keto-enol tautomerism body compound, (I) ionic compound as the fusing point 25 ~ 50 DEG C of static inhibitor and/or the ionic compound containing acryl, (J) polyether modified siloxane compound and (K) antioxidant.
In addition, it is the acrylic polymers of the multipolymer of 100 weight parts relative to total amount, preferred acrylic polymers contains: the carbonatoms of 50 ~ 95 weight parts (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, the copolymerisable monomer of 0.1 ~ 10 weight part (B) hydroxyl, 0.1 ~ 1.0 weight part (C) carboxylic copolymerisable monomer, 0 ~ 50 weight part (D) polyalkylene glycol mono (methyl) acrylate monomer, and 0 ~ 20 weight part (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group.
In addition, it is the acrylic polymers of the multipolymer of 100 weight parts relative to total amount, preferred binder composition contains the isocyanate compound of more than 0.1 ~ 10 weight part (F) two sense, the crosslinking catalyst of 0.001 ~ 0.5 weight part (G) metallo-chelate and 0.1 ~ 200 weight part (H) keto-enol tautomerism body compound, and, weight part ratio (H)/(G) of the crosslinking catalyst of aforementioned (H) keto-enol tautomerism body compound/(G) metallo-chelate is 1 ~ 700, and, containing the static inhibitor as institute's copolymerization in static inhibitor contained in the foregoing adhesives composition of (I) static inhibitor and aforementioned copolymer that total amount is 0.05 ~ 5.0 weight part, 0.01 ~ 1.0 weight part (J) polyether modified siloxane compound, and 0.01 ~ 5 tocopherols antioxidant as (K) antioxidant of weight part.
Carbonatoms as (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, can enumerate: (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) myristyl ester, the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, (methyl) vinylformic acid isocetyl ester, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid isooctadecane base ester etc.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the carbonatoms of (A) alkyl is the content of (methyl) acrylate monomer of C4 ~ C18 is 50 ~ 95 weight parts.
As the copolymerisable monomer of (B) hydroxyl, can enumerate: (methyl) hydroxyalkyl acrylates classes such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) acrylic amide etc. containing hydroxyl such as N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
The copolymerisable monomer of preferred above-mentioned hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the content of the copolymerisable monomer of aforementioned (B) hydroxyl is 0.1 ~ 10 weight part.
Preferably (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the content of aforementioned (C) carboxylic copolymerisable monomer is 0.1 ~ 1.0 weight part.In adhesive layer of the present invention, the content of (C) the carboxylic copolymerisable monomer in preferred binder composition, be as hereinafter described to make the content of the acid number of multipolymer in 0.01 ~ 8.0 scope.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, as long as the esterified compound for (methyl) acrylate of a hydroxyl in multiple hydroxyls of having of polyalkylene glycol.Be polymerizability base because (methyl) is acrylate-based, therefore, it is possible to carry out copolymerization with host polymkeric substance.Other hydroxyl, both can keep the state of OH, also can become the alkyl oxide of methyl ether, ether etc., or can become the saturated carboxylic acid esters etc. such as acetic ester.
As the alkylidene group that polyalkylene glycol has, vinyl, propenyl, butenyl etc. can be enumerated, but be not limited to these.Polyalkylene glycol also can be the multipolymer of the two or more polyalkylene glycols in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.As the multipolymer of polyalkylene glycol, can enumerate polyethylene glycol-propylene glycol, polyethylene glycol-butyleneglycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol-propylene glycol-polytetramethylene glycol etc., this multipolymer can be segmented copolymer, random copolymers.
The averaged repeating numbers preferably forming the alkylene oxide of polyalkylene glycol chain in (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14.So-called " averaged repeating numbers of alkylene oxide ", refers to the mean number that in " polyalkylene glycol chain " part contained in the molecular structure of (D) polyalkylene glycol mono (methyl) acrylate monomer, alkylene oxide unit repeats.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, be preferably selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
More specifically, can enumerate: polyoxyethylene glycol-mono-(methyl) acrylate, polypropylene glycol-mono-(methyl) acrylate, polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-mono-(methyl) acrylate, polyethylene glycol-butyleneglycol-mono-(methyl) acrylate, polypropylene glycol-polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-polytetramethylene glycol-mono-(methyl) acrylate; Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) acrylate, 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) acrylate, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate; Oxyethyl group polyoxyethylene glycol-(methyl) acrylate, oxyethyl group polypropylene glycol-(methyl) acrylate, oxyethyl group polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-butyleneglycol-(methyl) acrylate, oxyethyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-polytetramethylene glycol-(methyl) acrylate etc.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the content of aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 0 ~ 50 weight part.Adhesive composition in adhesive layer of the present invention also can not comprise (D) polyalkylene glycol mono (methyl) acrylate monomer.
In (E), as the vinyl monomer that (E-1) is nitrogenous, can enumerate: the vinyl monomer containing amido linkage, the vinyl monomer etc. containing amino vinyl monomer, there is nitrogenous heterocycle structure.More specifically, can enumerate: the ring-type nitrogen vinyl compound with the heterocycle structure of N-vinyl substituted of NVP, NVP, methyl ethylene pyrrolidone, N-vinyl pyridine, N-vinylpiperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-Yi Xi Ji oxazole, N-polyvinyl morpholinone, N-caprolactam, N-vinyl laurolactam etc., the ring-type nitrogen vinyl compound with the heterocycle structure that N-(methyl) acryl replaces of N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperazines, the rare acyl group aziridine of N-(methyl) third, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryloylpiperidine, N-(methyl) acryl azepan, N-(methyl) acryl Azacyclooctane etc., N-N-cyclohexylmaleimide, N-phenylmaleimide etc. have the ring-type nitrogen vinyl compound of the heterocycle structure containing nitrogen-atoms and vinyl-based unsaturated link(age) in ring, (methyl) acrylamide that (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide etc. do not replace or monoalkyl replaces, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl acrylamide, N, the dialkyl group such as N-di-isopropyl (methyl) acrylamide, N, N-dibutyl (methyl) acrylamide, N-ethyl-N-methyl (methyl) acrylamide, N-Methyl-N-propyl (methyl) acrylamide, N-methyl-N-isopropyl (methyl) acrylamide replace (methyl) acrylamide, N, N-dimethylaminomethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-dimethylamino sec.-propyl (methyl) acrylate, N, N-dimethrlaminobutyl (methyl) acrylate, N, N-diethylamino methyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-ethyl-N-methylamino ethyl (methyl) acrylate, N-methyl-N-propylamino ethyl (methyl) acrylate, N-methyl-N-isoproylamino ethyl (methyl) acrylate, N, N-Dibutylaminoethyl (methyl) acrylate, dialkyl amido (methyl) acrylate such as t-butylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethyl amino propyl (methyl) acrylamide, N, N-dipropylamino propyl group (methyl) acrylamide, N, the N of N-diisopropylaminoethyl propyl group (methyl) acrylamide, N-ethyl-N-methylamino propyl group (methyl) acrylamide, N-methyl-N-propylamino propyl group (methyl) acrylamide, N-methyl-N-isoproylamino propyl group (methyl) acrylamide etc., N-dialkyl group substituted-amino propyl group (methyl) acrylamide, the N-vinylcarboxylic acid amide type such as N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetaniide, (methyl) acrylic amides such as N-methoxymethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone acrylamide, N, N-methylene-bis (methyl) acrylamide, the unsaturated carboxylic acid nitriles such as (methyl) vinyl cyanide, Deng.
As the vinyl monomer that (E-1) is nitrogenous, preferably not hydroxyl, more preferably not hydroxyl and carboxyl.As this monomer, be preferably illustrative monomer above, such as: the acrylic monomer containing N, N-dialkyl group substituted-amino, N, N-dialkyl group substituted amido; The N-vinyl substituted lactams such as NVP, N-caprolactam, N-vinyl-2-piperidone; N-(methyl) the acryl substituted cyclic amines such as N-(methyl) acryloyl morpholine, N-(methyl) acryl tetramethyleneimine.
In (E), as (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group, can enumerate: (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy ethyl, (methyl) vinylformic acid 2-isopropoxyethyl cyanoacrylate, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-methoxyl group propyl ester, (methyl) vinylformic acid 2-oxyethyl group propyl ester, (methyl) vinylformic acid 2-propoxy-propyl ester, (methyl) vinylformic acid 2-isopropoxy propyl ester, (methyl) vinylformic acid 2-butoxy propyl ester, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 3-propoxy-propyl ester, (methyl) vinylformic acid 3-isopropoxy propyl ester, (methyl) vinylformic acid 3-butoxy propyl ester, (methyl) vinylformic acid 4-methoxybutyl, (methyl) vinylformic acid 4-Ethoxybutyl, (methyl) vinylformic acid 4-propoxy-butyl ester, (methyl) vinylformic acid 4-isopropoxy butyl ester, (methyl) vinylformic acid 4-butoxy butyl ester etc.
These are containing (methyl) alkyl acrylate monomer of alkoxyl group, the structure that the atom alkoxy with the alkyl in (methyl) alkyl acrylate replaces.
When the total amount of acrylic polymers setting multipolymer is 100 weight part, preferably (E-1) hydroxyl and nitrogenous vinyl monomer or (E-2) are not 0 ~ 20 weight part containing the content of (methyl) alkyl acrylate monomer of alkoxyl group.To (E-1), hydroxyl and nitrogenous vinyl monomer and (E-2), containing (methyl) alkyl acrylate monomer of alkoxyl group, both can not use one to can be used together two or more respectively yet.Also (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group can not be comprised in the adhesive composition of adhesive layer of the present invention.
As (F) two isocyanate compound more than sense, as long as more than at least one or two in being selected from a part the polyisocyanate compounds at least with plural isocyanic ester (NCO) base.Polyisocyanate compounds comprises the classification such as aliphatic category isocyanic ester, aromatic series kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate, and the present invention can be any kind wherein.As the object lesson of polyisocyanate compounds, can enumerate: the aliphatic category isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI); The aromatic series kind isocyanate compounds such as diphenylmethanediisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenated xylylene vulcabond (H6XDI), dimethyl diphenylene vulcabond (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, can enumerate: the biuret modified body of two functional isocyanate compounds (there is the compound of two NCO bases in a part) or isocyanurate-modified body, with the affixture (polyalcohol modified body) etc. of polyvalent alcohol (at least there is the compound of more than three OH bases in a part) more than the trivalents such as TriMethylolPropane(TMP) (TMP) or glycerine.
As (F) two isocyanate compound more than sense, also only can adopt (F-1) trifunctional isocyanates compound or only adopt (F-2) two functional isocyanate compound.In addition, also can be used together (F-1) trifunctional isocyanates compound and (F-2) two functional isocyanate compound.
And, as (F-1) trifunctional isocyanates compound used in the present invention, preferably include and be selected from more than at least one of (F-1-1) first in aliphatic category isocyanate compound group and be selected from more than at least one of (F-1-2) second in aromatic series kind isocyanate compound group, wherein, described (F-1-1) first aliphatic category isocyanate compound group be by the isocyanuric acid ester of hexamethylene diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, the affixture of hexamethylene diisocyanate compound, the affixture of isophorone diisocyanate compound, the biuret of hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound formed, described (F-1-2) second aromatic series kind isocyanate compound group be made up of the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, the affixture of hydrogenated xylylene diisocyanate cpd.Preferably and by (F-1-1) first aliphatic category isocyanate compound group and (F-1-2) the second aromatic series kind isocyanate compound group.In the present invention, as the isocyanate compound of (F-1) trifunctional, by and with being selected from more than at least one of (F-1-1) first in aliphatic category isocyanate compound group and being selected from more than at least one of (F-1-2) second in aromatic series kind isocyanate compound group, the balance of the cohesive force in low speed stripping area and high speed stripping area can be improved further.
In addition, preferably the isocyanate compound of (F-1) trifunctional comprises and is selected from more than at least one of aforementioned (F-1-1) first in aliphatic category isocyanate compound group and is selected from more than at least one of aforementioned (F-1-2) second in aromatic series kind isocyanate compound group, and relative to the aforementioned copolymer of 100 weight parts, the total content being somebody's turn to do the isocyanate compound of more than (F) trifunctional is 0.5 ~ 5.0 weight part.In addition, as being selected from more than at least one of (F-1-1) first in aliphatic category isocyanate compound group and the mixture ratio being selected from more than at least one of (F-1-2) second in aromatic series kind isocyanate compound group, calculating with weight ratio and being preferably (F-1-1): (F-1-2) is in the scope of 10%:90% ~ 90%:10%.
Further, as (F-2) two functional isocyanate compound that the present invention adopts, preferably non-ring type aliphatic isocyanates compound and be the compound that diisocyanate cpd and diol compound react and generate.
Such as, when with general formula " O=C=N-X-N=C=O " (wherein, X is divalent group) represent diisocyanate cpd, with general formula " HO-Y-OH " (wherein, Y is divalent group) when representing diol compound, to react generated compound as diisocyanate cpd and diol compound, such as, the compound that general formula Z below represents can be enumerated.
[general formula Z]
O＝C＝N-X-(NH-CO-O-Y-O-CO-NH-X)n-N＝C＝O
At this, n is the integer of more than 0.When n is 0, general formula Z is expressed as " O=C=N-X-N=C=O ".Also the compound (relative to the unreacted diisocyanate cpd of diol compound) that n in general formula Z is 0 can be comprised, preferably as containing the compound that n is the integer of more than 1 by composition as two senses non-ring type aliphatic isocyanates compound.The mixture that two senses non-ring type aliphatic isocyanates compound also can be made up of the multiple compounds that the n in general formula Z is not identical.
The diisocyanate cpd that general formula " O=C=N-X-N=C=O " represents is aliphatic diisocyanate.Preferred X is the aliphatic divalent group of non-ring type.As aforementioned aliphatic diisocyanate, form preferably by one or more being selected from the compound group that is made up of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate.
Diol compound shown in general formula " HO-Y-OH " is aliphatic diol.Preferred Y is the aliphatic divalent group of non-ring type.As foregoing glycols compound, preferably by being selected from by 2-methyl 1, ammediol, 2,2-dimethyl-1,3-propylene glycol, 2-methyl-2-propyl-1,3-PD, 2-ethyl-2-butyl-1, ammediol, 3-methyl isophthalic acid, one or more in the compound group that 5-pentanediol, 2，2-dimethyl-1，3-propanediol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol form are formed.
Preferably aforementioned (F-1) trifunctional isocyanates compound and (F-2) two the weight ratio (F-1/F-2) of functional isocyanate compound be 1 ~ 90.Relative to 100 weight part foregoing acrylic polymkeric substance, preferably aforementioned (F) two isocyanate compound more than sense is 0.1 ~ 10 weight part.
When using polyisocyanate compounds as linking agent, (G) as long as the crosslinking catalyst of metallo-chelate plays the material of function to the reaction (crosslinking reaction) of aforementioned copolymer and linking agent as catalyzer, can enumerate: the organometallic compound etc. such as aminated compounds, metallo-chelate, organo-tin compound, organo-lead compound, organic zinc compound of tertiary amine etc.Adopt metallo-chelate as crosslinking catalyst in the present invention.
The compound that more than one polydentate ligand L is bonded to central metal atom M as metallo-chelate.Metallo-chelate both can have the more than one unidentate ligand X that also can not have and be bonded on atoms metal M.Such as, when atoms metal M is that the general formula of the metallo-chelate of is with M (L) m(X) nduring expression, m>=1, n>=0.When m is more than 2, the L of m both can be identical part also can be different part.When n is more than 2, the X of n both can be identical part also can be different part.
As atoms metal M, Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn etc. can be enumerated.
As polydentate ligand L, can enumerate: the 'beta '-ketoester of methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid grease, lauryl acetoacetate, etheric acid stearyl ester etc.; The beta-diketon of methyl ethyl diketone (another name: 2,4-diacetylmethane), 2,4-hexanediones, benzoyl acetone etc.They are keto-enol tautomerism body compounds, also can be the enolate (such as, acetylacetonate) that enol carries out de-proton in polydentate ligand L.
As unidentate ligand X; the halogen atoms such as chlorine atom, bromine atoms can be enumerated; the acyloxy such as pentanoyl, caproyl, 2-ethyl hexyl acyl group, capryloyl, nonanoyl, decanoyl, Lauroyl, stearyl-, the alkoxyl groups etc. such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, butoxy.
Object lesson as metallo-chelate can, to enumerate: three (2,4-diacetylmethane) iron (III), praseodynium iron, praseodynium titanium, praseodynium ruthenium, diacetyl acetone zinc, praseodynium aluminium, four methyl ethyl diketone zirconiums, three (2,4-hexanedione) iron (III), two (2,4-hexanedione) zinc, three (2,4-hexanedione) titanium, three (2,4-hexanedione) aluminium, four (2,4-hexanedione) zirconium etc.
As organo-tin compound, can enumerate: the soap of dialkyl tin oxide, dialkyl tin, the soap etc. of sub-tin.In the past, in most of the cases employ dibutyltin compound, but the toxicity problem of organo-tin compound is noted in recent years, particularly contained in dibutyltin compound tributyl tin (TBT) is also worrying as endocrine disruptors.From the view point of security, the chain alkyl tin compound of preferred dioctyl tin compound etc.As concrete organo-tin compound, di-n-octyltin oxide, tin dilaurate dioctyl tin etc. can be enumerated.Although can also temporarily use Sn compound, in view of the trend having the material that requirement safety in utilization is higher in the future, preferred safety in utilization is higher than the metallo-chelate of Al, Ti, Fe etc. of Sn.
As the metallo-chelate in adhesive composition of the present invention, be preferably containing more than at least one be selected from the group that is made up of aluminum chelate, titanium chelate, iron chelate, tin inner complex (wherein not comprising TBT).
Relative to 100 weight part multipolymers, preferably the content of the crosslinking catalyst of (G) metallo-chelate is 0.001 ~ 0.5 weight part.
As (H) keto-enol tautomerism body compound, can enumerate: the 'beta '-ketoester of methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid grease, lauryl acetoacetate, etheric acid stearyl ester etc.; The beta-diketon of methyl ethyl diketone, 2,4-hexanediones, benzoyl acetone etc.They are using polyisocyanate compounds as in the adhesive composition of linking agent, closed by the isocyanate group that linking agent is had, can suppress to coordinate the excessive rising of adhesive composition viscosity or the phenomenon of gelation after linking agent, the storage period of adhesive composition can be extended.
Relative to the multipolymer of 100 weight parts, preferably the content of (H) keto-enol tautomerism body compound is 0.1 ~ 200 weight part.
(H) keto-enol tautomerism body compound has the crosslinked effect of the suppression contrary with the crosslinking catalyst of (G) metallo-chelate, therefore, the ratio of (H) keto-enol tautomerism body Compound Phase for the crosslinking catalyst of (G) metallo-chelate is preferably suitably set.In order to extend storage period, the raising storage stability of adhesive composition, preferably weight part ratio (H)/(G) of the crosslinking catalyst of (H) keto-enol tautomerism body compound/(G) metallo-chelate is high.Preferably the value of (H)/(G) is the scope of 1 ~ 700, is more preferably 30 ~ 300, most preferably is 80 ~ 300.
As (I) static inhibitor, the static inhibitor of institute's copolymerization in static inhibitor contained in adhesive composition and aforementioned copolymer can be enumerated.Relative to 100 weight part multipolymers, preferably the content of (I) static inhibitor is 0.05 ~ 5.0 weight part.
Preferably (I) static inhibitor to be (I-1) fusing point be ionic compound and/or (I-2) ionic compound containing acryl of 25 ~ 50 DEG C.
In the present invention, as (I) static inhibitor, the ionic compound being 25 ~ 50 DEG C by (I-1) fusing point to make an addition in multipolymer and/or by (I-2) ionic compound copolymerization containing acryl in multipolymer.Infer because the fusing point of these (I) static inhibitor is low and have chain alkyl, therefore, high with the affinity of acrylic copolymer.
As the ionic compound that (I-1) fusing point is 25 ~ 50 DEG C, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is the cationic nitrogenous Huo person phosphonium cation, sulfonium cation etc. of pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium cation etc., and negatively charged ion is hexafluoro-phosphate radical (PF 6 -), thiocyanate ion (SCN -), benzene sulfonamide acid group (RC 6h 4sO 3 -), perchlorate (ClO 4 -), tetrafluoroborate (BF 4 -), the compound of the inorganic or organic anion of two (fluorosulfonyl) imide root (FSI), two (trifyl) imide root (TFSI), trifluoromethanesulfonic acid root (TF) etc.Be preferably solid under normal temperature (such as 25 DEG C), and by selecting the chain length, substituent position, number etc. of alkyl, the compound that fusing point is 25 ~ 50 DEG C can be obtained.Preferred cationic is quaternary nitrogen positively charged ion, can enumerate: the quaternary ammonium cation etc. of the season glyoxaline cation, tetra-allkylammonium etc. of the season pyridylium, 1,3-dialkylimidazolium (carbon atom of 2,4,5 both can have substituting group and also can not have substituting group) etc. of 1-alkyl pyridine (carbon atom of 2 ~ 6 both can have substituting group and also can not have substituting group) etc.
Relative to the multipolymer of 100 weight parts, preferably (I-1) fusing point is the content of the ionic compound of 25 ~ 50 DEG C is 0.1 ~ 5.0 weight part.
As (I-2) ionic compound containing acryl, be the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is (methyl) acryloxyalkyl trialkyl ammonium (R 3n +-C nh 2n-OCOCQ=CH 2, wherein, Q=H or CH 3, R=alkyl) etc. containing the positively charged ion of (methyl) acryl; Negatively charged ion is hexafluoro-phosphate radical (PF 6 -), thiocyanate ion (SCN -), organic sulfonic acid root (RSO 3 -), perchlorate (ClO 4 -), tetrafluoroborate (BF 4 -), imide root (R containing F f 2n -) etc. the compound of inorganic or organic anion.As the imide root (R containing F f 2n -) R f, perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc. can be enumerated.As the imide root containing F, two (fluorosulfonyl) imide root ((FSO can be enumerated 2) 2n -), two (trifyl) imide root ((CF 3sO 2) 2n -), two (five fluorine ethylsulfonyls) imide root ((C 2f 5sO 2) 2n -) etc. two alkylsulfonyl imide roots.
Preferably (I-2) ionic compound containing acryl copolymerization amount is in the copolymer 0.1 ~ 5.0 % by weight.
As the object lesson of (I) static inhibitor, be not particularly limited, but as the object lesson that (I-1) fusing point is the ionic compound of 25 ~ 50 DEG C, the quaternary ammonium salt etc. of 1-octylpyridinium hexafluorophosphate, 1-nonylpyridine hexafluorophosphate, 2-methyl isophthalic acid-dococylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dococylpyridinium thiocyanate-, 1-dococylpyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octylpyridinium hexafluorophosphate, trifluoromethanesulfonic acid can be enumerated.In addition, as the object lesson of (I-2) ionic compound containing acryl, (methyl) acrylate methyl esters phosphofluoric acid methyl salt ((CH can be enumerated 3) 3n +cH 2oCOCQ=CH 2pF 6 -, wherein, Q=H or CH 3), two (trifyl) imide methyl salt ((CH of (methyl) acrylate 3) 3n +(CH 2) 2oCOCQ=CH 2(CF 3sO 2) 2n -, wherein, Q=H or CH 3), two (fluorosulfonyl) imide methyl salt ((CH of dimethylamine methyl esters 3) 3n +cH 2oCOCQ=CH 2(FSO 2) 2n -, wherein, Q=H or CH 3) etc.
Adhesive composition of the present invention contains (J) polyether modified siloxane compound.(J) polyether-modified silicone compounds is the silicone compounds with polyether-based, except common siloxane unit (-SiR 1 2-O-) outside, also there is the siloxane unit (-SiR comprising polyether-based 1(R 2o (R 3o) nr 4)-O-).At this, R 1represent one or more alkyl or aryl, R 2and R 3represent one or more alkylidene group, R 4represent (terminal group) such as one or more alkyl, acyl groups.Can enumerate as polyether-based: polyethylene oxide base ((C 2h 4o) n) or polyoxytrimethylene base ((C 3h 6o) n) etc. polyoxyalkylene.
Preferably (J) polyether modified siloxane compound to be HLB value be 7 ~ 15 polyether modified siloxane compound.In addition, relative to the multipolymer of 100 weight parts, preferably the content of (J) polyether modified siloxane compound is 0.01 ~ 1.0 weight part, is more preferably 0.1 ~ 0.5 weight part.
HLB refers to the hydrophilic-lipophilic balance (wetting ability and oil loving ratio) of the regulations such as such as JIS K3211 (tensio-active agent term).
(J) polyether modified siloxane compound, such as, obtains by following method: by hydrosilylation reactions, makes the organic compound with unsaturated link(age) and polyoxyalkylene be grafted on the main chain of the organopolysiloxane with silylation and obtain.Specifically, can enumerate: dimethyl siloxane-methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxytrimethylene) silicone copolymers etc.
By (J) polyether modified siloxane compound is matched with adhesive composition, cohesive force and the cycling processability of binding agent can be improved.When adhesive composition is not containing polyether modified siloxane compound, cost can be made lower.
Adhesive composition of the present invention contains (K) antioxidant.As (K) antioxidant, hindered phenol anti-oxidants, poly-phenol (polyphenol) compound, tocopherol compound etc. can be enumerated.Wherein be preferably tocopherol compound.Tocopherol compound is generally vitamin-E, is also from natural chemical substance.Thus, also few to the detrimentally affect of human body, the security on using is high, and does not also pollute environment.In addition, owing to having oil soluble and be liquid at normal temperatures, therefore with the intermiscibility of adhesive composition and resistance to precipitation also excellent.By coordinating the tocopherol compound as (K) antioxidant, the storage stability of binding agent being improved, therefore can improve the storage period of the adhesive composition being combined with solidifying agent.
As the tocopherol compound used in the present invention, carry out coordinating (be unlike in human body and the accept metabolism) angle used from adhesive composition, the phenolic hydroxyl group of preferred tocopherol is not transformed into ester etc. and compound containing phenolic hydroxyl group.Such as, tocopherol, tocotrienols can be enumerated.Known exist natural type compound (d-body), the compound (l-body) of non-natural type, the difference as the raceme (dl-body) etc. of their equal amount of mixture in tocopherol, tocotrienols.Because natural type compound (d-body), raceme (dl-body) can also be used as foodstuff additive etc., therefore preferably.
As concrete tocopherol compound, at least one in the compound group being selected from and being made up of d-alpha-tocopherol, dl-alpha-tocopherol, d-5,8-dimethyl tocol, dl-5,8-dimethyl tocol, d-Gamma-Tocopherol, dl-Gamma-Tocopherol, d-Delta-Tocopherol, dl-Delta-Tocopherol, d-alpha-tocotrienol, dl-alpha-tocotrienol, d-β-tocotrienols, dl-β-tocotrienols, d-γ-tocotrienols, dl-γ-tocotrienols, d-δ-tocotrienols, dl-δ-tocotrienols can be enumerated.Also can be used together two or more tocopherol compound.Being referred to as the material of " mixed tocopherol " as food additives, is the mixture using d-alpha-tocopherol, d-5,8-dimethyl tocol, d-Gamma-Tocopherol and d-Delta-Tocopherol as main component; Being referred to as the material of " tocotrienols ", is the mixture using d-alpha-tocotrienol, d-β-tocotrienols, d-γ-tocotrienols and d-δ-tocotrienols as main component.
Relative to the multipolymer of 100 weight parts, preferred adhesive composition of the present invention contains 0.01 ~ 5 weight part tocopherol compound.
And, as other composition, can suitably coordinate containing alkylene oxide (alkylene oxide) can the known additive such as (methyl) Acrylic Acid Monomer, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, tensio-active agent, curing catalysts, softening agent, weighting agent, curing inhibitors, processing aid, antiaging agent, antioxidant of copolymerization.These both may be used singly or in combination of two or more use.
As the multipolymer of adhesive composition of the present invention host used, can by by the carbonatoms of (A) alkyl be C4 ~ C18 (methyl) acrylate monomer at least one, with be selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one not in hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group carries out copolymerization to synthesize.To the polymerization process of multipolymer, there is no particular limitation, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.
When the ionic compound using (I-2) containing acryl as (I) static inhibitor, the multipolymer of adhesive composition of the present invention host used can by by the carbonatoms of (A) alkyl be C4 ~ C18 (methyl) acrylate monomer at least one, with be selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one not in hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group, and (I-2) carries out copolymerization to synthesize containing the ionic compound of acryl.
Adhesive composition of the present invention, by coordinating the crosslinking catalyst of (F) two isocyanate compound more than sense, (G) metallo-chelate, (H) keto-enol tautomerism body compound, (I) static inhibitor, (J) polyether modified siloxane compound, (K) antioxidant, also having suitable any additive to prepare in above-mentioned multipolymer.In addition; if when (I-2) ionic compound containing acryl being polymerized in host multipolymer; both can add (I) static inhibitor further to this multipolymer, also can not add (I) static inhibitor.
Preferred aforementioned copolymer is acrylic polymers, preferably contains (methyl) acrylate monomer or the acrylic monomer such as (methyl) vinylformic acid, (methyl) acrylic amide of 50 ~ 100 % by weight.
In addition, the acid number of preferred acrylic polymers is 0.01 ~ 8.0.Thereby, it is possible to improve contaminative and improve the performance preventing glue residue phenomenon from occurring.
At this, " acid number " is one of index representing acid content, be with in and 1g contain carboxyl polymkeric substance required for the mg number of potassium hydroxide represent.
The cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.Thereby, it is possible to obtain cohesive force with the little performance of the change of peeling rate, even also can peel off rapidly when peeling off at a high speed.Further, even if in order to again paste during temporary transient stripper surface protective membrane, also without the need to excessive strength, be easy to peel off from adherend.
The surface resistivity of the adhesive layer preferably making foregoing adhesives composition be cross-linked is 9.0 × 10 + 11Ω/below, stripping static voltage is ± 0 ~ 0.5kV.In addition, in the present invention, the meaning of so-called " ± 0 ~ 0.5kV " refers to " 0 ~-0.5kV " and " 0 ~+0.5kV ", i.e. "-0.5 ~+0.5kV ".If surface resistivity is large, then to the poor performance that the electrostatic produced because of charged when peeling off discharges, therefore, by making surface resistivity enough little, the stripping static voltage produced with the electrostatic that occurs when peeling off adhesive layer from adherend can be reduced, the impact on the electric control circuit of adherend etc. can be suppressed.
The gel fraction of the adhesive layer (binding agent after crosslinked) preferably making adhesive composition of the present invention be cross-linked is 95 ~ 100%.Because gel fraction is so high, when low peeling rate, cohesive force can not become excessive, reduce the phenomenon of stripping unconverted monomer or oligomer from multipolymer, thus the weather resistance under re-workability, high temperature/high humidity can be improved, and suppress the pollution of adherend.
Adhesive film of the present invention forms adhesive layer at the single or double of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In addition, surface protection film of the present invention forms adhesive layer at the one side of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In adhesive composition of the present invention; owing to being combined with each composition of above-mentioned (A) ~ (K) with good balance; so have excellent antistatic property; the balance of the cohesive force under low peeling rate and high peeling rate is excellent; and endurance quality and cycling processability (with ballpoint pen after adhesive layer is described on surface protection film, transferring the pollution to adherend) are also excellent.Therefore, can preferably be used as the surface protection film purposes of Polarizer.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, the resin moldings etc. such as polyester film can be used.
For base material film, can on the face contrary with being formed with adhesive layer side of resin molding, implement the antifouling process undertaken by releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of silicone, fluorine class, the antistatic treatment of being undertaken by the coating of static inhibitor or be mixed into etc. can be implemented.
For stripping film, carry out fitting on the face of side at the adhesive surface with adhesive layer, implement the demoulding process undertaken by the releasing agent etc. of silicone, fluorine class.
Embodiment
Below, the present invention is illustrated based on embodiment.
The manufacture > of < acrylic copolymer
[embodiment 1]
Nitrogen is imported in the reaction unit being furnished with agitator, thermometer, reflux exchanger and nitrogen ingress pipe, thus the air with nitrogen replacement in reaction unit.Then, in reaction unit, add the 2-EHA of 100 weight parts, the vinylformic acid 8-hydroxyl monooctyl ester of 3.0 weight parts, the vinylformic acid of 0.4 weight part, the polypropylene glycol mono acrylic ester (forming the averaged repeating numbers n=12 of the alkylene oxide of polyalkylene glycol chain) of 10 weight parts, and add the solvent (vinyl acetic monomer) of 60 weight parts simultaneously.Then, through the Diisopropyl azodicarboxylate as polymerization starter of 2 hours instillation 0.1 weight parts, at 65 DEG C, make it react 6 hours, obtain weight-average molecular weight be 500,000, for the acrylic acid copolymer soln 1 of embodiment 1.Get a part for acrylic copolymer, as determination of acid value sample described later.
[embodiment 2 ~ 6 and comparative example 1 ~ 7]
Except have adjusted the composition of each monomer respectively as described in (A) in table 1 ~ (E) and (I-2) except, operate in the same manner as the above-mentioned acrylic acid copolymer soln 1 for embodiment 1, obtain for the acrylic acid copolymer soln in embodiment 2 ~ 6 and comparative example 1 ~ 7.
Table 1
The manufacture > of < adhesive composition and surface protection film
[embodiment 1]
To the acrylic acid copolymer soln 1 according to the embodiment 1 manufactured as mentioned above, add 1.5 weight part 1-octylpyridinium hexafluorophosphates, 0.05 weight part polyether modified siloxane compound (HLB=7), 8.5 weight part methyl ethyl diketones, 0.1 weight part alpha-tocopherol after stirring, be uniformly mixed after adding 2.0 weight part Coronate HX (isocyanuric acid ester of コ ロ ネ ー ト HX, hexamethylene diisocyanate compound), 0.1 weight part praseodynium titanium, obtain the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film be made up of the polyethylene terephthalate scribbling silicone resin (PET) film, then at 90 DEG C, carries out drying and remove solvent, obtain the bonding sheet that adhesive layer thickness is 25 μm.
Then; prepare polyethylene terephthalate (PET) film face implementing antistatic treatment and antifouling process; and bonding sheet is transferred to this polyethylene terephthalate (PET) film with implement on the opposing face in face of antistatic treatment and antifouling process, obtain the surface protection film of the embodiment 1 of the stacked formation with " PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) implementing antistatic treatment and antifouling process ".
[embodiment 2 ~ 6 and comparative example 1 ~ 7]
Except have adjusted the composition of each additive respectively as described in (F) ~ (K) of table 2 except, operate in the same manner as the surface protection film of above-described embodiment 1, obtain the surface protection film of embodiment 2 ~ 6 and comparative example 1 ~ 7.
Table 2
Table 1 and table 2 to represent that the whole table of each components matching ratio is divided into the table of two parts, and the numerical value in bracket all represents that the total amount organized with (A) is set to 100 weight parts and the numerical value of each Parts by Ingredients obtained.In addition, the ratio of (H)/(G) is shown in Table 3.In addition, the compound title corresponding with the abbreviation of each composition used in table 1 and table 2 is shown in table 4 and table 5.In addition, Coronate (コ ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L is Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) trade name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N, D-120N is the trade name of Mitsui Chemicals, Inc, Desmodur (デ ス モ ジ ュ ー Le, registered trademark) N3400 is Sumika BayerUrethane Co., Ltd. the trade name (living to change バ イ エ Le ウ レ タ Application Co., Ltd.).
In Table 1, by (I-2) of the copolymerization in (I) static inhibitor in multipolymer containing (I) static inhibitor added after ionic compound of acryl and polymerization, be recorded in respectively in different hurdles.
Table 3
(H)/(G)
Embodiment 1 85
Embodiment 2 80
Embodiment 3 333
Embodiment 4 500
Embodiment 5 125
Embodiment 6 250
Comparative example 1 ―
Comparative example 2 0.6
Comparative example 3 16.7
Comparative example 4 ―
Comparative example 5 100
Comparative example 6 83.3
Comparative example 7 90
Table 4
Table 5
The synthesis > of < bis-functional isocyanate compound
Two functional isocyanate compounds of synthesis example 1 ~ 3 adopt following method to synthesize.That is, as shown in table 6 and table 7, vulcabond is mixed with the ratio of mol ratio NCO/OH=16 with diol compound, react 3 hours at 120 DEG C, then, adopt thin film evaporation unit under reduced pressure to remove unreacted vulcabond, obtain desired two functional isocyanate compounds.
Table 6
Synthesis example 1F-1 Synthesis example 2F-2 Synthesis example 3F-3
Diisocyanate cpd HDI HDI HDI
Diol compound L-1 L-2 L-3
Table 7
< test method and evaluation >
23 DEG C, under the environment of 50%RH, the surface protection film of embodiment 1 ~ 6 and comparative example 1 ~ 7, after aging 7 days, is peeled off stripping film (scribbling the PET film of silicone resin), thus adhesive layer is exposed, and as the sample of chart surface resistivity.
And then; by the surface protection film that this adhesive layer exposes; the surface of the Polarizer pasted on liquid crystal cell is fitted in by adhesive layer; place and under 50 DEG C, 5 normal atmosphere, carry out pressure kettle process 20 minutes after 1 day; at room temperature place after 12 hours further, the sample be used as to measure cohesive force, peeling off static voltage, re-workability and weather resistance.
< cohesive force >
Adopt tensile testing machine; with low peeling rate (0.3m/min) and high peeling rate (30m/min); above-mentioned obtained mensuration sample (surface protection film wide for 25mm being fitted in the sample on Polarizer surface) is peeled off to 180 ° of directions; determine stripping strength, and using this stripping strength as cohesive force.
< surface resistivity >
After weathering, before laminating Polarizer, peel stripping film (scribbling the PET film of silicone resin) off and adhesive layer is exposed, adopt resistivity meter HirestaUP-HT450 (Ha イ レ ス タ UP-HT450, Mitsubishi of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture), determine the surface resistivity of adhesive layer.
< peels off static voltage >
Adopt high precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (KeyenceCorporation) manufacture), measure when carrying out 180 ° of strippings to above-mentioned obtained mensuration sample with the draw speed of 30m/min, the voltage (static voltage) that Polarizer is charged and produce, using the maximum value of measured value as stripping static voltage.
< re-workability >
After carrying out describing (load be 500g, 3 times back and forth) with ballpoint pen on the surface protection film of mensuration sample obtained above, from Polarizer stripper surface protective membrane, observe the surface of Polarizer, be confirmed whether to transfer the pollution to Polarizer.Evaluation objective benchmark: be evaluated as "○" when not transferring the pollution to Polarizer; Be evaluated as " △ " when confirming that the track described along ballpoint pen at least displaced pollution to local; "×" is evaluated as when confirming that the track described along ballpoint pen has pollution transportation and also confirms from adhesive surface the disengaging having binding agent.
< > storage period
Measure the viscosities il of adhesive composition after coordinating the additive of (F) ~ (K) at once 0(initial stage viscosity), and then the viscosities il determining adhesive composition after placing adhesive composition in 23 DEG C × 8 hours under air-tight state 1(viscosity after 8 hours).As the index of storage period, obtain with η 0η when being 1.0 1value, namely obtained η 1/ η 0ratio.Evaluation objective benchmark is as follows: be evaluated as "○" during lower than initial stage viscosity 1.25 times of viscosity after 8 hours, be evaluated as " △ " lower than when 1.50 times more than 1.25 times, more than 1.50 times or placed through 8 hours and gelation occurs and be evaluated as "×".
< weather resistance >
60 DEG C, 90%RH environment transfers to be set up and states obtained mensuration sample after 250 hours, taken out under being placed in room temperature and places 12 hours further, then measure cohesive force, confirms whether there is obvious increase compared with initial stage cohesive force.Evaluation objective benchmark: is "○" when the cohesive force after test is the average evaluation of less than 1.5 times of initial stage cohesive force, average evaluation more than 1.5 times is "×".
Evaluation result is shown in Table 8.In addition, in surface resistivity, represent " m × 10 by " mE+n " + n" (wherein, m is arbitrary real number, and n is positive integer).
Table 8
For the surface protection film of embodiment 1 ~ 6, the cohesive force under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm, and surface resistivity is 9.0 × 10 + 11Ω/below; stripping static voltage is ± 0 ~ 0.5kV, and, use ballpoint pen across adhesive layer after surface protection film is described; do not transfer the pollution to adherend, storage period long and 60 DEG C, place 250 hours under the environment of 90%RH after weather resistance be also excellent.
That is, have excellent antistatic property, under low peeling rate and high peeling rate, the balance of cohesive force is excellent, and storage period is long, and weather resistance and re-workability are also excellent.
In addition, for the surface protection film of embodiment 1 ~ 6, owing to not containing organo-tin compound in adhesive composition, therefore security is high.
For the surface protection film of comparative example 1; may owing to not containing the cause as isocyanate compound more than linking agent (F) two sense; its cohesive force under low peeling rate 0.3m/min and high peeling rate 30m/min is excessive; stripping static voltage is high, re-workability and poor durability.
For the surface protection film of comparative example 2; may be because (H) keto-enol tautomerism body Compound Phase is little for the ratio of the crosslinking catalyst of (G) metallo-chelate; and (J) HLB value of polyether modified siloxane compound excessive, not containing the cause of (K) antioxidant; it is high that it peels off static voltage; storage period is short, poor durability.
The surface protection film of comparative example 3; it may be the crosslinking catalyst owing to using the crosslinking catalyst of organo-tin compound to replace (G) metallo-chelate; and not containing the cause of (K) antioxidant; its storage period becomes too short; owing to being cross-linked before coating, therefore cannot be coated with.
For the surface protection film of comparative example 4; may be due to crosslinking catalyst and (H) keto-enol tautomerism body compound not containing (G) metallo-chelate; and not containing (J) polyether modified siloxane compound, not containing the cause of (K) antioxidant; its cohesive force under high peeling rate 30m/min is excessive; storage period is short, poor durability.
So; for the surface protection film of comparative example 1 ~ 4; cannot meet simultaneously there is antistatic property, and the balance of cohesive force is excellent under low peeling rate and high peeling rate, and storage period is long, weather resistance and re-workability also whole performance requriements such as excellent.
In addition, in the surface protection film of comparative example 5 ~ 7, crosslinking catalyst is not metallo-chelate but organo-tin compound, is therefore likely noted safety issue from now on.

Claims (15)

1. an adhesive composition, wherein, this adhesive composition comprises:
Containing at least one in the carbonatoms of (A) alkyl (methyl) acrylate monomer that is C4 ~ C18 and be selected from as copolymerisable monomer group by least one in the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group, and acid number is the acrylic polymers of the multipolymer of 0.01 ~ 8.0;
Also comprise:
(F) isocyanate compound more than two senses;
(G) crosslinking catalyst of metallo-chelate;
(H) keto-enol tautomerism body compound;
(I) as the ionic compound of the fusing point 25 ~ 50 DEG C of static inhibitor and/or the ionic compound containing acryl;
(J) HLB value is the polyether modified siloxane compound of 7 ~ 15; And
(K) antioxidant.
2. adhesive composition as claimed in claim 1, wherein,
Relative to total amount 100 weight part of the acrylic polymers of described multipolymer, this acrylic polymers contains:
The carbonatoms of (A) alkyl described in 50 ~ 95 weight parts is (methyl) acrylate monomer of C4 ~ C18;
The copolymerisable monomer of (B) hydroxyl described in 0.1 ~ 10 weight part;
(C) copolymerisable monomer containing carboxyl described in 0.1 ~ 1.0 weight part;
(D) polyalkylene glycol mono (methyl) acrylate monomer described in 0 ~ 50 weight part; And
(E) described in 0 ~ 20 weight part be hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group not,
Described adhesive composition contains:
(F) two isocyanate compound more than sense described in 0.1 ~ 10 weight part;
The crosslinking catalyst of (G) metallo-chelate described in 0.001 ~ 0.5 weight part; And
(H) keto-enol tautomerism body compound described in 0.1 ~ 200 weight part; Further, weight part ratio (H)/(G) of the crosslinking catalyst of described (H) keto-enol tautomerism body compound/(G) metallo-chelate is 1 ~ 700,
And contain:
As the static inhibitor of institute's copolymerization in contained static inhibitor in described (I) static inhibitor total amount described adhesive composition that is 0.05 ~ 5.0 weight part and described multipolymer;
(J) HLB value described in 0.01 ~ 1.0 weight part is the polyether modified siloxane compound of 7 ~ 15; And
0.01 ~ 5 weight part is as the tocopherols antioxidant of described (K) antioxidant.
3. adhesive composition as claimed in claim 1 or 2, wherein,
The copolymerisable monomer of described (B) hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide
Described (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
4. adhesive composition as claimed in claim 1 or 2, wherein, described (D) polyalkylene glycol mono (methyl) acrylate monomer is that the averaged repeating numbers of the alkylene oxide forming polyalkylene glycol chain is 3 ~ 14 and is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
5. adhesive composition as claimed in claim 1 or 2, wherein, described acrylic polymers contains described (E) not hydroxyl and nitrogenous vinyl monomer or containing more than at least one in (methyl) alkyl acrylate monomer of alkoxyl group as described copolymerisable monomer group.
6. adhesive composition as claimed in claim 1 or 2, wherein,
For described (F) two isocyanate compound more than sense,
As two functional isocyanate compounds, be non-ring type aliphatic isocyanates compound and be the compound making diisocyanate cpd and diol compound carry out reacting and generate;
As described diisocyanate cpd, be aliphatic diisocyanate and be selected from the one in the compound group that is made up of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate;
As described diol compound, be selected from by 2-methyl 1, ammediol, 2，2-dimethyl-1，3-propanediol, 2-methyl-2-propyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1, one in the compound group that ammediol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol form
As trifunctional isocyanates compound, by the isocyanuric acid ester of hexamethylene diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, the affixture of hexamethylene diisocyanate compound, the affixture of isophorone diisocyanate compound, the biuret of hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound, the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, at least one in the compound group that the affixture of hydrogenated xylylene diisocyanate cpd forms.
7. adhesive composition as claimed in claim 1 or 2; wherein, described (I) static inhibitor be contain 0.1 ~ 5.0 weight part relative to the described multipolymer of 100 weight parts and fusing point is the ionic compound of 25 ~ 50 DEG C and/or the copolymerization amount in described multipolymer be 0.1 ~ 5.0 % by weight containing the ionic compound of acryl.
8. adhesive composition as claimed in claim 1, wherein, the crosslinking catalyst in described adhesive composition does not include machine tin compound.
9. adhesive composition as claimed in claim 2, wherein, as the tocopherol compound of described antioxidant, be selected from by d-alpha-tocopherol, dl-alpha-tocopherol, d-5,8-dimethyl tocol, dl-5,8-dimethyl tocol, d-Gamma-Tocopherol, dl-Gamma-Tocopherol, d-Delta-Tocopherol, dl-Delta-Tocopherol, d-alpha-tocotrienol, dl-alpha-tocotrienol, d-β-tocotrienols, dl-β-tocotrienols, d-γ-tocotrienols, dl-γ-tocotrienols, d-δ-tocotrienols, at least one in the compound group that dl-δ-tocotrienols forms.
10. adhesive composition as claimed in claim 1 or 2, wherein, the cohesive force of the adhesive layer that described adhesive composition is cross-linked under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.
11. adhesive compositions as claimed in claim 1 or 2, wherein, the surface resistivity of the adhesive layer that described adhesive composition is cross-linked is 9.0 × 10 + 11Ω/below, stripping static voltage is ± 0 ~ 0.5kV.
12. 1 kinds of adhesive films, it forms adhesive layer at the single or double of resin molding to form, and described adhesive layer the adhesive composition according to any one of claim 1 ~ 11 is cross-linked form.
13. 1 kinds of surface protection films; its one side at resin molding forms adhesive layer and forms; described adhesive layer the adhesive composition according to any one of claim 1 ~ 11 is cross-linked form; wherein; with ballpoint pen after described adhesive layer is described on surface protection film, do not transfer the pollution to adherend.
14. surface protection films as claimed in claim 13, its surface protection film purposes as Polarizer uses.
15. surface protection films as claimed in claim 14, wherein, on the face contrary with the side being formed with described adhesive layer of described resin molding, implement antistatic and antifouling process.
CN201510025694.9A 2014-02-21 2015-01-19 Adhesive Composition And Surface Protection Film Active CN104861905B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-032063 2014-02-21
JP2014032063A JP6222698B2 (en) 2014-02-21 2014-02-21 Adhesive film and surface protective film

Publications (2)

Publication Number Publication Date
CN104861905A true CN104861905A (en) 2015-08-26
CN104861905B CN104861905B (en) 2017-04-12

Family

ID=53908099

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510025694.9A Active CN104861905B (en) 2014-02-21 2015-01-19 Adhesive Composition And Surface Protection Film

Country Status (4)

Country Link
JP (1) JP6222698B2 (en)
KR (4) KR101697308B1 (en)
CN (1) CN104861905B (en)
TW (2) TWI575043B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107304242A (en) * 2016-04-25 2017-10-31 藤森工业株式会社 Adhesion agent composition and Antistatic surface diaphragm
CN107523246A (en) * 2016-06-16 2017-12-29 藤森工业株式会社 Adhesion agent composition and Antistatic surface diaphragm
CN108865017A (en) * 2017-05-15 2018-11-23 藤森工业株式会社 Adhesion agent composition and surface protection film
CN110951423A (en) * 2018-09-27 2020-04-03 藤森工业株式会社 Adhesive composition, and adhesive film and surface protective film using same
CN110951422A (en) * 2018-09-27 2020-04-03 藤森工业株式会社 Adhesive composition, and adhesive film and surface protective film using same
CN114075414A (en) * 2020-08-11 2022-02-22 三星Sdi株式会社 Adhesive film for polarizing plate, polarizing plate including the same, and optical display device including the same
CN114410229A (en) * 2022-01-04 2022-04-29 江苏皇冠新材料科技有限公司 Adhesive tape coating liquid composition, adhesive tape coating liquid, adhesive tape and preparation method thereof
CN115428194B (en) * 2020-08-31 2023-06-09 日本瑞翁株式会社 Binder composition for electrochemical element, conductive material dispersion for electrochemical element, slurry composition for electrochemical element electrode, electrode for electrochemical element, and electrochemical element

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6525321B2 (en) * 2015-09-10 2019-06-05 藤森工業株式会社 Surface protection film for polarizing plate
JP6613818B2 (en) * 2015-10-30 2019-12-04 東洋インキＳｃホールディングス株式会社 Pressure sensitive adhesive and pressure sensitive adhesive film
KR101962999B1 (en) * 2015-12-14 2019-03-27 삼성에스디아이 주식회사 Adhesive film, optical member comprising the same and optical display apparatus comprising the same
JP6800101B2 (en) * 2016-07-08 2020-12-16 日東電工株式会社 Adhesive composition, adhesive layer, optical film with adhesive layer, image display panel, and liquid crystal display device
CN106113849A (en) * 2016-08-17 2016-11-16 胡银坤 A kind of diamagnetic heat conducting film and preparation method thereof
JP2018076442A (en) * 2016-11-10 2018-05-17 日東電工株式会社 Reinforcement film with separator
CN110832361B (en) * 2017-08-21 2021-12-17 东丽株式会社 Color conversion composition, color conversion sheet, and light source module, display, and lighting device each comprising color conversion sheet
WO2019111343A1 (en) 2017-12-06 2019-06-13 三菱電機株式会社 Water circulation device construction method and scale removal device
KR102317975B1 (en) * 2018-10-10 2021-10-27 삼성에스디아이 주식회사 Adhesive film, optical member comprising the same and optical display apparatus comprising the same
JP6770045B2 (en) * 2018-11-01 2020-10-14 藤森工業株式会社 Adhesive film and surface protection film
JP7363319B2 (en) * 2019-10-02 2023-10-18 Dic株式会社 Polyurethane resin composition, molded product and shoe sole using the same
KR102375799B1 (en) * 2020-08-06 2022-03-16 울산과학기술원 Method for implementing instantaneous strain reversibility to stretchable/flexible adhesives using pre-straining strategy
JP7041213B2 (en) * 2020-08-12 2022-03-23 藤森工業株式会社 Adhesive film and surface protection film
CN112375515A (en) * 2020-11-09 2021-02-19 江苏皇冠新材料科技有限公司 Adhesive and optical member protection sheet
JP7090755B2 (en) * 2021-01-05 2022-06-24 藤森工業株式会社 Adhesive composition and antistatic surface protective film
WO2023022185A1 (en) 2021-08-20 2023-02-23 日東電工株式会社 Adhesive sheet

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012171963A (en) * 2011-02-17 2012-09-10 Toyo Ink Sc Holdings Co Ltd Pressure-sensitive adhesive and pressure-sensitive adhesive film using the same
CN103509502A (en) * 2012-06-20 2014-01-15 藤森工业株式会社 Adhesive composition and surface-protective film
CN103571400A (en) * 2012-07-27 2014-02-12 藤森工业株式会社 Adhesive composition and surface-protective adhesive film

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5733945A (en) 1995-07-20 1998-03-31 Rogers Corporation Process for manufacturing polyurethane using a metal acetyl acetonate/acetyl acetone catalyst system and the product made therefrom
JP2001003634A (en) * 1999-04-19 2001-01-09 Futaba Industrial Co Ltd Window regulator and method for mounting the same
JP5091434B2 (en) * 2006-07-04 2012-12-05 日本カーバイド工業株式会社 Pressure-sensitive adhesive composition and optical member surface protective film
US20100092772A1 (en) * 2007-05-07 2010-04-15 Lintec Corporation Pressure-sensitive adhesive sheet
JP2011001440A (en) 2009-06-18 2011-01-06 Toagosei Co Ltd Adhesive composition
JP5484035B2 (en) * 2009-12-22 2014-05-07 日本カーバイド工業株式会社 Adhesive composition and optical film
CN102031077B (en) * 2010-10-29 2012-05-09 明基材料有限公司 Adhesive composition and adhesive layer
JP5906064B2 (en) * 2011-11-21 2016-04-20 藤森工業株式会社 Adhesive composition and surface protective film
JP6279827B2 (en) * 2011-12-20 2018-02-14 日東電工株式会社 Adhesive composition, adhesive layer and adhesive sheet
JP5879160B2 (en) * 2012-03-06 2016-03-08 藤森工業株式会社 Adhesive composition and surface protective film
JP5909137B2 (en) * 2012-04-05 2016-04-26 藤森工業株式会社 Adhesive composition and surface protective film
JP5901399B2 (en) * 2012-04-05 2016-04-06 藤森工業株式会社 Adhesive composition and surface protective film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012171963A (en) * 2011-02-17 2012-09-10 Toyo Ink Sc Holdings Co Ltd Pressure-sensitive adhesive and pressure-sensitive adhesive film using the same
CN103509502A (en) * 2012-06-20 2014-01-15 藤森工业株式会社 Adhesive composition and surface-protective film
CN103571400A (en) * 2012-07-27 2014-02-12 藤森工业株式会社 Adhesive composition and surface-protective adhesive film

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107304242A (en) * 2016-04-25 2017-10-31 藤森工业株式会社 Adhesion agent composition and Antistatic surface diaphragm
CN107523246A (en) * 2016-06-16 2017-12-29 藤森工业株式会社 Adhesion agent composition and Antistatic surface diaphragm
CN107523246B (en) * 2016-06-16 2021-04-09 藤森工业株式会社 Adhesive composition and antistatic surface protective film
CN108865017B (en) * 2017-05-15 2021-08-24 藤森工业株式会社 Adhesive composition and surface protective film
CN108865017A (en) * 2017-05-15 2018-11-23 藤森工业株式会社 Adhesion agent composition and surface protection film
TWI741081B (en) * 2017-05-15 2021-10-01 日商藤森工業股份有限公司 Adhesive composition and surface-protective film
CN110951423A (en) * 2018-09-27 2020-04-03 藤森工业株式会社 Adhesive composition, and adhesive film and surface protective film using same
CN110951422A (en) * 2018-09-27 2020-04-03 藤森工业株式会社 Adhesive composition, and adhesive film and surface protective film using same
CN110951423B (en) * 2018-09-27 2022-08-30 藤森工业株式会社 Adhesive composition, and adhesive film and surface protective film using same
CN110951422B (en) * 2018-09-27 2022-09-16 藤森工业株式会社 Adhesive composition, and adhesive film and surface protective film using same
TWI816803B (en) * 2018-09-27 2023-10-01 日商藤森工業股份有限公司 Adhesive composition, and adhesive film, surface-protective film using the same
CN114075414A (en) * 2020-08-11 2022-02-22 三星Sdi株式会社 Adhesive film for polarizing plate, polarizing plate including the same, and optical display device including the same
CN114075414B (en) * 2020-08-11 2023-08-25 三星Sdi株式会社 Adhesive film for polarizing plate, polarizing plate including the same, and optical display apparatus including the same
CN115428194B (en) * 2020-08-31 2023-06-09 日本瑞翁株式会社 Binder composition for electrochemical element, conductive material dispersion for electrochemical element, slurry composition for electrochemical element electrode, electrode for electrochemical element, and electrochemical element
CN114410229A (en) * 2022-01-04 2022-04-29 江苏皇冠新材料科技有限公司 Adhesive tape coating liquid composition, adhesive tape coating liquid, adhesive tape and preparation method thereof

Also Published As

Publication number Publication date
KR101879623B1 (en) 2018-07-18
CN104861905B (en) 2017-04-12
KR101904754B1 (en) 2018-10-05
KR20170007717A (en) 2017-01-19
KR101828247B1 (en) 2018-02-13
TWI612124B (en) 2018-01-21
KR101697308B1 (en) 2017-01-17
TW201716533A (en) 2017-05-16
KR20150099393A (en) 2015-08-31
TWI575043B (en) 2017-03-21
TW201533189A (en) 2015-09-01
JP6222698B2 (en) 2017-11-01
JP2015157883A (en) 2015-09-03
KR20180019022A (en) 2018-02-22
KR20180084024A (en) 2018-07-24

Similar Documents

Publication Publication Date Title
CN104861905A (en) Adhesive Composition And Surface Protection Film
CN105001815A (en) Binder composition and surface protective film
CN104673142A (en) Adhesive composition and surface protection film
CN103571400B (en) Adhesive composition and surface protection film
CN104650779B (en) Adhesive composition and surface protection film
CN105315947A (en) Adhesive composition and surface protection film
CN103509503B (en) Adhesive composition and surface protection film
CN104449481B (en) Adhesive composition and surface protection film
CN104774569A (en) Antistatic surface protection film
CN103131357B (en) Adhesive composition and surface-protective adhesive film
CN103509502A (en) Adhesive composition and surface-protective film
CN103820058B (en) Adhesive composition, adhesive film, and surface-protective film
TW201245378A (en) Adhesive composition and surface protection film
CN105086862A (en) Antistatic surface protective film
CN105440988A (en) Adhesive composition and surface protective film
CN108300365A (en) Adhesive composition, adhesive film and surface protection film
CN103571401A (en) Adhesive composition and surface-protective adhesive film
CN104342072B (en) Adhesive composition, adhesive film and surface protection film
JP7503586B2 (en) Adhesive layer, adhesive film and surface protection film
JP6635611B2 (en) Surface protection film
JP6431153B2 (en) Adhesive film and surface protective film
JP2019052310A (en) Adhesive film and surface protective film
JP6368017B2 (en) Adhesive composition and surface protective film
JP6983959B2 (en) Surface protective film
JP6580759B2 (en) Surface protection film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant