CN106255733A - Adhesive sheet and optics - Google Patents

Adhesive sheet and optics Download PDF

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Publication number
CN106255733A
CN106255733A CN201580019596.2A CN201580019596A CN106255733A CN 106255733 A CN106255733 A CN 106255733A CN 201580019596 A CN201580019596 A CN 201580019596A CN 106255733 A CN106255733 A CN 106255733A
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CN
China
Prior art keywords
methyl
adhesive sheet
acid
agent
adhesion strength
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Granted
Application number
CN201580019596.2A
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Chinese (zh)
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CN106255733B (en
Inventor
片冈贤
片冈贤一
天野立巳
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN106255733A publication Critical patent/CN106255733A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The present invention provide a kind of be possible to prevent at a high speed through adhesion strength at present rising (adhesion strength rises preventing property, adhesion strength stability), adhesion strength when peeling off at a high speed is suppressed low, releasable and workability is excellent, shearing force is excellent adhesive sheet.The adhesive sheet of the present invention is characterised by, being the adhesive sheet at the single or double of support membrane with the adhering agent layer formed by adhesion agent composition, adhesion strength ratio (B/A) of the adhesion strength (B) when the adhesion strength (A) when the bonding plane of described adhering agent layer is pasted at 23 DEG C peeling rate after TAC face upper 30 minute 30m/ minute and the peeling rate being pasted at 70 DEG C by the bonding plane of described adhering agent layer on TAC face after 1 week 30m/ minute is less than 2.

Description

Adhesive sheet and optics
Technical field
The present invention relates to adhesive sheet and the optics protected by described adhesive sheet.
The adhesive sheet of the present invention, as the Polarizer of middle use, wavelength plate, phase contrasts such as protection liquid crystal displays The surface protection film that plate, optical compensation films, reflector plate, briliancy improve the purpose of the optical component surfaces such as film and use, is useful 's.
Background technology
In recent years, optics, electronic unit transport or when the installation of printed base plate, all parts is with predetermined State that sheet has been packed, the state being pasted with adhesion zone are transported.Wherein, surface protection film is particularly widely used Optics, electronic unit field in.
Surface protection film typically fits in adherend (by protective) via the sticker coating support membrane side, is used for Prevent damage, the purpose (patent documentation 1) of dirt produced when the processing of adherend, carrying.Such as, the panel of liquid crystal display By the optical member adhering such as Polarizer, wavelength plate being formed in liquid crystal cell via sticker.Surface protection film is via adhesion Agent and be bonded to these opticses, it is possible to prevent adherend processing, carrying time produce damage, dirt.
It addition, add man-hour with what the state of surface protection film of having fitted carried out adherend, sometimes carry out high-temperature process, but this In the case of sample, the adhesion strength of adhering agent layer is substantially increased sometimes, afterwards, becomes unwanted rank at this surface protection film Section, carries out peeling off when removing, and with the maximization, thin layer of the LCD panel etc. as adherend, peels off in engineering easily Occur as the Polarizer of adherend, the damage of liquid crystal cell, therefore after high-temperature process, when peeling off at a high speed, it is desirable to gently peel off.
For surface protection film, it is desirable to curling scalability, in order to make when being pasted on adherend (Polarizer etc.), Paste in the adherend (Polarizer etc.) of surface protection film, do not produced unnecessary curling, (curling refers in undesirable curling Turn over and stick up phenomenon, such as, any surface side globality of tabular object turn over stick up phenomenon, tabular object globality ground up-and-down Turn over and stick up phenomenon etc..).If producing unnecessary curling, undesirable curling, then operability is poor, such as, is glued by Polarizer etc. When thing is pasted on liquid crystal cell, the unfavorable condition such as intrusion of gassing sometimes.
During it addition, flat adherend occurs curling, in the adhering agent layer of the surface protection film fitting in adherend, with Curling power together works on shear direction, due to this power, slowly slides between adherend and adhering agent layer, misplaces Deng, therefore it is required that improve shearing force when low speed is peeled off.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 9-165460 publication
Summary of the invention
The technical problem to be solved in the present invention
Therefore, the invention aims to solve the problem in conventional adhesive sheet, it is provided that one is possible to prevent high temperature Through time adhesion strength rising (adhesion strength rise preventing property, adhesion strength stability), reduce adhesion strength when peeling off at a high speed, shell again , the adhesive sheet of shearing force excellence excellent from property and workability.
The scheme of solution problem
That is, the adhesive sheet of the present invention is characterised by, is to have to be combined by sticker on the single or double of support membrane The adhesive sheet of adhering agent layer that thing is formed, the stripping after the bonding plane of described adhering agent layer is pasted on TAC face 30 minutes at 23 DEG C Adhesion strength (A) when speed 30m/ minute with the bonding plane of described adhering agent layer is pasted on TAC face 1 week at 70 DEG C after stripping Adhesion strength ratio (B/A) of the adhesion strength (B) when speed 30m/ minute is less than 2.
The adhesive sheet of the present invention is preferably: described adhesion agent composition contains (methyl) acrylic acid with hydroxyl and carboxyl Based polymer.
The adhesive sheet of the present invention is preferably: described adhesion agent composition contains cross-linking agent, and described cross-linking agent contains aromatic series Isocyanates based compound and aliphatic isocyanates based compound.
The adhesive sheet of the present invention is preferably: in terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, Containing hydroxyl (methyl) acrylic monomers more than 5.1 mass %.
The adhesive sheet of the present invention is preferably: in terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, Containing 0.01 mass % less than 0.5 mass % containing carboxyl (methyl) acrylic monomer.
The adhesive sheet of the present invention is preferably: have anti-quiet with the one side of the described support membrane of described adhering agent layer opposition side Electric layer, described antistatic backing is by containing the poly-aminobenzenesulfonic acid as electric conductive polymer composition, the polyester tree as binding agent Fat and the antistatic agent compositions as the isocyanates system cross-linking agent of cross-linking agent are formed.
The adhesive sheet of the present invention is preferably: described antistatic agent compositions contains the fatty acid acyl as lubricant further Amine.
The optics that the optics of the present invention is preferably protected by described adhesive sheet.
Invention effect
The adhesive sheet of the present invention due to be possible to prevent high temperature through time the rising of adhesion strength (adhesion strength rises preventing property, viscous Put forth effort stability), reduce that adhesion strength when peeling off at a high speed, releasable and workability are excellent and then shearing force is excellent, therefore paste During together in adherend, curling unnecessary in adherend, undesirable curling can be suppressed, be useful.
Detailed description of the invention
Hereinafter, embodiments of the present invention are described in detail.
Overall structure ＞ of ＜ adhesive sheet (surface protection film)
The adhesive sheet (surface protection film) of the present invention is usually referred to as adhesive sheet, adhesive tape, adhesion label, adhesive film Etc. the material of form, (such as, Polarizer, wavelength plate etc. are constituted as panel of LCD to be particularly suitable as optics The optics of key element) add man-hour, carrying time protection optical component surfaces surface protection film.Adhesion in described adhesive sheet Oxidant layer, it is typical that be continuously formed, but it is not limited to described form, can also be such as to form the rule such as point-like, striated Or the adhering agent layer of random pattern.It addition, adhesive sheet disclosed herein can also be web-like, it is also possible to be single sheet.
It is typically constructed example as adhesive sheet disclosed herein (surface protection film), can enumerate at support membrane (base material) Single or double have the adhesive sheet of adhering agent layer, the antistatic backing possessing the one side being arranged on support membrane and be arranged on The adhesive sheet of the adhering agent layer on the surface of the antistatic backing opposition side of support film.Adhesive sheet is that this adhering agent layer is pasted on adherend (surfaces of the opticses such as protection object, such as Polarizer) use.The adhesion of (that is, attach to adherend before) before using Sheet can also be following form: the surface (towards the attaching face of adherend) of adhering agent layer is become stripping by least adhering agent layer side Release liner protection from face.Or, adhesive sheet can also be following form: by being rolled into a roll, adhering agent layer abuts and props up The back side (surface of antistatic backing) of support film, its surface is protected.
＜ support membrane ＞
The adhesive sheet of the present invention is characterised by having at the single or double of support membrane being formed by adhesion agent composition Adhering agent layer.The resin material constituting described support membrane can use without particular limitation, such as, the transparency, machine are preferably used The material of the excellents such as tool intensity, heat stability, moisture block, isotropism, flexibility, dimensional stability.The most logical Cross support membrane and there is flexibility, can be rolled into a roll with coating adhesion agent compositions such as roll coaters, be useful.
As described support membrane (base material), for example, it is preferable to can use by with polyethylene terephthalate (PET), The Polyester polymer such as PEN (PEN), polybutylene terephthalate (PBT)；Diacetyl cellulose, three second The cellulose-based polymer such as acyl cellulose；Merlon based polymer；The acrylic acid series polymeric compounds etc. such as polymethyl methacrylate Resin material as main resinous principle (main constituent in resinous principle, typically account for the composition of more than 50 mass %) The plastic foil constituted is used as described support membrane.As other examples of described resin material, can enumerate: polystyrene, third The styrenics such as alkene nitrile-styrol copolymer；Polyethylene, polypropylene, there is the ring-type or polyene of norborene structure The olefin polymer such as hydrocarbon, ethylene-propylene copolymer；Vinyl chloride-based polymer；The acyls such as nylon 6, nylon66 fiber, aromatic polyamide Amine based polymer etc. is used as resin material.As the still other examples of described resin material, can enumerate: imide series gathers Compound, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, ethenol system are polymerized Thing, vinylidene chloride based polymer, vinyl butyral based polymer, arylide based polymer, polyformaldehyde based polymer, ring Oxygen based polymer etc..It can also be the support membrane formed by the mixture of more than two kinds of above-mentioned polymer.
As described support membrane, the plastic foil formed by transparent thermoplastic resin material preferably can be used.Described mould Among material film, preferred mode is to use polyester film.Here, polyester film refer to polyethylene terephthalate (PET), PEN (PEN), polybutylene terephthalate (PBT) etc. have the polymerization of the main framing based on ester bond Thing material (polyester resin) is as the film of main resinous principle.Described polyester film has optical characteristics, excellent in dimensional stability The preferred characteristic Deng the support membrane as adhesive sheet, on the other hand it has the most charged character originally.
Constitute in the resin material of described support membrane, antioxidant, UV absorbent, increasing can also be coordinated as required Mould the various additives such as agent, coloring agent (pigment, dyestuff etc.).First for described support membrane (arranges antistatic backing side Surface), it is also possible to implement such as Corona discharge Treatment, plasma treatment, ultraviolet treatment with irradiation, acid treatment, alkali process, the end The surface process that the coating of varnish etc. are known or usual.It is quiet with anti-that the process of such surface such as could be for improving support membrane The process of the adaptation of electric layer.Can preferably employ to the surface of support membrane importing hydroxyl (-OH base) isopolarity group such Surface processes.It addition, second (forming the surface of adhering agent layer side) of support membrane can also be implemented same as described above Surface processes.Described surface processes the place that could be for improving film with the adaptation (the throwing anchor of adhering agent layer) of adhering agent layer Reason.
It addition, the adhesive sheet of the present invention, can have antistatic backing on support membrane, there is the situation of electrostatic-proof function Under, as described support membrane, it is possible to use carry out the plastic foil that antistatic processes further.By using described support Film, it is possible to the adhesive sheet self after suppression is peeled off is charged, the most preferably.It addition, support membrane is plastic foil, real to described plastic foil Execute antistatic to process, it is possible to obtain that to reduce adhesive sheet self charged and to the excellent adhesive sheet of the anti-static ability of adherend. Here, as the method giving electrostatic-proof function, it is not particularly limited, it is possible to use known method, such as, can lift Go out: the method for the static electricity resistance resin that coating is formed by antistatic agent and resinous principle, coating are containing electric conductive polymer, conduction Property the method for electroconductive resin of material, evaporation or the method for plated conductive material and mix the side of antistatic agent etc. Method etc..
As the thickness of described support membrane, usually 5～200 μm, about preferably 10～100 μm.Described support membrane If thickness is in the range of described, then the workability to adherend laminating and the workability excellence from adherend stripping, the most excellent Choosing.
＜ adhesion agent composition ＞
The adhesive sheet (surface protection film) of the present invention has described adhering agent layer, and described adhering agent layer is to be combined by sticker The layer that thing is formed, as described adhesion agent composition, then can use with no particular limitation as long as have adhesive material, Such as, acrylic acid series sticker, carbamate system sticker, synthetic rubber system sticker, natural rubber system sticker, silicone It is sticker etc., wherein, more preferably selects free acrylic acid series sticker, carbamate system sticker and silicone-based sticker At least one in the group of composition, particularly preferably uses the acrylic acid series sticker of (methyl) acrylic acid series polymeric compounds.
The described adhesion agent composition used in the present invention preferably comprises (methyl) acrylic acid series with hydroxyl and carboxyl Polymer.By having (methyl) acrylic acid series polymeric compounds of hydroxyl and carboxyl described in use, thus, described hydroxyl can be easy Ground carries out the control that cross-links, described carboxyl can improve shearing force or prevent adhesion strength through time rise, therefore become preferred side Formula.Owing to the shearing force of sticker (layer) improves, by described sticker is fitted in adherend, the volume of adherend can be suppressed Song, can suppress (interface) between sticker and adherend to slide, misplace, and this is particularly preferred.Here, in the present invention (methyl) acrylic acid series polymeric compounds refer to acrylic acid series polymeric compounds and/or metha crylic polymer, (methyl) acrylic acid Ester refers to acrylate and/or methacrylate.
It addition, described (methyl) acrylic acid series polymeric compounds is by using described hydroxyl (methyl) acrylic monomer conduct Monomer component, it is easy to control the crosslinking etc. of adhesion agent composition, and then the improvement of wettability that easily controllable flowing brings is with viscous Agent (layer) cohesiveness, peel off time the reduction (light fissility) of adhesion strength, the balance of shearing force.And then, in sticker Add in the case of antistatic agent, different from the carboxyl that typically can work as cross-linking part, sulphonate-base etc., hydroxyl due to Have and the interaction of the appropriateness such as ionic compound as antistatic agent, even if therefore the aspect at static electricity resistance also may be used To use the most suitably.
The adhesive sheet of the present invention is preferably: total relative to the monomer component constituting described (methyl) acrylic acid series polymeric compounds Amount, more than hydroxyl (methyl) acrylic monomer 5.1 mass %, more preferably 5.3～15 mass %, further preferred 7 ～12 mass %.If in the range of described, the wettability of the most easily controllable adhesion agent composition and the cohesion of sticker (layer) Power, the balance of shearing force, the most preferably.
As described hydroxyl (methyl) acrylic monomer, such as can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) third Olefin(e) acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 12-hydroxylauric ester, acrylic acid (4-hydroxyl Ylmethyl cyclohexyl) methyl ester, N-methylol (methyl) acrylamide etc..
The adhesive sheet of the present invention is preferably: to constitute the monomer component of described (methyl) acrylic acid series polymeric compounds as total amount Meter, containing mass % containing carboxyl (methyl) acrylic monomer 0.01 less than 0.5 mass %, more preferably more than 0.01 and Less than 0.4 mass %, further preferred 0.01 less than 0.3 mass %, and extremely preferred 0.01 less than 0.2 matter Amount %.If in the range of described, then can suppress adhesion strength through time rise, releasable, adhesion strength rise preventing property with And workability is excellent.It addition, not only the cohesiveness of adhering agent layer is excellent, and shearing force is the most excellent, is preferred.Here, as There is the such acid functional group of carboxyl that a lot of polarity effect is big in fruit, then when coordinating the ionic compound as antistatic agent, The acid functional groups such as carboxyl interact with ionic compound, thus hinder ionic conduction, and electrical efficiency reduces, and may become Sufficient static electricity resistance cannot be obtained, thus the most preferred.
As described containing carboxyl (methyl) acrylic monomer, such as, can enumerate: (methyl) acrylic acid, (methyl) propylene Acid carboxyethyl, (methyl) acrylic acid carboxyl pentyl ester, 2-(methyl) acryloyl-oxyethyl hexahydrobenzene dioctyl phthalate, 2-(methyl) third Alkene acryloxypropylethoxysilane hexahydrobenzene dioctyl phthalate, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloxy second Base succinic acid, 2-(methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2-(methyl) third Alkene trimethylammonium four hydrogen phthalate etc..
The described adhesion agent composition used in the present invention contains described (methyl) acrylic acid series polymeric compounds, as long as have Adhesive (methyl) acrylic acid series polymeric compounds, is not particularly limited, as the main constituent of monomer component, tool is preferably used There is (methyl) acrylic monomer of the alkyl of carbon number 1～14, more preferably there is (the first of the alkyl of carbon number 4～14 Base) acrylic monomer.As described (methyl) acrylic monomer, can make one kind or two or more as main constituent With.Here, to be to cooperate with ratio the highest for the meaning of " main constituent ".
As the object lesson of (methyl) acrylic monomer of the described alkyl with carbon number 1～14, such as may be used To enumerate (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding Ester, (methyl) tert-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid 2-ethyl Own ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid positive nonyl ester, (methyl) acrylic acid are different Nonyl ester, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) acrylic acid dodecyl ester, (methyl) third Olefin(e) acid n-tridecane base ester, (methyl) n-myristyl base ester etc..
Wherein, when the adhesive sheet of the use present invention is as surface protection film, as suitable monomer, (methyl) can be enumerated Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (first Base) acrylic acid positive nonyl ester, (methyl) acrylic acid different nonyl ester, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (first Base) propylene dodecyl acid esters, (methyl) acrylic acid n-tridecane base ester, (methyl) n-myristyl base ester etc. have (methyl) acrylate of the alkyl of carbon number 6～14.Be there is (methyl) third of the alkyl of carbon number 6～14 by use Olefin(e) acid ester, easily will control low to the adhesion strength of adherend, and releasable is excellent.
The adhesive sheet of the present invention is preferably: total relative to the monomer component constituting described (methyl) acrylic acid series polymeric compounds Amount, contain described in there is (methyl) acrylic monomer 50～94.99 mass % of alkyl of carbon number 1～14, more preferably 60～94.9 mass %, further preferred 70～94.8 mass %, most preferably 80～94.7 mass %.By in described scope In, adhesion agent composition has the wettability of appropriateness, and the cohesiveness of sticker (layer) is the most excellent, is preferred.
It addition, as other polymerizable monomer composition, for the reason of the balance easily obtaining adhesive performance, Ke Yi Do not damage and use in the range of effect of the present invention for adjusting the glass transition temperature of (methyl) acrylic acid series polymeric compounds, stripping Property polymerizable monomer etc. so that Tg becomes less than 0 DEG C (generally more than-100 DEG C).
As described hydroxyl (methyl) acrylic monomer used in described (methyl) acrylic acid series polymeric compounds, containing carboxylic Other beyond (methyl) acrylic monomer of base (methyl) acrylic monomer and the alkyl with carbon number 1～14 gather Conjunction property monomer, as long as in the range of the characteristic not damaging the present invention, then can be not particularly limited to use.Such as can fit When using the monomer of cyano-containing, vinyl ester monomers, aromatic vinyl monomer etc. to improve cohesiveness, the composition of thermostability, contain The monomer of amide groups, the monomer containing imide, the monomer containing amino, the monomer containing epoxy radicals, N-acryloyl morpholine, ethylene Base ether monomers etc. improve adhesion (bonding) power or have had the composition of functional group of Cross-linked basic point effect.These polymerizable monomers Can be used alone, additionally two or more can also be used in mixed way.
As the monomer of described cyano-containing, such as, can enumerate acrylonitrile, methacrylonitrile.
As described vinyl ester monomers, such as, can enumerate vinyl acetate, propionate, vinyl laurate Deng.
As described aromatic vinyl monomer, such as can enumerate styrene, chlorostyrene, 1-chloro-4-methyl-benzene, α- Methyl styrene, other substituted phenylethylene etc..
As the monomer of described amide-containing, such as, can enumerate acrylamide, Methacrylamide, diethyl acryloyl Amine, NVP, N, N-DMAA, N, N-dimethylmethacryl amide, N, N-diethyl propylene Amide, N, N-diethyhnethacrylamide, N, N '-methylene-bisacrylamide, N, N-dimethylaminopropylacryl amide, N, N-dimethylaminopropyl Methacrylamide, N-[2-(2-methyl-4-oxopentyl) etc..
As the described monomer containing imide, such as, can enumerate N-cyclohexylmaleimide, isopropyl maleimide Amine, N-N-cyclohexylmaleimide, clothing health acid imide etc..
As the described monomer containing amino, such as, can enumerate (methyl) acrylate, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, N-dimethylamino propyl ester etc..
As the described monomer containing epoxy radicals, such as, can enumerate glycidyl (methyl) acrylate, methylglycidyl Glyceryl (methyl) acrylate, allyl glycidyl ether etc..
As described vinyl ether monomers, such as, can enumerate methyl vinyl ether, ethyl vinyl ether, iso-butyl vinyl Base ether etc..
In the present invention, described containing carboxyl (methyl) acrylic monomer, hydroxyl (methyl) acrylic monomer with have Other polymerizable monomers beyond (methyl) acrylic monomer of the alkyl of carbon number 1～14, are constituting described (methyl) In the monomer component total amount (whole monomer component) of acrylic acid series polymeric compounds, preferably 0～40 mass %, more preferably 0～30 Quality %.By using other polymerizable monomers described in the range of described, can suitably regulate with as antistatic agent from Good the interacting and good releasable of sub-property compound.
The weight average molecular weight of described (methyl) acrylic acid series polymeric compounds is 100,000～5,000,000, preferably 200,000～4,000,000, More preferably 300,000～3,000,000.When weight average molecular weight is less than 100,000, the cohesiveness of the sticker (layer) obtained diminishes, because of And have the tendency producing cull.On the other hand, when weight average molecular weight is more than 5,000,000, the mobility of polymer reduces, to adherend The moistening of (such as, as the Polarizer etc. of optics) becomes insufficient, has the sticker group becoming adherend with adhesive sheet The tendency of the reason of the foaming occurred between compound layer.Here, weight average molecular weight is to be measured by GPC (gel permeation chromatography) Arrive.
It addition, the glass transition temperature (Tg) of described (methyl) acrylic acid series polymeric compounds is preferably less than 0 DEG C, more preferably For less than-10 DEG C, more preferably less than-20 DEG C (generally more than-100 DEG C).When glass transition temperature is higher than 0 DEG C, poly- Compound is difficult to flow, and the such as moistening to adherend (such as, as the Polarizer etc. of optics) becomes insufficient, has and becomes The tendency of the reason of the foaming occurred between the adhesion agent composition layer of adherend and adhesive sheet.Turn especially by making vitrification Temperature is less than-61 DEG C, is readily available the wettability to adherend and the adhesion agent composition of light fissility excellence.Here, By suitably changing monomer component, the ratio of components used, can be by the glass transition temperature of (methyl) acrylic acid series polymeric compounds Degree adjusts in the range of described.
The polymerization of (methyl) acrylic acid series polymeric compounds used in the present invention is not particularly limited, and can pass through solution The known method such as polymerization, emulsion polymerization, polymerisation in bulk, suspension polymerisation is polymerized, particularly from the viewpoint of workability, to being glued From the standpoint of the characteristics such as the low stain of thing, polymerisation in solution is preferred mode.It addition, the polymer of gained is random copolymerization Thing, block copolymer, alternate copolymer, graft copolymer etc..
For the adhesive sheet of the present invention, described adhesion agent composition can contain antistatic agent (antistatic composition), makees For described antistatic agent, ionic compound can be contained.As described ionic compound, can enumerate alkali metal salt and/ Or the ionic compound of low melting point (fusing point less than 150 DEG C).By containing these ionic compounds, excellence can be given Static electricity resistance.
It addition, be in terms of 100 mass parts by described (methyl) acrylic acid series polymeric compounds, the content of described ionic compound is excellent Elect below 1 mass parts, more preferably 0.001～0.9 mass parts, more preferably 0.005～0.8 mass parts as.If In the range of described, the most easily take into account static electricity resistance and low stain, the most preferably.
For the adhesive sheet of the present invention, described adhesion agent composition can be containing the organic poly-silicon with polyoxyalkylene chain Oxygen alkane.Speculate by using described organopolysiloxane, it is achieved when the surface free energy on sticker surface reduces, high speed is peeled off Light separation.
Described organopolysiloxane has an organopolysiloxane of polyoxyalkylene chain known to can suitably using, such as, As commercially available product, trade name X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889, KF-can be enumerated 351A、KF-352A、KF-353、KF-354L、KF-355A、KF-615A、KF-945、KF-640、KF-642、KF-643、KF- 6022, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (are above SHIN-ETSU HANTOTAI Chemical industrial company's system), BY16-201, SF8427, SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ-2122, FZ-2164, FZ-2203, FZ-7001, SH8400, SH8700, SF8410, SF8422 (with Shang Shidongli Dow Corning Corporation system), IM22 (above, Wa Ke company of Asahi Chemical Industry system), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (being above MomentivePerformanceMaterials's system), BYK-333, BYK- 307, the commodity of BYK-377, BYK-UV3500, BYK-UV3570 (being above Bi Ke Japanese firm system) etc..These can be independent Use, additionally two or more can also be used in mixed way.
The above-mentioned organopolysiloxane used as the present invention, HLB (hydrophile-lipophile balance, parent Hydrophile-lipophile balance value) value is preferably 1～16, more preferably 3～14.If HLB value is outside described scope, then to adherend Contaminative is deteriorated, and is inappropriate.
It addition, relative to described (methyl) acrylic acid series polymeric compounds 100 mass parts, the content of described organopolysiloxane is excellent Elect 0.01～5 mass parts, more preferably 0.03～3 mass parts, more preferably 0.05～1 mass parts as.If described In the range of, the most easily take into account static electricity resistance and light fissility (releasable), the most preferably.
For the adhesive sheet of the present invention, described adhesion agent composition preferably comprises cross-linking agent, and described cross-linking agent preferably contains There are aromatic isocyanate based compound and aliphatic isocyanates based compound (sometimes, by two kinds of isocyanates based compounds It is collectively referred to as isocyanates based compound or isocyanates system cross-linking agent).It addition, described cross-linking agent is by according to described (methyl) third The Component units of olefin(e) acid based polymer, component ratio etc. suitably regulate selection and the interpolation ratio etc. of cross-linking agent and hand over Connection, it is possible to obtain the adhesive sheet (adhering agent layer) that thermostability is more excellent.Described cross-linking agent is by containing aromatic isocyanate system Compound and aliphatic isocyanates based compound, be possible to prevent adhesion strength through time rise (adhesion strength rise preventing property), be Useful.
It addition, as cross-linking agent used in the present invention, except described aromatic isocyanate based compound and aliphatic Beyond isocyanates based compound, it is also possible to suitably use epoxide, melamine series resin, aziridine derivative Thing and metal chelate compound etc..It addition, these compounds can be used alone a kind, it is also possible to two or more is used in mixed way.
As described aliphatic isocyanates based compound, such as, can enumerate trimethylene diisocyanate, butylidene The aliphatic polymeric isocyanate classes such as diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, ring is sub- The alicyclic isocyanate classes such as amyl group diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI). It addition, as described aromatic isocyanate based compound, 2 can be enumerated, 4-toluenediisocyanate, 4,4 '-diphenyl The aromatic isocyanate classes such as methane diisocyanate, xylylene diisocyanate (XDI).And then, can enumerate above-mentioned Isocyanates based compound (isocyanates system cross-linking agent) allophanic acid ester bond, biuret linkage, isocyanurate-bond, urea diketone The modified ester modified bodies of polyisocyanate such as key, urea bond, carbodiimides key, uretonimine key, oxadiazines three ketonic bond.
Such as, as the commercially available product of described isocyanates based compound (isocyanates system cross-linking agent), commodity can be enumerated Name TAKENATE 300S, TAKENATE 500, TAKENATE D110N, TAKENATE D140N, TAKENATE D165N, TAKENATE D178N (being above Mitsui Chemicals, Inc.'s system), SUMIDUR T80, SUMIDUR L, DESMODUR N3400 (with On being Bayer polyurethane company system), MILLIONATE MR, MILLIONATE MT, COLONATE L, COLONATE HL, COLONATE HX (being above Japanese polyurethane industrial group system) etc..These isocyanate compounds can also two or more mixing Use, it is also possible to and use with the isocyanate compound more than isocyanate compound of 2 functional groups and 3 functional groups.Logical Cross and use with cross-linking agent, it is possible to prevent adhesion strength through time rise or obtain the adhesive sheet that shearing force is excellent.
As described epoxide, such as, can enumerate N, N, N ', N '-four glycidyl group-meta-xylene base diamidogen (trade name TETRAD-X, Rhizoma Sparganii gas chemical company system), double (N, the N-diglycidyl amino methyl) hexamethylene (business of 1,3- Name of an article TETRAD-C, Rhizoma Sparganii gas chemical company system) etc..
As described melamine series resin, hexakis(hydroxymethyl)melamine etc. can be enumerated.Derive as aziridine Thing, such as, can enumerate trade name HDU as commercially available product, TAZM, TAZO (being above mutual Yao Gong company system) etc..
As described metal chelate compound, as metal ingredient, aluminum, ferrum, stannum, titanium, nickel etc. can be enumerated, as chelating Composition, can enumerate acetylene, methyl acetoacetate, ethyl lactate etc..
The content (total) of cross-linking agent used in the present invention, such as, with described (methyl) acrylic acid series polymeric compounds for 100 Mass parts meter, preferably comprises 0.01～10 mass parts, more preferably contains 0.1～8 mass parts, further preferably containing 0.5～5 matter Amount part, most preferably 1.0～4 mass parts.When described content is less than 0.01 mass parts, based on cross-linking agent being cross-linked to form becomes Insufficient, the cohesiveness of the adhering agent layer of gained diminishes, and sometimes can not obtain sufficient thermostability, additionally have and become the former of cull The tendency of cause.On the other hand, when content is more than 10 mass parts, the cohesiveness of polymer is big, and mobility reduces, to adherend (example As the Polarizer etc. of optics) moistening become insufficient, have become between adherend and adhesion agent composition layer send out The tendency of the raw reason swelled.Further, if cross-linked dosage is many, there is the tendency that stripping charge characteristic reduces.It addition, these are handed over Connection agent can be used alone, and additionally can also two or more be used in mixed way.
It addition, as described aromatic isocyanate based compound and the match ratio of aliphatic isocyanates based compound Example, is not particularly limited, and such as (aromatic isocyanate based compound/aliphatic isocyanates based compound) (mass ratio) is excellent Elect 3/1～1/50 as, more preferably 2/1～1/40, more preferably 1/1～1/30.If described mixing ratio, then may be used With prevent through time adhesion strength rise, be useful.
In described adhesion agent composition, in order to more effectively advance any of the above-described cross-linking reaction, friendship can be contained further Connection catalyst.As described crosslinking catalyst, such as, can use the stannum such as dibutyl tin laurate, tin dilaurate dioctyl tin Series catalysts, tri acetylacetonato ferrum, three (hexane-2,4-diketone) ferrum, three (heptane-2,4-diketone) ferrum, three (heptane-3,5- Diketone) ferrum, three (5-methyl hexane-2,4-diketone) ferrum, three (octane-2,4-diketone) ferrum, three (6-methyl heptane-2,4-diketone) Ferrum, three (2,6-dimethyl heptane-3,5-diketone) ferrum, three (nonane-2,4-diketone) ferrum, three (nonane-4,6-diketone) ferrum, three (2,2,6,6-tetramethyl heptane-3,5-diketone) ferrum, three (tridecane-6,8-diketone) ferrum, three (1-phenyl butane-1,3-diketone) Ferrum, three (hexafluoroacetylacetone) ferrum, three (ethyl acetoacetate) ferrum, three (acetoacetic acid n-propyl) ferrum, three (acetoacetic acid isopropyls Ester) ferrum, three (acetoacetic acid N-butyl) ferrum, three (the secondary butyl ester of acetoacetic acid) ferrum, three (tert-butyl acetoacetate) ferrum, three (propionyl Methyl acetate) ferrum, three (Propionylacetic acid ethyl ester) ferrum, three (propionyl n-propyl acetate) ferrum, three (propionyl isopropyl acetate) ferrum, three (propionyl n-butyl acetate) ferrum, three (propionyl sec-butyl acetate) ferrum, three (propionyl tert-butyl acetate) ferrum, three (acetoacetic acid benzyls Ester) ferrum, three (dimethyl malenate) ferrum, three (diethyl malonate) ferrum, trimethoxy ferrum, triethoxy ferrum, three isopropoxies The Fe-series catalyst such as ferrum, iron chloride.These crosslinking catalysts can use a kind, it is also possible to and use two or more.
The content (usage amount) of described crosslinking catalyst is not particularly limited, such as, with (methyl) acrylic acid series polymeric compounds It is 100 mass parts meters, the most preferably 0.0001～1 mass parts, more preferably 0.001～0.5 mass parts.If at described model In enclosing, then when forming adhering agent layer, the speed of cross-linking reaction is fast, and the preservation life-span of adhesion agent composition is the most elongated, becomes preferred Mode.
Can also be containing the chemical combination containing polyoxyalkylene chain without organopolysiloxane in the adhesion agent composition of the present invention Thing.By containing above-claimed cpd in adhesion agent composition, it is possible to obtain the sticker more excellent to the wettability of adherend Compositions.
As the concrete example of the described compound containing polyoxyalkylene chain without organopolysiloxane, such as, can enumerate poly- Oxyalkylene alkylamine, polyoxyalkylene diamines, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan alcohol fatty acid ester, polyoxygenated Allylic alkylation phenyl ether, polyoxyalkylene alkyl, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl allyl ether etc. are non- Ionic surfactant；Polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl phosphate, polyoxyalkylene alkyl phenyl ether The anionic surfactants such as sulfate, polyoxyalkylene alkyl phenyl ether phosphate；And, there is polyoxyalkylene chain (polycyclic Oxygen alkane chain) cationic surfactant, zwitterionic surfactant, have polyoxyalkylene chain polyether compound (bag Include its derivant), there is the petchem (including its derivant) of polyoxyalkylene chain, there is the acrylic compounds of polyoxyalkylene chain Compound (including its derivant) etc..Alternatively, it is also possible to using the monomer containing polyoxyalkylene chain as the chemical combination containing polyoxyalkylene chain Thing and be matched with acrylic acid series polymeric compounds.The described compound containing polyoxyalkylene chain can be used alone, it is also possible to by two or more It is applied in combination.
As the concrete example of the described polyether compound with polyoxyalkylene chain, polypropylene glycol (PPG)-poly-second can be enumerated Glycol (PEG) block copolymer, PPG-PEG-PPG block copolymer, PEG-PPG-PEG block copolymer etc..As described tool There is the derivant of the polyether compound of polyoxyalkylene chain, the compound (PPG containing oxypropylene group that end is etherified can be enumerated Monoalky lether, PEG-PPG monoalky lether etc.), compound (the terminated acetylated PPG containing oxypropylene group that is acetylation of end Deng) etc..
It addition, have the concrete example of the acrylic compounds of polyoxyalkylene chain described in as, can enumerate and there is oxidation (methyl) acrylate polymer of alkene.As described oxyalkylene group, from the viewpoint of ionic compound is coordinated, oxyalkylene The addition molal quantity of unit is preferably 1～50, more preferably 2～30, and more preferably 2～20.It addition, described oxyalkylene group End can be hydroxyl originally, it is also possible to replaced by alkyl, phenyl etc..
Described (methyl) acrylate polymer with oxyalkylene preferably comprises (methyl) acrylic acid epoxy alkyl ester and makees For the polymer of monomeric unit (composition), as the concrete example of described (methyl) acrylic acid epoxy alkyl ester, can enumerate containing second two (methyl) acrylate of alcohol radical, such as, can enumerate methoxyl group-diethylene glycol (methyl) acrylate, methoxyl group-three second two Methoxypolyethylene glycol (methyl) acrylic ester types such as alcohol (methyl) acrylate, ethyoxyl-diethylene glycol (methyl) acrylic acid Ethyoxyl-Polyethylene Glycol (methyl) acrylic ester types such as ester, ethyoxyl-triethylene glycol (methyl) acrylate, butoxy-diethyl Butoxy-Polyethylene Glycol (methyl) acrylic acid such as glycol (methyl) acrylate, butoxy-triethylene glycol (methyl) acrylate Ester type, the phenoxy group-poly-second such as phenoxy group-diethylene glycol (methyl) acrylate, phenoxy group-triethylene glycol (methyl) acrylate Glycol (methyl) acrylic ester type, 2-ethylhexyl-Polyethylene Glycol (methyl) acrylate, nonyl phenol-Polyethylene Glycol (first Base) acrylic ester type, methoxyl group-polypropylene glycol (methyl) acrylic ester type such as methoxyl group-dipropylene glycol (methyl) acrylate Deng.
It addition, as described monomeric unit (composition), it is possible to use beyond described (methyl) acrylic acid epoxy alkyl ester Other monomeric units (composition).As the concrete example of other monomeric units, (methyl) acrylic acid methyl ester., (methyl) third can be enumerated Olefin(e) acid ethyl ester, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene Acid isobutyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) third The different monooctyl ester of olefin(e) acid, (methyl) acrylic acid positive nonyl ester, (methyl) acrylic acid different nonyl ester, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) third Olefin(e) acid isodecyl ester, (methyl) acrylic acid dodecyl ester, (methyl) acrylic acid n-tridecane base ester, (methyl) acrylic acid positive ten Tetraalkyl ester etc. has acrylate and/or the methacrylate of the alkyl of carbon number 1～14.
And then, as other monomeric units (composition) beyond described (methyl) acrylic acid epoxy alkyl ester, it is also possible to suitably Use carboxylic (methyl) acrylate, (methyl) acrylate of phosphorous acidic group, (methyl) acrylate of cyano-containing, second Thiazolinyl esters, aromatic ethenyl compound, (methyl) acrylate containing anhydride group, (methyl) acrylate of hydroxyl, (methyl) acrylate of amide-containing, (methyl) acrylate containing amino, (methyl) acrylate containing epoxy radicals, N-third Enoyl-morpholine, vinyl ethers etc..
As a preferred mode, the above-mentioned compound containing polyoxyalkylene chain without organopolysiloxane is at least one Part has the compound of (gathering) ethylene oxide chain.By coordinating the compound of described (gathering) ethylene oxide chain, base polymer Thing improves with the intermiscibility of antistatic composition, is suppressed well to the leakage of adherend, it is possible to obtain the adhesion of low stain Agent compositions.Wherein, especially with PPG-PEG-PPG block copolymer time, it is possible to obtain the sticker that low stain is excellent Compositions.As the above-mentioned compound containing polyethylene oxide chain, (gathering) ethylene oxide chain is shared in described compound entirety Functionality, quality and appealing design elects 5～90 mass % as, more preferably 5～85 mass %, more preferably 5～80 mass %, most preferably 5～ 75 mass %.
As the molecular weight of the above-mentioned compound containing polyoxyalkylene chain without organopolysiloxane, number is preferably used and divides equally Son amount (Mn) less than 50000 compound, more preferably 200～30000, further preferred 200～10000, particularly preferred 200～ 5000.If Mn and 50000 compares excessive, then the intermiscibility with acrylic acid series polymeric compounds is had to reduce, adhering agent layer generation albefaction Tendency.If Mn and 200 compares too small, then may become easily to produce the pollution that described polyoxyalkylene compounds causes.Separately Outward, here, Mn refers to the polystyrene conversion value obtained by GPC (gel permeation chromatography).
It addition, the concrete example of the commercially available product as the above-mentioned compound containing polyoxyalkylene chain without organopolysiloxane, Such as can enumerate Adeka Pluronic 17R-4, Adeka Pluronic 25R-2 (being ADEKA company system above), EMULGEN120 (KAO. Corp. SA's system) etc..
As the use level of the above-mentioned compound containing polyoxyalkylene chain without organopolysiloxane, with described (methyl) third Olefin(e) acid based polymer is 100 mass parts meters, such as, can be 0.005～20 mass parts, and preferably 0.01～10 mass parts are more excellent Electing 0.05～5 mass parts as, extremely preferred is 0.1～1 mass parts.If use level is very few, then prevent antistatic composition from leaking Effect reduce, if too much, then may become easily to produce the pollution that described polyoxyalkylene compounds causes.
And then, described adhesion agent composition can also contain acrylic acid oligomer.The Weight-average molecular of acrylic acid oligomer Amount is preferably 1000 less than 30000, and more preferably 1500 less than 20000, and more preferably more than 2000 And less than 10000.When the stripping again of present embodiment is with use in acrylic acid series adhesion agent composition, as tackifying resin Function, makes adhesion (bonding) property improve, and heaves effective to suppression adhesive sheet.
Described acrylic acid oligomer can use (methyl) acrylate monomer, such as, can enumerate (methyl) acrylic acid Methyl ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (first Base) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) heptylacrylate, (first Base) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, (methyl) acrylic acid different nonyl ester, (methyl) third Olefin(e) acid ester in the last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate are so (methyl) alkyl acrylate；
(methyl) phenyl acrylate, (methyl) benzyl acrylate such (methyl) benzyl acrylate；
(methyl) acrylate etc. obtained by terpene compound derivatives alcohol.
It addition, described acrylic acid oligomer can use (methyl) acrylic monomer with ester ring type structure, example As can enumerate methacrylic acid bicyclopentyl ester, acrylic acid bicyclopentyl ester, methacrylic acid bicyclopentyl oxygen ethyl ester, third Olefin(e) acid bicyclopentyl oxygen ethyl ester, methacrylic acid three cyclopentyl ester, acrylic acid three cyclopentyl ester, methacrylic acid 1-diamantane (obsolete) Base ester, acrylic acid 1-adamantane esters, methacrylic acid 2-methyl-2-adamantane esters, acrylic acid 2-methyl-2-adamantyl (methyl) acrylate etc. such as ester, methacrylic acid 2-ethyl-2-adamantane esters, acrylic acid 2-ethyl-2-adamantane esters. Such (methyl) acrylic monomer can be used alone or two or more is applied in combination.
It addition, described acrylic acid oligomer can also make outside described (methyl) acrylic monomer ingredient units can Obtain with other monomer components (combined polymerization monomer) combined polymerization of described (methyl) acrylic monomer combined polymerization.
The weight average molecular weight of described acrylic acid oligomer is 1000 less than 30000, preferably more than 1500 and little In 20000, more preferably 2000 less than 10000.If weight average molecular weight is more than 30000, then adhesion is (viscous Connect) property reduction.If it addition, weight average molecular weight is less than 1000, then becoming low-molecular-weight, therefore causing the adhesion strength of adhesive sheet to drop Low.
And then, it is possible to so that described adhesion agent composition contains the generation ketoenol tautomerization as crosslinking delay agent Compound.Such as, the adhesion agent composition containing cross-linking agent maybe can coordinate cross-linking agent and in the adhesion agent composition that uses, can In the way of preferably employing the compound comprising described generation ketoenol tautomerization.Thus, gluing after suppression cross-linking agent coordinates The excess stickiness rising of agent compositions, gelation, it is possible to realize extending the effect preserving the life-span of adhesion agent composition.At least When using isocyanate compound as described cross-linking agent, the most meaningful containing the compound producing ketoenol tautomerization. It is organic solvent solution or the occasion of solvent-free form that this technology can be preferably applied to the most described adhesion agent composition.
Compound as described generation ketoenol tautomerization, it is possible to use various beta-dicarbonyl compounds.As tool Style, can enumerate: acetylacetone,2,4-pentanedione, 2,4-acetyl butyryl, 3,5-heptadione, 2-methyl hexane-3, and 5-diketone, 6-methyl heptane- The beta-diketon classes such as 2,4-diketone, 2,6-dimethyl heptane-3,5-diketone；Methyl acetoacetate, ethyl acetoacetate, acetoacetic acid The acetoacetic ester such as isopropyl ester, tert-butyl acetoacetate；Propionylacetic acid ethyl ester, Propionylacetic acid ethyl ester, propionyl isopropyl acetate, The propionyl acetate esters such as propionyl tert-butyl acetate；Ethyl isobutyryl, ethyl isobutyryl, isobutyryl isopropyl acetate, The isobutyryl acetate esters such as isobutyryl tert-butyl acetate；The malonic acid esters such as methylmalonate, malonic ester；Deng.As it In preferred compound, acetylacetone,2,4-pentanedione and acetoacetic ester can be enumerated.The compound of described generation ketoenol tautomerization May be used alone, or two or more kinds may be used in combination.
The content of the compound of described generation ketoenol tautomerization, relative to described (methyl) acrylic acid series polymeric compounds 100 mass parts, such as, can be 0.1～20 mass parts, and usual 0.5～15 mass parts (such as 1～10 mass parts) are suitable. If the amount of described compound is very few, the most sometimes become to be difficult to play sufficient using effect.On the other hand, if use more than The described compound of necessary amount, remains in adhering agent layer the most sometimes, makes cohesiveness reduce.
And then, adhesion agent composition used in the adhesive sheet of the present invention can also be containing additive known to other, example As, according to the purposes used, the powder body such as coloring agent, pigment, surfactant, plasticizer, viscosifier, low can be properly added Polydispersity polymer, surface lubricant, levelling agent, antioxidant, anticorrosive, light stabilizer, UV absorbent, polymerization are prohibited Only agent, silane coupler, inorganic or organic filler, metal powder, particle shape, foil-like thing etc..
The adhesive sheet of the present invention is characterised by, is to have by described sticker group at the single or double of described support membrane Compound forms the adhering agent layer of (adhesion agent composition crosslinking being formed), and now, the crosslinking of adhesion agent composition is usually Carry out after coating adhesion agent composition but it also may the adhering agent layer formed by the adhesion agent composition after cross-linking is transferred to On support membrane etc..It addition, the method forming adhering agent layer on described support membrane is not particularly limited, such as, can make as follows Make: described adhesion agent composition is coated on support membrane, the dry removal such as polymer solvent, support membrane is formed sticker Layer.Afterwards, the purposes such as the adjustment moved for the composition of adhering agent layer, the adjustment of cross-linking reaction, it is also possible to carry out maintenance.Separately Outward, adhesion agent composition is coated on when making adhesive sheet on support membrane, in order to be uniformly coated on support membrane, it is also possible to Again more than one the solvent beyond polymer solvent is added in described adhesion agent composition.
It addition, as the forming method of adhering agent layer when manufacturing the adhesive sheet of the present invention, it is possible to use pressure-sensitive adhesive sheets Known method used in manufacture.Specifically, rolling method, gravure coating process, trans rubbing method, roller brush, spray can such as be enumerated Coating, air knife coating method, utilize the extrusion coating methods etc. of die coating machine etc..
The adhesive sheet of the present invention is normally manufactured as being preferably 3～100 μm so that the thickness of above-mentioned adhering agent layer, more preferably About 5～50 μm.If the thickness of adhering agent layer is in the range of described, then the releasable being readily available appropriateness is (viscous with adhesion Connect) balance of property, the most preferably.
＜ dividing plate ＞
In the adhesive sheet (surface protection film) of the present invention, as required for the purpose of protection bonding plane, can be at sticker Layer surface laminating dividing plate.
As the material of the described dividing plate of composition, there are paper, plastic foil, but from the aspect of surface smoothness excellence, preferably Use plastic foil.As this film, as long as the film of described adhering agent layer can be protected, it is not particularly limited, the most permissible Enumerate polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, chloroethylene copolymer Thing film, polyethylene terephthalate film, polybutylene terephthalate (PBT) film, polyurethane film, ethane-acetic acid ethyenyl ester are common Polymers film etc..
The thickness of described dividing plate is usually 5～200 μm, preferably 10～100 μm degree.If in the range of described, then Workability to adhering agent layer laminating and the workability excellence from adhering agent layer stripping, the most preferably.For described dividing plate, according to Need, it is also possible to carry out utilizing silicone-based, fluorine system, chain alkyl system or the releasing agent of fatty acid amide system, silicon dioxide powder etc. The demoulding and the antistatic such as antifouling process, application type, doped, evaporation type process.
It addition, the adhesive sheet of the present invention is, the single or double at support membrane has by gluing that adhesion agent composition is formed The adhesive sheet of oxidant layer, the peeling rate 30m/ after the bonding plane of described adhering agent layer is pasted on TAC face 30 minutes at 23 DEG C Minute time adhesion strength (A) with the bonding plane of described adhering agent layer is pasted on TAC face 1 week at 70 DEG C after peeling rate 30m/ Minute time adhesion strength ratio (B/A) of adhesion strength (B) less than 2, preferably 0.5～1.9, more preferably 0.7～1.8.By In the range of described, though high temperature through time after high speed peel off time, it is also excellent that adhesion strength rises preventing property (adhesion strength stability), Releasable and workability are excellent, become preferred mode.
It addition, as the peeling rate after the bonding plane of described adhering agent layer is pasted on TAC face 30 minutes at 23 DEG C Adhesion strength (A) when 30m/ minute, preferably below 2.0N/25mm, more preferably 0.1～1.9N/25mm, more preferably 0.1～1.8N/25mm.If described adhesion strength (A) is more than 2.0N/25mm, then adhesive sheet (surface protection film) is difficult to from being glued Thing is peeled off, and the overburden operation that adhesive sheet becomes when need not is poor, and then, due to stripping process, adherend is caused damage Deng, therefore it is inappropriate.
As during by the bonding plane of described adhering agent layer peeling rate after 70 DEG C are pasted on TAC face 1 week 30m/ minute Adhesion strength (B), preferably below 4.0N/25mm, more preferably 0.1～3.5N/25mm, more preferably 0.1～3.0N/ 25mm.If described adhesion strength (B) is more than 4.0N/25mm, then adhesive sheet (surface protection film) is difficult to peel off from adherend, adhesion The overburden operation that sheet becomes when need not is poor, and then, due to stripping process, adherend is caused damage etc., therefore do not conform to Fit.
It addition, for the adhesive sheet of the present invention, the bonding plane of described adhering agent layer is pasted on 30 points of TAC face at 23 DEG C Adhesion strength (A) during the peeling rate after clock 30m/ minute with the bonding plane of described adhering agent layer is pasted on TAC face 1 at 70 DEG C Adhesion strength ratio (B/A) of the adhesion strength (B) during the peeling rate after week 30m/ minute less than 2, preferably 0.5～1.9, more preferably It is 0.7～1.8.By in the range of described, releasable and workability are excellent, become preferred mode.
It addition, for the adhesive sheet of the present invention, by the adhesion area 1cm of described adhering agent layer2Fit in TAC polarisation Plate, it is preferably 10N/ in 23 DEG C of shearing forces pasted when peeling off along shear direction for 0.06mm/ minute with peeling rate after 30 minutes cm2Above, more preferably 10～50N/cm2, more preferably 10～40N/cm2.If described shearing force is in described scope In, then can bear the power of the shear direction produced when adherend will crimp, the slip of adhesive sheet, dislocation do not occur, permissible The curling of suppression adherend, the most preferably.
＜ antistatic backing (top coat) ＞
The adhesive sheet of the present invention preferably has antistatic at the one side with the described support membrane of described adhering agent layer opposition side Layer, described antistatic backing is by containing the poly-aminobenzenesulfonic acid as electric conductive polymer composition, the polyester resin as binding agent Formed with the antistatic agent compositions of the isocyanates system cross-linking agent as cross-linking agent.Described adhesive sheet is by having antistatic backing (top coat), thus the static electricity resistance of adhesive sheet improves, and becomes optimal way.
＜ electric conductive polymer ＞
Described antistatic backing preferably comprises poly-aminobenzenesulfonic acid as electric conductive polymer composition.By using described conduction Property polymer, can meet static electricity resistance based on antistatic backing.It addition, described poly-aminobenzenesulfonic acid is " water solublity ", logical Cross and use isocyanates system described later cross-linking agent, can immobilization in antistatic backing, resistance to water can be improved.Contained by use The aqueous solution of described water-soluble conducting polymer, it is possible to obtain through time the excellent antistatic backing of sheet resistance value, become excellent The mode of choosing.On the other hand, when forming electric conductive polymer used during antistatic backing for " water dispersible ", if used containing institute The solution stating aqueous-dispersible conductive polymer forms antistatic backing, then become easily to produce condensation product, it is impossible to be coated with equably, Have through time the tendency that is significantly deteriorated of sheet resistance value, the most preferred.
The usage amount of described electric conductive polymer, is 100 mass parts with binding agent contained in antistatic backing (top coat) Meter, preferably 10～200 mass parts, more preferably 25～150 mass parts, more preferably 40～120 mass parts.If institute The usage amount stating electric conductive polymer is very few, and anti-static effect reduces the most sometimes, if the usage amount of electric conductive polymer is too much, Then antistatic backing declines to the adaptation of support membrane, or the transparency may reduce, and is inappropriate.
The weight average with polystyrene conversion of the poly-aminobenzenesulfonic acid used as described electric conductive polymer composition divides Son amount (Mw) is preferably 5 × 105Hereinafter, more preferably 3 × 105Below.It addition, the weight average molecular weight of these electric conductive polymers It is preferably generally 1 × 103Above, more preferably 5 × 103Above.
As the method forming described antistatic backing, can use antistatic backing formation coating material (antistatic agent Compositions) it is coated on first of support membrane and makes its method being dried (or solidification), preferably comprise in the preparation of coating material Use the poly-aminobenzenesulfonic acid as electric conductive polymer composition, the polyester resin as binding agent and, as cross-linking agent Isocyanates system cross-linking agent, it may be preferred to use described essential component to be dissolved in the material (electric conductive polymer of form of water Aqueous solution or referred to as aqueous solution.).Described electric conductive polymer aqueous solution such as can be by making have hydrophilic functional group Electric conductive polymer (can synthesize by making the methods such as the intramolecular monomer copolymerization with hydrophilic functional group.) be dissolved in Prepared by water.As described hydrophilic functional group, illustrate have sulfonic group, amino, amide groups, imino group, hydroxyl, sulfydryl, diazanyl, Carboxyl, quaternary ammonium group, sulfate group (-O-SO3H), phosphate-based (such as-O-PO (OH)2) etc..Described hydrophilic functional group also may be used To form salt.
It addition, as the commercially available product of described poly-amino phenyl sulfonyl aqueous acid, illustrate the commodity having Rhizoma Sparganii Li Yang company to manufacture The product etc. of name " aquaPASS ".
Antistatic backing disclosed herein contains the poly-aminobenzenesulfonic acid (polyaniline type) as electric conductive polymer composition and makees For essential component, but such as can also contain in the lump other one kind or two or more antistatic composition (electric conductive polymer with Outer organic conductive material, inorganic conductive material, antistatic agent etc.).Here, as a preferred mode, described anti- Electrostatic layer contains substantially no the antistatic composition beyond described electric conductive polymer, i.e. anti-quiet contained by described antistatic backing The mode that electricity composition is the most only formed by electric conductive polymer can more preferably be implemented.
As described organic conductive material, quaternary ammonium salt, pyridiniujm can be enumerated, there is primary amino radical, secondary amino group, tertiary ammonia Bases etc. have the cationic antistatic agent of cationic functional group；Sulfonate, sulfuric acid, phosphonate, phosphate ester salt etc. have There is the anionic antistatic agent of anionic property functional group；Alkyl betaine and derivant, imidazoline and its derivative, the third ammonia The amphoteric ion type antistatic agents such as acid and derivant thereof；Amino alcohol and derivant, glycerol and derivant thereof, Polyethylene Glycol and The non-ionic antistatic agent such as derivant；By described cationic, anionic, amphoteric ion type there is ionic conductivity base The monomer polymerization of (such as, quaternary ammonium salt base) or combined polymerization and the ionic-conductive polymer that obtains；Polythiophene, polyaniline, poly-pyrrole Cough up, the electric conductive polymer such as polymine, allyl amine based polymer.Such antistatic agent can be used alone a kind, also Two or more can be applied in combination.
As described inorganic conductive material, stannum oxide, stibium oxide, Indium sesquioxide., Aska-Rid., titanium oxide, oxygen can be enumerated Change zinc, indium, stannum, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, ferrum, cobalt, Copper diiodide, ITO (indium oxide/tin oxide), ATO (oxidation Antimony/stannum oxide) etc..Such inorganic conductive material can be used alone a kind, it is also possible to two or more is applied in combination.
As described antistatic agent, cationic antistatic agent, anionic antistatic agent, amphoteric ion type can be enumerated Antistatic agent, non-ionic antistatic agent, will there is the ionic conductivity of described cationic, anionic, amphoteric ion type Ionic-conductive polymer etc. obtained by the monomer polymerization of base or combined polymerization.
＜ binding agent ＞
Described antistatic backing preferably comprises polyester resin as binding agent.Described polyester resin preferably comprises polyester conduct The resinous wood of main constituent (typically accounting for more than the composition more than 50 mass, preferably 75 mass %, more than such as 90 mass %) Material.Described polyester, typically, preferably has a structure that the polybasic carboxylic acid class (allusion quotation in 1 molecule with more than 2 carboxyls It is omega-dicarboxylic acids type) and the one kind or two or more change of derivant (anhydride of this polybasic carboxylic acid, carboxylate, halogenide etc.) Compound (polybasic carboxylic acid composition) and a kind of polyalcohols (typically glycols) in 1 molecule with more than 2 hydroxyls Or the structure of compound (polyol component) of more than two kinds condensation.
As the example of the compound that can act as described polybasic carboxylic acid composition, oxalic acid, malonic acid, difluoro can be enumerated Malonic acid, alkyl malonic acid, succinic acid, tetrafluoro succinic acid, alkyl succinic acid, (±)-malic acid, mesotartaric acid, clothing health Acid, maleic acid, citraconic acid, fumaric acid, mesaconic acid, acetylenedicarboxylic acid, 1,3-propanedicarboxylic acid, hexafluoro 1,3-propanedicarboxylic acid, methylpent two Acid, glutaconate, adipic acid, dithio adipic acid, methyl adipic acid, dimethyl adipic acid, tetramethyl adipic acid, methylene oneself Diacid, glutinous furancarboxylic acid, galactosaccharic acid, 1,5-pentanedicarboxylic acid., suberic acid, perfluor suberic acid, 3,3,6,6-tetramethyl suberic acid, Azelaic Acid, The fat such as decanedioic acid, perfluor decanedioic acid, tridecandioic acid, dodecanedicarboxylic acid, tridecyl dicarboxylic acids, myristyl dicarboxylic acids Fat race omega-dicarboxylic acids；Cycloalkyl dicarboxylic acids (such as 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid), (ice drops to 1,4-in 2- Sheet alkene) dicarboxylic acids, 5-norborene-2,3-dicarboxylic acids (double-heptene dicarboxylic acids, himic acid), diamantane (obsolete) dicarboxylic acids, spiral shell The ester ring type omega-dicarboxylic acids such as heptane dicarboxylic acid；Phthalic acid, M-phthalic acid, dithio M-phthalic acid, methylresorcinol two Formic acid, dimethyl M-phthalic acid, chlorine M-phthalic acid, dichloro M-phthalic acid, p-phthalic acid, methylterephthalic acid, Dimethyl terephthalic acid, chlorine p-phthalic acid, bromo terephthalic acid, naphthalene dicarboxylic acids, Fluorenone dicarboxylic acids, anthracene dicarboxylic acids, biphenyl Dicarboxylic acids, biphenylene dicarboxylic acid, dimethyl biphenylene dicarboxylic acid, 4,4 "-p-tetraphenyl dicarboxylic acids (4,4 "-p- Terephenylenel dicarboxylic acid), 4,4 "-p-quaterphenyl dicarboxylic acids (4,4-"-p-quaterphenyl Dicarboxylic acid), dibenzyl dicarboxylic acids, azoaromatic diacid, high phthalic acid, phenylenediacetic acid, phenylene Dipropionic acid, naphthalene dicarboxylic acids, naphthalene dipropionic acid, biphenyl oxalic acid, biphenyl dipropionic acid, 3,3'-[4,4 '-(methylene two-p-sub-biphenyl Base) virtue such as dipropionic acid, 4,4 '-dibenzyl oxalic acid, 3,3 ' (4,4 '-dibenzyl) dipropionic acid, oxygen two-p-phenylene oxalic acid Fragrant race omega-dicarboxylic acids；The anhydride of any of the above-described polybasic carboxylic acid；Ester (the e.g. Arrcostab of any of the above-described polybasic carboxylic acid.Can also It is monoesters, diester etc..)；Sour halogenide (such as dicarboxylic acid chloride) corresponding to any of the above-described polybasic carboxylic acid；Deng.
As the suitable example of the compound that may serve as described polybasic carboxylic acid composition, can enumerate p-phthalic acid, The aromatic dicarboxylic acid class such as M-phthalic acid, naphthalene dicarboxylic acids and anhydride thereof；Adipic acid, decanedioic acid, Azelaic Acid, succinic acid, rich horse Aliphatic dicarboxylic acid class and the anhydride thereof such as acid, maleic acid, double-heptene dicarboxylic acids, 1,4-cyclohexane dicarboxylic acid；And described two Lower alkyl esters of carboxylic acids (such as and the ester of monohydric alcohol that carbon number is 1～3) etc..
On the other hand, as the example of the compound that can act as described polyol component, can enumerate ethylene glycol, third Glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 butylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-oneself two Alcohol, 3-methyl pentanediol, diethylene glycol, 1,4 cyclohexane dimethanol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, 3-the third two Alcohol, 2,2-diethyl-1,3-propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, xyxylene glycol (xylene Glycol), the glycols such as hydrogenated bisphenol A, biphenol A.As other example, the alkylene oxide addition of these compounds can be enumerated Thing (such as, ethylene oxide adduct, propylene oxide adduct etc.).
About the molecular weight of described polyester resin, as the polystyrene standard measured by gel permeation chromatography (GPC) The weight average molecular weight (Mw) of conversion, such as, can be 5 × 103～1.5 × 105Left and right (preferably 1 × 104～6 × 104Left and right). It addition, the glass transition temperature of described polyester resin (Tg) can be such as 0～120 DEG C (preferably 10～80 DEG C).
As described polyester resin, it is possible to use the trade name of company " VYLONAL MD-1480 " is spun by commercially available Japan Deng.
Described antistatic backing (top coat), as long as the most significantly damaging the performance of adhesive sheet disclosed herein (surface protection film) Performances such as (such as) static electricity resistances, can contain further resin beyond polyester resin (such as, selected from acrylic resin, third Olefin(e) acid-carbamate resins, acrylic-styrene resin, acrylic acid-silicone resin, silicone resin, polysilazane resin, One kind or two or more resin in polyurethane resin, fluororesin, vistanex etc.) it is used as binding agent.Disclosed herein One of technology it is preferable that: the situation that the binding agent of antistatic backing is the most only formed by polyester resin.For example, it is preferable to it is poly- The antistatic backing that ratio is 98～100 mass % that ester resin is shared in binding agent.Binding agent is institute in antistatic backing entirety The ratio accounted for, such as, can be set to 50～95 mass %, and it is suitable for being typically set to 60～90 mass %.
＜ lubricant ＞
Described antistatic backing (top coat) is preferably used fatty acid amide as lubricant.By using fatty acid amide to make For lubricant, even if not implementing further lift-off processing (such as, by silicone-based remover, long-chain on the surface of antistatic backing The known stripping treatment agent such as alkyl series stripping agent be coated with and makes its dry process) mode in, it is also possible to obtain taking into account Sufficiently sliding and the antistatic backing (top coat) of lettering adaptation, therefore, it is possible to become optimal way.So anti-quiet The mode of further lift-off processing is not implemented on the surface of electric layer, is preventing the albefaction (example that causes because of stripping treatment agent in advance Under the conditions of, warming and humidifying, preserve caused albefaction) etc. in terms of be preferred.It addition, consider from solvent resistance, it is also advantageous that 's.
As the concrete example of described fatty acid amide, can enumerate lauric amide, palmitamide, stearic amide, Docosanoic acid amide, hydroxy stearic acid amide, oleamide, erucyl amide, N-oleyl palmitamide, N-stearyl Stearic amide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide, hydroxymethylstearic acid The double capric acid acidamide of amide, di-2-ethylhexylphosphine oxide stearic amide, ethylene, ethylene dilaurate amide, ethylene double stearic amide, ethylene The double docosanoic acid amide of di-hydroxy stearic acid amide, ethylene, the double stearic amide of hexa-methylene, hexa-methylene double 22 Carbon alkanoic acid amide, hexa-methylene hydroxy stearic acid amide, N, N '-distearyl adipic acid amide, N, N '-distearyl decanedioic acid The double erucyl amide of amide, ethylene bis-oleamide, ethylene, hexa-methylene double oleamide, N, N '-two oleyl adipic acid acyl Amine, N, N '-two oleyl decanedioic acid amide, m-phenylenedimethylim-double stearic amide, m-phenylenedimethylim-di-hydroxy stearic acid Amide, N, N '-stearyl M-phthalic acid amide etc..These lubricants can be used alone a kind, it is also possible to by two or more group Close and use.
Lubricant ratio shared by described antistatic backing entirety can be set to 1～50 mass %, is typically set to 5～40 Quality % is suitable.If the content ratio of lubricant is very few, then have the tendency that sliding is easily reduced.If lubricant Content ratio too much, lettering adaptation reduces the most sometimes.
Technology disclosed herein, as long as the most significantly damaging its application effect, then can also be with in antistatic backing (top coat) The mode also comprising other lubricants in addition to described fatty acid amide is implemented.As the example of other lubricants described, can To enumerate petroleum wax (paraffin etc.), mineral system wax (lignite wax etc.), higher fatty acids (cerinic acid etc.), neutral fat (Palmic acid Triglyceride etc.) various waxes.Or, in addition to described wax, it is also possible to secondarily contain general silicone-based lubricant, fluorine Base lubricant etc..Technology disclosed herein is preferably in the way of being substantially free of described silicone-based lubricant, fluorine base lubricant etc. Implement.But, in the limit of application effect the most significantly damaging technology disclosed herein, so-called lubricant, it is not excluded that Containing the silicone-based used for other purposes (such as, as the defoamer of antistatic backing formation coating material described later) Compound.
＜ cross-linking agent ＞
Described antistatic backing preferably comprises isocyanates system cross-linking agent as cross-linking agent.By using described isocyanates system Cross-linking agent, when forming antistatic backing, can be fixed on the water-soluble poly aminobenzenesulfonic acid as essential component in binding agent, Excellent water resistance, and then, it is possible to achieve the effects such as the raising of lettering adaptation.
As described isocyanates system cross-linking agent, use the most stable blocked isocyanates system cross-linking agent It it is preferred mode.Concrete example as described blocked isocyanates system cross-linking agent, it is possible to use general adhering agent layer, anti- (such as, aforesaid adhering agent layer is used the isocyanates system cross-linking agent that can use during the preparation of electrostatic layer (top coat) Isocyanate compound (isocyanates system cross-linking agent)) with alcohols, phenol, thio phenyl phenols, amine, acid imide, oximes, Lactams, activity methene compound class, thio-alcohol, imines, carbamide class, biaryl compound class and, bisulfite The material of the blocks such as sodium.
Antistatic backing in technology disclosed herein can contain antistatic composition, antioxidant, coloring as desired Agent (pigment, dyestuff etc.), mobility regulator (thixotropic agent, thickening agent etc.), membrane producing promoter, surfactant (defoamer etc.), The additives such as preservative.
The formation ＞ of ＜ antistatic backing
Described antistatic backing (top coat) can be by including liquid composition (antistatic backing formation coating material) Giving the method for support membrane and formed well, described liquid composition is by essential components such as described electric conductive polymer compositions The additive used as required is dissolved in and is formed in suitable solvent (water etc.).Such as preferably employ following methods: Described coating material coated first of support membrane and makes it be dried, carrying out cured (heat treatment, ultraviolet as required Line process etc.).The NV (nonvolatile component) of described coating material, such as, can be set to below 5 mass % (typically 0.05～5 Quality %), it is suitable for being typically set to below 1 mass % (typically 0.10～1 mass %).Form the antistatic backing that thickness is little Time, preferably the NV of described coating material is set to such as 0.05～0.50 mass % (such as 0.10～0.40 mass %).Pass through Use the coating material of the lowest NV, it is possible to form antistatic backing evenly.
As the solvent of the described antistatic backing formation coating material of composition, it is preferably able to the shape of stabilizing dissolved antistatic backing Become the solvent of composition.Described solvent can be organic solvent, water or their mixed solvent.As described organic solvent, such as Can use selected from esters such as ethyl acetate；The ketones such as methyl ethyl ketone, acetone, Ketohexamethylene；Oxolane (THF), dioxane Etc. ring-type ethers；The aliphatic such as normal hexane, hexamethylene or alicyclic hydro carbons；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Methanol, second Aliphatic or the alicyclic alcohols such as alcohol, normal propyl alcohol, isopropanol, Hexalin；Alkylene glycol monoalkyl ethers (such as, ethylene glycol list Methyl ether, ethylene glycol monomethyl ether), one kind or two or more in the glycol ethers such as two alkylene glycol monoalkyl ethers etc..One In individual optimal way, the solvent of described coating material is that (such as, water and ethanol is mixed for water or mixed solvent with water as main constituent Bonding solvent).
Character ＞ of ＜ antistatic backing
The thickness of described antistatic backing is typically 3～500nm, preferably 3～100nm, more preferably 3～60nm.As Really the thickness of antistatic backing is too small, then become to be difficult to be formed uniformly antistatic backing (such as, for the thickness of antistatic backing, The thickness deviation caused because position is different becomes big), therefore, the outward appearance of adhesive sheet (surface protection film) there may come a time when easily to produce Uneven.On the other hand, if blocked up, the characteristic (optical characteristics, dimensional stability etc.) of support membrane is affected the most sometimes.
In one optimal way of adhesive sheet disclosed herein (surface protection film), as the surface measurements at antistatic backing Sheet resistance value (Ω/), preferably less than 1.0 × 1011, more preferably less than 5.0 × 1010, further preferably less than 2.0×1010.The adhesive sheet of the sheet resistance value in the range of described in showing, such as such as liquid crystal cell, semiconductor device etc. Abstain from the adhesive sheet used in processing or the handling process etc. of the article of electrostatic like that, it is possible to be well used.Here, described Sheet resistance value can be by using commercially available determination of insulation resistance device 23 DEG C, the sheet resistance that measures in the environment of 50%RH Value calculates.
Adhesive sheet disclosed herein (surface protection film) preferably has the property that its back side (surface of antistatic backing) leads to Cross water color ink, oil-based ink (such as using permanent pen) and can the character of easily lettering.Described adhesive sheet is suitable to During to have pasted the processing of adherend (such as optics), carrying that the state of adhesive sheet carries out etc., will be as guarantor The identiflication number etc. of the adherend protecting object is documented on described table adhesive sheet and represents.It is therefore preferable that excellent the gluing of lettering Sheet.For example, it is preferable to be that the oil-based ink of alcohol system and the type containing pigment has high lettering to solvent.Additionally, it is preferred that print Ink after word is difficult to because of scouring, turns and glue and come off (that is, lettering excellent adhesion).It addition, adhesive sheet disclosed herein is preferred Have: when amendment or cancellation lettering, i.e. using alcohol (such as ethanol) to wipe lettering, outward appearance does not the most occur the degree of significant change Solvent resistance.
Adhesive sheet disclosed herein (surface protection film) can also be with except support membrane (base material), adhering agent layer and antistatic Also include outside Ceng that the mode of other layers is implemented.As the configuration of described " other layers ", can be with example arrangement at support membrane Between first (back side) and antistatic backing, between second (above) and the adhering agent layer of support membrane etc..It is arranged in support membrane Layer above and between adhering agent layer, such as, can be to improve adhering agent layer to described second the priming coat (end throwing anchor Glue-line), antistatic backing etc..Can also be following adhesive sheet: at support membrane former configuration antistatic backing, on antistatic backing Configuration primer layer, it configures the adhesive sheet of the composition of adhering agent layer.
The optics that the optics of the present invention is preferably protected by described adhesive sheet.Described adhesive sheet due to can in case Only through time (under high temperature) adhesion strength above-mentioned, peel off at a high speed time adhesion strength is low, releasable and workability excellent, therefore may be used For surface protection purposes when processing, carry, deliver etc., so for the table protecting described optics (Polarizer etc.) Face, is useful.It addition, described adhesive sheet is excellent due to shearing force, therefore can suppress to be fitted with being glued of described adhesive sheet The curling of thing (optics), operability is excellent, is therefore useful.
[embodiment]
Hereinafter, the embodiment etc. of the composition and effect that are particularly shown the present invention is illustrated, but the invention is not restricted to this. Here, about the cooperation content in embodiment etc. and evaluating characteristics, it is determined as described below.It addition, table 1 shows The physics value of (methyl) acrylic acid series polymeric compounds that adhesion agent composition is used, the mixing ratio of adhesion agent composition, in table 2 Show the cooperation content of antistatic backing, table 3 shows the evaluation result of characteristic.
＜ evaluates ＞
Evaluation of measuring method specifically set forth below.
Mensuration ＞ of ＜ weight average molecular weight (Mw)
Weight average molecular weight (Mw) uses east Cao Zhushihui company GPC device (HLC-8220GPC) to be measured.Measure bar Part is as follows.
Sample concentration: 0.2 mass % (THF solution)
Sample injection rate: 10 μ l
Eluent: THF
Flow velocity: 0.6ml/ minute
Mensuration temperature: 40 DEG C
Post:
Sample column；TSK guard column Super HZ-H (1)+TSK gel SuperHZM-H (2)
Reference column；TSK gel SuperH-RC (1)
Detector: differential refraction detector (RI)
Here, weight average molecular weight is obtained with polystyrene conversion value.
Theoretical value ＞ of ＜ glass transition temperature
Glass transition temperature Tg (DEG C) is by using following literature value to turn as the vitrification of the homopolymer of each monomer Temperature Tgn (DEG C), is obtained by following formula.
Formula: 1/ (Tg+273)=Σ [Wn/ (Tgn+273)]
(in formula, Tg (DEG C) represent the glass transition temperature of copolymer, Wn (-) represent the mass fraction of each monomer, Tgn (DEG C) represents that the glass transition temperature of the homopolymer of each monomer, n represent the kind of each monomer.〕
Literature value:
2-EHA (2EHA) :-70 DEG C
N-butyl acrylate (BA) :-55 DEG C
Acrylic acid (AA): 106 DEG C
Carboxyethyl acrylates (β-CEA): 37 DEG C
Acrylic acid 2-hydroxy methacrylate (HEA) :-15 DEG C
Acrylic acid 4-hydroxybutyl (HBA) :-32 DEG C
Hydroxyethyl methacrylate (HEMA): 55 DEG C
N, N acrylamide (DEAA): 81 DEG C
Here, (central authorities manage as literature value, to reference to " carrying out of the synthesis of acrylic resin, design and new application " Development centre publishing department publishes) and " Polymer Handbook (polymer handbook) " (john wiley & sons).
Mensuration ＞ of ＜ initial stage adhesion strength (A)
By TAC Polarizer (Dong electrician company system, SEG1423DU Polarizer, wide: 70mm, long: 100mm) 23 DEG C × Place after 24 hours in the environment of 50%RH, by be cut into wide 25mm, long 100mm adhesive sheet with the pressure of 0.25MPa, The velocity layer of 0.3m/ minute is stacked on above-mentioned adherend, makes evaluation sample.
After above-mentioned stacking, place after 30 minutes in the environment of 23 DEG C × 50%RH, mensuration universal tensile testing machine with Peeling rate 30m/ minute (peeling off at a high speed), initial stage adhesion strength (A) (N/25mm) time peel angle 180 ° is peeled off.Measure Carry out in the environment of 23 DEG C × 50%RH.
Here, described adhesion strength (A) preferably below 2.0N/25mm, more preferably 0.1～1.9N/25mm, the most excellent Elect 0.1～1.8N/25mm as.If described adhesion strength (A) is more than 2.0N/25mm, then adhesive sheet (surface protection film) be difficult to from Adherend is peeled off, and the overburden operation that adhesive sheet becomes when need not is poor, and then, due to stripping process, adherend is caused damage Wounds etc., are therefore inappropriate.
＜ high temperature through time adhesion strength (B) mensuration ＞
By TAC Polarizer (Dong electrician company system, SEG1423DU Polarizer, wide: 70mm, long: 100mm) 23 DEG C × Place after 24 hours in the environment of 50%RH, by be cut into wide 25mm, long 100mm adhesive sheet with the pressure of 0.25MPa, The velocity layer of 0.3m/ minute is stacked on above-mentioned adherend, makes evaluation sample.
After above-mentioned stacking, after placing 1 week (7 days) in the environment of 70 DEG C, mensuration universal tensile testing machine is to peel off speed Spend 30m/ minute (peel off at a high speed), peel angle 180 ° when peeling off through time adhesion strength (B) (N/25mm).Mensuration is 23 DEG C × 50%RH in the environment of carry out.
Here, described adhesion strength (B) preferably less than 4.0N/25mm, more preferably 0.1～3.5N/25mm, the most excellent Elect 0.1～3.0N/25mm as.If described adhesion strength (B) is more than 4.0N/25mm, then adhesive sheet (surface protection film) is difficult to Peeling off from adherend, the overburden operation that adhesive sheet becomes when need not is poor, and then, due to stripping process, adherend is caused Damages etc., are therefore inappropriate.
The evaluation ＞ of ＜ adhesion strength ratio (B/A)
Adhesion strength ratio (B/A) of described adhesion strength (A) and described adhesion strength (B) less than 2, preferably 0.5～1.9, more excellent Elect 0.7～1.8 as.By in the range of described, releasable and workability are excellent, become preferred mode.It addition, it is described viscous Put forth effort than be as high temperature through time adhesion strength rise the index of preventing property and evaluate.
Mensuration ＞ of ＜ shearing force
Adhesive sheet is cut into wide 10mm, the size of long 100mm, after peeling off dividing plate, according to the adhesion making described adhesive sheet Adhesion (bonding) area of oxidant layer becomes 1cm2Mode fit in TAC Polarizer (day work company system, SEG1423DU be inclined Tabula rasa, width: 25mm, length: 100mm), after room temperature (23 DEG C × 50%RH) stands 30 minutes, divide with peeling rate 0.06mm/ Clock, along shear direction tractive, by maximum load (N/cm now2) as shearing force.
Here, described shearing force (N/cm2) it is preferably more than 10, more preferably 10～50, more preferably 10～40. If described shearing force is in the range of described, then can bear adherend and want the power of the shear direction produced during curling, will not There is the slip of adhesive sheet, dislocation, the curling of adherend can be suppressed, the most preferably.
Mensuration ＞ of ＜ sheet resistance value
In the environment of temperature 23 DEG C, humidity 50%RH, with resistrivity meter (Mitsubishi Chemical Analytech, Hiresta-UP MCP-HT450 type), it is measured according to JIS-K-6911.
Here, as the sheet resistance value (Ω/) on the antistatic backing surface in the present invention, initial stage and room temperature (23 DEG C × 50%RH) × 1 week (7 days) stand time, preferably less than 1.0 × 1011, more preferably less than 5.0 × 1010, further preferably For less than 2.0 × 1010.The adhesive sheet (surface protection film) of the sheet resistance value in the range of described in showing, such as such as liquid The adhesive sheet used in processing or the handling process etc. of the article of electrostatic is afraid of like that by brilliant box, semiconductor device etc., can be well It is utilized.
Mensuration ＞ of ＜ sliding (kinetic force of friction)
Adhesive sheet (surface protection film) is cut into wide 70mm, the size of long 100mm, and (Rhizoma Sparganii is beautiful to fit in acrylic panel Sun company system, trade name " ACRYLITE ", thickness: 1mm, width: 70mm, length: 100mm), it is prepared as test film.By this test film The back side (antistatic backing surface) downward, be placed on the smooth PET film of holding level, load on this test film The load of 1.5kg.The line of the described test film inductility being loaded with load is arranged on cupping machine, to measure temperature Spend 25 DEG C under conditions of draw rate 300mm/ minute, distance drawn 300mm, flatly distraction test sheet, obtain and be applied to The meansigma methods (n=3) of the kinetic force of friction (N) on test film.
Here, as the sliding (kinetic force of friction) (N) in the present invention, preferably less than 5, more preferably less than 4.5, enter One step is preferably less than 4.If in the range of described, then when the adherend being pasted with adhesive sheet being processed, at support membrane The sliding at the back side (antistatic backing surface) is good and workability aspect, is favourable.
The evaluation ＞ of ＜ lettering (lettering adaptation)
Under the mensuration environment of 23 DEG C × 50%RH, use Qi Pai company Xstamper, enterprising on antistatic backing surface After row lettering, this lettering is pasted the Selltotape (registered trade mark) of meter Qi Bang company, then at peeling rate 30m/ Minute, peel off under conditions of peel angle 180 °.Afterwards, the surface after visual observations stripping, more than 50% quilt of lettering area Situation about peeling off is evaluated as × (lettering is bad), and more than 50% situation about remaining for being stripped of lettering area is evaluated as zero (lettering is good).
＜ preparation method ＞
The preparation method of concrete (methyl) acrylic acid series polymeric compounds, adhesion agent composition etc. set forth below.
The preparation ＞ of ＜ (methyl) acrylic acid series polymeric compounds
2-ethylhexyl propylene is loaded in the four-hole boiling flask possessing stirring blade, thermometer, nitrogen ingress pipe, condenser Acid esters (2EHA) 94.5 mass parts, 4-hydroxyethylmethacry,ate (HEA) 5.32 mass parts, acrylic acid (AA) 0.18 mass parts, As the 2 of polymerization initiator, 2 '-azobis isobutyronitrile 0.2 mass parts, ethyl acetate 150 mass parts, it is slowly stirred Importing nitrogen, the liquid temperature in flask be maintained near 65 DEG C, carry out 6 hours polyreactions, preparation (methyl) acrylic acid series gathers Polymer solution (40 mass %).The weight average molecular weight of described acrylic acid series polymeric compounds is 520,000, glass transition temperature (Tg) is- 67 DEG C (with reference to hurdle of the adhesion agent composition 1 in table 1).
The preparation ＞ of ＜ adhesion agent composition 1
By ethyl acetate, above-mentioned (methyl) acrylic polymer solution (40 mass %) is diluted to 20 mass %, at this Solution 500 mass parts (solid composition 100 mass parts) adds the fragrant family isocyanate compound that is three as cross-linking agent Isocyanuric acid ester body (Japanese polyurethane industrial group system, COLONATE L) 1 mass of hydroxymethyl-propane/toluene di-isocyanate(TDI) Part (solid composition 1 mass parts) and the isocyanuric acid ester body of the fat i.e. hexamethylene diisocyanate of family isocyanate compound (Japanese polyurethane industrial group system, COLONATE HX) 1 mass parts (solid composition 1 mass parts), as the two of crosslinking catalyst Dibutyl tin laurate (1 mass % ethyl acetate solution) 3 mass parts (solid composition 0.03 mass parts), carry out mix and blend, Prepare adhesion agent composition 1 (solution).
The ＜ antistatic backing preparation ＞ of aqueous solution (back side inorganic agent A)
Using the polyester resin VYLONAL MD-1480 (company's system is spun by 25% aqueous solution, Japan) as binding agent, as leading The poly-aminobenzenesulfonic acid (aquaPASS, weight average molecular weight 40,000, Rhizoma Sparganii Li Yang company system) of conductive polymers, as cross-linking agent Isocyanuric acid ester body using the hexamethylene diisocyanate of diisopropylamine block, the oleamide as lubricant add In the mixed solvent of water/ethanol (1/3), binding agent is calculated as 100 mass parts, electric conductive polymer with solid with solid content component amount Component amount is calculated as 75 mass parts, cross-linking agent is calculated as 10 mass parts with solid content component amount, lubricant is calculated as with solid content component amount 30 mass parts, stir about is sufficiently mixed for 20 minutes.So, the antistatic backing aqueous solution of NV about 0.4% is prepared.
The ＜ antistatic backing preparation ＞ of aqueous solution (back side inorganic agent B)
Using the polyester resin VYLONAL MD-1480 (company's system is spun by 25% aqueous solution, Japan) as binding agent, as leading The poly-aminobenzenesulfonic acid (aquaPASS, weight average molecular weight 40,000, Rhizoma Sparganii Li Yang company system) of conductive polymers, as cross-linking agent The mixed solvent of water/ethanol (1/3) is added with the isocyanuric acid ester body of the hexamethylene diisocyanate of diisopropylamine block In, binding agent with solid content component amount be calculated as 100 mass parts, electric conductive polymer with solid content component amount be calculated as 75 mass parts, Cross-linking agent is calculated as 10 mass parts with solid content component amount, and stir about is sufficiently mixed for 20 minutes.So, preparation NV is about The antistatic backing aqueous solution of 0.4%.
The ＜ antistatic backing preparation ＞ of aqueous solution (back side inorganic agent C)
Using the polyester resin VYLONAL MD-1480 (company's system is spun by 25% aqueous solution, Japan) as binding agent, as leading Conductive polymers containing poly-(3,4-ethene dioxythiophene) (PEDOT) 0.5% and PSS (weight average molecular weight 15 Ten thousand) (PSS) 0.8% aqueous solution (BytronP, H.C.Stark company system), as cross-linking agent with diisopropylamine block The isocyanuric acid ester body of hexamethylene diisocyanate adds in the mixed solvent of water/ethanol (1/1), and binding agent is with solid composition Amount is calculated as 100 mass parts, electric conductive polymer is calculated as 50 mass parts with solid component amount, cross-linking agent is calculated as 10 with solid component amount Mass parts, stir about is sufficiently mixed for 20 minutes.So, the antistatic backing aqueous solution of NV about 0.4% is prepared.
The ＜ antistatic backing preparation ＞ of aqueous solution (back side inorganic agent D)
Using the polyester resin VYLONAL MD-1480 (company's system is spun by 25% aqueous solution, Japan) as binding agent, as leading The poly-aminobenzenesulfonic acid (aquaPASS, weight average molecular weight 40,000, Rhizoma Sparganii Li Yang company system) of conductive polymers adds water/ethanol (1/ 3), in mixed solvent, binding agent is calculated as 100 mass parts with solid component amount, electric conductive polymer is calculated as 75 with solid component amount Mass parts, stir about is sufficiently mixed for 20 minutes.So, the antistatic backing aqueous solution of NV about 0.4% is prepared.
The making ＞ of the support membrane of ＜ band antistatic backing
The face (the first face) of a side has been carried out thickness 38 μm of sided corona treatment, wide 30cm, long 40cm transparent poly-to benzene On naphthalate (PET) film (polyester film), it is coated with the arbitrary water-soluble of described antistatic backing (back side inorganic agent A～D) Liquid, makes dried thickness reach 30nm.This coating material being heated 1 minute at 130 DEG C makes it be dried, thus is formed in PET First mask of film has the support membrane of the band antistatic backing of antistatic backing.
＜ embodiment 1 ＞
The making ＞ of ＜ adhesive sheet
Above-mentioned adhesion agent composition 1 (solution) is coated on support membrane contrary with antistatic backing of described band antistatic backing Face, 130 DEG C heat 1 minute, formed thickness 15 μm adhering agent layer.Then, on the surface of described adhering agent layer, laminating is single Face implements the silicone-treated face of the dividing plate i.e. polyethylene terephthalate film (thickness 25 μm) of silicone-treated, is made for gluing Sheet (surface protection film).
＜ embodiment 2～17 and comparative example 1～4 ＞
Mixing ratio based on Tables 1 and 2, similarly to Example 1, makes adhesive sheet.Here, the use level in table 1 Represent solid content composition.
According to above-mentioned evaluation methodology, measure the initial stage adhesion strength A when high speed of the adhesive sheet made is peeled off and high temperature through time Adhesion strength B, evaluate adhesion strength ratio (B/A), shearing force, the initial stage and through time sheet resistance value, sliding and lettering closely sealed Property.The result obtained is shown in table 3.
[table 1]
[table 2]
Electric conductive polymer Binding agent Cross-linking agent Lubricant
Back side inorganic agent A Poly-aminobenzenesulfonic acid Polyester Isocyanates Oleamide
Back side inorganic agent B Poly-aminobenzenesulfonic acid Polyester Isocyanates -
Back side inorganic agent C PEDOT/PSS Polyester Isocyanates -
Back side inorganic agent D Poly-aminobenzenesulfonic acid Polyester - -
Hereinafter the abbreviation in Tables 1 and 2 is illustrated.
2EHA: 2-EHA
BA: n-butylacrylate
AA: acrylic acid (containing carboxyl (methyl) acrylic monomer)
β-CEA: carboxyethyl acrylates (containing carboxyl (methyl) acrylic monomer)
HEA: acrylic acid 2-hydroxy methacrylate (hydroxyl (methyl) acrylic monomer)
HBA: acrylic acid 4-hydroxybutyl (hydroxyl (methyl) acrylic monomer)
HEMA: hydroxyethyl methacrylate (hydroxyl (methyl) acrylic monomer)
DEAA:N, N acrylamide
CL: fragrance family isocyanate compound, trimethylolpropane/inferior cresyl vulcabond (Japanese polyurethane Industrial group's system, trade name: COLONATE L)
HX: fat family isocyanate compound, the isocyanuric acid ester body (Japanese polyurethane of hexamethylene diisocyanate Company's system, trade name: COLONATE HX)
HL: fat family isocyanate compound, trimethylolpropane/hexamethylene diisocyanate addition product (Japan Polyurethane company system, trade name: COLONATE HL)
D110N: fragrance family isocyanate compound, trimethylolpropane/bis-inferior cresyl vulcabond addition product (Mitsui Chemicals system, trade name: TAKENATE D110N)
D140N: fat family isocyanate compound, TAKENATE D140N, trimethylolpropane/isophorone two are different Cyanate addition product (Mitsui Chemicals system, trade name: TAKENATE D110N)
PEDOT: electric conductive polymer, poly-(3,4-ethene dioxythiophene)
PSS: electric conductive polymer, PSS
[table 3]
Note) " ＞ 1E+13 " in table 3 represented more than the higher limit that can measure with resistrivity meter.
According to above-mentioned table 3 as a result, it is possible to confirm in all of the embodiments illustrated, adhesion strength ratio (B/A) is in desired scope In, relative to initial stage adhesion strength when peeling off at a high speed, under high temperature through time the rising of adhesion strength be suppressed, shearing force is excellent.
On the other hand, can confirm that in all of comparative example, adhesion strength ratio (B/A), outside desired scope, is shelled at a high speed From time initial stage adhesion strength high, and then, under high temperature through time the rising of adhesion strength become big, rise (the adhesion of preventing property in adhesion strength Power stability), releasable, workability and then shearing force aspect, all poor than embodiment.
It addition, according to the result of above-mentioned table 3, as antistatic backing, have and employ desired raw material (conductive poly Polymer component: poly-aminobenzenesulfonic acid, binding agent: polyester resin and, cross-linking agent: isocyanates system cross-linking agent) coordinate (anti-quiet Electricity agent compositions) and the embodiment 1,5,9～11 of the antistatic backing of back side inorganic agent A that manufactures and the adhesive sheet of 13～17 In, meet all assessment items of the sheet resistance, sliding and the lettering adaptation that cause because of antistatic backing.On the other hand, close Do not coordinate desired raw material and the antistatic backing of back side inorganic agent B～D that manufactures in a part, confirm as be unsatisfactory for because of The antistatic backing of all assessment items of sheet resistance, sliding and lettering adaptation that antistatic backing causes.

Claims (8)

1. an adhesive sheet, it is characterised in that be to have to be formed by adhesion agent composition on the single or double of support membrane The adhesive sheet of adhering agent layer,
The bonding plane of described adhering agent layer be pasted at 70 DEG C on TAC face after 1 week when peeling rate is 30m/ minute The bonding plane of adhesion strength (B) and described adhering agent layer at 23 DEG C, be pasted on TAC face upper 30 minute after at peeling rate be The ratio (B/A) of the adhesion strength between adhesion strength (A) when 30m/ minute is less than 2.
Adhesive sheet the most according to claim 1, it is characterised in that
Described adhesion agent composition contains (methyl) acrylic acid series polymeric compounds with hydroxyl and carboxyl.
Adhesive sheet the most according to claim 1 and 2, it is characterised in that
Described adhesion agent composition contains cross-linking agent, and described cross-linking agent contains aromatic isocyanate based compound and aliphatic is different Cyanate based compound.
4. according to the adhesive sheet described in Claims 2 or 3, it is characterised in that
In terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, containing hydroxyls more than 5.1 mass % (methyl) acrylic monomer.
5. according to the adhesive sheet according to any one of claim 2～4, it is characterised in that
In terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, containing 0.01 mass % less than 0.5 mass % containing carboxyl (methyl) acrylic monomer.
6. according to the adhesive sheet according to any one of Claims 1 to 5, it is characterised in that
Having antistatic backing on the one side of the described support membrane of described adhering agent layer opposition side, described antistatic backing is by containing Polyaniline sulfonic acid, the polyester resin as binding agent and the Carbimide. as cross-linking agent as electric conductive polymer composition The antistatic agent compositions of ester system cross-linking agent is formed.
Adhesive sheet the most according to claim 6, it is characterised in that
Described antistatic agent compositions contains the fatty acid amide as lubricant further.
8. an optics, it is characterised in that
Protected by the adhesive sheet according to any one of claim 1～7.
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