CN106232755A - Adhesive sheet and optics - Google Patents

Adhesive sheet and optics Download PDF

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Publication number
CN106232755A
CN106232755A CN201580019597.7A CN201580019597A CN106232755A CN 106232755 A CN106232755 A CN 106232755A CN 201580019597 A CN201580019597 A CN 201580019597A CN 106232755 A CN106232755 A CN 106232755A
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CN
China
Prior art keywords
methyl
acid
adhesive sheet
cation
ester
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Granted
Application number
CN201580019597.7A
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Chinese (zh)
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CN106232755B (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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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2483/00—Presence of polysiloxane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provide a kind of be pasted on adherend state processing (manufacture) time, the time of carrying, be exposed to high temperature in the case of, by described adhesive sheet when adherend is peeled off, stripping charge can be constrained prepared low and high temperature through time preserve after the adhesive sheet of stripping charge excellent in stability.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, the absolute value of the release band voltage when bonding plane of described adhering agent layer is pasted on TAC face at 70 DEG C peeling rate after 1 week 30m/ minute is less than 0.5kV.

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 with regulation State that sheet has been packed or be stained with the state of adhesive tape and transport.Wherein, surface protection film is particularly widely made It is used in optics, electronic parts sectors.
Surface protection film typically fits in adherend (by protective) by coating the sticker of 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 by sticker.Surface protection film is by adhesion Agent and be bonded to these opticses, it is possible to prevent adherend processing, carrying time produce damage, dirt.And, this table Surface protective film becomes the unwanted stage and is stripped removing.
It addition, when processing, carrying through time process after (preservation), when adherend stripping surface protection film, due to surface Protecting film, optics are typically molded of plastic material, and therefore electrical insulating property is high, rub, produce electrostatic when peeling off.Particularly exist Under high temperature through time process after (preservation), by antistatic agent to the infiltration etc. of adherend, there is (transfer) in adherend surface Antistatic agent tail off, from adherend (Polarizer etc.) peel off surface protection film time, with just fit after compared with, confirm release band Voltage rises, stripping charge poor stability, produces electrostatic, if at this when adherend (Polarizer etc.) peels off surface protection film Time produce electrostatic residual state under lose to liquid crystal applied voltages, the then orientation having liquid crystal molecule, panel generation The situation of defect.Add man-hour with what the state of surface protection film of having fitted carried out adherend, sometimes carry out high-temperature process,
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 though a kind of at high temperature warp After Shi Baocun, the adhesive sheet that stripping charge stability is also excellent.
The scheme of solution problem
That is, the adhesive sheet of the present invention is characterised by, is to have by adhesion agent composition at the single or double of support membrane The adhesive sheet of the adhering agent layer formed, is pasted on the stripping after 1 week on TAC face at 70 DEG C by the bonding plane of described adhering agent layer The absolute value of release band voltage during speed 30m/ minute is less than 0.5kV.
The adhesive sheet of the present invention is preferably: described adhesion agent composition contains compound and the room temperature with oxyalkylene group chain For the ionic compound with organic cation of solid under (25 DEG C).
The adhesive sheet of the present invention is preferably: described in have the compound of oxyalkylene group chain be have oxyalkylene group chain organic Polysiloxanes.
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: 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 polyaniline sulfonic 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.
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 above-mentioned adhesive sheet.
Invention effect
When the adhesive sheet of the present invention processes (manufacture) with the state being pasted on adherend, the time of carrying, it is exposed to the feelings of high temperature Under condition, by described adhesive sheet when adherend is peeled off, stripping charge can be constrained prepared low and high temperature through time preserve after stripping Charging stability is excellent, is useful.
Accompanying drawing explanation
Fig. 1 is the schematic diagram in potential measurement portion.
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, adhesion zone, adhesion label, adhesive film etc. The material of form, (such as, Polarizer, wavelength plate etc. are wanted as panel of LCD composition to be particularly suitable as optics Element optics) add man-hour, carrying time protection optical component surfaces surface protection film.Sticker in described adhesive sheet Layer, it is typical that be continuously formed, but be not limited to described form, can also be such as formed point-like, striated etc. rule 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.Here, (methyl) acrylic acid series polymeric compounds in the present invention refers to acrylic acid series polymeric compounds and/or metha crylic polymerization Thing, (methyl) acrylate refers to acrylate and/or methacrylate.
It addition, described (methyl) acrylic acid series polymeric compounds can use hydroxyl (methyl) acrylic monomer as monomer Composition.By using described hydroxyl (methyl) acrylic monomer as monomer component, it is easy to control adhesion agent composition Crosslinking etc., and then the improvement of wettability that brings of easily controllable flowing and the cohesiveness of sticker (layer), the balance of shearing force.Enter And, different from the carboxyl that typically can work as cross-linking part, sulphonate-base etc., hydroxyl due to have with as antistatic agent The interaction of the appropriateness such as ionic compound, even if therefore the aspect at static electricity resistance can also 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 cohesiveness of the wettability of the most easily controllable adhesion agent composition and sticker (layer), 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..
It addition, described (methyl) acrylic acid series polymeric compounds is described containing carboxyl (methyl) acrylic monomer conduct by using Monomer component, can control adhesive sheet (adhering agent layer) through time adhesion strength rise, releasable, adhesion strength rise preventing property Excellent with workability, and the cohesiveness of adhering agent layer and shearing force the most 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, 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 most preferably 0.01 less than 0.2 matter Amount %.If within the above range, 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.And then, logical Cross the interaction of the appropriateness of ionic compound with solid, cause ionic dissociation, good static electricity resistance can be showed, because of This is preferred.Here, if there is the such acid functional group of the carboxyl that too much polarity effect is big, then coordinate as antistatic agent During ionic compound, the acid functional group such as carboxyl plays strongly with the interaction of ionic compound, thus hinders ion to pass Leading, electrical efficiency reduces, and may become to obtain sufficient static electricity resistance, 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 (methyl) acrylate, (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) acrylic acid dodecyl ester, (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: to constitute the monomer component of described (methyl) acrylic acid series polymeric compounds as total amount Meter, contain described in there is (methyl) acrylic monomer 50～95 mass % of alkyl of carbon number 1～14, more preferably 60～ 95 mass %, further preferred 70～94.9 mass %, most preferably 80～94.8 mass %.By in the range of described, adhere Agent compositions 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 being readily obtained 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 raising cohesiveness, the composition of thermostability of the use monomer of cyano-containing, vinyl ester monomers, aromatic vinyl monomer etc., The monomer of amide-containing, the monomer containing imide, the monomer containing amino, the monomer containing epoxy radicals, N-acryloyl morpholine, second Alkene ether monomers etc. improve adhesion (bonding) power or have had the composition of functional group of Cross-linked basic point effect.These polymerism lists Body can be used alone, and additionally can also two or more 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 (methyl) glycidyl acrylate, (methyl) propylene Acid methyl ethylene oxidic ester, 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 adhesion agent composition diminishes, thus has Produce the tendency of cull.On the other hand, when weight average molecular weight is more than 5,000,000, the mobility of polymer reduces, to adherend (example As, as the Polarizer etc. of optics) moistening become insufficient, have the adhesion agent composition becoming adherend with adhesive sheet The tendency of the reason of the foaming occurred between Ceng.Here, weight average molecular weight is to be measured by GPC (gel permeation chromatography) to obtain 's.
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, can contain under ionic compound, particularly room temperature (25 DEG C), for solid, there is organic cation Ionic compound.By containing under room temperature (25 DEG C) for the ionic compound with organic cation of solid, become Apply more than room temperature hot time the stability of ionic compound high, high temperature through time preserve after stripping charge excellent in stability Material, become preferred mode.
As under room temperature (25 DEG C) for the ionic compound with organic cation of solid, be preferably used comprise following (A)～(E) represents simultaneously organic cation composition and anion component.By having the ionic chemical combination of these cationes Thing, it is possible to obtain the material that antistatic performance is more excellent.
[changing 1]
R in described formula (A)aRepresent the alkyl of carbon number 4～20, it is also possible to be that a part for described alkyl is by miscellaneous former The substituted functional group of son, RbAnd RcIdentical or different, represent hydrogen or the alkyl of carbon number 1～16, it is also possible to be described alkyl The functional group that a part is exchanged for heteroatoms.But, when nitrogen-atoms comprises double bond, there is no Rc。
R in described formula (B)dRepresent the alkyl of carbon number 2～20, it is also possible to be that a part for described alkyl is by miscellaneous former The substituted functional group of son, Re、RfAnd RgIdentical or different, represent hydrogen or the alkyl of carbon number 1～16, it is also possible to be described hydrocarbon The functional group that a part for base is exchanged for heteroatoms.
R in described formula (C)hRepresent the alkyl of carbon number 2～20, it is also possible to be that a part for described alkyl is by miscellaneous former The substituted functional group of son, Ri、RjAnd RkIdentical or different, represent hydrogen or the alkyl of carbon number 1～16, it is also possible to be described hydrocarbon The functional group that a part for base is exchanged for heteroatoms.
Z in described formula (D) represents nitrogen, sulfur or phosphorus atoms, Rl、Rm、RnAnd RoIdentical or different, represent carbon number 1～ The alkyl of 20, it is also possible to be the functional group that is exchanged for heteroatoms of a part for described alkyl.But, when Z is sulphur atom, do not have Ro。
R in described formula (E)pRepresent the alkyl of carbon number 1～18, it is also possible to be that a part for described alkyl is by miscellaneous former The substituted functional group of son.
As the cation represented by formula (A), such as, can enumerate pyridylium, piperidines cation, pyrrolidine Cation, there is the cation of pyrrolin skeleton, there is the cation of pyrrole skeleton, morpholine cation etc..
As object lesson, such as, can enumerate 1-ethylpyridinium cations, 1-butyl-pyridinium cation, 1-hexyl Pyridylium, 1-butyl-3-methylpyridinium cations, 1-butyl-4-methylpyridinium cations, 1-hexyl-3-first Pyridinium cations, 1-butyl-3,4-lutidines cation, 1,1-dimethyl pyrrolidine cation, 1-ethyl- 1-crassitude cation, 1-methyl isophthalic acid-propyl pyrrole alkane cation, 1-methyl isophthalic acid-butyl pyrrolidine cation, 1-methyl-1-pentene base pyrrolidine cation, 1-methyl isophthalic acid-hexyl pyrrolidine cation, 1-methyl isophthalic acid-heptyl pyrrolidine Cation, 1-ethyl-1-propyl pyrrole alkane cation, 1-ethyl-1-butyl pyrrolidine cation, 1-ethyl-1-amyl group Pyrrolidine cation, 1-ethyl-1-hexyl pyrrolidine cation, 1-ethyl-1-heptyl pyrrolidine cation, 1,1-bis- Propyl pyrrole alkane cation, 1-propyl group-1-butyl pyrrolidine cation, 1,1-dibutyl pyrrolidine cation, pyrroles Alkane-2-ketone cation, 1-propylpiperdine cation, 1-amyl piperidine cation, 1,1-dimethyl piperidinium cations, 1-methyl isophthalic acid-ethyl piperidine cation, 1-methyl isophthalic acid-propylpiperdine cation, 1-methyl isophthalic acid-butyl piperidine sun from Son, 1-methyl-1-pentene phenylpiperidines cation, 1-methyl isophthalic acid-hexyl piperidines cation, 1-methyl isophthalic acid-heptyl piperidines sun Ion, 1-ethyl-1-propylpiperdine cation, 1-ethyl-1-butyl piperidine cation, 1-ethyl-1-amyl piperidine Cation, 1-ethyl-1-hexyl piperidines cation, 1-ethyl-1-heptyl piperidines cation, 1,1-dipropyl piperidines sun Ion, 1-propyl group-1-butyl piperidine cation, 1,1-dibutyl piperidines cation, 2-methyl isophthalic acid-pyrrolin cation, 1-ethyl-2-phenylindone cation, 1,2-dimethyl indole cation, 1-ethyl carbazole cation, N-ethyl-N-methyl Cation moiety etc..
As the cation represented by formula (B), such as can enumerate Imidazole cation, tetrahydropyrimidine cation, Dihydro-pyrimidin cation etc..
As object lesson, such as, can enumerate 1,3-methylimidazole cation moiety, 1,3-diethyl imidazolium quinoline Cation, 1-ethyl-3-methylimidazole cation moiety, 1-butyl-3-Methylimidazole. cation moiety, 1-hexyl-3-methyl Imidazole cation, 1-octyl group-3-Methylimidazole. cation moiety, 1-decyl-3-Methylimidazole. cation moiety, 1-12 Alkyl-3-Methylimidazole. cation moiety, 1-myristyl-3-Methylimidazole. cation moiety, 1,2-dimethyl-3-propyl group miaow Oxazoline cation, 1-ethyl-2,3-methylimidazole cation moiety, 1-butyl-2,3-methylimidazole cation moiety, 1-hexyl-2,3-methylimidazole cation moiety, 1-(2-methoxy ethyl)-3-Methylimidazole. cation moiety, 1,3-bis- Methyl isophthalic acid, 4,5,6-tetrahydropyrimidine cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidine cation, 1,2,3,4- Tetramethyl-1,4,5,6-tetrahydropyrimidine cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidine cation, 1,3- Dimethyl-1,4-dihydro-pyrimidin cation, 1,3-dimethyl-1,6-dihydro-pyrimidin cation, 1,2,3-trimethyl-1,4- Dihydro-pyrimidin cation, 1,2,3-trimethyl-1,6-dihydro-pyrimidin cation, 1,2,3,4-tetramethyl-1,4-dihydro are phonetic Pyridine cation, 1,2,3,4-tetramethyl-1,6-dihydro-pyrimidin cation etc..
As the cation represented by formula (C), such as, can enumerate pyrazoles cation, pyrazoline cation etc..
As object lesson, such as, can enumerate 1-methylpyrazole cation, 3-methylpyrazole cation, 1-second Base-2-methylpyrazole cation moiety, 1-ethyl-2,3,5-trimethylpyrazol cation, 1-propyl group-2,3,5-trimethyl pyrrole Azoles cation, 1-butyl-2,3,5-trimethylpyrazol cation, 1-ethyl-2,3,5-trimethylpyrazol cation moiety, 1-propyl group-2,3,5-trimethylpyrazol cation moiety, 1-butyl-2,3,5-trimethylpyrazol cation moiety etc..
As the cation represented by formula (D), such as can enumerate tetraalkylammonium cation, trialkylsulfonium cation, four Alkyl cation, described alkyl a part by alkenyl, alkoxyl, epoxy radicals replace after group etc..
As object lesson, such as can enumerate tetramethylammonium cation, tetraethylammonium cation, TBuA sun from Son, four pentyl ammonium cation, tetrahexyl ammonium cation, four heptyl ammonium cations, triethyl methyl ammonium cation, tributyl ethyl Ammonium cation, trimethyldecylammonium ammonium cation, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, epoxy third Base trimethyl ammonium cation, trimethylsulfonium cation, triethyl group sulfonium cation, tributyl sulfonium cation, three hexyl sulfonium cations, Diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, dimethyl decyl sulfonium cation, tetramethyl cation, tetrem Base cation, tetrabutyl cation, four hexyl cationes, four octyl group cationes, triethyl methyl cation, three Butyl ethyl cation, trimethyldecylammonium cation, diallyl dimethyl ammonium cation, tributyl-(2-methoxyl group second Base) cation etc..Wherein, triethyl methyl ammonium cation, tributyl ethyl ammonium cations, trimethyldecylammonium ammonium are preferably used Cation, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, dimethyl decyl sulfonium cation, triethyl methyl Asymmetrical tetraalkylammonium cation, the trialkyl sulfoniums such as cation, tributyl ethyl cation, trimethyldecylammonium cation Cation, tetra alkyl phosphonium cation, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyl front three Base ammonium cation, diallyl dimethyl ammonium cation, N, N-dimethyl-N-ethyl-N-propyl ammonium cation, N, N-diformazan Base-N-ethyl-N-butyl ammonium cation, N, N-dimethyl-N-ethyl-N-amyl group ammonium cation, N, N-dimethyl-N-ethyl- N-hexyl ammonium cation, N, N-dimethyl-N-ethyl-N-heptyl ammonium cation, N, N-dimethyl-N-ethyl-N-nonyl ammonium sun Ion, N, N-dimethyl-N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butyl ammonium cation, N, N-diformazan Base-N-propyl group-N-amyl group ammonium cation, N, N-dimethyl-N-propyl group-N-hexyl ammonium cation, N, N-dimethyl-N-propyl group- N-heptyl ammonium cation, N, N-dimethyl-N-butyl-N-hexyl ammonium cation, N, N-diethyl-N-butyl-N-heptyl ammonium sun Ion, N, N-dimethyl-N-amyl group-N-hexyl ammonium cation, N, N-dimethyl-N, N-dihexyl ammonium cation, trimethyl heptan Base ammonium cation, N, N-diethyl-N-Methyl-N-propyl ammonium cation, N, N-diethyl-N-methyl--V-pentyl ammonium cation, N, N-diethyl-N-methyl-N-heptyl ammonium cation, N, N-diethyl-N-propyl-N-amyl group ammonium cation, triethyl group propyl group Ammonium cation, triethyl group amyl group ammonium cation, triethyl group heptyl ammonium cation, N, N-dipropyl-N-methyl-N ethyl ammonium sun from Son, N, N-dipropyl-N-methyl--V-pentyl ammonium cation, N, N-dipropyl-N-butyl-N-hexyl ammonium cation, N, N-dipropyl Base-N, N-dihexyl ammonium cation, N, N-dibutyl-N-methyl--V-pentyl ammonium cation, N, N-dibutyl-N-methyl-N-are own Base ammonium cation, tricaprylmethyl ammonium cation, N-methyl-N ethyl-N-propyl group-N-amyl group ammonium cation.
As the cation represented by formula (E), such as, can enumerate sulfonium cation etc..It addition, as in described formula (E) RpObject lesson, methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl, tridecane can be enumerated Base, myristyl, octadecyl etc..
On the other hand, as anion component, as long as the ionic chemical combination for solid can be formed under room temperature (25 DEG C) The anion component of thing, is not particularly limited, such as, can enumerate Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、 ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、C4F9SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、 (C2F5SO2)2N-、C3F7COO-、(CF3SO2)(CF3CO)N-、C9H19COO-、(CH3)2PO4 -、(C2H5)2PO4 -、C2H5OSO3 -、 C6H13OSO3 -、C8H17OSO3 -、CH3(OC2H4)2OSO3 -、C6H4(CH3)SO3 -、(C2F5)3PF3 -、CH3CH(OH)COO-(FSO2)2N-Deng.
It addition, as anion component, it is possible to use the anion etc. represented by following formula (F).
[changing 2]
As the object lesson of the ionic compound that the present invention uses, can become with anion from described cation constituent The combination divided suitably selects use, such as, can enumerate 1-butyl-pyridinium bromide, 1-butyl-pyridinium chloride, 1- Butyl-pyridinium hexafluorophosphate, 1-butyl-3-picoline bromide, 1-butyl-3-picoline chloride, 1-fourth Base-3-picoline hexafluorophosphate, 1-butyl-4-picoline bromide, 1-butyl-4-picoline chlorination Thing, 1-butyl-4-picoline hexafluorophosphate, 1-hexyl pyridinium bromide, 1-hexyl pyridinium chloride, 1-hexyl Pyridine hexafluorophosphate, 1-octylpyridinium hexafluorophosphate, 1-nonylpyridine hexafluorophosphate, 2-methyl isophthalic acid-ten two Alkyl pyridine hexafluorophosphate, 4-methyl isophthalic acid-octylpyridinium hexafluorophosphate, 1-octylpyridinium DBSA Salt, 1-dococylpyridinium rhodanate, 1-dococylpyridinium dodecyl benzene sulfonate, 1-butyl-1-pyrrolidine Bromide, 1-butyl-1-pyrrolidine chloride, 1-butyl-1-pyrrolidine hexafluorophosphate, 1-butyl-1-pyrrolidine Tetrafluoroborate, 1-butyl-1-methylpiperidinium bromide, 1-pi-allyl-3-Methylimidazole. quinoline chloride, 1-benzyl- 3-Methylimidazole. quinoline chloride, 1-benzyl-3-Methylimidazole. quinoline hexafluorophosphate, 1-benzyl-3-Methylimidazole. quinoline four Borofluoride, 1-butyl-2,3-methylimidazole quinoline bromide, 1-butyl-2,3-methylimidazole quinoline chloride, 1-fourth Base-2,3-methylimidazole quinoline hexafluorophosphate, 1-butyl-2,3-methylimidazole quinoline trifluoro-methanyl sulfonate, 1-fourth Base-3-Methylimidazole. quinoline bromide, 1-butyl-3-Methylimidazole. quinoline chloride, 1-butyl-3-Methylimidazole. quinoline, 1- Ethyl-2,3-methylimidazole quinoline chloride, 1-ethyl-2,3-methylimidazole quinoline hexafluorophosphate, 1-ethyl-2,3- Methylimidazole quinoline tetrafluoroborate, 1-ethyl-3-methylimidazole quinoline bromide, 1-ethyl-3-methylimidazole quinoline chlorine Compound, 1-ethyl-3-methylimidazole quinoline hexafluorophosphate, 1-ethyl-3-methylimidazole quinoline-p-toluene fulfonate, four fourths Base ammonium bromide, TBuA chloride, TBuA benzoate, TBuA methane sulfonates, TBuA nine fluorine fourth Alkyl sulfonate, TBuA hexafluorophosphate, TBuA tetrafluoroborate, TBuA trifluoro-methanyl sulfonate, the tetrabutyl Double (fluoroform sulphonyl) acid imide of ammonium, tetraethyl ammonium trifluoroacetate, tetraethyl ammonium perchlorate, tetraethyl ammonium chloride, Tetraethyl ammonium bromide, tetraethyl ammonium tetrafluoroborate, tetrahexyl ammonium bromide, tetrahexyl ammonium chloride, tetrahexyl ammonium tetrafluoro Borate, four heptyl ammonium bromides, four heptyl ammonium chlorides, four octyl group ammonium bromides, four octyl group ammonium chlorides, four pentyl ammonium sulfur Cyanate, four pentyl ammonium bromide, four pentyl ammonium chloride, hexyl trimethyl ammonium double (fluoroform sulphonyl) acid imide, hexyl Trimethyl ammonium bromide, hexyl trimethylammonium chloride, tetrabutyl phosphonium bromide thing, tetrabutyl chloride, tetrabutyl tetrafluoro Borate, tetrabutyl methane sulfonates, tetrabutyl cetyl bromide etc..
Described such ionic compound, it is possible to use commercially available product, it is also possible to synthesize as follows.As ionic compound Synthetic method, be just not particularly limited as long as object ion compound can be obtained, typically can use document " ionic liquid The forefront of body-exploitation and future-" halide as [(strain) CMC publication and distribution] are described, hydroxide process, acid Ester process, complexometry and neutralisation etc..
Below in relation to halide, hydroxide process, acid esters method, complexometry and neutralisation, it is shown that containing nitrogen salt to be The synthetic method of example, about other containing other ionic compounds such as sulfosalt, phosphorous salts, can be by same method Obtain.
Halide be by following formula (1)～(3) as shown in reaction and the method that carries out.First, make tertiary amine with Halogenated alkane reacts and obtains halogenide.Make halogenide obtained by (reaction equation (1) employs chlorine, bromine, iodine as halogen) with There is the anion structure (A of object ion compound-) acid (HA) or salt (MA, M are that ammonium, lithium, sodium, potassium etc. and target are cloudy Ion forms the cation of salt) reaction, obtain object ion compound (R4NA)。
[changing 3]
(1)R3N+RX→R4NX(X:Cl,Br,I)
(2)R4N+HA→R4NA+HX
(3)R4N+MA→R4NA+MX(M:NH4, Li, Na, K, Ag etc.)
Hydroxide process be by (4)～(8) as shown in the method that carries out of reaction.First, by halogenide (R4NX) By ion hand over embrane method electrolysis (reaction equation (4)), OH type ion-exchange-resin process (reaction equation (5)) or with oxidation (Ag2O) Reaction (reaction equation (6)) and obtain hydroxide (R4NOH).Hydroxide obtained by (chlorine, bromine, iodine being used as halogen) Thing uses reaction equation (7)～the reaction of (8) to obtain object ion compound according to the mode identical with above-mentioned halogen process (R4NA)。
[changing 4]
(4)R4NX+H2O→R4NOH+1/2H2+1/2X2(X:Cl,Br,I)
(5)R4NX+P→R4NOH+P-X (P-OH:OH type ion exchange resin)
(6)R4NX+1/2Ag2O+1/2H2O→R4NOH+AgX
(7)R4NOH+HA→R4NA+H2O
(8)R4NOH+MA→R4NA+MOH(M:NH4, Li, Na, K, Ag etc.)
Acid esters method be by (9)～(11) as shown in reaction carry out.First, tertiary amine (R is made3N) react with acid esters And obtain acid esters thing.Will (ester of mineral acid, the methane sulphur such as reaction equation (9), use sulphuric acid, sulfurous acid, phosphoric acid, phosphorous acid, carbonic acid The esters of the organic acid such as acid, methylphosphonic acid, formic acid etc. are as acid esters) obtained by acid esters thing according to the side identical with above-mentioned halogen process Formula uses reaction equation (10)～the reaction of (11) to obtain object ion compound (R4NA).It addition, by using methyl three Fluoromethane sulfonate, methyl trifluoro acetate etc. are used as acid esters, it is also possible to directly obtain ionic compound.
[changing 5]
(9)R3N+ROY→R4NOY
(OY:Deng)
(10)R4NOY+HA→R4NA+HOY
(OY:In the case of,)
(11)R4NOY+MA→R4NA+MOY (M:NH4, Li, Na, K, Ag etc.)
Complexometry be by (12)～(15) as shown in the method that carries out of reaction.First, the halogenide of quaternary ammonium is made (R4NX), the hydroxide (R of quaternary ammonium4NOH), the carbonic ester compound (R of quaternary ammonium4NOCO2CH3) etc. with fluohydric acid gas (HF), ammonium fluoride (NH4F) react and obtain quaternary ammonium fluoride salt.By the quaternary ammonium fluoride salt obtained by (reaction equation (12)～(14)) and BF3, AlF3, PF5, AsF5, SbF5, NbF5, TaF5Carry out complex reaction in fluoride, ionic compound can be obtained.
(reaction equation (15))
[changing 6]
(12)R4NX+HF→R4NF+HX (X:Cl, Br, I)
(13)R4NY+HF→R4NF+HY (Y:OH, OCO2CH3)
(14)R4NY+NH4F→R4NF+NH3+ HY (Y:OH, OCO2CH3)
(15)R4NF+MFn-1→R4NMFn
(MFn-1: BF3, AlF3, PF5, AsF5, SbF5, NbF5, TaF5Deng)
Neutralisation be by (16) as shown in the method that carries out of reaction.Can be by making tertiary amine and HBF4, HPF6, CH3COOH, CF3COOH, CF3SO3H, (CF3SO2)2NH, (CF3SO2)3CH, (C2F5SO2)2The organic acid reactions such as NH and obtain.
[changing 7]
(16)R3N+HZ→R3HN+Z-
[HZ:HBF4, HPF6, CH3COOH, CF3COOH, CF3SO3H, (CF3SO2)2NH, (CF3SO2)3CH, (C2F5SO2)2NH Deng organic acid]
R described in above-mentioned formula (1)～(16) represents hydrogen or the alkyl of carbon number 1～20, it is also possible to be described alkyl The functional group that is exchanged for heteroatoms of a part.
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 2 mass parts, more preferably 0.001～1.5 mass parts, more preferably 0.005～1 mass parts as.If institute In the range of stating, 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 preferably comprises the compound with oxyalkylene chain.Institute State the compound with oxyalkylene chain owing to having oxyalkylene chain, thus interact with above-mentioned ionic compound, electric conductivity Improve, the most preferably.The compound described in it addition, with oxyalkylene chain more preferably has the organic poly-silica of oxyalkylene chain Alkane.Speculate by using described organopolysiloxane, it is achieved the surface free energy on sticker surface reduces, light when peeling off at a high speed Separation.
Described organopolysiloxane has the organopolysiloxane of polyoxyalkylene chain main chain known to can suitably using, excellent Select the material shown in following formula.
(in formula, R1And/or R2Having the oxyalkylene chain of carbon number 1～6, the alkylidene in described oxyalkylene chain can be Straight or branched, the end of described oxyalkylene chain can be alkoxyl or hydroxyl.It addition, R1Or R2Either one can be hydroxyl, Or can also be alkyl, alkoxyl, it is also possible to be the functional group that is exchanged for heteroatoms of described alkyl, a part for alkoxyl.n It it is the integer of 1～300.)
Described organopolysiloxane uses with the position (siloxanes position) of silicone-containing as main chain, at the end of this main chain It is combined with the material of oxyalkylene chain.Be there is the organosiloxane of described oxyalkylene chain by use, thus it is speculated that (methyl) can be obtained The balance of the compatibility of acrylic acid series polymeric compounds and ionic compound, it is achieved light separation.
It addition, as the described organopolysiloxane of the present invention, such as following such composition can be used.Specifically, R in formula1And/or R2There is the oxyalkylene chain of the hydrocarbon of carbon atom quantity 1～6, as described oxyalkylene chain, oxidation can be enumerated Methylene, oxyethylene group, oxypropylene group, butylene oxide etc., wherein, preferential oxidation vinyl, oxypropylene group.It addition, R1And R2In the case of being respectively provided with oxyalkylene chain, can be identical, it is also possible to different.
[changing 9]
It addition, the hydrocarbon of described oxyalkylene chain can be straight chain, it is also possible to be side chain.
And then, the end of described oxyalkylene chain can be alkoxyl or hydroxyl, wherein, and more preferably alkoxyl.For protection The purpose of bonding plane and in the case of adhering agent layer surface laminating dividing plate, if end is the organopolysiloxane of hydroxyl, Then interacting with dividing plate, the peeling force when adhering agent layer sur-face peeling dividing plate rises sometimes.
It addition, the integer that n is 1～300, preferably 10～200, more preferably 20～150.If n is in the range of described, Then can obtain the balance of the compatibility with base polymer, be preferred mode.And then, molecule can also have (methyl) Acryloyl group, pi-allyl, hydroxyl isoreactivity substituent group.Described organopolysiloxane can be used alone, it is also possible to by 2 kinds with On be used in mixed way.
As the object lesson of the above-mentioned organopolysiloxane with oxyalkylene chain, such as, as commercially available product, can enumerate Trade name X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889 (are above chemical industrial company of SHIN-ETSU HANTOTAI System), BY16-201, SF8427 (being above Dong Li Dow Corning Corporation system), IM22 (Wa Ke company of Asahi Chemical Industry system) etc..These chemical combination Thing may be used alone, can also be 2 or more kinds in combination..
It addition, except main chain have (in conjunction with) in addition to the organosiloxane of oxyalkylene chain, it is possible to use side chain has (knot Close) organosiloxane of oxyalkylene chain, with main chain, there is oxyalkylene chain compared with, use side chain to have organic silica of oxyalkylene chain Alkane is preferred mode.Described organopolysiloxane can suitably use the organic poly-silicon with known polyoxalkylene side chains Oxygen alkane, the preferably organopolysiloxane shown in following formula.
[changing 10]
(in formula, R1It is 1 valency organic group, R2, R3And R4It is alkylidene, R5Being hydrogen or organic group, m and n is 0～1000 Integer.But, it is 0 during m, n difference.A and b is the integer of 0～100.But, it is 0 during a, b difference.)
It addition, as the described organopolysiloxane of the present invention, such as can the most such composition.Specifically, in formula R1It it is 1 valency illustrated in the aryl such as the alkyl such as methyl, ethyl, propyl group, phenyl, tolyl or the aralkyl such as benzyl, phenethyl Organic group, each can have the substituent groups such as hydroxyl.R2、R3And R4The carbon such as methylene, ethylidene, propylidene can be used former The alkylidene of subnumber 1～8.Here, R3And R4It is different alkylidenes, R2Can be with R3Or R4Identical, it is also possible to different.In order to carry The concentration of the high ionic compound that can dissolve in its polyoxalkylene side chains, R3And R4Either one be preferably ethylidene or Propylidene.R5Can be 1 valency organic group illustrated in the alkyl such as methyl, ethyl, propyl group or the acyl group such as acetyl group, propiono, Each can have the substituent groups such as hydroxyl.These compounds may be used alone, can also be 2 or more kinds in combination.It addition, Molecule can also have (methyl) acryloyl group, pi-allyl, hydroxyl isoreactivity substituent group.Above-mentioned have polyoxalkylene side chains Organosiloxane in, thus it is speculated that the organosiloxane of the polyoxalkylene side chains with C-terminal easily obtains the compatibility Balance, the most preferably.
[changing 11]
As the concrete ion of above-mentioned organopolysiloxane, such as, can enumerate trade name KF-as commercially available product 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), 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 (are above Dong Li Dow Corning Corporation System), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (be above step figure New high-tech material company system), BYK-333, BYK-307, BYK-377, BYK-UV3500, BYK-UV3570 (be above Bi Ke Japan Company's system) etc. commodity.These can be used alone, and additionally can also two or more 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, then it is that the ionic compound with organic cation of solid is under room temperature (25 DEG C) with above-mentioned organopolysiloxane Make the most also to be stable, can interact, electric conductivity improve, can by high temperature through time preserve after release band voltage Suppress low, and then light fissility (releasable) can also be met, the most preferably.
For the surface protection film of the present invention, described adhesion agent composition preferably comprises cross-linking agent.It addition, the present invention In, use described adhesion agent composition to make adhering agent layer.Such as, described sticker contains described (methyl) acrylic polymeric During thing, the suitably described Component units of (methyl) acrylic acid series polymeric compounds of regulation, component ratio, the selection of cross-linking agent and interpolation ratio Rate etc. and cross-link, it is possible to obtain the adhesive sheet (adhering agent layer) that thermostability is more excellent.
As cross-linking agent used in the present invention, it is possible to use isocyanate compound, epoxide, tripolycyanamide It is resin, aziridine derivative and metal chelate compound etc..It addition, these compounds can be used alone, it is also possible to Two or more is used in mixed way.
As described isocyanate compound (isocyanates system cross-linking agent), such as, can enumerate trimethylene two Carbimide. The aliphatic poly Carbimide .s such as ester, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate Esters, ring pentamethylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI) etc. are alicyclic different Cyanate, 2,4-toluenediisocyanates, 4,4 '-methyl diphenylene diisocyanate, xylylene diisocyanate (XDI) the aromatic isocyanate class such as, uses allophanate by above-mentioned isocyanates based compound (isocyanates system cross-linking agent) Key, biuret linkage, isocyanurate-bond, urea two ketonic bond, urea bond, carbodiimides key, uretonimine key, oxadiazines three ketonic bond etc. The ester modified body of modified polyisocyanate.Such as, as commercially available product, trade name TAKENATE 300S, TAKENATE can be enumerated 500, TAKENATE D165N, TAKENATE D178N (be above Wu Tian pharmaceutical industries company system), SUMIDUR T80, SUMIDUR L, DESMODUR N3400 (being above Bayer polyurethane company system), MILLIONATE MR, MILLIONATE MT, COLONATE L, COLONATE HL, COLONATE HX (being above Japanese polyurethane industrial group system) etc..These isocyanides Ester compound may be used alone, can also be two or more kinds in combination, it is also possible to and with the isocyanates chemical combination of 2 functional groups Isocyanate compound more than thing and 3 functional groups uses.By and use with cross-linking agent, it is possible to take into account adhesion strength and resistance to Least (cementability to curved surface), can obtain the surface protection film that bonding reliability is more 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 of cross-linking agent used in the present invention, such as, is 100 mass parts with described (methyl) acrylic acid series polymeric compounds Meter, preferably comprises 0.01～10 mass parts, more preferably contains 0.1～8 mass parts, further preferably containing 0.5～5 mass parts, Most contain 1.0～2.5 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 has the inclining of reason becoming cull To.On the other hand, when content is more than 10 mass parts, the cohesiveness of polymer is big, and mobility reduces, to adherend (such as polarisation Plate) moistening become insufficient, have and become foaming former occurred between adherend and adhering agent layer (adhesion agent composition layer) The tendency of cause.Further, if cross-linked dosage is many, there is the tendency that stripping charge characteristic reduces.It addition, these cross-linking agent can be independent Use, additionally two or more can also be used in mixed way.
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 (comprises the compound with polyoxyalkylene chain).By containing above-claimed cpd in adhesion agent composition, it is possible to obtain right The adhesion agent composition that the wettability of adherend is more excellent.
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 Olefin(e) acid isooctyl acrylate, (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) Isodecyl acrylate, (methyl) acrylic acid dodecyl ester, (methyl) acrylic acid n-tridecane base ester, (methyl) acrylic acid are just Myristyl 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 be susceptible to produce the pollution that described polyoxyalkylene compounds causes.It addition, this In, 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 be susceptible 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.As described acrylic acid oligomer, it it is (the first comprising and there is the ester ring type structure that following formula (1) represents Base) acrylic monomer is as (methyl) acrylic acid series polymeric compounds of monomeric unit, at the stripping propylene again of present embodiment When acid is to use in adhesion agent composition, the function as tackifying resin, make adhesion (bonding) property improve, to suppression adhesion Heaving of sheet is effective.
CH2=C (R1)COOR2 (1)
[in formula (1), R1It is hydrogen atom or methyl, R2It is the ester ring type hydrocarbon with ester ring type structure]
As the ester ring type hydrocarbon R in formula (1)2, the ester ring type hydrocarbon such as cyclohexyl, isobornyl, bicyclopentyl can be enumerated Deng.As having (methyl) acrylate of this ester ring type hydrocarbon, such as, can enumerate (methyl) acrylic acid with cyclohexyl Cyclohexyl, there is (methyl) isobornyl acrylate of isobornyl, there is (methyl) acrylic acid bicyclo-pentyl ester of bicyclopentyl Ester Deng (methyl) acrylic acid alicyclic alcohol.By making acrylic acid oligomer with so having the third of the bigger structure of volume Olefin(e) acid system monomer is used as monomeric unit, and adhesion (bonding) property can be made to improve.
And then, in present embodiment, the ester ring type hydrocarbon constituting described acrylic acid oligomer preferably has caged scaffold.Bridged ring Structure refers to the ester ring type structure of more than three rings.By making acrylic acid oligomer have this bulky structure of caged scaffold, As the adhesion agent composition (removable adhesive sheet) peeled off again, adhesion (bonding) property can be made more to improve.
As the described ester ring type hydrocarbon i.e. R with caged scaffold2, such as, can enumerate the bicyclo-represented by following formula (3a) Dicyclopentenyl represented by amyl group, following formula (3b), the adamantyl represented by following formula (3c), following formula (3d) are represented Three cyclopenta, three cyclopentenyls etc. represented by following formula (3e).It addition, during synthesizing propylene acid oligomer, make sticker In the case of using UV polymerization during compositions, from the viewpoint of being difficult to cause polymerization to hinder, with having the three of caged scaffold Among (methyl) acrylic monomer of ester ring type structure more than ring, can particularly preferably use and there is following formula (3a) institute The saturated knots such as the adamantyl represented by the bicyclopentyl of expression, following formula (3c), three cyclopenta represented by following formula (3d) (methyl) acrylic monomer of structure is used as constituting the monomer of acrylic acid oligomer.
[changing 12]
It addition, as described (methyl) acrylic acid series list with the ester ring type structure with more than three rings of caged scaffold The example of body, can enumerate methacrylic acid bicyclopentyl ester, acrylic acid bicyclopentyl ester, methacrylic acid bicyclopentyl oxygen second Base ester, acrylic acid bicyclopentyl oxygen ethyl ester, methacrylic acid three cyclopentyl ester, acrylic acid three cyclopentyl ester, methacrylic acid 1-adamantane esters, acrylic acid 1-adamantane esters, methacrylic acid 2-methyl-2-adamantane esters, acrylic acid 2-methyl-2- (methyl) third such as adamantane esters, methacrylic acid 2-ethyl-2-adamantane esters, acrylic acid 2-ethyl-2-adamantane esters Olefin(e) acid ester etc..Such (methyl) acrylic monomer can be used alone or two or more is applied in combination.
The acrylic acid oligomer of present embodiment can be have ester ring type structure (methyl) acrylic monomer equal Polymers, or there are (methyl) acrylic monomer and other (methyl) acrylate monomer or copolymerizables of ester ring type structure The copolymer of monomer.
As the example of described (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) acrylic acid Isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid are different Pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) heptylacrylate, (methyl) propylene are misery Ester, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, (methyl) acrylic acid different nonyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate such (methyl) Alkyl acrylate；(methyl) phenyl acrylate, (methyl) benzyl acrylate such (methyl) benzyl acrylate；By (methyl) acrylate etc. that terpene compound derivatives alcohol obtains.Such (methyl) acrylate 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.
As can with other monomers of described (methyl) acrylic ester copolymer, can enumerate acrylic acid, methacrylic acid, Carboxyethyl acrylate, carboxy pentyl acrylate, itaconic acid, maleic acid, fumaric acid .beta.-methylacrylic acid, iso-crotonic acid etc. are containing carboxylic The monomer of base；
(methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid propoxy ethyl, (methyl) acrylate, butoxy ethyl, (methyl) ethioxy propyl ester such (methyl) alkoxyalkyl acrylate system Monomer；
The salt such as (methyl) alkali metal salts of acrylic acids；
Two (methyl) acrylate of ethylene glycol, two (methyl) acrylate of diethylene glycol, two (first of triethylene glycol Base) acrylate, two (methyl) acrylate of Polyethylene Glycol, two (methyl) acrylate of propylene glycol, the two of dipropylene glycol (methyl) acrylate, two (methyl) acrylic acid of two (methyl) acrylate such (gathering) aklylene glycol of tripropylene glycol Ester monomer；
Trimethylolpropane tris (methyl) acrylate such polynary (methyl) acrylate monomer；
The vinyl esters such as vinyl acetate, propionate；
Vinylidene chloride, (methyl) acrylic acid-2-chloroethene ester such vinyl halides based compound；
2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline are such Oxazoline base contains polymerizable compound；
(methyl) acryloyl aziridine, (methyl) acrylic acid-2-aziridine base ethyl are such containing azepine The polymerizable compound of cyclopropane base；
Allyl glycidyl ether, (methyl) glycidyl base ether, (methyl) acrylic acid-2-ethyl shrink sweet The such vinyl monomer containing epoxy radicals of oleyl ether；
(methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, lactone and (methyl) acrylic acid-2-hydroxyl The such vinyl monomer containing hydroxyl of addition product of ethyl ester；
The copolymer of polypropylene glycol, Polyethylene Glycol, polytetramethylene glycol, polytetramethylene glycol, Polyethylene Glycol and polypropylene glycol, Polytetramethylene glycol is combined with (methyl) acryloyl group, styrene with the end of the such poly alkylene glycol of copolymer of Polyethylene Glycol The macromonomer of the unsaturated group such as base, vinyl；
Fluorine replaces the such fluorine-containing vinyl monomer of (methyl) alkyl acrylate；
The monomer containing anhydride group such as maleic anhydride, itaconic anhydride；
The aromatic ethenyl compound system monomers such as styrene, α-methyl styrene, vinyltoluene；
The such vinyl monomer containing reactive halogen of 2-chloroethyl vinyl ether, monochloro acetic acid vinyl acetate；
(methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-ethoxy (methyl) Acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, N-methoxy ethyl (methyl) acrylamide, N-butoxymethyl The such vinyl monomer containing amide groups of (methyl) acrylamide, N-acryloyl morpholine；
N-(methyl) acryloyl-oxy methylene butanimide, N-(methyl) acryloyl-6-oxygen hexa-methylene succinyl are sub- The butanimide system monomers such as amine, N-(methyl) acryloyl-8-oxygen hexa-methylene butanimide；
N-N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenyl maleoyl The maleimide system monomers such as imines；
N-methyl clothing health acid imide, N-ethyl clothing health acid imide, N-butyl clothing health acid imide, N-octyl group clothing health acid imide, The clothing health imide series lists such as N-2-ethylhexyl clothing health acid imide, N-cyclohexyl clothing health acid imide, N-lauryl clothing health acid imide Body；
NVP, N-methyl ethylene ketopyrrolidine, N-vinylpyridine, N-vinylpiperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-vinyl are disliked Azoles, N-(methyl) acryloyl-2-Pyrrolidone, N-(methyl) Antiepilepsirin, N-(methyl) acryloyl pyrrolidine, N-vinyl Morpholine, N-vinyl pyrazoles, N-vinyl isoxazole, N-vinylthiazole, N-vinyl isothiazole, N-vinyl pyridazine etc. contain Nitrogen condensed ring system monomer；
N-vinylcarboxylic acid amide type；
The lactams system monomers such as N-caprolactam；
The cyanoacrylate monomers such as (methyl) acrylonitrile；
(methyl) acrylate, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, N- (methyl) acrylate system monomers such as dimethylamino ethyl ester, (methyl) tbutylaminoethylacrylate；
The monomer containing imide such as N-cyclohexylmaleimide, isopropylmaleimide；
The monomer containing isocyanuric acid ester group such as 2-isocyanuric acid ester group ethyl (methyl) acrylate；
Vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, pi-allyl trimethoxy silicon The such ethylene containing organosilicon of alkane, trimethoxysilylpropyl allyl amine, 2-methoxy ethoxy trimethoxy silane Base monomer；
(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) The own ester of dihydroxypropyl, (methyl) dihydroxypropyl monooctyl ester, (methyl) dihydroxypropyl ester in the last of the ten Heavenly stems, (methyl) dihydroxypropyl Laurel The monomer of the hydroxyls such as (methyl) hydroxyalkyl acrylates such as base ester, (4-Hydroxymethyl-cyclo-hexyl) methyl methacrylate；
(methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylate containing fluorine atom, silicone (methyl) acrylate Etc. the acrylic ester monomer with condensed ring, halogen atom, silicon atom etc.；
The olefinic monomers such as isoprene, butadiene, isobutene.；
The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether system monomer；
Alkene or the dienes such as ethylene, butadiene, isoprene, isobutene.；
The vinyl ethers such as vinyl alkyl ethers；
Vinyl chloride；
And, monomer end after vinyl polymerization there is the macromonomer class etc. of free-radical polymerised vinyl.This A little monomers can individually or combine and described (methyl) acrylic ester copolymer.
As described acrylic acid oligomer, such as, can enumerate cyclohexyl methacrylate (CHMA) different with methacrylic acid The copolymer of the copolymer of butyl ester (IBMA), cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA), Methyl methacrylate (MMA) and the copolymer of isobornyl methacrylate (IBXMA), cyclohexyl methacrylate (CHMA) It is total to acrylamide (DEAA's) with copolymer, the cyclohexyl methacrylate (CHMA) of acryloyl morpholine (ACMO) Polymers, 1-adamantyl acrylate (ADA) and the copolymer of methyl methacrylate (MMA), methacrylic acid bicyclo-pentyl ester (DCPMA) with the copolymer of isobornyl methacrylate (IBXMA), methacrylic acid bicyclo-pentyl ester (DCPMA) and methyl-prop The copolymer of e pioic acid methyl ester (MMA), methacrylic acid bicyclo-pentyl ester (DCPMA) are total to NVP (NVP's) Polymers, methacrylic acid bicyclo-pentyl ester (DCPMA) and the copolymer of hydroxyethyl methylacrylate (HEMA), methacrylic acid bicyclo- Pentyl ester (DCPMA) and the copolymer of acrylic acid (AA), methacrylic acid bicyclo-pentyl ester (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), acrylic acid bicyclo-pentyl ester (DCPA), 1- Adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA), methyl methacrylate (MMA) each all Polymers etc..
And then, described acrylic acid oligomer can also import to be had and epoxy radicals or the sense of the reactivity of NCO Base.As the example of such functional group, hydroxyl, carboxyl, amino, amide groups, sulfydryl can be enumerated, make acrylic acid oligomer Time, it is possible to use there is the monomer of such functional group.
Described acrylic acid oligomer is made (methyl) acrylic monomer and other (first with ester ring type structure Base) copolymer of acrylate monomer or combined polymerization monomer time, there is (methyl) acrylic monomer of ester ring type structure Content ratio, is more than 5 mass % in the whole monomers constituting acrylic acid oligomer, more than preferably 10 mass %, more excellent Elect more than 20 mass % as, more preferably more than 30 mass % (typically smaller than 100 mass %, preferably 90 mass % with Under).If containing (methyl) acrylic monomers with ester ring type structure more than 5 mass %, then can not reduce transparent Property and make adhesion (bonding) property improve.
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 the crosslinking of adhesion agent composition is usually in coating viscous Carry out after agent compositions but it also may the adhering agent layer formed by the adhesion agent composition after cross-linking is transferred to support membrane On Deng.It addition, the method forming adhering agent layer on described support membrane is not particularly limited, such as, can make as follows: by institute State adhesion agent composition to be coated on support membrane, by dry removings such as polymer solvents, support membrane forms adhering agent layer.It After, the purpose such as the adjustment moved for the composition of adhering agent layer, adjustment of cross-linking reaction, it is also possible to carry out maintenance.It addition, will be viscous Agent compositions and be coated on when making adhesive sheet on support membrane, in order to be uniformly coated on support membrane, it is also possible to described Adhesion agent composition adds more than one solvent beyond polymer solvent again.
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, about preferably 10～100 μm.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 (including the situation for surface protection film) is, by gluing used by described adhesive sheet The bonding plane of oxidant layer at 70 DEG C, be pasted on the stripping speed of (Polarizer surface) on TAC face after 1 week (high temperature through time preserve after) Release band voltage when spending 30m/ minute is less than 0.5kV (absolute value), preferably below 0.4kV, more preferably below 0.3kV.If Described release band voltage is more than 0.5kV, such as, may cause the damage of liquid crystal driver etc., is inappropriate.
＜ 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.Particularly having for solid under room temperature (25 DEG C) Even if the ionic compound of organic cation and above-mentioned organopolysiloxane are the most also stable, there is phase interaction With, such that it is able to by high temperature through time preserve after stripping charge constrain prepare low.And then, by having antistatic backing, it is also possible to Make the sheet resistance value of antistatic backing through time stable, overall as adhesive sheet, be pasted on adherend, even if high temperature through time preserve During the described adhesive sheet of rear stripping, it is possible to so that stripping charge stability provides, be useful.
＜ 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 State aqueous-dispersible conductive polymer solution formed antistatic backing, then be prone 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 trade name having Rhizoma Sparganii Li Yang company The product etc. of " 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 The cationic antistatic agent of the cationic functional groups such as base；Sulfonate, sulfuric acid, phosphonate, phosphate ester salt etc. have the moon The anionic property antistatic agent of ionic functional group；Alkyl betaine and derivant thereof, imidazoline and its derivative, alanine and The amphion antistatic agents such as its derivant；Amino alcohol and derivant, glycerol and derivant thereof, Polyethylene Glycol and derivative The nonionic antistatic agents such as thing；By described cationic, anionic property, amphion there is ionic conductivity base (example Such as, quaternary ammonium salt base) monomer polymerization or combined polymerization and the ionic-conductive polymer that obtains；Polythiophene, polyaniline, polypyrrole, The electric conductive polymers such as polymine, allyl amine based polymer.Such antistatic agent can be used alone a kind, it is possible to So that two or more is 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 property antistatic agent, amphion can be enumerated Antistatic agent, nonionic antistatic agent, will there is the ionic conductivity of described cationic, anionic property, amphion 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 The lower alkyl esters (ester of the monohydric alcohol with carbon number 1～3 being such as) etc. of carboxylic acids.
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, bisphenol-A.As other example, the alkylene oxide addition product of these compounds can be enumerated (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 wax etc.), mineral system wax (lignite wax etc.), higher fatty acids (cerinic acid etc.), neutral fat (Petiolus Trachycarpi Acid glycerol three ester 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 to be substantially free of the side of described silicone-based lubricant, fluorine base lubricant etc. Formula is implemented.But, in the limit of application effect the most significantly damaging technology disclosed herein, so-called lubricant, do not arrange Except containing the silicone used for other purposes (such as, as the defoamer of antistatic backing formation coating material described later) Based 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 by include by liquid composition (antistatic backing formation coating material, Antistatic agent compositions) give the method for support membrane and formed well, described liquid composition is described electric conductivity to be polymerized The compositions such as thing composition and the additive used as required are dissolved in and are formed in suitable solvent (water etc.).The most preferably adopt Using the following method: described coating material is coated first of support membrane and makes it be dried, cured is carried out as required (heat treatment, UV treatment etc.).The NV (nonvolatile component) of described coating material, such as, can be set to below 5 mass % (allusion quotation Type ground 0.05～5 mass %), it is suitable for being typically set to below 1 mass % (typically 0.10～1 mass %).Form thickness During little antistatic backing, preferably the NV of described coating material is set to such as 0.05～0.50 mass % (such as 0.10～0.40 Quality %).By using 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/), 23 DEG C × 50%RH place after 1 day (initial stage) and 70 DEG C place 1 week after (high temperature through time preservation It is both preferably afterwards) less than 1.0 × 1011, more preferably less than 5.0 × 1010, further preferably less than 3.0 × 1010.Show The adhesive sheet of the sheet resistance value in the range of described, such as abstaining from electrostatic as liquid crystal cell, semiconductor device etc. The adhesive sheet used in the processing of article or handling process etc., it is possible to be well used.Here, described sheet resistance value is permissible By use commercially available determination of insulation resistance device 23 DEG C, the sheet resistance value that measures in the environment of 50%RH 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 left and right 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 between the back side and antistatic backing, such as, can be the layer (described antistatic backing) comprising antistatic composition.It is arranged in support Layer before film and between adhering agent layer, such as, can be to improve adhering agent layer to described second priming coat throwing anchor (primer layer), antistatic backing etc..Can also be following adhesive sheet: at support membrane former configuration antistatic backing, at antistatic backing On configure primer layer, the adhesive sheet of composition of configuration adhering agent layer it on.
The optics that the optics of the present invention is preferably protected by described adhesive sheet.Described adhesive sheet is owing to using Surface protection purposes in time processing, carry, deliver etc., so for the surface protecting described optics (Polarizer etc.), It is useful.Particularly under high temperature through time process after, generally by the antistatic agent infiltration to adherend (optics etc.) Deng, there is (transfer) antistatic agent in adherend surface tails off, and stripping charge characteristic is poor, but the optics of the present invention due to Protected by described adhesive sheet, therefore from adherend (Polarizer etc.) peel off adhesive sheet (surface protection film) time, even if with just paste The situation that after conjunction, (initial stage) carries out peeling off compares, and does not find being substantially increased of release band voltage, though high temperature through time preserve after, Stripping charge stability is the most excellent, therefore in electrostatic becomes the technical field that the optics of serious problems, electronic unit are relevant, right It is highly useful in antistatic purposes.
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 weight 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
Acrylic acid 2-hydroxy methacrylate (HEA) :-15 DEG C
Acrylic acid 4-hydroxybutyl (HBA) :-32 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).
＜ initial stage and high temperature through time preserve after mensuration ＞ of release band voltage
Adhesive sheet is cut into wide 70mm, the size of long 130mm, after peeling off dividing plate, is connected on hands roll-in and fits in advance On the TAC Polarizer on acrylic board (thick 2mm, wide 70mm, long 100mm) having removed electric (Dong electrician company system, SEG1423DU Polarizer, wide 70mm, long 100mm) surface (TAC face) so that 30mm is exposed in an end of adhesive sheet.
About (high after placing after 1 day (the release band voltage at initial stage) under 23 DEG C × 50%RH and placing at 70 DEG C 1 week Release band voltage after preserving during warming the meridian), as it is shown in figure 1, sample is arranged on precalculated position.An end of 30mm will be exposed It is fixed on sutomatic winding machine, within 30m/ minute, peels off in the way of (peeling off at a high speed) by peel angle 150 °, peeling rate.With The potential measurement machine (springtime Motor Corporation's system, KSD-1030) being fixed on Polarizer middle position measures the Polarizer now produced The current potential (release band voltage: absolute value, kV) on surface.Carry out in the environment of 23 DEG C × 50%RH during mensuration.
The bonding plane of the adhering agent layer that described adhesive sheet is used in the condition of 23 DEG C × 50%RH to TAC face (polarisation Plate surface) paste (placement) after 1 day, within 30m/ minute, carry out peeling off (stripping at a high speed), now with peel angle 150 °, peeling rate The current potential (release band voltage: absolute value, kV) on the Polarizer surface produced preferably smaller than 0.5kV, more preferably below 0.4kV, More preferably below 0.3kV.If described release band voltage is more than 0.5kV, the most such as, can cause liquid crystal driver etc. Damage, be inappropriate.
TAC face (Polarizer surface) attaching (is put by the bonding plane of the adhering agent layer used by described adhesive sheet in 70 DEG C Put) after 1 day, within 30m/ minute, carry out peeling off (peeling off at a high speed), the Polarizer table now produced with peel angle 150 °, peeling rate The current potential (release band voltage: absolute value, kV) in face preferably smaller than 0.5kV, more preferably below 0.4kV, more preferably Below 0.3kV.If described release band voltage is more than 0.5kV, the most such as, can cause the damage of liquid crystal driver etc., be not conform to Fit.
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), in 23 DEG C with peeling rate 0.06mm/ minute, along shear direction tractive, by Heavy load (N/cm2) 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 withstand adherend and want the power of the shear direction produced during curling, no The slip of adhesive sheet, dislocation can occur, the curling of adherend can be suppressed, the most preferably.
＜ initial stage and high temperature through time preserve after 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, transfer in 23 DEG C × 50%RH After putting 1 day (initial stage sheet resistance) and after placing at 70 DEG C 1 week (high temperature through time preserve after sheet resistance), it is preferably to for Less than 1.0 × 1011, more preferably less than 5.0 × 1010, further preferably less than 3.0 × 1010.In the range of described in showing The adhesive sheet (surface protection film) of sheet resistance value, such as abstaining from electrostatic as liquid crystal cell, semiconductor device etc. The adhesive sheet used in the processing of article or handling process etc., can be utilized well.
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℃。
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 fatty family isocyanate compound that is six as cross-linking agent Isocyanuric acid ester body (Japanese polyurethane industrial group system, the COLONATE HX) 2 mass parts (solids of methylene diisocyanate Composition 2 mass parts), as crosslinking catalyst dibutyl tin laurate (1 mass % ethyl acetate solution) 3 mass parts (Gu Form point 0.03 mass parts), as ionic compound TBuA hexafluorophosphate (Tokyo chemical conversion industrial group system, TBA, fusing point 245 DEG C) 0.2 mass parts, the organopolysiloxane with oxyalkylene chain as the compound containing oxyethylene group (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-6020) 0.2 mass parts, carries out mix and blend, prepares 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 with solid component amount, electric conductive polymer becomes with solid Component is calculated as 75 mass parts, cross-linking agent is calculated as 10 mass parts with solid component amount, lubricant is calculated as 30 mass with solid component amount Part, 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 becomes with solid content Component is calculated as 100 mass parts, electric conductive polymer is calculated as 50 mass parts, cross-linking agent with solid content component amount with solid content component amount Being calculated as 10 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, electric conductive polymer with solid content composition gauge with solid content component amount Being 75 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: support membrane), it is coated with the arbitrary of described antistatic backing (back side inorganic agent A～D) The aqueous solution planted, makes dried thickness reach 30nm.This coating material being heated 1 minute at 130 DEG C makes it be dried, thus makes Become the support membrane of band antistatic backing having antistatic backing at the first mask of PET film.
＜ 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.Bonding, 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 2～14 and comparative example 1～3 ＞
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 initial stage of the adhesive sheet made and high temperature through time after release band voltage, shearing Power, initial stage and high temperature through time after sheet resistance value, sliding and lettering adaptation.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)
HEA: acrylic acid 2-hydroxy methacrylate (hydroxyl (methyl) acrylic monomer)
HBA: acrylic acid 4-hydroxybutyl (hydroxyl (methyl) acrylic monomer)
DEAA:N, N acrylamide
C/L: fragrance family isocyanate compound, trimethylolpropane/inferior cresyl vulcabond (Japanese polyurethane Industrial group's system, trade name: COLONATE L)
C/HX: fat family isocyanate compound, isocyanuric acid ester body (the Japanese poly-ammonia of hexamethylene diisocyanate Ester company system, trade name: COLONATE HX)
The double trifluoromethanesulfonimide (fusing point=35 DEG C) of TMHA: trimethyl ammonium (kishida chemical company system, from Sub-property compound)
HP:2-hexyl pyridine hexafluorophosphate (fusing point=45 DEG C) (kishida chemical company system, ionic compound)
BMP:1-butyl-4-picoline hexafluorophosphate (fusing point=42 DEG C) (Tokyo chemical conversion industrial group system, ion Property compound)
MEIM:1-methyl-3-ethyl imidazol(e) hexafluorophosphate (fusing point=61 DEG C) (Tokyo chemical conversion industrial group system, from Sub-property compound)
BP:1-butyl-pyridinium hexafluorophosphate (fusing point=75 DEG C) (Tokyo chemical conversion industrial group system, ionic compound)
TBA: TBuA hexafluorophosphate (fusing point=245 DEG C) (Tokyo chemical conversion industrial group system, ionic compound)
KF6020: have oxyalkylene chain organopolysiloxane (HLB value 4) (chemical industrial company of SHIN-ETSU HANTOTAI system, trade name: KF-6020)
KF353: have oxyalkylene chain organopolysiloxane (HLB value 10) (chemical industrial company of SHIN-ETSU HANTOTAI system, trade name: KF-353)
KF355A: have oxyalkylene chain organopolysiloxane (HLB value 12) (chemical industrial company of SHIN-ETSU HANTOTAI system, trade name: KF-355A)
Compound containing EO base: the compound (there is the compound of oxyalkylene chain) containing oxyethylene group
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, high temperature through time preserve after (70 DEG C 1 week after) Release band voltage (high temperature through time preserve after stripping charge stability) excellent.On the other hand, can confirm that and do not contain ion Property the comparative example 1 of compound and comparative example 2 in, from the initial stage, release band voltage is high, high temperature through time preserve even release band voltage also It is high.Shearing force is excellent.Furthermore it is possible to confirm in comparative example 3, although containing ionic compound, but high temperature through time preserve After sheet resistance value difference, high temperature through time preserve after release band voltage the poorest.It addition, in all of comparative example, shearing force is all Difference.
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 in the adhesive sheet of the embodiment 1～5,7～11 and 13 of the antistatic backing of back side inorganic agent A that manufactures, full All assessment items of sheet resistance, sliding and lettering adaptation that foot causes because of antistatic backing.On the other hand, about use The antistatic backing of back side inorganic agent B～D that a part does not coordinate desired raw material and manufactures, 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.
Symbol description
1 potential measurement device
2 adhesive sheets
3 Polarizers
4 acrylic boards
5 fixed stations

Claims (7)

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 is pasted at 70 DEG C on TAC face after 1 week when peeling rate is 30m/ minute The absolute value peeling off electrostatic pressure less than 0.5kV.
Adhesive sheet the most according to claim 1, it is characterised in that
Described adhesion agent composition contain have oxyalkylene group chain compound and at room temperature 25 DEG C for solid have organic The ionic compound of cation.
Adhesive sheet the most according to claim 2, it is characterised in that
The described compound with oxyalkylene group chain is the organopolysiloxane with oxyalkylene group chain.
4. according to the adhesive sheet according to any one of claims 1 to 3, it is characterised in that
Described adhesion agent composition contains (methyl) acrylic acid series polymeric compounds with hydroxyl and carboxyl.
5. according to the adhesive sheet according to any one of Claims 1 to 4, 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 5, it is characterised in that
Described antistatic agent compositions contains the fatty acid amide as lubricant further.
7. an optics, it is characterised in that
Protected by the adhesive sheet according to any one of claim 1～6.
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