CN106459687A - Adhesive sheet and optical member - Google Patents

Adhesive sheet and optical member Download PDF

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Publication number
CN106459687A
CN106459687A CN201580019603.9A CN201580019603A CN106459687A CN 106459687 A CN106459687 A CN 106459687A CN 201580019603 A CN201580019603 A CN 201580019603A CN 106459687 A CN106459687 A CN 106459687A
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CN
China
Prior art keywords
methyl
acid
adhesive sheet
agent
acrylic acid
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Pending
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CN201580019603.9A
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Chinese (zh)
Inventor
片冈贤
片冈贤一
天野立巳
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN106459687A publication Critical patent/CN106459687A/en
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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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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

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

Abstract

Provided are: an adhesive sheet having excellent shearing force during low-speed peeling and capable of suppressing curling of an adherend when pasted to the adherend; and an optical member having the adhesive sheet pasted thereto as surface protection. This adhesive sheet has an adhesive agent layer formed from an adhesive agent composition on one or both surfaces of a support film and is characterized by having a shear force of at least 10N/cm2 when peeled in the shear direction at a peeling speed of 0.06 mm/min after an adhesion area of 1 cm2 of the adhesive agent layer has been pasted on to a TAC polarizing plate for 30 minutes at 23 DEG C.

Description

Adhesive sheet and opticses
Technical field
The present invention relates to adhesive sheet and the opticses protected by described adhesive sheet.
The adhesive sheet of the present invention, as Polarizer, wavelength plate, phase contrast used in protection liquid crystal display etc. The surface protection film that plate, optical compensation films, reflector plate, briliancy improve the purposes of optical component surfaces such as film and use, is useful 's.
Background technology
In recent years, opticses, the transport of electronic unit or to printed base plate installation when, all parts with regulation State that piece has been packed or be pasted with the state of adhesive tape and transported.Wherein, surface protection film is particularly widely made In optics, the field of electronic unit.
Surface protection film typically fits in adherend (by protective) by coating the sticker of support membrane side, is used for Prevent adherend processing, carrying when produce damage, dirt purpose (patent documentation 1).For example, the panel of liquid crystal display By the optical member adherings such as Polarizer, wavelength plate being formed in liquid crystal cell by sticker.Surface protection film passes through adhesion Agent and be bonded on these opticses, be prevented from adherend processing, carrying when produce damage, dirt.
It is desirable to crimp scalability for surface protection film, so that when being pasted on adherend (Polarizer etc.), Paste in the adherend (Polarizer etc.) of surface protection film, do not produced unnecessary curling, (curling refers to for undesirable curling Turn over and stick up phenomenon, for example, arbitrary surface side globality of tabular object turn over stick up phenomenon, tabular object globality ground up-and-down Turn over and stick up phenomenon etc.).If producing unnecessary curling, undesirable curling, operability is poor, for example, Polarizer etc. is glued When thing is pasted on liquid crystal cell, sometimes a problem that the intrusion of gassing.
In addition, when flat adherend occurs curling, in the adhering agent layer of the surface protection film fitting in adherend, with Curling power together works on shear direction, due to this power, occurs lentamente to slide between adherend and adhering agent layer, wrong Position etc., therefore it is required that improve shearing force when low speed is peeled off.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 9-165460 publication
Content of the invention
The technical problem to be solved in the present invention
Therefore, the invention aims to solving the problems, such as in conventional adhesive sheet, when providing a kind of low speed to peel off The excellent adhesive sheet of shearing force.
Solution to problem
That is, the adhesive sheet of the present invention is characterised by, is to have to be combined by sticker on the single or double of support membrane The adhesive sheet of the adhering agent layer that thing is formed, by the adhesion area 1cm of described adhering agent layer2Fit on TAC Polarizer, in 23 DEG C Lower paste 30 minutes after with peeling rate 0.06mm/ minute along shear direction peel off when shearing force as 10N/cm2More than.
The adhesive sheet of the present invention is preferably described adhesion agent composition and contains (methyl) acrylic acid with hydroxyl and carboxyl Based polymer.
The adhesive sheet of the present invention is preferably in terms of the monomer component total amount to constitute described (methyl) acrylic acid series polymeric compounds, contains There is hydroxyl (methyl) acrylic monomer of more than 5.1 mass %.
The adhesive sheet of the present invention is preferably in terms of the monomer component total amount to constitute described (methyl) acrylic acid series polymeric compounds, contains There is 0.01 mass % less than 0.5 mass % containing carboxyl (methyl) acrylic monomer.
The adhesive sheet of the present invention preferably has anti-quiet in the one side with the described support membrane of described adhering agent layer opposition side Electric layer, described antistatic backing is by containing the poly- aminobenzenesulfonic acid as electric conductive polymer composition, the polyester tree as binding agent Fat and the antistatic agent compositionss as the isocyanates system cross-linking agent of cross-linking agent are formed.
The adhesive sheet of the present invention is preferably described antistatic agent compositionss and contains the fatty acid acyl as lubricant further Amine.
The opticses that the opticses of the present invention are preferably protected by described adhesive sheet.
Invention effect
The adhesive sheet of the present invention is excellent due to shearing force when low speed is peeled off, and when therefore fitting in adherend, can suppress In adherend, unnecessary curling, undesirable curling, are useful.
Specific embodiment
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 typically known as adhesive sheet, adhesive tape, adhesion label, adhesive film Etc. the material of form, (for example, Polarizer, wavelength plate etc. are used as panel of LCD composition to be particularly suitable as opticses The opticses of key element) processing when, carrying when protection optical component surfaces surface protection film.Adhesion in described adhesive sheet Oxidant layer is it is typical that be continuously formed, but is not limited to described form, for example, can also be to form the rule such as point-like, striated Or the adhering agent layer of random pattern.In addition, adhesive sheet disclosed herein can also be web-like, can also 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 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) are come to use.Adhesion using front (that is, to before adherend attaching) Piece 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 that single or double in support membrane has and is formed by adhesion agent composition Adhering agent layer.The resin material constituting described support membrane can use without particular limitation, for example, preferably use the transparency, machine The material of the excellents such as tool intensity, heat stability, moisture block, isotropism, flexibility, dimensional stability.Particularly logical Cross support membrane and there is flexibility, adhesion agent composition can be coated with roll coater etc., can be rolled into a roll, be useful.
As described support membrane (base material), for example, it is preferable to can use by with polyethylene terephthalate (PET), The polyester based polymers such as PEN (PEN), polybutylene terephthalate (PBT)；Diacetyl cellulose, three second The cellulose-based polymer such as acyl cellulose；Merlon based polymer；Acrylic acid series polymeric compounds such as polymethyl methacrylate etc. Resin material as main resinous principle (main constituent in resinous principle, typically account for the composition of more than 50 mass %) The plastic foil constituting is used as described support membrane.As the other examples of described resin material, can enumerate：Polystyrene, third The styrenics such as alkene nitrile-styrol copolymer；Polyethylene, polypropylene, there is ring-type or the polyene of norborene structure The olefin polymers such as hydrocarbon, ethylene-propylene copolymer；Vinyl chloride-based polymer；The acyls such as nylon 6, nylon66 fiber, aromatic polyamide Amine system polymer etc. is used as resin material.As the still other examples of described resin material, can enumerate：Imide series gather Compound, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, ethenol system polymerization 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 being formed by the mixture of more than two kinds of above-mentioned polymer.
As described support membrane, preferably can be using the plastic foil being formed by transparent thermoplastic resin material.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 easily powered property originally.
Constitute in the resin material of described support membrane, antioxidant, UV absorbent, increasing can also be coordinated as needed Mould the various additives such as agent, coloring agent (pigment, dyestuff etc.).The first face (setting antistatic backing side for described support membrane Surface) it is also possible to implement such as Corona discharge Treatment, plasma treatment, ultraviolet treatment with irradiation, acid treatment, alkali process, bottom Coating of varnish etc. is known or usual surface treatment.It is quiet with anti-that such surface treatment for example could be for raising support membrane The process of the adaptation of electric layer.Can preferably employ such to surface importing hydroxyl (- OH base) the isopolarity group of support membrane Surface treatment.In addition, the second face to support membrane (forming the surface of adhering agent layer side) can also implement same as described above Surface treatment.Described surface treatment could be for improving the place of film and the adaptation (the throwing anchor of adhering agent layer) of adhering agent layer Reason.
In addition, the adhesive sheet of the present invention, can have antistatic backing on support membrane, there is electrostatic-proof function Under, as described support membrane, it is possible to use carry out the plastic foil of antistatic process further.By using described support Film, the adhesive sheet itself after can suppressing to peel off is powered, therefore preferably.In addition, support membrane is plastic foil, real to described plastic foil Apply antistatic process, be obtained in that and reduce powered and excellent to the anti-static ability of the adherend adhesive sheet of adhesive sheet itself. Here, as the method giving electrostatic-proof function, it is not particularly limited, it is possible to use known method, for example, can lift Go out：It is coated with the method for static electricity resistance resin being formed by antistatic agent and resinous principle, coating contains electric conductive polymer, conduction Property the method for the method of electroconductive resin, evaporation or plated conductive material of the material and side mixing antistatic agent etc. Method etc..
As the thickness of described support membrane, usually 5～200 μm, preferably 10～100 μm about.Described support membrane If thickness is in described scope, to adherend laminating workability and from adherend peel off workability excellent, therefore 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, as long as there is adhesive material then can use with no particular limitation, For example, acrylic acid seriess sticker, carbamate system sticker, synthetic rubber system sticker, natural rubber system sticker, silicone It is sticker etc..Wherein, more preferably it is selected from acrylic acid seriess sticker, carbamate system sticker and silicone-based sticker At least one in the group of composition, particularly preferably using the acrylic acid seriess sticker using (methyl) acrylic acid series polymeric compounds.
Used in the present invention, described adhesion agent composition preferably comprises (methyl) acrylic acid seriess with hydroxyl and carboxyl Polymer.By using described (methyl) acrylic acid series polymeric compounds with hydroxyl and carboxyl, thus, described hydroxyl can be easy Ground carry out crosslinking control, described carboxyl can improve shearing force or prevent adhesion strength through when rise, therefore become preferred side Formula.Shearing force due to sticker (layer) improves, and by described sticker is fitted in adherend, can suppress the volume of adherend Song, can suppress (interface) between sticker and adherend to slide, misplace, this is particularly preferred.Here, in the present invention (methyl) acrylic acid series polymeric compounds refer to acrylic acid series polymeric compounds and/or metha crylic polymer, (methyl) acrylic acid Ester refers to acrylate and/or methacrylate.
In addition, described (methyl) acrylic acid series polymeric compounds are by using described hydroxyl (methyl) acrylic monomer conduct Monomer component it is easy to control crosslinking etc. of adhesion agent composition, and then the improvement of wettability that brings of easily controllable flowing with viscous The cohesiveness of agent (layer), the balance of shearing force.And then, in the case of adding antistatic agent in sticker, can make with general The differences such as the carboxyl that works for cross-linking part, sulphonate-base, hydroxyl is due to having and the ionic chemical combination as antistatic agent The interaction of the appropriateness such as thing, even if therefore can also suitably use at the aspect of static electricity resistance very much.
The adhesive sheet of the present invention is preferably：Total with respect 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 described scope, the cohesiveness of the wettability of easily controllable adhesion agent composition and sticker (layer), The balance of shearing force, therefore preferably.
As described hydroxyl (methyl) acrylic monomer, for example can enumerate (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) third Olefin(e) acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester, acrylic acid (4- hydroxyl Ylmethyl cyclohexyl) methyl ester, N- methylol (methyl) acrylamide etc..
In addition, described (methyl) acrylic acid series polymeric compounds by using described containing carboxyl (methyl) acrylic monomer conduct Monomer component, such that it is able to suppress adhesive sheet (adhering agent layer) adhesion strength through when rise, releasable, adhesion strength rise anti- Only property and workability are excellent, in addition, not only the cohesiveness of adhering agent layer is excellent, and shearing force is also excellent, is preferred.
The adhesive sheet of the present invention is preferably：Total with respect 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, can suppress adhesion strength through when rise, releasable, adhesion strength rise preventing property with And workability is excellent.In addition, not only the cohesiveness of adhering agent layer is excellent, and shearing force is also excellent, is preferred.Here, such as There is the big such acid functional group of carboxyl of a lot of polarity effects in fruit, then when coordinating the ionic compound as antistatic agent, The acid functional groups such as carboxyl are interacted with ionic compound, thus hinder ionic conduction, and electrical efficiency reduces, and may become Sufficient static electricity resistance cannot be obtained, thus not preferred.
As described containing carboxyl (methyl) acrylic monomer, for example, can enumerate：(methyl) acrylic acid, (methyl) propylene Sour carboxyethyl, (methyl) acrylic acid carboxyl pentyl ester, 2- (methyl) acryloyl-oxyethyl hexahydro phthalic acid, 2- (methyl) third Alkene acryloxypropylethoxysilane hexahydro phthalic acid, 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..
Used in the present invention, described adhesion agent composition contains described (methyl) acrylic acid series polymeric compounds, as long as having Adhesive (methyl) acrylic acid series polymeric compounds, are not particularly limited, as the main constituent of monomer component, preferably use tool There is (methyl) acrylic monomer of the alkyl that carbon number is 1～14, more preferably there is the alkyl that carbon number is 4～14 (methyl) acrylic monomer.As described (methyl) acrylic monomer, can come one kind or two or more as main constituent Use.Here, the meaning of " main constituent " is mixing ratio highest.
As the specific example of described (methyl) acrylic monomer with the alkyl that carbon number is 1～14, for example (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding can be enumerated Ester, (methyl) tert-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) ethyl acrylate, (methyl) acrylic acid 2- ethyl Own ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid are different Nonyl ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid n-dodecane base ester, (methyl) third Olefin(e) acid n-tridecane base ester, (methyl) n-myristyl base ester etc..
Wherein, when the adhesive sheet that the present invention is used 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, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (first Base) acrylic acid n-dodecane base ester, (methyl) acrylic acid n-tridecane base ester, (methyl) n-myristyl base ester etc. have Carbon number is (methyl) acrylate of 6～14 alkyl.By using having (the first of the alkyl that carbon number is 6～14 Base) acrylate, easily will the adhesion strength of adherend be controlled low, releasable is excellent.
The adhesive sheet of the present invention is preferably：In terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, Containing described (methyl) acrylic monomer 50～94.99 mass % with the alkyl that carbon number is 1～14, more preferably 60 ～94.9 mass %, further preferred 70～94.8 mass %, most preferably 80～94.7 mass %.By in described scope, Adhesion agent composition has the wettability of appropriateness, and the cohesiveness of sticker (layer) is also excellent, is preferred.
In addition, as other polymerizable monomer compositions, for be readily obtained adhesive performance balance the reasons why, Ke Yi Do not damage in the range of effect of the present invention using the glass transition temperature for adjusting (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 hydroxyl (methyl) acrylic monomer described used in described (methyl) acrylic acid series polymeric compounds, contain carboxylic Base (methyl) acrylic monomer and other beyond there is (methyl) acrylic monomer of the alkyl that carbon number is 1～14 Polymerizable monomer, as long as in the range of the characteristic not damaging the present invention, then can be not particularly limited to use.For example permissible Suitably using the raising cohesiveness of the monomer of cyano-containing, vinyl ester monomers, aromatic vinyl monomer etc., the one-tenth of thermostability Point, the monomer of amide-containing, the monomer containing imide, the monomer containing amino, the monomer containing epoxy radicals, N- acryloyl group Quinoline, vinyl ether monomers etc. improve adhesion (bonding) power or have had the composition of the functional group of Cross-linked basic point effect.These gather Conjunction property monomer can be used alone, and in addition can also be used in mixed way two or more.
As the monomer of described cyano-containing, for example, can enumerate acrylonitrile, methacrylonitrile.
As described vinyl ester monomers, for example, can enumerate vinyl acetate, propionate, vinyl laurate Deng.
As described aromatic vinyl monomer, for example can enumerate styrene, chlorostyrene, 1-chloro-4-methyl-benzene, α- Methyl styrene, other substituted phenylethylene etc..
As the monomer of described amide-containing, for example, 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, for example, can enumerate N-cyclohexylmaleimide, isopropyl maleimide Amine, N- N-cyclohexylmaleimide, clothing health acid imide etc..
As the described monomer containing amino, for example, 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, for example, can enumerate (methyl) glycidyl acrylate, (methyl) propylene Acid methyl ethylene oxidic ester, allyl glycidyl ether etc..
As described vinyl ether monomers, for example, 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 Carbon number is other polymerizable monomers beyond (methyl) acrylic monomer of 1～14 alkyl, is constituting described (first Base) acrylic acid series polymeric compounds monomer component total amount (whole monomer component) in, preferably 0～40 mass %, more preferably 0～ 30 mass %.By using other polymerizable monomers described, can suitably adjust in described scope with as antistatic agent Good the interacting and good releasable of ionic compound.
The weight average molecular weight of described (methyl) acrylic acid series polymeric compounds is 100,000～5,000,000, preferably 200,000～4,000,000, More preferably 300,000～3,000,000.When weight average molecular weight is less than 100,000, the cohesiveness of the sticker (layer) obtaining diminishes, because And have the tendency of to produce cull.On the other hand, when weight average molecular weight is more than 5,000,000, the mobility of polymer reduces, to adherend The moistening of (for example, as the Polarizer etc. of opticses) becomes insufficient, has the sticker group becoming adherend and adhesive sheet Tendency the reason foaming occurring between compound layer.Here, weight average molecular weight is to be measured by GPC (gel permeation chromatography) Arrive.
In 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, gather Compound is difficult to flow, and the such as moistening to adherend (for example, as the Polarizer etc. of opticses) becomes insufficient, has and becomes Tendency the reason foaming occurring 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 excellent adhesion agent composition of light fissility.Here, Change used monomer component, ratio of components by suitable, can be by the glass transition temperature of (methyl) acrylic acid series polymeric compounds Degree adjusts to described scope.
Used in the present invention, the polymerization of (methyl) acrylic acid series polymeric compounds is not particularly limited, and can pass through solution The known method such as polymerization, emulsion polymerization, polymerisation in bulk, suspension polymerisation being polymerized, particularly from the viewpoint of workability, to being glued From the aspect of the characteristics such as the low stain of thing, polymerisation in solution is preferred mode.In addition, the polymer of gained is random copolymerization Thing, block copolymer, alternate copolymer, graft copolymer etc..
For the adhesive sheet of the present invention, described adhesion agent composition can contain antistatic agent (antistatic composition), makees For described antistatic agent, ionic compound can be contained.As described ionic compound, can enumerate alkali metal salt and/ Or the ionic compound of low melting point (below 150 DEG C of fusing point).By containing these ionic compounds, giving excellent Static electricity resistance.
In addition, with respect to described (methyl) acrylic acid series polymeric compounds 100 mass parts, the content of described ionic compound is excellent Elect below 1 mass parts, more preferably 0.001～0.9 mass parts, more preferably 0.005～0.8 mass parts as.If In described scope, then easily take into account static electricity resistance and low stain, therefore preferably.
For the adhesive sheet of the present invention, described adhesion agent composition can contain the organic poly- silicon with polyoxyalkylene chain Oxygen alkane.Speculate by using described organopolysiloxane, when realizing the surface free energy reduction on sticker surface, peeling off at a high speed Light separation.
Described organopolysiloxane can suitably using the known organopolysiloxane with polyoxyalkylene chain, for example, As commercially available product, trade name X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889, KF- can be enumerated 351A、KF-352A、KF-353、KF-354L、KF-355A、KF-615A、KF-945、KF-640、KF-642、KF-643、KF- 6022nd, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (are SHIN-ETSU HANTOTAIs above Chemical industrial company's system), BY16-201, SF8427, SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ-2122, FZ-2164, FZ-2203, FZ-7001, SH8400, SH8700, SF8410, SF8422 (with Shang Shidongli Dow Corning Corporation system), IM22 (above, Asahi Chemical Industry watt gram company system), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (being MomentivePerformanceMaterials' system above), BYK-333, BYK- 307th, the commodity of BYK-377, BYK-UV3500, BYK-UV3570 (above Shi Bike Japanese firm system) etc..These can be independent Use, in addition two or more can also be used in mixed way.
The above-mentioned organopolysiloxane using as the present invention, HLB (hydrophile-lipophile balance, parent Hydrophile-lipophile balance value) value preferably 1～16, more preferably 3～14.If HLB value is outside described scope, to adherend Contaminative is deteriorated, and is inappropriate.
In addition, with respect 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 easily take into account static electricity resistance and light fissility (releasable), therefore preferably.
For the adhesive sheet (surface protection film) of the present invention, described adhesion agent composition preferably comprises cross-linking agent.In addition, In the present invention, described adhesion agent composition is used as adhering agent layer.For example, described adhesion agent composition contains described (methyl) During acrylic acid series polymeric compounds, by the suitable construction unit adjusting described (methyl) acrylic acid series polymeric compounds, structural ratio, crosslinking The selection of agent and add ratio etc. and carry out crosslinking, it is possible to obtain the more excellent adhesive sheet of thermostability (adhering agent layer).
As cross-linking agent used in the present invention, it is possible to use isocyanate compound, epoxide, melamine series Resin, aziridine derivative and metal chelate compound etc., particularly preferably using isocyanate compound.In addition, these Compound may be used alone, can also be 2 or more kinds in combination.
As described isocyanate compound (isocyanates system cross-linking agent), for example, can enumerate trimethylene two Carbimide. The aliphatic polymeric isocyanates such as ester, butene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate Class, the alicyclic isocyanide such as ring pentamethylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI) Esters of gallic acid, 2,4- toluenediisocyanates, 4,4 '-methyl diphenylene diisocyanate, xylylene diisocyanate (XDI) Deng aromatic isocyanate class, by described isocyanate compound allophanic acid ester bond, biuret linkage, isocyanurate-bond, The modified polyisocyanate modified bodies such as urea two ketonic bond, urea bond, carbodiimides key, uretonimine key, oxadiazines three ketonic bond. For example, as commercially available product, can enumerate trade name TAKENATE 300S, TAKENATE 500, TAKENATE D165N, TAKENATE D178N (being Mitsui Chemicals, Inc.'s system above), SUMIDUR T80, SUMIDUR L, DESMODUR N3400 (with On being Bayer polyurethane company system), MILLIONATE MR, MILLIONATE MT, COLONATE L, COLONATE HL, COLONATE HX (being Japanese polyurethane industrial group system above) etc..These isocyanate compounds can be used alone, and also may be used Be used in mixed way with two or more, can also and the isocyanate compound with 2 functional groups and 3 functional groups more than isocyanation esterification Compound is using.By and used with cross-linking agent, cohesiveness and resistance to repellency (cementability to curved surface) can be taken into account, can Obtain the more excellent adhesive sheet of bonding reliability (surface protection film).
As described epoxide, for example, can enumerate N, N, N ', N '-four glycidyl group-meta-xylene base diamidogen Double (N, the N- diglycidyl amino methyl) hexamethylene (business of (trade name TETRAD-X, Rhizoma Sparganii gas chemical company system), 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, for example, can enumerate trade name HDU, TAZM as commercially available product, TAZO (being mutual medicine work company system above) 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, for example, with described (methyl) acrylic acid series polymeric compounds for 100 mass parts Meter, preferably comprises 0.01～10 mass parts, further preferably 0.1～8 mass parts, further preferably 0.5～5 mass parts, Most preferably 1.0～2.5 mass parts.When described content is less than 0.01 mass parts, become not based on being cross-linked to form of cross-linking agent Fully, the cohesiveness of the adhering agent layer of gained diminishes, and sometimes can not obtain sufficient thermostability, in addition have the reason become cull Tendency.On the other hand, when content is more than 10 mass parts, the cohesiveness of polymer is big, and mobility reduces, to adherend (for example Polarizer) moistening become insufficient, have become between adherend and adhering agent layer (adhesion agent composition layer) occur foaming The reason tendency.Further, if cross-linked dosage is many, there is stripping charge characteristic and reduce.In addition, these cross-linking agent are permissible It is used alone, in addition 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, for example, 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 base 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 catalysts such as ferrum, iron chloride.These crosslinking catalysts can be using a kind it is also possible to and use two or more.
The content (usage amount) of described crosslinking catalyst is not particularly limited, and for example, is gathered with described (methyl) acrylic acid seriess Compound is 100 mass parts meters, substantially preferably 0.0001～1 mass parts, more preferably 0.001～0.5 mass parts.If institute In the range of stating, then when forming adhering agent layer, the speed of cross-linking reaction is fast, and the preservation life-span of adhesion agent composition is also elongated, becomes excellent The mode of choosing.
The chemical combination containing polyoxyalkylene chain can also be contained without organopolysiloxane in the adhesion agent composition of the present invention Thing.By containing above-claimed cpd in adhesion agent composition, it is possible to obtain the sticker more excellent to the wettability of adherend Compositionss.
As the concrete example of the described compound without organopolysiloxane containing polyoxyalkylene chain, for example, 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 are 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..
In addition, as the concrete example of the described acrylic compounds with polyoxyalkylene chain, can enumerate with oxidation (methyl) acrylate polymer of alkene.As described oxyalkylene group, from the viewpoint of ionic compound coordination, oxyalkylene The addition molal quantity of unit is preferably 1～50, more preferably 2～30, more preferably 2～20.In addition, described oxyalkylene group End can be script hydroxyl it is also possible to by alkyl, phenyl etc. replace.
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, for example, can enumerate methoxyl group-diethylene glycol (methyl) acrylate, methoxyl group-three second two Methoxypolyethylene glycol (methyl) acrylic ester type 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.
In addition, as described monomeric unit (composition), it is possible to use beyond described (methyl) acrylic acid epoxy alkyl ester Other monomers unit (composition).As the concrete example of other monomers unit, (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 Sour isobutyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) third The different monooctyl ester of olefin(e) acid, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid isodecyl ester, (methyl) acrylic acid n-dodecane ester, (methyl) acrylic acid n-tridecane ester, (methyl) n-myristyl Ester etc. has acrylate and/or the methacrylate of the alkyl that carbon number is 1～14.
And then, as the other monomers unit (composition) beyond described (methyl) acrylic acid epoxy alkyl ester it is also possible to suitably Using carboxylic (methyl) acrylate, (methyl) acrylate of phosphorous acidic group, (methyl) acrylate of cyano-containing, second Thiazolinyl esters, aromatic ethenyl compound, containing (methyl) acrylate of 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 without organopolysiloxane containing polyoxyalkylene chain is at least one There is in partly the compound of (gathering) ethylene oxide chain.By the compound of described (gathering) the ethylene oxide chain of cooperation, base polymer Thing is improved with the intermiscibility of antistatic composition, is suppressed well to the leakage of adherend, can obtain the adhesion of low stain Agent compositionss.When wherein, especially with PPG-PEG-PPG block copolymer, the excellent sticker of low stain can be obtained Compositionss.As the above-mentioned compound containing polyethylene oxide chain, (gathering) ethylene oxide chain is shared in described compound entirety Quality preferably 5～90 mass %, more preferably 5～85 mass %, more preferably 5～80 mass %, most preferably 5～ 75 mass %.
As the molecular weight of the above-mentioned compound without organopolysiloxane containing polyoxyalkylene chain, preferably use number and divide equally The compound of son amount (Mn) less than 50000, more preferably 200～30000, further preferred 200～10000, particularly preferred 200～ 5000.If Mn is excessive compared with 50000, the intermiscibility with acrylic acid series polymeric compounds is had to reduce, adhering agent layer occurs albefaction Tendency.If Mn is too small compared with 200, may be susceptible to produce the pollution that described polyoxyalkylene compounds cause.In addition, this In, Mn refers to the polystyrene conversion value obtaining by GPC (gel permeation chromatography).
In addition, the concrete example of the commercially available product as the above-mentioned compound without organopolysiloxane containing polyoxyalkylene chain, For example can enumerate Adeka Pluronic 17R-4, Adeka Pluronic 25R-2 (being ADEKA company system above), EMULGEN 120 (KAO. Corp. SA's system) etc..
As the use level of the above-mentioned compound without organopolysiloxane containing polyoxyalkylene chain, with described (methyl) third Olefin(e) acid based polymer is 100 mass parts meters, for example, can be 0.005～20 mass parts, and preferably 0.01～10 mass parts are more excellent Elect 0.05～5 mass parts as, extremely preferred is 0.1～1 mass parts.If use level is very few, prevent antistatic composition from leaking Effect reduce, if excessively, may be susceptible to produce the pollution that described polyoxyalkylene compounds cause.
And then, acrylic acid oligomer can also be contained in described adhesion agent composition.The Weight-average molecular of acrylic acid oligomer Amount is preferably 1000 less than 30000, more preferably 1500 less than 20000, more preferably more than 2000 And it is less than 10000.Present embodiment peel off again with acrylic acid seriess adhesion agent composition use when, as tackifying resin Function, makes adhesion (bonding) property improve, effective to heaving of suppression adhesive sheet.
(methyl) acrylate monomer can be used in described acrylic acid oligomer, for example, can enumerate (methyl) acrylic acid Methyl ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (first Base) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) heptylacrylate, (first Base) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid last of the ten Heavenly stems ester, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate are so (methyl) alkyl acrylate；
(methyl) phenyl acrylate, (methyl) benzyl acrylate such (methyl) benzyl acrylate；
(methyl) acrylate being obtained by terpene compound derivatives alcohol etc..
In addition, can be using (methyl) acrylic monomer with ester ring type structure, example in described acrylic acid oligomer As can enumerate methacrylic acid bicyclopentyl ester, acrylic acid bicyclopentyl ester, methacrylic acid bicyclopentyl oxygen ethyl ester, third Olefin(e) acid bicyclopentyl oxygen ethyl ester, methacrylic acid three cyclopentyl ester, acrylic acid three cyclopentyl ester, methacrylic acid 1- diamantane (obsolete) Base ester, acrylic acid 1- adamantane esters, methacrylic acid 2- methyl -2- adamantane esters, acrylic acid 2- methyl -2- adamantyl (methyl) acrylate such as ester, methacrylic acid 2- ethyl -2- adamantane esters, acrylic acid 2- ethyl -2- adamantane esters etc.. Such (methyl) acrylic monomer can be used alone or is applied in combination two or more.
In addition, described acrylic acid oligomer can also make outside described (methyl) acrylic monomer ingredient units can Obtain with other monomers composition (combined polymerization monomer) combined polymerization of described (methyl) acrylic monomer combined polymerization.
The weight average molecular weight of described acrylic acid oligomer is less than 30000, preferably more than 1500 and little for 1000 In 20000, more preferably 2000 less than 10000.If weight average molecular weight is more than 30000, adhesion is (viscous Connect) property reduction.In addition, if weight average molecular weight is less than 1000, then it is changed into low-molecular-weight, therefore causes the adhesion strength of adhesive sheet to drop Low.
And then it is also possible to make described adhesion agent composition contain the generation ketoenol tautomerization as crosslinking delay agent Compound.For example, in the adhesion agent composition containing cross-linking agent or the adhesion agent composition that cross-linking agent can be coordinated and use, can In the way of preferably employing the compound comprising described generation ketoenol tautomerization.Thus, viscous after the cooperation of suppression cross-linking agent Excess stickiness rising, the gelation of agent compositionss, be capable of extending the effect in the preservation life-span of adhesion agent composition.At least When isocyanate compound is used as described cross-linking agent, especially meaningful containing the compound producing ketoenol tautomerization. This technology can be preferably applied to the occasion that for example described adhesion agent composition is organic solvent solution or solvent-free form.
As the described compound producing 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 -3,5- 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 esters 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 described compound producing ketoenol tautomerization May be used alone, or two or more kinds may be used in combination.
The content of the described compound producing ketoenol tautomerization, with respect to described (methyl) acrylic acid series polymeric compounds 100 mass parts, for example, can be 0.1～20 mass parts, usual 0.5～15 mass parts (such as 1～10 mass parts) are suitable. If the amount of described compound is very few, sometimes become to be difficult to play sufficient using effect.On the other hand, if use more than The described compound of necessary amount, then remain in adhering agent layer sometimes, so that cohesiveness is reduced.
And then, in the adhesive sheet of the present invention, adhesion agent composition used can also contain additive, example known to other As according to the purposes being used, 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 suppression Preparation, 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 on the single or double of described support membrane Compositionss form the adhering agent layer of (will adhesion agent composition crosslinked and formed), and now, the crosslinking of adhesion agent composition is usually Carry out after coating adhesion agent composition but it is also possible to the adhering agent layer forming the adhesion agent composition after by crosslinking transfers To on support membrane etc..In addition, the method forming adhering agent layer on described support membrane is not particularly limited, for example, can make as follows Make：Described adhesion agent composition is coated on support membrane, polymer solvent etc. is dried and removes, sticker is formed on support membrane Layer.Afterwards, for purposes such as the adjustment of the composition movement of adhering agent layer, the adjustment of cross-linking reaction it is also possible to carry out maintenance.Separately Outward, when adhesion agent composition being coated on support membrane to make adhesive sheet, in order to be uniformly coated on support membrane it is also possible to Again add more than one the solvent beyond polymer solvent in described adhesion agent composition.
In addition, as manufacture the present invention adhesive sheet when adhering agent layer forming method, 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 for example be enumerated Coating, air knife coating method, using die coating machine etc. extrusion coating methods etc..
The adhesive sheet of the present invention is normally manufactured as making the thickness of above-mentioned adhering agent layer to be preferably 3～100 μm, more preferably 5～50 μm about.If the thickness of adhering agent layer is in described scope, the releasable being readily available appropriateness is (viscous with adhesion Connect) balance of property, therefore preferably.
＜ dividing plate ＞
In the adhesive sheet (surface protection film) of the present invention, as needed for the purpose of protecting bonding plane, can be in sticker Layer surface laminating dividing plate.
As the material constituting described dividing plate, there are paper, plastic foil, but from the excellent aspect of surface smoothness, preferably Using plastic foil.As this film, as long as the film of described adhering agent layer can be protected, it is not particularly limited, for example permissible Enumerate polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, chloroethylene copolymer Thing film, polyethylene terephthalate film, polybutylene terephthalate (PBT) film, polyurethane film, ethane-acetic acid ethyenyl ester are common Polymers film etc..
The thickness of described dividing plate is usually 5～200 μm, preferably 10～100 μm degree.If in described scope, To adhering agent layer laminating workability and from adhering agent layer peel off workability excellent, therefore preferably.For described dividing plate, according to Need it is also possible to carry out using silicone-based, the releasing agent of fluorine system, chain alkyl system or fatty acid acyl amine system, silicon dioxide powder etc. The demoulding and the antistatic process such as antifouling process, application type, doped, evaporation type.
In addition, the adhesive sheet of the present invention is, by the adhesion area 1cm of described adhering agent layer2Fit in TAC Polarizer, in 23 DEG C paste 30 minutes after with peeling rate 0.06mm/ minute along shear direction peel off when shearing force as 10N/cm2More than, excellent Elect 10～50N/cm as2, more preferably 10～40N/cm2.If described shearing force is in described scope, can bear and be glued , there is not slip, the dislocation of adhesive sheet, the curling of adherend can be suppressed in the power of the shear direction that thing will produce when will crimp, Therefore preferred.
＜ antistatic backing (top coat) ＞
The adhesive sheet of the present invention preferably has antistatic in 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 compositionss 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, becomes optimal way.
＜ electric conductive polymer ＞
Described antistatic backing preferably comprises poly- aminobenzenesulfonic acid as electric conductive polymer composition.By using described conduction Property polymer, can meet the static electricity resistance based on antistatic backing.In addition, described poly- aminobenzenesulfonic acid is " water solublity ", lead to Cross use isocyanates system described later cross-linking agent, can immobilization in antistatic backing, resistance to water can be improved.By using containing The aqueous solution of described water-soluble conducting polymer, be obtained in that through when 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 using containing institute The solution stating aqueous-dispersible conductive polymer forms antistatic backing, then become easily to produce condensation product it is impossible to equably be coated with, Have the tendency of through when sheet resistance value notable be deteriorated, therefore not preferred.
The usage amount of described electric conductive polymer, with antistatic backing (top coat), contained binding agent is for 100 mass parts 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, then anti-static effect reduces sometimes, if the usage amount of electric conductive polymer is excessive, 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 using as described electric conductive polymer composition divides Son amount (Mw) is preferably 5 × 105Hereinafter, more preferably 3 × 105Below.In addition, the weight average molecular weight of these electric conductive polymers It is preferably generally 1 × 103More than, more preferably 5 × 103More than.
Method as forming described antistatic backing, can adopt antistatic backing formation coating material (antistatic agent Compositionss) method that is coated on the first face of support membrane and makes it that (or solidification) is dried, preferably comprise in the preparation of coating material The poly- aminobenzenesulfonic acid as electric conductive polymer composition that is used, the polyester resin as binding agent and, as cross-linking agent Isocyanates system cross-linking agent it may be preferred to be dissolved in the material (electric conductive polymer of the form of water using described essential component Aqueous solution or referred to as aqueous solution.).Described electric conductive polymer aqueous solution for example can be by making with hydrophilic functional group Electric conductive polymer (can be synthesized by making intramolecular have the methods such as the monomer copolymerization of hydrophilic functional group.) be dissolved in Water is preparing.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 With forming salt.
In addition, as the commercially available product of described poly- amino phenyl sulfonyl aqueous acid, illustrating the commodity having Rhizoma Sparganii Li Yang company to manufacture Product of name " aquaPASS " etc..
The poly- aminobenzenesulfonic acid (polyaniline type) that antistatic backing disclosed herein contains as electric conductive polymer composition is made For essential component, but for example can also contain in the lump other one kind or two or more antistatic compositions (electric conductive polymer with Outer organic conductive material, inorganic conductive material, antistatic agent etc.).Here, as a preferred mode, described anti- Electrostatic layer contain substantially no described electric conductive polymer beyond antistatic composition, i.e. anti-quiet contained by described antistatic backing The mode that electric composition is substantially 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 Base etc. has the cationic antistatic agent of cationic functional group；Sulfonate, sulfuric acid, phosphonate, phosphate ester salt etc. have There is the anionic antistatic agent of anionic property functional group；Alkyl betaine and its derivant, imidazoline and its derivative, the third ammonia The amphoteric ion type antistatic agent such as acid and its derivant；Amino alcohol and its derivant, glycerol and its derivant, Polyethylene Glycol and its The non-ionic antistatic agent such as derivant；By described cationic, anionic, amphoteric ion type there is ionic conductivity base The monomer polymerization of (for example, quaternary ammonium salt base) or ionic-conductive polymer obtained from combined polymerization；Polythiophene, polyaniline, poly- pyrrole Cough up, the electric conductive polymer such as polyethyleneimine, allyl amine based polymer.Such antistatic agent can be used alone a kind, Two or more can be applied in combination.
As described inorganic conductive material, stannum oxide, stibium oxide, Indium sesquioxide., Aska-Rid., titanium oxide, oxygen can be enumerated Change zinc, indium, stannum, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, ferrum, cobalt, Copper diiodide, ITO (indium oxide/tin oxide), ATO (oxidation Antimony/stannum oxide) etc..Such inorganic conductive material can be used alone a kind it is also possible to be applied in combination two or more.
As described antistatic agent, cationic antistatic agent, anionic antistatic agent, amphoteric ion type can be enumerated Antistatic agent, non-ionic antistatic agent, will there is the ionic conductivity of described cationic, anionic, amphoteric ion type The monomer polymerization of base or ionic-conductive polymer etc. obtained by 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 account for more than more than 50 mass, preferably 75 mass %, such as compositions more than 90 mass %) Material.Described polyester, typically, preferably has following structure：There is in 1 molecule the polybasic carboxylic acid class (allusion quotation of more than 2 carboxyls Omega-dicarboxylic acids type) and its derivant (anhydride of this polybasic carboxylic acid, carboxylate, halogenide etc.) one kind or two or more change Compound (polybasic carboxylic acid composition) with there is in 1 molecule a kind of polyalcohols (typically glycolss) of 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 are own 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；(ice drops in 2- for cycloalkyl dicarboxylic acids (such as 1,4- cyclohexane dicarboxylic acid, 1,2- cyclohexane dicarboxylic acid), 1,4- Piece 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- tetrad phenyl 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- Asia 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 its anhydride；Adipic acid, decanedioic acid, Azelaic Acid, succinic acid, rich horse Aliphatic dicarboxylic acid class and its anhydride such as acid, maleic acid, double-heptene dicarboxylic acids, 1,4- cyclohexane dicarboxylic acid；And described two Lower alkyl esters ester of monohydric alcohol that carbon number is 1～3 (such as and) of carboxylic acidss etc..
On the other hand, as the example of the compound that can act as described polyol component, can enumerate ethylene glycol, third Glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, neopentyl glycol, 1,5- pentanediol, 1,6- oneself two Alcohol, 3- methyl pentanediol, diethylene glycol, 1,4 cyclohexane dimethanol, 3- methyl isophthalic acid, 5- pentanediol, 2- methyl isophthalic acid, 3- the third two Alcohol, 2,2- diethyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, xyxylene glycol (xylene Glycol), the glycolss such as hydrogenated bisphenol A, bisphenol-A.As other examples, the alkylene oxide addition product of these compounds can be enumerated (for example, ethylene oxide adduct, propylene oxide adduct etc.).
With regard to the molecular weight of described polyester resin, as the polystyrene standard being measured by gel permeation chromatography (GPC) The weight average molecular weight (Mw) of conversion, for example, can be 5 × 103～1.5 × 105Left and right (preferably 1 × 104～6 × 104Left and right). In addition, the glass transition temperature (Tg) of described polyester resin can be for example 0～120 DEG C (preferably 10～80 DEG C).
As described polyester resin, it is possible to use the trade name " VYLONAL MD-1480 " of company system is spun by commercially available Japan Deng.
Described antistatic backing (top coat), as long as significantly do not damage the performance of adhesive sheet disclosed herein (surface protection film) (for example, performance such as static electricity resistance), can further containing beyond polyester resin resin (for example, be 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 substantially only formed by polyester resin.For example, it is preferable to it is poly- The shared ratio in binding agent of ester resin is the antistatic backing of 98～100 mass %.Binding agent institute in antistatic backing entirety The ratio accounting for, for example, 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) preferably uses fatty acid amide as lubricant.Make by using fatty acid amide For lubricant, even if not implementing further lift-off processing (for example, by silicone series stripping agent, long-chain on the surface of antistatic backing The known stripping treatment agent such as alkyl series stripping agent is coated with and makes the process that it is dried) mode in it is also possible to obtain taking into account The sufficiently antistatic backing (top coat) of sliding and 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 Preserve caused albefaction under the conditions of, the warming and humidifying) etc. in terms of be preferred.In addition, considering 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, the double stearic amide of ethylene, ethylene are double Hydroxy stearic acid amide, ethylene double docosanoic acid amide, hexamethylene bis stearic amide, hexamethylene bis docosane Sour amide, hexa-methylene hydroxy stearic acid amide, N, N '-distearyl adipic acid amide, N, N '-distearyl decanedioic acid amide, Ethylene bis-oleamide, ethylene double erucyl amide, hexamethylene bis oleamide, N, N '-two oleyl adipic acid amide, 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 be applied in combination two or more.
The shared ratio in described antistatic backing entirety of lubricant 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, have the tendency that sliding is easily reduced.If lubricant Content ratio excessive, then lettering adaptation reduces sometimes.
Technology disclosed herein, as long as significantly not damaging its application effect, then can also be with antistatic backing (top coat) The mode also comprising other lubricants in addition to described fatty acid amide is implemented.As the example of other lubricants described, can To enumerate petroleum wax (paraffin etc.), mineral system wax (lignite wax etc.), higher fatty acids (cerinic acid etc.), (Palmic acid is sweet for neutral fat Oily three esters etc.) various waxes.Or, in addition to described wax, can also secondarily contain general silicone base lubricant, fluorine system profit Lubrication prescription etc..Technology disclosed herein preferably to be implemented in the way of being substantially free of described silicone base lubricant, fluorine system lubricant etc.. But, in the limit of application effect significantly not damaging technology disclosed herein, so-called lubricant it is not excluded that containing in order to Other purposes (for example, as the defoamer of antistatic backing formation coating material described later) and the silicone compound that uses.
＜ 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, the water-soluble poly aminobenzenesulfonic acid as essential component can be fixed in binding agent, Excellent water resistance, and then, it is possible to achieve raising of lettering adaptation and other effects.
As described isocyanates system cross-linking agent, using blocked isocyanates system cross-linking agent also stable in aqueous It is preferred mode.Concrete example as described blocked isocyanates system cross-linking agent, it is possible to use general adhering agent layer, anti- (for example, aforesaid adhering agent layer is used the isocyanates system cross-linking agent that can use during the preparation of electrostatic layer (top coat) Isocyanate compound (isocyanates system cross-linking agent)) with alcohols, phenol, thio phenyl phenols, amine, acid imide, oximes, Lactams, activity methene compound class, thio-alcohol, imines, carbamide class, biaryl compound class and, bisulfite The material of the blocks such as sodium.
Antistatic backing in technology disclosed herein can contain antistatic composition, antioxidant, coloring as desired Agent (pigment, dyestuff etc.), mobility regulator (thixotropic agent, thickening agent etc.), membrane producing promoter, surfactant (defoamer etc.), The additives such as preservative.
The formation ＞ of ＜ antistatic backing
Described antistatic backing (top coat) can be by including liquid composition (antistatic backing formation coating material) Give the method for support membrane and formed well, described liquid composition is by essential components such as described electric conductive polymer compositions The additive using as needed is dissolved in formation in suitable solvent (water etc.).For example preferably employ following methods： Described coating material is coated the first face of support membrane and so that it is dried, carry out cured (heat treatment, ultraviolet as needed Line process etc.).The NV (nonvolatile component) of described coating material, for example, can be set to below 5 mass % (typically 0.05～5 Quality %), it is suitable for being typically set to below 1 mass % (typically 0.10～1 mass %).Form the little antistatic backing of thickness When, preferably the NV of described coating material is set to such as 0.05～0.50 mass % (such as 0.10～0.40 mass %).Pass through Using the coating material of so low NV, antistatic backing evenly can be formed.
As the solvent constituting described antistatic backing formation coating material, 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, for example may be used With using selected from esters such as ethyl acetate；The ketones such as methyl ethyl ketone, acetone, Ketohexamethylene；The rings such as oxolane (THF), dioxane Shape ethers；The aliphatic such as normal hexane, hexamethylene or alicyclic hydro carbons；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Methanol, ethanol, positive third The aliphatic such as alcohol, isopropanol, Hexalin or alicyclic alcohols；Alkylene glycol monoalkyl ethers (for example, ethylene glycol single methyl ether, Ethylene glycol monomethyl ether), one kind or two or more in glycol ethers such as two alkylene glycol monoalkyl ethers etc..Preferably square at one In formula, the solvent of described coating material is water or the mixed solvent (for example, mixed solvent of water and ethanol) with water as main constituent.
Character ＞ of ＜ antistatic backing
The thickness of described antistatic backing is typically 3～500nm, preferably 3～100nm, more preferably 3～60nm.As The thickness of fruit antistatic backing is too small, then become to be difficult to be formed uniformly antistatic backing (for example, for the thickness of antistatic backing, The thickness deviation causing 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, affect the characteristic (optical characteristics, dimensional stability etc.) of support membrane sometimes.
In one optimal way of adhesive sheet (surface protection film) disclosed herein, as the surface measurements in antistatic backing Sheet resistance value (Ω/), preferably less than 1.0 × 1011, more preferably less than 5.0 × 1010, further preferably less than 2.0 ×1010.Show the adhesive sheet of the sheet resistance value in described scope, such as conduct is being avoided as liquid crystal cell, semiconductor device etc. Avoid as taboo adhesive sheet used in the processing of article or handling process of electrostatic etc., can be well used.Here, described sheet resistance Value can be calculated by using the sheet resistance value that commercially available determination of insulation resistance device measures in the environment of 23 DEG C, 50%RH.
Adhesive sheet (surface protection film) disclosed herein preferably has the following properties that：Its back side (surface of antistatic backing) leads to Cross water color ink, oil-based ink (for example using permanent pen) and be capable of the property of easily lettering.Described adhesive sheet is suitable to During the processing of the adherend (such as opticses) being carried out with the state having pasted adhesive sheet, carrying etc., will be used as guarantor Identiflication number of adherend of shield object etc. is documented in represent on described table adhesive sheet.It is therefore preferable that excellent the gluing of lettering Piece.For example, it is preferable to there is high lettering to solvent for the oil-based ink of alcohol system and the type containing pigment.Additionally, it is preferred that print Ink after word is difficult because of scouring, turns viscous and come off (that is, lettering excellent adhesion).In addition, adhesive sheet disclosed herein is preferred Have：When changing or eliminate lettering, wipe lettering using alcohol (such as ethanol), outward appearance does not occur the degree of significant change yet Solvent resistance.
Adhesive sheet (surface protection film) disclosed herein can also be with except support membrane (base material), adhering agent layer and antistatic Also include the mode of other layers outside layer to implement.As the configuration of described " other layers ", can be with example arrangement in support membrane First face (back side) is and antistatic backing between, the second face of support membrane (above) is and adhering agent layer between etc..Configuration is in support membrane The above layer and adhering agent layer between, for example, can be the priming coat (bottom of the throwing anchor improving adhering agent layer to described second face Glue-line), antistatic backing etc..It can also be following adhesive sheet：In support membrane former configuration antistatic backing, on antistatic backing Configuration primer layer, the adhesive sheet of the composition of configuration adhering agent layer thereon.
The opticses that the opticses of the present invention are preferably protected by described adhesive sheet.Described adhesive sheet is excellent due to shearing force Different, therefore can suppress to be fitted with the curling of the adherend (opticses) of described adhesive sheet, operability is excellent, is therefore useful.
Embodiment
Hereinafter, illustrate to being particularly shown the composition of the present invention and the embodiment of effect etc., but the invention is not restricted to this. Here, with regard to the cooperation content in embodiment etc. and evaluating characteristics, it is determined as described below.In addition, showing in table 1 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, in table 3, show the evaluation result of characteristic.
＜ evaluates ＞
Hereinafter describe specific mensure, evaluation methodology.
Mensure ＞ of ＜ weight average molecular weight (Mw)
Weight average molecular weight (Mw) can company system GPC device (HLC-8220GPC) be measured using eastern Cao's strain formula.Measure bar Part is as follows.
Sample concentration：0.2 mass % (THF solution)
Sample injection rate：10μl
Eluent：THF
Flow velocity：0.6ml/ minute
Temperature of the measurement：40℃
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 that the vitrification of the homopolymer by using following literature values as each monomer turns 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 mass fraction, the Tgn of each monomer (DEG C) represents that the glass transition temperature of homopolymer of each monomer, n represent the species of each monomer.〕
Literature value：
2-EHA (2EHA)：-70℃
N-butyl acrylate (BA)：-55℃
Acrylic acid (AA)：106℃
Carboxyethyl acrylates (β-CEA)：37℃
Acrylic acid 2- hydroxy methacrylate (HEA)：-15℃
Acrylic acid 4- hydroxybutyl (HBA)：-32℃
Hydroxyethyl methacrylate (HEMA)：55℃
N, N acrylamide (DEAA)：81℃
Here, as literature value, (central authorities manage to reference to " development of the synthesis of acrylic resin, design and new application " Development centre publishing department publishes) and " Polymer Handbook (polymer handbook) " (john wiley ＆ sons).
Mensure ＞ of ＜ shearing force
Adhesive sheet is cut into the size of wide 10mm, long 100mm, after peeling off dividing plate, according to the adhesion making described adhesive sheet Adhesion (bonding) area of oxidant layer becomes 1cm2Mode fit on TAC Polarizer (day east electrician's company system, SEG1423DU Polarizer, width：25mm, length：100mm), after (23 DEG C × 50%RH) standings of room temperature 30 minutes, divided with peeling rate 0.06mm/ Clock, along shear direction tractive, by maximum load (N/cm now2) as shearing force.
Here, described shearing force (N/cm2) it is more than 10, preferably 10～50, more preferably 10～40.Described shearing force If the power of the shear direction that adherend is wanted to produce when crimping within the above range, can be born, adhesive sheet will not occur Slip, dislocation, the curling of adherend can be suppressed, therefore preferably.
Mensure ＞ of ＜ sheet resistance value
In the environment of 23 DEG C of temperature, humidity 50%RH, with resistrivity meter (Mitsubishi Chemical Analytech, Hiresta-UP MCP-HT450 type), it is measured according to JIS-K-6911.
Here, as the sheet resistance value (Ω/) on the antistatic backing surface in the present invention, initial stage and (23 DEG C of room temperature × 50%RH) × 1 week (7 days) standing when it is preferably to be less than 1.0 × 1011, more preferably less than 5.0 × 1010, more preferably Less than 2.0 × 1010.Show the adhesive sheet (surface protection film) of the sheet resistance value in described scope, for example as liquid crystal cell, Adhesive sheet used in the processing of article or handling process of electrostatic etc. is afraid of like that by semiconductor device etc., can be utilized well.
Mensure ＞ of ＜ sliding (kinetic force of friction)
Adhesive sheet (surface protection film) is cut into the size of wide 70mm, long 100mm, (Rhizoma Sparganii is beautiful to fit in acrylic panel Positive company system, trade name " ACRYLITE ", thickness：1mm, width：70mm, length：100mm), it is prepared into test film.By this test film The back side (antistatic backing surface) downwards, be placed in 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 piece, obtain and be applied to The meansigma methodss (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 described scope, when the adherend being pasted with adhesive sheet is processed, in 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 determination of the environment of 23 DEG C × 50%RH, using flag board company system Xstamper, enterprising on antistatic backing surface The Selltotape (registered trade mark) of meter Qi Bang company system, after row lettering, is pasted on this lettering, then in peeling rate 30m/ Peel off under conditions of minute, 180 ° of peel angle.Afterwards, the surface after visual observations are peeled off, 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 ＞
Hereinafter record the preparation method of specific (methyl) acrylic acid series polymeric compounds, adhesion agent composition etc..
The preparation ＞ of ＜ (methyl) acrylic acid series polymeric compounds
Possessing stirring blade, thermometer, nitrogen ingress pipe, loading 2- ethylhexyl propylene in the four-hole boiling flask of 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 Import nitrogen, the liquid temperature in flask is maintained near 65 DEG C, carry out 6 hours polyreactions, preparation (methyl) acrylic acid seriess gather Polymer solution (40 mass %).The weight average molecular weight of described acrylic acid series polymeric compounds be 520,000, glass transition temperature (Tg) be- 67 DEG C (with reference to hurdle of the adhesion agent composition 1 in table 1).
The preparation ＞ of ＜ adhesion agent composition 1
With ethyl acetate, above-mentioned (methyl) acrylic polymer solution (40 mass %) is diluted to 20 mass %, at this The fatty family isocyanate compound as cross-linking agent is added to be six in solution 500 mass parts (solid composition 100 mass parts) Isocyanuric acid ester body (the Japanese polyurethane industrial group system, COLONATE HX) 1 mass parts (solid of methylene diisocyanate Composition 1 mass parts), as crosslinking catalyst dibutyl tin laurate (1 mass % ethyl acetate solution) 3 mass parts (Gu Form point 0.03 mass parts), carry out mix and blend, prepare adhesion agent composition 1 (solution).
The ＜ antistatic backing preparation ＞ of aqueous solution (back side process agent A)
Using the polyester resin VYLONAL MD-1480 (25% aqueous solution, Japan spin company system) as binding agent, as leading The poly- aminobenzenesulfonic acid (aquaPASS, weight average molecular weight 40,000, Rhizoma Sparganii beautiful sun company system) of conductive polymers, as cross-linking agent Using the isocyanuric acid ester body of the hexamethylene diisocyanate of diisopropylamine block, add as the oleamide of lubricant In the mixed solvent of water/ethanol (1/3), binding agent is calculated as 100 mass parts, electric conductive polymer with solid with solid content component amount Thing component amount is calculated as 75 mass parts, cross-linking agent is calculated as 10 mass parts, lubricant with solid content composition gauge with solid content component amount For 30 mass parts, stir about is sufficiently mixed for 20 minutes.So, prepare the antistatic backing aqueous solution of NV about 0.4%.
The ＜ antistatic backing preparation ＞ of aqueous solution (back side process agent B)
Using the polyester resin VYLONAL MD-1480 (25% aqueous solution, Japan spin company system) as binding agent, as leading The poly- aminobenzenesulfonic acid (aquaPASS, weight average molecular weight 40,000, Rhizoma Sparganii beautiful sun company system) of conductive polymers, as cross-linking agent Add the mixed solvent of water/ethanol (1/3) 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, prepare NV about 0.4% antistatic backing aqueous solution.
The ＜ antistatic backing preparation ＞ of aqueous solution (back side process agent C)
Using the polyester resin VYLONAL MD-1480 (25% aqueous solution, Japan spin company system) 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) aqueous solution (BytronP, H.C.Stark company system) of (PSS) 0.8%, as cross-linking agent with diisopropylamine block The isocyanuric acid ester body of hexamethylene diisocyanate adds in the mixed solvent of water/ethanol (1/1), and binding agent is become 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 It is calculated as 10 mass parts, stir about is sufficiently mixed for 20 minutes.So, prepare the antistatic backing aqueous solution of NV about 0.4%.
The ＜ antistatic backing preparation ＞ of aqueous solution (back side process agent D)
Using the polyester resin VYLONAL MD-1480 (25% aqueous solution, Japan spin company system) as binding agent, as leading The poly- aminobenzenesulfonic acid (aquaPASS, weight average molecular weight 40,000, Rhizoma Sparganii beautiful sun 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 For 75 mass parts, stir about is sufficiently mixed for 20 minutes.So, prepare the antistatic backing aqueous solution of NV about 0.4%.
The making ＞ with the support membrane of antistatic backing for the ＜
38 μm of the thickness of sided corona treatment, wide 30cm, the transparent poly- terephthaldehyde of long 40cm have been carried out on one side (the first face) On sour glycol ester (PET) film (polyester film), it is coated with the aqueous solution of any one of described antistatic backing (back side process agent A～D), Dried thickness is made to reach 30nm.This coating material is heated 1 minute at 130 DEG C makes it be dried, thus being formed in PET film First face has the support membrane with antistatic backing of antistatic backing.
＜ embodiment 1 ＞
The making ＞ of ＜ adhesive sheet
Above-mentioned adhesion agent composition 1 (solution) is coated on the contrary with antistatic backing of the described support membrane with antistatic backing Face, 130 DEG C heat 1 minute, formed 15 μm of thickness adhering agent layer.Then, on the surface of described adhering agent layer, laminating is single The dividing plate that face implements silicone-treated is the silicone-treated face of polyethylene terephthalate film (25 μm of thickness), is made for gluing Piece (surface protection film).
＜ embodiment 2～16 and comparative example 1～4 ＞
Based on the mixing ratio of Tables 1 and 2, similarly to Example 1, make adhesive sheet.Here, the use level in table 1 Represent solid content composition.
According to above-mentioned evaluation methodology, to the shearing force of the adhesive sheet making, the initial stage and through when sheet resistance value, slip Property and lettering adaptation are evaluated.The result obtaining is shown in table 3.
【Table 1】
【Table 2】
Electric conductive polymer Binding agent Cross-linking agent Lubricant
Back side process agent A Poly- aminobenzenesulfonic acid Polyester Isocyanates Oleamide
Back side process agent B Poly- aminobenzenesulfonic acid Polyester Isocyanates -
Back side process agent C PEDOT/PSS Polyester Isocyanates -
Back side process agent D Poly- aminobenzenesulfonic acid Polyester - -
Hereinafter the abbreviation in Tables 1 and 2 is illustrated.
2EHA：2-EHA
BA：N-butyl acrylate
AA：Acrylic acid (containing carboxyl (methyl) acrylic monomer)
β-CEA：Carboxyethyl acrylates (containing carboxyl (methyl) acrylic monomer)
HEA：Acrylic acid 2- hydroxy methacrylate (hydroxyl (methyl) acrylic monomer)
HBA：Acrylic acid 4- hydroxybutyl (hydroxyl (methyl) acrylic monomer)
HEMA：Hydroxyethyl methacrylate (hydroxyl (methyl) acrylic monomer)
DEAA：N, N acrylamide
C/L：Fragrant family isocyanate compound, trimethylolpropane/inferior cresyl vulcabond (Japanese polyurethane Industrial group's system, trade name：COLONATE L)
C/HX：Fatty family isocyanate compound, isocyanuric acid ester body (the Japanese poly- ammonia of hexamethylene diisocyanate Ester company system, trade name：COLONATE HX)
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 be measured with resistrivity meter.
According to above-mentioned table 3 as a result, it is possible to confirm in all of the embodiments illustrated, carry out low speed peel off when shearing force excellent Different.On the other hand, in all of comparative example, shearing force is all poor than embodiment.
In addition, according to the result of above-mentioned table 3, as antistatic backing, having 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 and (prevent quiet Electric agent compositionss) and the adhesive sheet of the embodiment 1,5,9～11 and 13～16 of the antistatic backing of back side process agent A of manufacture In, all assessment items of sheet resistance, sliding and lettering adaptation that satisfaction causes because of antistatic backing.On the other hand, close In the antistatic backing employing back side process agent B～D that a part does not coordinate desired raw material and manufactures, confirm as being not The antistatic backing of all assessment items of sheet resistance, sliding and lettering adaptation that satisfaction causes because of antistatic backing.

Claims (7)

1. a kind of adhesive sheet is 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,
Adhesion area 1cm by described adhering agent layer2Fit in after pasting 30 minutes on TAC Polarizer, at 23 DEG C to peel off speed Degree 0.06mm/ minute along shear direction peels off when shearing force be 10N/cm2More than.
2. adhesive sheet according to claim 1 it is characterised in that
Described adhesion agent composition contains (methyl) acrylic acid series polymeric compounds with hydroxyl and carboxyl.
3. adhesive sheet according to claim 2 it is characterised in that
In terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, containing hydroxyls more than 5.1 mass % (methyl) acrylic monomer.
4. the adhesive sheet according to Claims 2 or 3 it is characterised in that
In terms of the monomer component total amount constituting described (methyl) acrylic acid series polymeric compounds, containing 0.01 mass % less than 0.5 mass % containing carboxyl (methyl) acrylic monomer.
5. the adhesive sheet according to any one of Claims 1 to 4 it is characterised in that
With the one side of the described support membrane of described adhering agent layer opposition side on there is antistatic backing, described antistatic backing is by containing As the polyaniline sulfonic acid of electric conductive polymer composition, the polyester resin as binding agent and the Carbimide. as cross-linking agent The antistatic agent compositionss of ester system cross-linking agent are formed.
6. adhesive sheet according to claim 5 it is characterised in that
Described antistatic agent compositionss contain the fatty acid amide as lubricant further.
7. a kind of opticses it is characterised in that
Protected by the adhesive sheet any one of claim 1～6.
CN201580019603.9A 2014-04-16 2015-04-03 Adhesive sheet and optical member Pending CN106459687A (en)

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* Cited by examiner, † Cited by third party
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JP6697876B2 (en) * 2015-12-28 2020-05-27 日東電工株式会社 Protective film for transparent conductive film and laminate
CN108473781B (en) * 2016-01-12 2022-03-22 信越聚合物株式会社 Conductive polymer dispersion, method for producing same, and method for producing conductive thin film
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1243062A (en) * 1998-06-22 2000-02-02 东洋纺绩株式会社 High-anti-static laminated material
CN101313043A (en) * 2005-11-21 2008-11-26 综研化学株式会社 Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition
JP2009019162A (en) * 2007-07-13 2009-01-29 Cheil Industries Inc Surface protection sheet for optical member

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09165460A (en) 1995-12-14 1997-06-24 Hitachi Chem Co Ltd Antistatic treatment method
JP4306024B2 (en) * 1998-06-22 2009-07-29 東洋紡績株式会社 Highly antistatic laminate and molded product using the same
JP4498711B2 (en) * 2003-09-26 2010-07-07 日本カーバイド工業株式会社 Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film
JP5577620B2 (en) * 2009-05-11 2014-08-27 Ｄｉｃ株式会社 Adhesive, adhesive film, and surface protective film for optical member
JP5500362B2 (en) * 2010-05-19 2014-05-21 Ｄｉｃ株式会社 Adhesive, adhesive film, surface protective film for optical member, and laminate to which it is attached
JP5723618B2 (en) * 2011-02-04 2015-05-27 日東電工株式会社 Adhesive sheet and surface protective film
JP2014111705A (en) * 2012-03-30 2014-06-19 Nitto Denko Corp Pressure sensitive adhesive sheet
JP5721805B2 (en) * 2013-11-01 2015-05-20 日東電工株式会社 Transparent film and surface protective film using the film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1243062A (en) * 1998-06-22 2000-02-02 东洋纺绩株式会社 High-anti-static laminated material
CN101313043A (en) * 2005-11-21 2008-11-26 综研化学株式会社 Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition
JP2009019162A (en) * 2007-07-13 2009-01-29 Cheil Industries Inc Surface protection sheet for optical member

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王建清: "《包装材料学》", 30 June 2004, 国防工业出版社 *

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