CN104650792A - Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive - Google Patents

Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive Download PDF

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Publication number
CN104650792A
CN104650792A CN201410659742.5A CN201410659742A CN104650792A CN 104650792 A CN104650792 A CN 104650792A CN 201410659742 A CN201410659742 A CN 201410659742A CN 104650792 A CN104650792 A CN 104650792A
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Prior art keywords
sensitive adhesive
pressure
polyurethane
protection film
pasted
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Inventor
佐佐木翔悟
内田翔
伊关亮
安藤雅彦
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to urethane-based pressure-sensitive adhesive and a surface protective film using the pressure-sensitive adhesive. The invention also provides optical member and electronic member employing the surface protective film. The urethane-based pressure-sensitive adhesive contains urethane-based resin wherein the urethane-based resin is obtained by curing the composition containing polyhydric alcohols (A) and Polyfunctional isocyanate compound(B), wherein the ratio of NCO base to OH base, NCO base/OH base in the polyhydric alcohols (A) and the Polyfunctional isocyanate compound(B) is greater than 1.0 and lower than 5.0. The urethane-based pressure-sensitive adhesive contains ionic liquid containing fluorinated organic anion.

Description

The surface protection film of polyurethane-base pressure-sensitive adhesive and use pressure-sensitive adhesive
Technical field
The present invention relates to polyurethane-base pressure-sensitive adhesive.Although usual known polyurethane-base pressure-sensitive adhesive is easy to the fact causing adhesive residue so far, polyurethane-base pressure-sensitive adhesive of the present invention prevents aspect of performance extremely excellent at adhesive residue.The invention still further relates to the surface protection film using this polyurethane-base pressure-sensitive adhesive.Surface protection film of the present invention comprises substrate layer and formation of pressure-sensitive adhesive layer, and the surface being preferred for such as wherein being pasted to by film optical component or electronic component is to protect the application on described surface.
Background technology
Optical component and electronic component attach to its exposing surface side to prevent the surface protection film cracked in its surface when processing, assembling, inspection, transport etc. as LCD, OLED display, the contact panel of this indicating meter of use, the lens component of photographic camera and electronic installation have separately usually.When no longer needing surface protection, this surface protection film is peeled off from optical component or electronic component.
In increasing situation, from the manufacturing step of optical component or electronic component, by number of assembling steps, check step, trafficking step etc., until final transport, identical surface protection film is used as this surface protection film continuously.In this case many, in each step, this surface protection film attached by hand, peel off and attach again.
When by manual for surface protection film attaching, (trapped) bubble may be involved between adherend and surface protection film.Therefore, reported some for improving the wettability of surface protection film, thus make can the technology of non-involvement bubble when attaching.Such as, known use in its formation of pressure-sensitive adhesive layer has the surface protection film of the silicone resin of high wetting rate.But when being used in formation of pressure-sensitive adhesive layer by silicone resin, its pressure-sensitive adhesive composition is easy to pollute adherend, thus surface protection film is thrown into question as during optical component or electronic component surperficial for the protection of needing the component of low especially pollution.
As the surface protection film of reduced contamination being derived from its pressure-sensitive adhesive composition, the known surface protection film using acrylic resin in its formation of pressure-sensitive adhesive layer.But, in formation of pressure-sensitive adhesive layer, use the wettability of the surface protection film of acrylic resin poor, therefore, when by manual for surface protection film attaching, bubble may be involved between adherend and surface protection film.In addition; when acrylic resin is used in formation of pressure-sensitive adhesive layer; exist and be easy to produce the problem of adhesive residue when peeling off, thus surface protection film is thrown into question as during optical component or electronic component surperficial for the protection of the component undesirably introducing impurity especially.
As can realize excellent wettability and low stain performance and adhesive residue reduce both surface protection film; have recently been reported in its formation of pressure-sensitive adhesive layer, use polyurethane-base pressure-sensitive adhesive surface protection film (see; such as, Japanese Patent Application Laid-Open 2006-182795).
But the polyurethane-base pressure-sensitive adhesive of known correlation technique is easy to cause adhesive residue.Such as, when being stored under warm-up mode after pressure-sensitive adhesive is pasted to adherend, produce following point.Be easy to produce adhesive residue on adherend.
In addition, when surface protection film is pasted to adherend by hand, described film needs not only have excellent wettability, and has light separability.This is because, after the surface protection film being pasted to adherend is peeled off, described film be pasted to again adherend and be again used as surface protection film.Even if when its wettability is good, when its separability is heavy, when surface protection film is peeled off, surface protection film deforms, and this makes described film to be used as surface protection film again.In order to avoid this problem; surface protection film for optical component or electronic component needs to have so-called re-workability strongly, the non-involvement bubble by means of described film can repeatedly attach by described re-workability and described film gently can be peeled off and it is not deformed.But the surface protection film of polyurethane-base pressure-sensitive adhesive that uses in its formation of pressure-sensitive adhesive layer of hitherto reported relates to following point.The adhesivity of formation of pressure-sensitive adhesive layer is passed in time and the performance that increases is high and therefore when the state that described film is pasted to adherend continues for a long time, its separability becomes heavy and described film becomes re-workability difference.
In addition, as noted before, do not need the time point of surface protection by surface protection film from adherend as optical component or electronic component are peeled off.As constituent material and therefore now, the substrate layer of surface protection film, optical component, electronic component etc. comprises plastic material this layer or component has high electric insulation performance and produce electrostatic when rubbing or peel off.Therefore, by surface protection film from optical component as also produced electrostatic when polaroid is peeled off, and when under the state at residual this electrostatic to liquid crystal applied voltages time, the orientation of liquid crystal molecule is lost or the loss of panel is occurred.
Summary of the invention
An object of the present invention is to provide a kind of polyurethane-base pressure-sensitive adhesive, the antistatic property of described polyurethane-base pressure-sensitive adhesive is extremely excellent and adhesive residue prevents performance and re-workability also excellent.Another object of the present invention is to provide the surface protection film using this polyurethane-base pressure-sensitive adhesive in its formation of pressure-sensitive adhesive layer, and the antistatic property of described surface protection film is extremely excellent and adhesive residue prevents performance and re-workability also excellent.Another object of the present invention is to provide the optical component or electronic component that are pasted with this surface protection film.
Polyurethane-base pressure-sensitive adhesive of the present invention comprises polyurethane-based resin, wherein:
The polyurethane-based resin that described polyurethane-based resin comprises the composition solidification by comprising polyvalent alcohol (A) and polyfunctional isocyanate compound (B) and obtains;
Described polyvalent alcohol (A) and the middle equivalence ratio " NCO base/OH yl " between NCO base and OH base of described polyfunctional isocyanate compound (B) are greater than 1.0 and are less than 5.0; And
Described polyurethane-base pressure-sensitive adhesive comprises the ionic liquid containing fluorine organic anion.
In a preferred embodiment, described ionic liquid by described fluorine organic anion and positively charged ion is formed.
In a preferred embodiment, described in positively charged ion comprise be selected from nitrogenous positively charged ion, sulfur-bearing positively charged ion and phosphorous cationic at least one.
In a preferred embodiment, described polyvalent alcohol (A) comprises the polyvalent alcohol that number-average molecular weight Mn is 400 ~ 20,000.
In a preferred embodiment, described polyfunctional isocyanate compound (B) is 5 % by weight ~ 60 % by weight relative to the content of described polyvalent alcohol (A).
Surface protection film of the present invention comprises:
Substrate layer; With
Formation of pressure-sensitive adhesive layer,
Wherein said formation of pressure-sensitive adhesive layer comprises polyurethane-base pressure-sensitive adhesive of the present invention.
Optical component of the present invention has the surface protection film of the present invention attached on it.
Electronic component of the present invention has the surface protection film of the present invention attached on it.
According to an embodiment of the invention, antistatic property can be provided extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent.According to another implementation of the invention; can be provided in its formation of pressure-sensitive adhesive layer the surface protection film using this polyurethane-base pressure-sensitive adhesive, the antistatic property of described surface protection film is extremely excellent and adhesive residue prevents performance and re-workability also excellent.According to another implementation of the invention, the optical component being pasted with this surface protection film or electronic component can be provided.
Accompanying drawing explanation
Fig. 1 is the schematic sectional view of surface protection film according to the preferred embodiment of the present invention.
Embodiment
<<A. polyurethane-base pressure-sensitive adhesive >>
<A-1. polyurethane-based resin >
Polyurethane-base pressure-sensitive adhesive of the present invention comprises polyurethane-based resin.
The lower value of the content of polyurethane-based resin in polyurethane-base pressure-sensitive adhesive of the present invention is preferably more than 40 % by weight, more preferably more than 50 % by weight, also more preferably more than 55 % by weight, also more preferably 60 % by weight, particularly preferably 65 % by weight, most preferably 70 % by weight.The higher limit of described content is preferably less than 99.999 % by weight, and more preferably less than 99.99 % by weight, also more preferably less than 99.9 % by weight, also more preferably less than 99 % by weight, particularly preferably less than 95 % by weight, most preferably less than 90 % by weight.The content of polyurethane-based resin in polyurethane-base pressure-sensitive adhesive of the present invention is regulated and such as antistatic property can be provided in described scope extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent in addition.
Polyurethane-based resin is that the composition by comprising polyvalent alcohol (A) and polyfunctional isocyanate compound (B) solidifies and the polyurethane-based resin of acquisition.
The species number of polyvalent alcohol (A) can be only a kind of, or can be two or more.
Any suitable polyvalent alcohol can be adopted as polyvalent alcohol (A), as long as described polyvalent alcohol has two or more OH base.The example of this polyvalent alcohol (A) comprises the polyvalent alcohol (glycol) with two OH bases, the polyvalent alcohol (triol) with three OH bases, the polyvalent alcohol (tetrol) with four OH bases, the polyvalent alcohol (pentol) with five OH bases and the polyvalent alcohol (six alcohol) with six OH bases.
In the present invention, preferably the neccessary composition of polyvalent alcohol (triol) as polyvalent alcohol (A) of three OH bases will be had.When described above by there are three OH bases the neccessary composition of polyvalent alcohol (triol) as polyvalent alcohol (A) time, such as antistatic property can be provided extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent in addition.The content of polyvalent alcohol (triol) in polyvalent alcohol (A) with three OH bases is preferably 50 % by weight ~ 100 % by weight, more preferably 70 % by weight ~ 100 % by weight, also more preferably 80 % by weight ~ 100 % by weight, also more preferably 90 % by weight ~ 100 % by weight, particularly preferably 95 % by weight ~ 100 % by weight, most preferably substantially 100 % by weight.
Polyvalent alcohol (A) preferably comprises the polyvalent alcohol that number-average molecular weight Mn is 400 ~ 20,000.Number-average molecular weight Mn is 400 ~ 20, the content of polyvalent alcohol in polyvalent alcohol (A) of 000 is preferably 50 % by weight ~ 100 % by weight, more preferably 70 % by weight ~ 100 % by weight, also more preferably 90 % by weight ~ 100 % by weight, particularly preferably 95 % by weight ~ 100 % by weight, most preferably substantially 100 % by weight.By number-average molecular weight Mn be 400 ~ 20,000 the content of polyvalent alcohol in polyvalent alcohol (A) regulate and antistatic property can be provided in described scope extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent.
In the present invention, when the neccessary composition of the polyvalent alcohol (triol) that will there are three OH bases as polyvalent alcohol (A), preferably combination uses number-average molecular weight Mn to be 7, 000 ~ 20, the triol of 000, number-average molecular weight Mn is 2, 000 ~ 6, the triol of 000 and number-average molecular weight Mn are 400 ~ 1, the triol of 900, more preferably combinationally using number-average molecular weight Mn is 8, 000 ~ 15, the triol of 000, number-average molecular weight Mn is 2, 000 ~ 5, the triol of 000 and number-average molecular weight Mn are 500 ~ 1, the triol of 800, and also more preferably to combinationally use number-average molecular weight Mn be 8, 000 ~ 12, the triol of 000, number-average molecular weight Mn is 2, 000 ~ 4, the triol of 000 and number-average molecular weight Mn are 500 ~ 1, the triol of 500.The combinationally using of this three kinds of triols can provide such as antistatic property extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent in addition.
The example of polyvalent alcohol (A) comprises polyester polyol, polyether glycol, polycaprolactone polyol, polycarbonate polyol and castor oil-base polyvalent alcohol.
Polyester polyol can be obtained by the esterification such as between polyhydroxy reactant and sour composition.
The example of polyhydroxy reactant comprises ethylene glycol, Diethylene Glycol, 1,3 butylene glycol, BDO, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-butyl-2-ethyl-1, ammediol, 2,4-diethyl-1,5-PD, 1,2-hexylene glycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 1,8-decanediol, octadecandiol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, hexanetriol and polypropylene glycol.
The example of acid composition comprises succsinic acid, methylsuccinic acid, hexanodioic acid, pimelic acid, nonane diacid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecane diacid, dimeracid, 2-methyl isophthalic acid, 4-cyclohexane dicarboxylic acid, 2-ethyl-1,4-cyclohexane dicarboxylic acid, terephthalic acid, m-phthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acids, 4,4'-diphenyl dicarboxylic acids and their acid anhydrides.
The example of polyether glycol is the polyether glycol by using initiator to carry out addition polymerization to oxirane as oxyethane, propylene oxide or butylene oxide ring as water, low molecular weight polyols (such as propylene glycol, ethylene glycol, glycerine, TriMethylolPropane(TMP) or tetramethylolmethane), bis-phenol (such as dihydroxyphenyl propane) or dihydroxy-benzene (such as pyrocatechol, Resorcinol or quinhydrones) and obtain.Its specific examples comprises polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol.
The example of polycaprolactone polyol be by cyclic ester monomer as 6-caprolactone or σ-valerolactone carry out the lactone-based polyester diols that ring-opening polymerization obtains.
The example of polycarbonate polyol comprises: the polycarbonate polyol obtained by carrying out polycondensation to polyhydroxy reactant photoreactive gas; By to polyhydroxy reactant and carbonic diester as methylcarbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, Texacar PC, diphenyl carbonate or carbonic acid dibenzyl ester carry out transesterify and condensation and the polycarbonate polyol obtained; The polycarbonate polyol of the copolymerization obtained by combinationally using two or more polyhydroxy reactant; The polycarbonate polyol obtained by carrying out esterification to each in above-mentioned various polycarbonate polyol and carboxylic compound; The polycarbonate polyol obtained by carrying out etherification reaction to the compound of each in above-mentioned various polycarbonate polyol and hydroxyl; By the polycarbonate polyol that each in above-mentioned various polycarbonate polyol and ester cpds are carried out to transesterification reaction and obtained; The polycarbonate polyol obtained by carrying out transesterification reaction to the compound of each in above-mentioned various polycarbonate polyol and hydroxyl; By the polyester type polycarbonate polyol that each in above-mentioned various polycarbonate polyol and dicarboxylic acid compound are carried out to polycondensation and obtained; With the polyether-type polycarbonate polyol of the copolymerization by carrying out copolyreaction to each in above-mentioned various polycarbonate polyol and oxirane and obtain.
The example of castor oil-base polyvalent alcohol is the castor oil-base polyvalent alcohol obtained by making Castor Oil Fatty Acid and polyhydroxy reactant react to each other.Its specific examples is the castor oil-base polyvalent alcohol obtained by making Castor Oil Fatty Acid and polypropylene glycol react to each other.
The species number of polyfunctional isocyanate compound (B) can be only a kind of or can for two or more.
Any suitable polyfunctional isocyanate compound that can be used for urethane forming reactions can be used as polyfunctional isocyanate compound (B).The example of this polyfunctional isocyanate compound (B) comprises polyfunctional aliphatic isocyanate's compound, multifunctional alicyclic isocyanate compound and multifunctional aromatic isocyanate compound.
The example of polyfunctional aliphatic isocyanate's compound comprises trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-trimethylene diisocyanate, 1,3-tetramethylene diisocyanate, ten dimethylene diisocyanates and 2,4,4-trimethyl hexamethylene diisocyanate.
The example of multifunctional alicyclic isocyanate compound comprises 1,3-cyclopentene diisocyanate, 1,3-cyclohexyl diisocyanate, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation of benzene dimethylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenation tetramethylxylylene diisocyanate.
The example of multifunctional aromatic diisocyanate compounds comprises phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethanediisocyanate, 4,4'-diphenylmethanediisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.
Other example of polyfunctional isocyanate compound (B) comprise various polyfunctional isocyanate compound as above trimethylolpropane adduct, by the reaction of they and water and its biuret obtained and its tripolymer separately with isocyanurate ring.In addition, they can combinationally use.
Polyfunctional isocyanate compound (B) is preferably 5 % by weight ~ 60 % by weight relative to the content of polyvalent alcohol (A), and more preferably 8 % by weight ~ 60 % by weight, also more preferably 10 % by weight ~ 60 % by weight.The content of polyfunctional isocyanate compound (B) is regulated and such as antistatic property can be provided in described scope extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent in addition.
Equivalence ratio " NCO base/OH yl " in polyvalent alcohol (A) and polyfunctional isocyanate compound (B) between NCO base and OH base is for being greater than 1.0 and be less than 5.0, preferably 1.1 ~ 5.0, more preferably 1.2 ~ 4.0, also more preferably 1.5 ~ 3.5, particularly preferably 1.8 ~ 3.0.Equivalence ratio " NCO base/OH yl " is regulated and such as antistatic property can be provided in described scope extremely excellent and the adhesive residue polyurethane-base pressure-sensitive adhesive that prevents performance and re-workability also excellent.
Polyurethane-based resin obtains by comprising the composition solidification of polyvalent alcohol (A) and polyfunctional isocyanate compound (B).Except polyvalent alcohol (A) and polyfunctional isocyanate compound (B), in the scope not damaging effect of the present invention, this composition can also comprise any other suitable composition.The example of other composition this comprises other resinous principle outside catalyzer, polyurethane-based resin, tackifier, mineral filler, organic filler, metal-powder, pigment, foil-like material, tenderizer, softening agent, antiaging agent, conductive agent, antioxidant, UV light absorber, photostabilizer, surface lubricant, levelling agent, corrosion inhibitor, thermo-stabilizer, polymerization retarder, lubricant and solvent.
Polyurethane-based resin preferably comprises anti-deterioration agent as antioxidant, UV light absorber or photostabilizer.When polyurethane-based resin comprises anti-deterioration agent, the adhesive residue of pressure-sensitive adhesive prevents performance can be excellent.Particularly, even if when being stored under warm-up mode after pressure-sensitive adhesive is pasted to adherend, adherend also produces adhesive residue hardly.The species number of anti-deterioration agent can be only one maybe can for two or more.Anti-deterioration agent is particularly preferably antioxidant.
Relative to polyvalent alcohol (A), the content of anti-deterioration agent is preferably 0.01 % by weight ~ 20 % by weight, more preferably 0.02 % by weight ~ 15 % by weight, also more preferably 0.03 % by weight ~ 10 % by weight, also more preferably 0.05 % by weight ~ 7 % by weight, also more preferably 0.1 % by weight ~ 5 % by weight, particularly preferably 0.1 % by weight ~ 3 % by weight, most preferably 0.1 % by weight ~ 1 % by weight.Regulated by the content of anti-deterioration agent to make the adhesive residue of pressure-sensitive adhesive prevent performance additionally excellent in described scope.Particularly, even if when being stored under warm-up mode after pressure-sensitive adhesive is pasted to adherend, adherend also not easily produces adhesive residue.When the content of anti-deterioration agent is too small, may becomes and can not fully show adhesive residue and prevent performance.When the content of anti-deterioration agent is excessive, may following point be produced: the inferior position occurring cost aspect, can not keep pressure-sensitive adhesive characteristic or adherend contaminated.
The example of antioxidant comprises free radical chain inhibitor and peroxide decomposer.
The example of free radical chain inhibitor comprises phenol antioxidant and amine antioxidants.
The example of peroxide decomposer comprises sulphur class antioxidant and phosphorus antioxidants.
The example of phenol antioxidant comprises single phenol antioxidant, Bis-phenolic antioxidants and high molecular weight phenolic antioxidant.
The example of single phenol antioxidant comprises 2,6-di-t-butyl-p-cresol, butylated BHA, 2,6-di-t-butyl-4-ethylphenols and stearyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester.
The example of Bis-phenolic antioxidants comprises 2,2'-methylene radical two (4-methyl-6-tert-butylphenol), 2,2'-methylene radical two (4-ethyl-6-tert.-butyl phenol), 4,4'-sulfo-two (3 methy 6 tert butyl phenol), 4,4'-butylidene two (3 methy 6 tert butyl phenol) and 3,9-bis-[1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl] 2,4,8,10-tetra-oxaspiro [5.5] undecane.
The example of high molecular weight phenolic antioxidant comprises 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, four-[methylene radical-3-(3', 5'-di-t-butyl-4'-hydroxy phenyl) propionic ester] methane, two [3,3'-bis--(4'-hydroxyl-3'-tert-butyl-phenyl) butyric acid] glycol ester, 1,3,5-tri-(3', 5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H, 3H, 5H) triketone and tocopherol.
The example of sulphur class antioxidant comprises 3,3'-Tyox B, 3,3'-thio-2 acid two myristins and 3,3'-thio-2 acid distearyl ester.
The example of phosphorus antioxidants comprises triphenyl phosphite, diphenylisodecyl base ester and diisodecyl phenyl phosphite.
The example of UV light absorber comprises benzophenone ultraviolet absorption agent, Benzotriazole Ultraviolet Stabilizer, salicylic acid UV light absorber, oxanilide class UV light absorber, cyanoacrylate ultraviolet absorption agent and triazine-based ultraviolet absorption agent.
The example of benzophenone ultraviolet absorption agent comprises 2; 4-dihydroxy benaophenonel, ESCALOL 567,2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-dodecyl oxygen base benzophenone, 2; 2'-dihydroxyl-4-dimethoxy-benzophenone, 2; 2'-dihydroxyl-4,4'-dimethoxy-benzophenone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone and two (2-methoxyl group-4-hydroxyl-5-benzoylphenyl) methane.
The example of Benzotriazole Ultraviolet Stabilizer comprises 2-(2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole, 2-(2'-hydroxyl-5'-tert-butyl-phenyl) benzotriazole, 2-(2'-hydroxyl-3', 5'-bis--tert-butyl-phenyl) benzotriazole, 2-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3', 5'-bis--tert-butyl-phenyl) 5-chlorobenzotriazole, 2-(2'-hydroxyl-3', 5'-bis--tert-pentyl phenyl) benzotriazole, 2-(2'-hydroxyl-4'-octyloxyphenyl) benzotriazole, 2-[2'-hydroxyl-3'-(3 ", 4 ", 5 ", 6 "-tetrahydrochysene phthalimidomethyl)-5'-aminomethyl phenyl] benzotriazole, 2, 2'-methylene radical two [4-(1, 1, 3, 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol] and 2-(2'-hydroxyl-5'-methacryl-oxyphenyl)-2H-benzotriazole.
The example of salicylic acid UV light absorber comprises salol, p-t-butylphenyl salicylate and p-octylphenyl salicylate.
The example of cyanoacrylate ultraviolet absorption agent comprises 2-ethylhexyl-2-cyano group-3,3'-diphenylacrylate ester and ethyl-2-cyano group-3,3'-diphenylacrylate ester.
The example of photostabilizer comprises hindered amine light stabilizer and ultra-violet stabilizer.
The example of hindered amine light stabilizer can comprise [two (2,2,6,6-tetramethyl--4-piperidyl) sebate], two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate and 1,2,2,6,6-pentamethyl--4-piperidyl sebacic acid methyl esters.
The example of ultra-violet stabilizer comprises two (octyl phenyl) nickelous sulfide, [2,2'-sulfo-two (4-tert-octyl phenol nickel)]-n-butylamine, nickel complex-3,5-bis--tertiary butyl-4-hydroxy benzyl-monoethyl phosphate, aminobenzoate type quencher and nickel dibutyl dithiocarbamate.
Anti-deterioration agent preferably has the anti-deterioration agent of hindered phenol structure.When comprise there is hindered phenol structure anti-deterioration agent as anti-deterioration agent time, relative to polyvalent alcohol (A), its content is preferably 0.01 % by weight ~ 10 % by weight, more preferably 0.05 % by weight ~ 10 % by weight, also more preferably 0.1 % by weight ~ 10 % by weight.Regulated by the content with the anti-deterioration agent of hindered phenol structure to make the adhesive residue of pressure-sensitive adhesive prevent performance additionally excellent in described scope.Particularly, even if when being stored under warm-up mode after pressure-sensitive adhesive is pasted to adherend, adherend also not easily produces adhesive residue.When the content of the anti-deterioration agent with hindered phenol structure is too small, may becomes and can not fully show adhesive residue and prevent performance.When the content of the anti-deterioration agent with hindered phenol structure is excessive, may following point be produced: the inferior position occurring cost aspect, can not keep pressure-sensitive adhesive characteristic or adherend contaminated.
Can by any suitable anti-deterioration agent as the anti-deterioration agent with hindered phenol structure, as long as described anti-deterioration agent has the group such as wherein with large steric hindrance as the hindered phenol structure of at least one in the tertiary butyl the is bonded to carbon atom adjacent with the carbon atom on the aromatic ring of the phenol of bonding OH base.Compared with conventional anti-deterioration agent, use the specific anti-deterioration agent with the anti-deterioration agent of this hindered phenol structure extremely can amplify the inhibition reduced the molecular weight of polyvalent alcohol, and therefore pressure-sensitive adhesive can show following effect: compared with conventional pressure-sensitive adhesive, its adhesive residue prevents performance significantly excellent.
The specific examples as mentioned above with the anti-deterioration agent of hindered phenol structure comprises: butylated hydroxytoluene (BHT), hindered phenol anti-oxidants is as the hindered phenol anti-oxidants that can obtain with following trade(brand)name: trade(brand)name " IRGANOX 1010 " (being manufactured by BASF), trade(brand)name " IRGANOX 1010FF " (being manufactured by BASF), trade(brand)name " IRGANOX 1035 " (being manufactured by BASF), trade(brand)name " IRGANOX 1035FF " (being manufactured by BASF), trade(brand)name " IRGANOX 1076 " (being manufactured by BASF), trade(brand)name " IRGANOX 1076FD " (being manufactured by BASF), trade(brand)name " IRGANOX 1076DWJ " (being manufactured by BASF), trade(brand)name " IRGANOX 1098 " (being manufactured by BASF), trade(brand)name " IRGANOX 1135 " (being manufactured by BASF), trade(brand)name " IRGANOX 1330 " (being manufactured by BASF), trade(brand)name " IRGANOX 1726 " (being manufactured by BASF), trade(brand)name " IRGANOX 1425WL " (being manufactured by BASF), trade(brand)name " IRGANOX 1520L " (being manufactured by BASF), trade(brand)name " IRGANOX 245 " (being manufactured by BASF), trade(brand)name " IRGANOX 245FF " (being manufactured by BASF), trade(brand)name " IRGANOX 259 " (being manufactured by BASF), trade(brand)name " IRGANOX3114 " (being manufactured by BASF), trade(brand)name " IRGANOX 565 " (being manufactured by BASF) and trade(brand)name " IRGANOX 295 " (being manufactured by BASF), Benzotriazole Ultraviolet Stabilizer is as the Benzotriazole Ultraviolet Stabilizer that can obtain with following trade(brand)name: trade(brand)name " TINUVINP " (being manufactured by BASF), trade(brand)name " TINUVIN P FL " (being manufactured by BASF), trade(brand)name " TINUVIN 234 " (being manufactured by BASF), trade(brand)name " TINUVIN 326 " (being manufactured by BASF), trade(brand)name " TINUVIN 326FL " (being manufactured by BASF), trade(brand)name " TINUVIN328 " (being manufactured by BASF), trade(brand)name " TINUVIN 329 " (being manufactured by BASF) and trade(brand)name " TINUVIN 329FL " (being manufactured by BASF), liquid ultraviolet absorber is as the liquid ultraviolet absorber that can obtain with following trade(brand)name: trade(brand)name " TINUVIN 213 " (being manufactured by BASF) and trade(brand)name " TINUVIN 571 " (being manufactured by BASF), triazine-based ultraviolet absorption agent is as the triazine-based ultraviolet absorption agent that can obtain with trade(brand)name " TINUVIN 1577ED " (being manufactured by BASF), benzoates UV light absorber is as the benzoates UV light absorber that can obtain with trade(brand)name " TINUVIN120 " (being manufactured by BASF), with hindered amine light stabilizer as the hindered amine light stabilizer that can obtain with trade(brand)name " TINUVIN 144 " (being manufactured by BASF).
Polyurethane-based resin preferably comprises fatty acid ester.When polyurethane-based resin comprises fatty acid ester, its wetting rate can improve.The species number of fatty acid ester can be only one maybe can for two or more.
Fatty acid ester is preferably 5 % by weight ~ 50 % by weight relative to the content of polyvalent alcohol (A), more preferably 7 % by weight ~ 40 % by weight, also more preferably 8 % by weight ~ 35 % by weight, particularly preferably 9 % by weight ~ 30 % by weight, most preferably 10 % by weight ~ 20 % by weight.The content of fatty acid ester is regulated additionally can improve wetting rate in described scope.When the content of fatty acid ester is too small, fully wetting rate may not be improved.When the content of fatty acid ester is excessive, may following point be produced: the inferior position occurring cost aspect, can not keep pressure-sensitive adhesive characteristic or adherend contaminated.
The number-average molecular weight Mn of fatty acid ester is preferably 200 ~ 400, and more preferably 210 ~ 395, also more preferably 230 ~ 380, particularly preferably 240 ~ 360, most preferably 270 ~ 340.The number-average molecular weight Mn of fatty acid ester is regulated additionally can improve wetting rate in described scope.When the number-average molecular weight Mn of fatty acid ester is too small, even if when its interpolation number is large, wetting rate may also not improve.When the number-average molecular weight Mn of fatty acid ester is excessive, the solidified nature of pressure-sensitive adhesive when it is dry may be deteriorated, thus not only adversely affect its wetting property, and adversely affect its other pressure-sensitive adhesive characteristic.
In the scope not damaging effect of the present invention, any suitable fatty acid ester can be used as described fatty acid ester.The example of this fatty acid ester comprises polyoxyethylene bisphenol A laurate, butyl stearate, palmitinic acid 2-(ethyl hexyl) ester, stearic acid 2-(ethyl hexyl) ester, behenic acid monoglyceride, 2 ethyl hexanoic acid cetyl ester, Isopropyl myristate, Wickenol 111, Unimac 5680 cholesterol ester, lauryl methacrylate(LMA), coconut acid methylester, Laurate methyl, Witconol 2301, methyl stearate, Tetradecyl tetradecanoate, tetradecanoic acid octyldodecyl, pentaerythritol monooleate, pentaerythritol monostearate, tetramethylolmethane four cetylate, stearyl stearate, stearic acid isotridecyl ester, 2 ethyl hexanoic acid triglyceride level, butyl laurate and oleic acid monooctyl ester.
Preferably, polyurethane-based resin comprises levelling agent.Levelling agent is introduced in polyurethane-based resin the outward appearance that can prevent from being caused by orange peel surface uneven.The species number of levelling agent can be only one maybe can for two or more.
Levelling agent is preferably 0.001 % by weight ~ 1 % by weight relative to the content of polyvalent alcohol (A), more preferably 0.002 % by weight ~ 0.5 % by weight, also more preferably 0.003 % by weight ~ 0.1 % by weight, particularly preferably 0.004 % by weight ~ 0.05 % by weight, most preferably 0.005 % by weight ~ 0.01 % by weight.Regulated by the content of levelling agent the outward appearance that can additionally prevent from being caused by orange peel surface in described scope uneven.When the content of levelling agent is too small, may not prevent by the surperficial outward appearance caused of orange peel uneven.When the content of levelling agent is excessive, may following point be produced: the inferior position occurring cost aspect, can not keep pressure-sensitive adhesive characteristic or adherend contaminated.
In the scope not damaging effect of the present invention, any suitable levelling agent can be used as levelling agent.The example of this levelling agent comprises acrylic acid or the like levelling agent, fluorine class levelling agent and silicon class levelling agent.The example of acrylic acid or the like levelling agent comprises POLYFLOW No.36, POLYFLOWNo.56, POLYFLOW No.85HF and POLYFLOW No.99C (manufacturing by Kyoeisha Chemical Co., Ltd. (KYOEISHA CHEMICAL Co., LTD)).The example of fluorine class levelling agent comprises MEGAFACE F-470N and MEGAFACE F-556 (manufacturing by Dainippon Ink Chemicals (DIC Corporation)).The example of silicon class levelling agent is GRANDIC PC-4100 (being manufactured by Dainippon Ink Chemicals).
In the scope not damaging effect of the present invention, the urethane forming reactions method that any suitable method uses mass polymerization, solution polymerization etc. as related to can be used as the method obtaining polyurethane-based resin by the composition solidification of polyvalent alcohol (A) and polyfunctional isocyanate compound (B) will be comprised.But, there is following possibility: can not show effect of the present invention in the conventional polyurethanes base resin obtained by so-called polyurethane prepolymer, the method that the composition therefore by comprising polyvalent alcohol (A) and polyfunctional isocyanate compound (B) solidifies and obtains polyurethane-based resin preferably relates to the method outside by the method for polyurethane prepolymer acquisition polyurethane-based resin.
In order to the composition solidification of polyvalent alcohol (A) and polyfunctional isocyanate compound (B) will be comprised, preferably use catalyzer.The example of this catalyzer comprises organometallic compound and tertiary amine compound.
The example of organometallic compound can comprise iron compound, tin compound, titanium compound, Zirconium compound, Pb compound, cobalt compounds and zinc compounds.Wherein, from the viewpoint of the working life of speed of reaction and formation of pressure-sensitive adhesive layer, iron compound and tin compound are preferred.
The example of iron compound comprises ferric acetyl acetonade and 2 ethyl hexanoic acid iron.
The example of tin compound comprises dibutyl tin dichloride, Dibutyltin oxide, dibutyl tin dibromide, dibutyitin maleate, dibutyl tin laurate, dibutyltin diacetate, dibutyltin sulfide, tributyl methoxyl group tin, tributyltin acetate, triethyl oxyethyl group tin, tributyl oxyethyl group tin, di-n-octyltin oxide, tin dilaurate dioctyl tin, tributyltin chloride, trichoroacetic acid(TCA) tributyl tin and 2 ethyl hexanoic acid tin.
The example of titanium compound comprises dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanous chloride.
The example of Zirconium compound comprises zirconium naphthenate and methyl ethyl diketone zirconium.
The example of Pb compound comprises lead oleate, 2 ethyl hexanoic acid lead, lead benzoate and lead naphthenate.
The example of cobalt compounds comprises 2 ethyl hexanoic acid cobalt and cobaltous benzoate.
The example of zinc compounds comprises zinc naphthenate and 2 ethyl hexanoic acid zinc.
The example of tertiary amine compound comprises triethylamine, triethylenediamine and 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene.
The species number of catalyzer can be only one maybe can for two or more.In addition, catalyzer and crosslinking delay agent etc. can be combinationally used.Relative to polyvalent alcohol (A), the amount of catalyzer is preferably 0.02 % by weight ~ 0.10 % by weight, and more preferably 0.02 % by weight ~ 0.08 % by weight, also more preferably 0.02 % by weight ~ 0.06 % by weight, particularly preferably 0.02 % by weight ~ 0.05 % by weight.When the amount of catalyzer being regulated in described scope, such as antistatic property can be provided extremely excellent and adhesive residue prevents the polyurethane-base pressure-sensitive adhesive that performance and re-workability, initial wetting property and the transparency are also excellent in addition.
<A-2. ionic liquid >
Polyurethane-base pressure-sensitive adhesive of the present invention comprises the ionic liquid containing fluorine organic anion.When polyurethane-base pressure-sensitive adhesive of the present invention comprises the ionic liquid containing fluorine organic anion, the polyurethane-base pressure-sensitive adhesive that antistatic property is extremely excellent can be provided.The species number being incorporated into the ionic liquid in polyurethane-base pressure-sensitive adhesive of the present invention can be only a kind of or can for two or more.
Term used herein " ionic liquid " refers to the melting salt (ionic compound) for liquid at 25 DEG C.
In the scope not damaging effect of the present invention, any suitable ionic liquid can be used as ionic liquid, as long as described ionic liquid comprises fluorine organic anion.This ionic liquid be preferably such as by fluorine organic anion and the ionic liquid that positively charged ion is formed.Will by fluorine organic anion and the ionic liquid that positively charged ion is formed is used as the polyurethane-base pressure-sensitive adhesive that described ionic liquid can provide antistatic property extremely excellent.
In the scope not damaging effect of the present invention, can by any suitable positively charged ion is used as to be formed ionic liquid positively charged ion.This positively charged ion is preferably selected from nitrogenous positively charged ion, sulfur-bearing positively charged ion and phosphorous cationic at least one.Select this arbitrarily the polyurethane-base pressure-sensitive adhesive that positively charged ion can provide antistatic property extremely excellent.
Ionic liquid can be formed positively charged ion is preferably selected from the cationic at least one with the structure represented by general formula (1) ~ (5).
In general formula (1), R aexpression has the alkyl of 4 ~ 20 carbon atoms and can comprise heteroatoms, and R that can be mutually identical or different band R crespective expression hydrogen or there is the alkyl of 1 ~ 16 carbon atom and can heteroatoms be comprised separately; Condition is when nitrogen-atoms comprises double bond, there is not R c.
In general formula (2), R dexpression has the alkyl of 2 ~ 20 carbon atoms and can comprise heteroatoms, and R that can be mutually identical or different e, R fand R grespective expression hydrogen or there is the alkyl of 1 ~ 16 carbon atom and can heteroatoms be comprised separately.
In general formula (3), R hexpression has the alkyl of 2 ~ 20 carbon atoms and can comprise heteroatoms, and R that can be mutually identical or different i, R jand R krespective expression hydrogen or there is the alkyl of 1 ~ 16 carbon atom and can heteroatoms be comprised separately.
In general formula (4), Z represents nitrogen-atoms, sulphur atom or phosphorus atom, and R that can be mutually identical or different l, R m, R nand R orespective expression has the alkyl of 1 ~ 20 carbon atom and can comprise heteroatoms separately; Condition is when Z represents sulphur atom, there is not R o.
In general formula (5), X represents Li atom, Na atom or K atom.
The cationic example represented by general formula (1) comprises pyridine positively charged ion, tetramethyleneimine positively charged ion, piperidines positively charged ion, there is the positively charged ion of pyrroline skeleton and there is the positively charged ion of pyrrole skeleton.
The cationic specific examples represented by general formula (1) comprises: pyridine positively charged ion is as 1-ethylpyridine positively charged ion, 1-butyl-pyridinium positively charged ion, 1-hexyl pyridine positively charged ion, 1-ethyl-3-picoline positively charged ion, 1-butyl-3-picoline positively charged ion, 1-hexyl-3-picoline positively charged ion, 1-butyl-4-picoline positively charged ion, 1-octyl group-4-picoline positively charged ion, 1-butyl-3,4-lutidine positively charged ion or 1,1-dimethyl pyrrolidine positively charged ion; Tetramethyleneimine positively charged ion is as 1-ethyl-1-crassitude positively charged ion, 1-methyl isophthalic acid-propyl pyrrole alkane positively charged ion, 1-methyl isophthalic acid-butyl pyrrolidine positively charged ion, 1-methyl-1-pentene base tetramethyleneimine positively charged ion, 1-methyl isophthalic acid-hexyl tetramethyleneimine positively charged ion, 1-methyl isophthalic acid-heptyl tetramethyleneimine positively charged ion, 1-ethyl-1-propyl pyrrole alkane positively charged ion, 1-ethyl-1-butyl pyrrolidine positively charged ion, 1-ethyl-1-amyl group tetramethyleneimine positively charged ion, 1-ethyl-1-hexyl tetramethyleneimine positively charged ion, 1-ethyl-1-heptyl tetramethyleneimine positively charged ion, 1,1-dipropyl tetramethyleneimine positively charged ion, 1-propyl group-1-butyl pyrrolidine positively charged ion or 1,1-dibutyl tetramethyleneimine positively charged ion; Piperidines positively charged ion is as 1-propylpiperdine positively charged ion, 1-amyl piperidine positively charged ion, 1-methyl isophthalic acid-ethyl piperidine positively charged ion, 1-methyl isophthalic acid-propylpiperdine positively charged ion, 1-methyl isophthalic acid-butyl piperidine positively charged ion, 1-methyl-1-pentene phenylpiperidines positively charged ion, 1-methyl isophthalic acid-hexyl piperidines positively charged ion, 1-methyl isophthalic acid-heptyl piperidines positively charged ion, 1-ethyl-1-propylpiperdine positively charged ion, 1-ethyl-1-butyl piperidine positively charged ion, 1-ethyl-1-amyl piperidine positively charged ion, 1-ethyl-1-hexyl piperidines positively charged ion, 1-ethyl-1-heptyl piperidines positively charged ion, 1-propyl group-1-butyl piperidine positively charged ion, 1,1-lupetidine positively charged ion, 1,1-dipropyl piperidines positively charged ion or 1,1-dibutyl piperidines positively charged ion; 2-methyl isophthalic acid-pyrroline positively charged ion; 1-ethyl-2-phenylindone positively charged ion; 1,2-dimethyl indole positively charged ion; With 1-ethyl carbazole positively charged ion.
In described positively charged ion, from can the viewpoint of displayed additional effect of the present invention, preferred example comprises: pyridine positively charged ion is as 1-ethylpyridine positively charged ion, 1-butyl-pyridinium positively charged ion, 1-hexyl pyridine positively charged ion, 1-ethyl-3-picoline positively charged ion, 1-butyl-3-picoline positively charged ion, 1-hexyl-3-picoline positively charged ion, 1-butyl-4-picoline positively charged ion or 1-octyl group-4-picoline positively charged ion; Tetramethyleneimine positively charged ion is as 1-ethyl-1-crassitude positively charged ion, 1-methyl isophthalic acid-propyl pyrrole alkane positively charged ion, 1-methyl isophthalic acid-butyl pyrrolidine positively charged ion, 1-methyl-1-pentene base tetramethyleneimine positively charged ion, 1-methyl isophthalic acid-hexyl tetramethyleneimine positively charged ion, 1-methyl isophthalic acid-heptyl tetramethyleneimine positively charged ion, 1-ethyl-1-propyl pyrrole alkane positively charged ion, 1-ethyl-1-butyl pyrrolidine positively charged ion, 1-ethyl-1-amyl group tetramethyleneimine positively charged ion, 1-ethyl-1-hexyl tetramethyleneimine positively charged ion or 1-ethyl-1-heptyl tetramethyleneimine positively charged ion; And piperidines positively charged ion is as 1-methyl isophthalic acid-ethyl piperidine positively charged ion, 1-methyl isophthalic acid-propylpiperdine positively charged ion, 1-methyl isophthalic acid-butyl piperidine positively charged ion, 1-methyl-1-pentene phenylpiperidines positively charged ion, 1-methyl isophthalic acid-hexyl piperidines positively charged ion, 1-methyl isophthalic acid-heptyl piperidines positively charged ion, 1-ethyl-1-propylpiperdine positively charged ion, 1-ethyl-1-butyl piperidine positively charged ion, 1-ethyl-1-amyl piperidine positively charged ion, 1-ethyl-1-hexyl piperidines positively charged ion, 1-ethyl-1-heptyl piperidines positively charged ion or 1-propyl group-1-butyl piperidine positively charged ion.1-hexyl pyridine positively charged ion, 1-ethyl-3-picoline positively charged ion, 1-butyl-3-picoline positively charged ion, 1-octyl group-4-picoline positively charged ion, 1-methyl isophthalic acid-propyl pyrrole alkane positively charged ion or 1-methyl isophthalic acid-propylpiperdine positively charged ion is preferred.
The cationic example represented by general formula (2) comprises imidazoles positively charged ion, tetrahydropyrimidine positively charged ion and dihydro-pyrimidin positively charged ion.
The cationic specific examples represented by general formula (2) comprises: imidazoles positively charged ion is as 1,3-methylimidazole positively charged ion, 1,3-diethyl imidazolium positively charged ion, 1-ethyl-3-methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-hexyl-3-Methylimidazole positively charged ion, 1-octyl group-3-Methylimidazole positively charged ion, 1-decyl-3-Methylimidazole positively charged ion, 1-dodecyl-3-Methylimidazole positively charged ion, 1-tetradecyl-3-Methylimidazole positively charged ion, 1,2-dimethyl-3-propyl imidazole positively charged ion, 1-ethyl-2,3-methylimidazole positively charged ion, 1-butyl-2,3-methylimidazole positively charged ion or 1-hexyl-2,3-methylimidazole positively charged ion; Tetrahydropyrimidine positively charged ion is as 1,3-dimethyl-1,4,5,6-tetrahydrochysene pyrimidine positively charged ion, 1,2,3-trimethylammonium-Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,2,3,4-tetramethyl--Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion or 1,2,3,5-tetramethyl--Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion; And dihydro-pyrimidin positively charged ion is as 1,3-dimethyl-Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,3-dimethyl-1,6-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-1,6-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion or 1,2,3,4-tetramethyl--1,6-dihydro-pyrimidin positively charged ion.
In described positively charged ion, from can the viewpoint of displayed additional effect of the present invention, preferred example comprises imidazoles positively charged ion is as 1,3-methylimidazole positively charged ion, 1,3-diethyl imidazolium positively charged ion, 1-ethyl-3-methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-hexyl-3-Methylimidazole positively charged ion, 1-octyl group-3-Methylimidazole positively charged ion, 1-decyl-3-Methylimidazole positively charged ion, 1-dodecyl-3-Methylimidazole positively charged ion or 1-tetradecyl-3-Methylimidazole positively charged ion.1-ethyl-3-methylimidazole positively charged ion or 1-hexyl-3-Methylimidazole positively charged ion is preferred.
The cationic example represented by general formula (3) comprises pyrazoles positively charged ion and pyrazoline positively charged ion.
The cationic specific examples represented by general formula (3) comprises: pyrazoles positively charged ion is as 1-methylpyrazole positively charged ion, 3-methylpyrazole positively charged ion, 1-Ethyl-2-Methyl pyrazoline positively charged ion, 1-ethyl-2,3,5-trimethylpyrazol positively charged ion, 1-propyl group-2,3,5-trimethylpyrazol positively charged ion or 1-butyl-2,3,5-trimethylpyrazol positively charged ion; And pyrazoline positively charged ion is as 1-ethyl-2,3,5-trimethylammonium pyrazoline positively charged ion, 1-propyl group-2,3,5-trimethylammonium pyrazoline positively charged ion or 1-butyl-2,3,5-trimethylammonium pyrazoline positively charged ion.
The cationic example represented by general formula (4) comprises tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl positively charged ion and by the part of thiazolinyl or alkoxyl group or epoxy group(ing) substituted alkyl and the positively charged ion obtained.
The cationic specific examples represented by general formula (4) comprises: tetramethylammonium cation, tetraethylammonium cation, tetrabutyl ammonium cation, four pentyl ammonium cation, tetrahexyl ammonium positively charged ion, four heptyl ammonium cations, triethyl methyl ammonium cation, tributyl ethyl ammonium cations, thmethylpropyl ammonium cation, trimethyldecylammonium ammonium cation, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyltrimetiiylammonium ammonium cation, trimethylsulfonium positively charged ion, triethyl sulfonium cation, tributyl sulfonium cation, three hexyl sulfonium cations, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, dimethyl decyl sulfonium cation, tetramethyl- positively charged ion, tetraethyl- positively charged ion, the tetrabutyl positively charged ion, four hexyls positively charged ion, four octyl groups positively charged ion, triethyl methyl positively charged ion, tributyl ethyl positively charged ion, trimethyldecylammonium positively charged ion and diallyl dimethyl ammonium positively charged ion.
In described positively charged ion, from can the viewpoint of displayed additional effect of the present invention, preferred example comprises: asymmetric tetraalkylammonium cation, trialkylsulfonium cation or tetraalkyl positively charged ion is as triethyl methyl ammonium cation, tributyl ethyl ammonium cations, trimethyldecylammonium ammonium cation, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, dimethyl decyl sulfonium cation, triethyl methyl positively charged ion, tributyl ethyl positively charged ion or trimethyldecylammonium positively charged ion, and N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyltrimetiiylammonium ammonium cation, diallyl dimethyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-propyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-butyl ammonium cation, N, N-dimethyl-N-ethyl-N-amyl group ammonium cation, N, N-dimethyl-N-ethyl-N-hexyl ammonium cation, N, N-dimethyl-N-ethyl-N-heptyl ammonium cation, N, N-dimethyl-N-ethyl-N-nonyl ammonium cation, N, N-dimethyl-N, N-dipropylammonium positively charged ion, N, N-diethyl-N-propyl-N-butyl ammonium cation, N, N-dimethyl-N-propyl group-N-amyl group ammonium cation, N, N-dimethyl-N-propyl group-N-hexyl ammonium cation, N, N-dimethyl-N-propyl group-N-heptyl ammonium cation, N, N-dimethyl-N-butyl-N-hexyl ammonium cation, N, N-diethyl-N-butyl-N-heptyl ammonium cation, N, N-dimethyl-N-amyl group-N-hexyl ammonium cation, N, N-dimethyl-N, N-dihexyl ammonium cation, trimethylammonium heptyl ammonium cation, N, N-diethyl-N-Methyl-N-propyl ammonium cation, N, N-diethyl-N-methyl--V-pentyl ammonium cation, N, N-diethyl-N-methyl-N-heptyl ammonium cation, N, N-diethyl-N-propyl-N-amyl group ammonium cation, triethyl propyl ammonium positively charged ion, triethyl amyl group ammonium cation, triethyl heptyl ammonium cation, N, N-dipropyl-N-methyl-N ethyl ammonium cation, N, N-dipropyl-N-methyl--V-pentyl ammonium cation, N, N-dipropyl-N-butyl-N-hexyl ammonium cation, N, N-dipropyl-N, N-dihexyl ammonium cation, N, N-dibutyl-N-methyl--V-pentyl ammonium cation, N, N-dibutyl-N-methyl-N-hexyl ammonium cation, tricaprylmethyl ammonium cation and N-methyl-N ethyl-N-propyl group-N-amyl group ammonium cation.Thmethylpropyl ammonium cation is preferred.
In the scope not damaging effect of the present invention, any suitable fluorine organic anion can be used as the fluorine organic anion that can form ionic liquid.This fluorine organic anion can be (fluoridized) fluoridized completely or can for partially fluorinated.
The example of this fluorine organic anion comprises the aryl sulfonic acid root fluoridized, perfluoro alkane base sulfonate radical, two (fluorine sulphonyl) imines (bis (fluorosulfonyl) imide), two (perfluoro alkane base sulphonyl) imines, cyano group perfluoro alkane base sulphonamide, two (cyano group) perfluoro alkane base sulfonyl methide, cyano group-two (perfluoro alkane base alkylsulfonyl) methide, three (perfluoro alkane base alkylsulfonyl) methide, trifluoroacetic acid root, perfluoroalkyl compound, three (perfluoro alkane base alkylsulfonyl) methide and (perfluoro alkane base alkylsulfonyl) trifluoroacetamide.
In described fluorine organic anion, perfluoro alkyl sulfonic acid root, two (fluorine sulphonyl) imines or two (perfluoro alkane base sulphonyl) imines are preferred.Its more specifically example comprise trifluoromethane sulfonic acid root, pentafluoroethyl group sulfonate radical, seven fluoropropyl sulfonate radicals, nine fluorine butyl sulfonic acid roots, two (fluorine sulphonyl) imines and two (trimethyl fluoride sulfonyl) imines.
As the specific examples of the ionic liquid be incorporated in polyurethane-base pressure-sensitive adhesive of the present invention, the suitable ionic liquid being selected from the combination of cation constituent and anionic component can be used.The instantiation of this ionic liquid comprises 1-hexyl pyridine Two (fluorine sulphonyl) imines, 1-ethyl-3-picoline Trifluoromethyl sulfonic acid, 1-ethyl-3-picoline Pentafluoroethyl group sulfonate, 1-ethyl-3-picoline Seven fluoropropyl sulfonate, 1-ethyl-3-picoline Nine fluorine butyl sulfosalts, 1-butyl-3-picoline Trifluoromethyl sulfonic acid,1-butyl-3-picoline Two (trimethyl fluoride sulfonyl) imines, 1-butyl-3-picoline Two (pentafluoroethyl group sulphonyl) imines, 1-octyl group-4-picoline Two (fluorine sulphonyl) imines, 1,1-dimethyl pyrrolidine Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-ethyl pyrrolidine Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane Two (fluorine sulphonyl) imines, 1-methyl isophthalic acid-butyl pyrrolidine Two (trimethyl fluoride sulfonyl) imines, 1-methyl-1-pentene base pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-hexyl pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-heptyl pyrrolidines Two (trimethyl fluoride sulfonyl) imines,1-ethyl-1-propyl pyrrole alkane Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-butyl pyrrolidine Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-amyl group pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-hexyl pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-heptyl pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1,1-dipropyl pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1-propyl group-1-butyl pyrrolidine Two (trimethyl fluoride sulfonyl) imines, 1,1-dibutyl pyrrolidines Two (trimethyl fluoride sulfonyl) imines, 1-propylpiperdine Two (trimethyl fluoride sulfonyl) imines, 1-amyl piperidine Two (trimethyl fluoride sulfonyl) imines, 1,1-lupetidine Two (trimethyl fluoride sulfonyl) imines,1-methyl isophthalic acid-ethyl piperidine Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-propylpiperdine Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-propylpiperdine Two (fluorine sulphonyl) imines, 1-methyl isophthalic acid-butyl piperidine Two (trimethyl fluoride sulfonyl) imines, 1-methyl-1-pentene phenylpiperidines Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-hexyl piperidines Two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-heptyl piperidines Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-propylpiperdine Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-butyl piperidine Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-amyl piperidine Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-1-hexyl piperidines Two (trimethyl fluoride sulfonyl) imines,1-ethyl-1-heptyl piperidines Two (trimethyl fluoride sulfonyl) imines, 1,1-dipropyl piperidines Two (trimethyl fluoride sulfonyl) imines, 1-propyl group-1-butyl piperidine Two (trimethyl fluoride sulfonyl) imines, 1,1-dibutyl piperidines Two (trimethyl fluoride sulfonyl) imines, 1,1-dimethyl pyrrolidine Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-ethyl pyrrolidine Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-butyl pyrrolidine Two (pentafluoroethyl group sulphonyl) imines, 1-methyl-1-pentene base pyrrolidines Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-hexyl pyrrolidines Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-heptyl pyrrolidines Two (pentafluoroethyl group sulphonyl) imines,1-ethyl-1-propyl pyrrole alkane Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-butyl pyrrolidine Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-amyl group pyrrolidines Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-hexyl pyrrolidines Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-heptyl pyrrolidines Two (pentafluoroethyl group sulphonyl) imines,1,1-dipropyl pyrrolidines Two (pentafluoroethyl group sulphonyl) imines, 1-propyl group-1-butyl pyrrolidine Two (pentafluoroethyl group sulphonyl) imines, 1,1-dibutyl pyrrolidines Two (pentafluoroethyl group sulphonyl) imines, 1-propylpiperdine Two (pentafluoroethyl group sulphonyl) imines, 1-amyl piperidine Two (pentafluoroethyl group sulphonyl) imines, 1,1-lupetidine Two (pentafluoroethyl group sulphonyl) imines,1-methyl isophthalic acid-ethyl piperidine Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-propylpiperdine Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-butyl piperidine Two (pentafluoroethyl group sulphonyl) imines, 1-methyl-1-pentene phenylpiperidines Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-hexyl piperidines Two (pentafluoroethyl group sulphonyl) imines, 1-methyl isophthalic acid-heptyl piperidines Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-propylpiperdine Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-butyl piperidine Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-amyl piperidine Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-hexyl piperidines Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-1-heptyl piperidines Two (pentafluoroethyl group sulphonyl) imines,1,1-dipropyl piperidines Two (pentafluoroethyl group sulphonyl) imines, 1-propyl group-1-butyl piperidine Two (pentafluoroethyl group sulphonyl) imines, 1,1-dibutyl piperidines Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-3-methylimidazole Trifluoroacetate, 1-ethyl-3-methylimidazole Hyptafluorobutyric acid salt, 1-ethyl-3-methylimidazole Trifluoromethyl sulfonic acid,1-ethyl-3-methylimidazole Seven fluoropropyl sulfonate, 1-ethyl-3-methylimidazole Nine fluorine butyl sulfosalts, 1-ethyl-3-methylimidazole Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-3-methylimidazole Two (fluorine sulphonyl) imines, 1-ethyl-3-methylimidazole Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-3-methylimidazole Three (trifluoromethyl sulfonyl) methide, 1-butyl-3-methylimidazole Trifluoroacetate, 1-butyl-3-methylimidazole Hyptafluorobutyric acid salt, 1-butyl-3-methylimidazole Trifluoromethyl sulfonic acid, 1-butyl-3-methylimidazole Perfluoro butyl sulfosalt, 1-butyl-3-methylimidazole Two (trimethyl fluoride sulfonyl) imines, 1-hexyl-3-methylimidazole Trifluoromethyl sulfonic acid, 1-hexyl-3-methylimidazole Two (fluorine sulphonyl) imines, 1,2-dimethyl-3-propyl imidazole Two (trimethyl fluoride sulfonyl) imines, 1-ethyl-2,3,5-trimethylpyrazol Two (trimethyl fluoride sulfonyl) imines, 1-propyl group-2,3,5-trimethylpyrazol Two (trimethyl fluoride sulfonyl) imines, 1-butyl-2,3,5-trimethylpyrazol Two (trimethyl fluoride sulfonyl) imines,1-ethyl-2,3,5-trimethylpyrazol Two (pentafluoroethyl group sulphonyl) imines, 1-propyl group-2,3,5-trimethylpyrazol Two (pentafluoroethyl group sulphonyl) imines, 1-butyl-2,3,5-trimethylpyrazol Two (pentafluoroethyl group sulphonyl) imines, 1-ethyl-2,3,5-trimethylpyrazol (trifluoromethyl sulfonyl) trifluoroacetamide, 1-propyl group-2,3,5-trimethylpyrazol (trifluoromethyl sulfonyl) trifluoroacetamide,1-butyl-2,3,5-trimethylpyrazol (trifluoromethyl sulfonyl) trifluoroacetamide, trimethylpropylammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-ethyl-N-propyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-ethyl-N-butyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-ethyl-N-amyl group ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-ethyl-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-ethyl-N-heptyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-ethyl-N-nonyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N, N-dipropylammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-propyl group-N-butyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-propyl group-N-amyl group ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-propyl group-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-propyl group-N-heptyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-butyl-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-butyl-N-heptyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N-amyl group-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dimethyl-N, N-dihexyl ammonium two (trimethyl fluoride sulfonyl) imines, trimethyl heptyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-diethyl-N-Methyl-N-propyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-diethyl-N-methyl--V-pentyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-diethyl-N-methyl-N, N-heptyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-diethyl-N-propyl-N-amyl group ammonium two (trimethyl fluoride sulfonyl) imines, triethyl group propyl ammonium two (trimethyl fluoride sulfonyl) imines, triethyl group amyl group ammonium two (trimethyl fluoride sulfonyl) imines, triethyl group heptyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dipropyl-N-methyl-N ethyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dipropyl-N-methyl--V-pentyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dipropyl-N-butyl-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dipropyl-N, N-dihexyl ammonium two (trimethyl fluoride sulfonyl) imines, N, N-dibutyl-N-methyl--V-pentyl ammonium two (trimethyl fluoride sulfonyl) imines,N, N-dibutyl-N-methyl-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines, tricaprylmethylammonium two (trimethyl fluoride sulfonyl) imines, N-methyl-N ethyl-N-propyl group-N-amyl group ammonium two (trimethyl fluoride sulfonyl) imines, 1-butyl-pyridinium (trifluoromethyl sulfonyl) trifluoroacetamide, 1-butyl-3-picoline (trifluoromethyl sulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazole (trifluoromethyl sulfonyl) trifluoroacetamide, tetrahexyl ammonium two (trimethyl fluoride sulfonyl) imines, diallyl dimethyl ammonium trifluoromethyl sulfonic acid, diallyl dimethyl ammonium two (trimethyl fluoride sulfonyl) imines, diallyl dimethyl ammonium two (pentafluoroethyl group sulphonyl) imines, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium trifluoromethyl sulfonic acid, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium two (trimethyl fluoride sulfonyl) imines, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium two (pentafluoroethyl group sulphonyl) imines, glycidyltrimetiiylammonium ammonium trifluoromethyl sulfonic acid, glycidyltrimetiiylammonium ammonium two (trimethyl fluoride sulfonyl) imines, glycidyltrimetiiylammonium ammonium two (pentafluoroethyl group sulphonyl) imines, diallyl dimethyl ammonium two (trimethyl fluoride sulfonyl) imines, diallydimethyl two (pentafluoroethyl group sulphonyl) imines, two (trimethyl fluoride sulfonyl) imine lithiums and two (fluorine sulphonyl) imine lithium.
In described ionic liquid, 1-hexyl pyridine two (fluorine sulphonyl) imines, 1-ethyl-3-picoline trifluoromethyl sulfonic acid, 1-ethyl-3-picoline pentafluoroethyl group sulfonate, 1-ethyl-3-picoline seven fluoropropyl sulfonate, 1-ethyl-3-picoline nine fluorine butyl sulfosalts, 1-butyl-3-picoline trifluoromethyl sulfonic acid, 1-butyl-3-picoline two (trimethyl fluoride sulfonyl) imines, 1-octyl group-4-picoline two (fluorine sulphonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane two (fluorine sulphonyl) imines, 1-methyl isophthalic acid-propylpiperdine two (trimethyl fluoride sulfonyl) imines, 1-methyl isophthalic acid-propylpiperdine two (fluorine sulphonyl) imines, 1-ethyl-3-methylimidazole trifluoromethyl sulfonic acid, 1-ethyl-3-methylimidazole seven fluoropropyl sulfonate, 1-ethyl-3-methylimidazole two (trimethyl fluoride sulfonyl) imines, 1-ethyl-3-methylimidazole two (fluorine sulphonyl) imines, 1-hexyl-3-Methylimidazole two (fluorine sulphonyl) imines, trimethylpropylammonium two (trimethyl fluoride sulfonyl) imines, two (trimethyl fluoride sulfonyl) imine lithiums or two (fluorine sulphonyl) imine lithium are preferred.
Although commercially available product can be used as described ionic liquid, can according to synthesis ionic liquid as described below.Although the method for synthesis ionic liquid is not particularly limited, as long as obtain object ion liquid, but usually use such as such described in document " Ionic Liquid:The Front andFuture of Material Development " (being published by CMC Publishing CO., LTD.) halide, hydroxide process, acid esters method, complexometry and neutralisation separately.
Although below by employing by nitrogenous salt synthetic method as an example describes halide, hydroxide process, acid esters method, complexometry and neutralisation, but also can obtain other ionic liquid any as sulfur-bearing by identical method salt or phosphorous salt.
Halide is the method that this reaction by being represented by reaction formula (1) ~ (3) is carried out.First, tertiary amine and alkyl halide are reacted to each other and halogenide (chlorine, bromine or iodine are used as halogen by reaction formula (1)) is provided.
By making gained halogenide and the anion structure (A with object ion liquid -) acid (HA) or salt (MA, wherein M represents that the positively charged ion forming salt with desired anion is as ammonium, lithium, sodium or potassium) react and obtain object ion liquid (R 4nA).
(1)R 3N+RX→R 4NX(X：Cl，Br，I)
(2)R 4NX+HA→R 4NA+HX
(3) R 4nX+MA → R 4nA+MX (M:NH 4, Li, Na, K, Ag etc.)
Hydroxide process is the method that this reaction by being represented by reaction formula (4) ~ (8) is carried out.First, by ion exchange membrane electrolysis (reaction formula (4)), OH type ion-exchange-resin process (reaction formula (5)) or with silver suboxide (Ag 2o) (reaction formula (6)) (chlorine, bromine or iodine are used as halogen) is reacted by halogenide (R 4nX) oxyhydroxide (R is obtained 4nOH).
By the reaction represented by reaction formula (7) and (8) is obtained object ion liquid (R for gained oxyhydroxide 4nA).
(4)R 4NX+H 2O→R 4NOH+1/2H 2+1/2X 2（X：Cl，Br，I)
(5) R 4nX+P-OH → R 4nOH+P-X (P-OH:OH type ion exchange resin)
(6)R 4NX+1/2Ag 2O+1/2H 2O→R 4NOH+AgX
(7)R 4NOH+HA→R 4NA+H 2O
(8) R 4nOH+MA → R 4nA+MOH (M:NH 4, Li, Na, K, Ag etc.)
Acid esters method is the method that this reaction by being represented by reaction formula (9) ~ (11) is carried out.First, tertiary amine (R is made 3n) and acid esters react to each other and Esterification product (reaction formula (9) be provided, by the ester of mineral acid as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid or carbonic acid, organic acid such as the ester of methylsulphonic acid, methyl-phosphorous acid or formic acid etc. is used as acid esters).
By the reaction represented by reaction formula (10) and (11) is obtained object ion liquid (R for the Esterification product of gained 4nA).In addition, by using such as trifluoromethane sulfonic acid methyl esters or trifluoro-acetate directly can obtain ionic liquid as acid esters.
(9)R 3N+ROY→R 4NOY
(OY: deng)
(10)R 4NOY+HA→R 4NA+HOY
(OY: when, )
(11) R 4nOY+MA → R 4nA+MOY (M:NH 4, Li, Na, K, Ag etc.)
Neutralisation is the method that this reaction by being represented by reaction formula (12) is carried out.Can by making tertiary amine and organic acid as CF 3cOOH, CF 3sO 3h, (CF 3sO 2) 2nH, (CF 3sO 2) 3cH or (C 2f 5sO 2) 2nH reacts to each other and obtains ionic liquid.
(12)R 3N+HZ→R 3HN +Z -
[HZ:CF 3cOOH, CF 3sO 3h, (CF 3sO 2) 2nH, (CF 3sO 2) 3cH, (C 2f 5sO 2) 2the organic acid of NH etc.]
R shown in reaction formula (1) ~ (12) represent hydrogen separately or have 1 ~ 20 carbon atom alkyl and can each self-contained heteroatoms.
Although the combined amount of ionic liquid can not indistinguishably limit, because combined amount changes according to the consistency between polymkeric substance used and ionic liquid, but usually, relative to the polyurethane-based resin of 100 weight parts, combined amount is preferably 0.001 weight part ~ 50 weight part, more preferably 0.01 weight part ~ 40 weight part, also more preferably 0.01 weight part ~ 30 weight part, particularly preferably 0.01 weight part ~ 20 weight part, most preferably 0.01 weight part ~ 10 weight part.The combined amount of ionic liquid is regulated the polyurethane-base pressure-sensitive adhesive that antistatic property can be provided in described scope extremely excellent.When the combined amount of ionic liquid is less than 0.001 weight part, sufficient antistatic property may not be obtained.When the combined amount of ionic liquid is more than 50 weight part, the contaminated degree of adherend is tended to expand.
<A-3. other composition >
In the scope not damaging effect of the present invention, except polyurethane-based resin as above and ionic liquid, polyurethane-base pressure-sensitive adhesive of the present invention can also comprise any other suitable composition.The example of other composition this comprises other resinous principle outside polyurethane-based resin, tackifier, mineral filler, organic filler, metal-powder, pigment, foil-like material, tenderizer, softening agent, antiaging agent, conductive agent, UV light absorber, antioxidant, photostabilizer, surface lubricant, levelling agent, corrosion inhibitor, thermo-stabilizer, polymerization retarder, lubricant and solvent.
Polyurethane-base pressure-sensitive adhesive of the present invention can comprise modified silicon oil.When polyurethane-base pressure-sensitive adhesive of the present invention comprises modified silicon oil, effect of the present invention can be showed with extra efficient manner.
When polyurethane-base pressure-sensitive adhesive of the present invention comprises modified silicon oil, relative to 100 parts by weight of polyurethane base resins, its content is preferably 0.001 weight part ~ 50 weight part, more preferably 0.01 weight part ~ 40 weight part, also more preferably 0.01 weight part ~ 30 weight part, particularly preferably 0.01 weight part ~ 20 weight part, most preferably 0.01 weight part ~ 10 weight part.Regulated by the content of modified silicon oil makes the present invention can show its effect with extra efficient manner in described scope.
In the scope not damaging effect of the present invention, any suitable modified silicon oil can be used as described modified silicon oil.This modified silicon oil is the modified silicon oil that such as can derive from Shin-Etsu Chemial Co., Ltd (Shin-Etsu Chemical Co., Ltd).
Modified silicon oil is preferably polyether modified silicon oil.Polyether modified silicon oil is adopted to make the present invention can show its effect with extra efficient manner.
The example of polyether modified silicon oil comprises side chain type polyether modified silicon oil and two tip type polyether modified silicon oils.Wherein, two tip type polyether modified silicon oils are preferred, because can show effect of the present invention with fully extra efficient manner.
<A-4. characteristic >
The antistatic property of polyurethane-base pressure-sensitive adhesive of the present invention is extremely excellent and it is preferably less than 4.0kV relative to the absolute value of the stripping charge voltage of sheet glass, more preferably below 3.5kV, also more preferably below 3.0kV, also more preferably below 2.5kV, also more preferably below 2.0kV, also more preferably below 1.5kV, also more preferably below 1.0kV, particularly preferably below 0.5kV, most preferably below 0.3kV.When stripping charge voltage drops in described scope, the antistatic property of polyurethane-base pressure-sensitive adhesive of the present invention is extremely excellent.
Polyurethane-base pressure-sensitive adhesive of the present invention is to the adhesive power of sheet glass, at once initial adhering force after being pasted to sheet glass in it, be preferably below 0.5N/25mm, more preferably 0.005N/25mm ~ 0.5N/25mm, also more preferably 0.005N/25mm ~ 0.4N/25mm, particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When initial adhering force drops in described scope, polyurethane-base pressure-sensitive adhesive of the present invention has the initial pressure sensitive glueyness of appropriateness and therefore can show extra excellent re-workability.
It should be noted that can the measurement carrying out initial adhering force as described below.The surface protection film with the formation of pressure-sensitive adhesive layer comprising polyurethane-base pressure-sensitive adhesive of the present invention is cut into width and is 25mm and length is the evaluation sample of 150mm.By 2.0kg roller being made a round trip under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C, thus the formation of pressure-sensitive adhesive layer surface of evaluation sample is pasted to sheet glass (by Song Langxiaozi Industrial Co., Ltd (Matsunami Glass Ind., Ltd.), trade(brand)name: Micro Slide Glass S), under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C aging 30 minutes subsequently.Thereafter, by under the draw rate of the peel angle of 180 ° and 300mm/ minute, general tensile testing machine (being manufactured by minebea Co., Lt (MinebeaCo., Ltd.), ProductName: TCM-1kNB) is utilized to carry out peeling off and measure the adhesive power of sample.
Be pasted to sheet glass and after store 7 days under 50 DEG C and 50%RH, the adhesive power of polyurethane-base pressure-sensitive adhesive of the present invention to sheet glass is preferably below 0.5N/25mm, more preferably 0.005N/25mm ~ 0.5N/25mm, also more preferably 0.005N/25mm ~ 0.4N/25mm, particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described adhesive power drops in described scope, polyurethane-base pressure-sensitive adhesive of the present invention can show extra excellent re-workability.
It should be noted that the measurement can passing through to carry out described adhesive power as follows: by the method manufacture evaluation sample identical with situation about measuring the initial adhering force of sheet glass; And by the adhesive power measuring sample after 7 days will be being stored under the humidity of described sample at the temperature of 50 DEG C and 50%RH with identical method in the situation measuring initial adhering force.
Be pasted to sheet glass and after store 7 days under 60 DEG C and 90%RH, the adhesive power of polyurethane-base pressure-sensitive adhesive of the present invention to sheet glass is preferably below 0.5N/25mm, more preferably 0.005N/25mm ~ 0.5N/25mm, also more preferably 0.005N/25mm ~ 0.4N/25mm, particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described adhesive power drops in described scope, polyurethane-base pressure-sensitive adhesive of the present invention can show extra excellent re-workability.
It should be noted that the measurement can passing through to carry out described adhesive power as follows: by the method manufacture evaluation sample identical with situation about measuring the initial adhering force of sheet glass; And by the adhesive power measuring sample after 7 days will be being stored under the humidity of described sample at the temperature of 60 DEG C and 90%RH with identical method in the situation measuring initial adhering force.
Be pasted to sheet glass and after store 7 days under 85 DEG C and 50%RH, the adhesive power of polyurethane-base pressure-sensitive adhesive of the present invention to sheet glass is preferably below 0.5N/25mm, more preferably 0.005N/25mm ~ 0.5N/25mm, also more preferably 0.005N/25mm ~ 0.4N/25mm, particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described adhesive power drops in described scope, polyurethane-base pressure-sensitive adhesive of the present invention can show extra excellent re-workability.
It should be noted that the measurement can passing through to carry out described adhesive power as follows: by the method manufacture evaluation sample identical with situation about measuring the initial adhering force of sheet glass; And by the adhesive power measuring sample after 7 days will be being stored under the humidity of described sample at the temperature of 85 DEG C and 50%RH with identical method in the situation measuring initial adhering force.
Under any one condition of following condition, the adhesive power of polyurethane-base pressure-sensitive adhesive of the present invention to sheet glass is preferably below 0.5N/25mm, more preferably 0.005N/25mm ~ 0.5N/25mm, also more preferably 0.005N/25mm ~ 0.4N/25mm, particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm: after being pasted to sheet glass at once, be pasted to sheet glass and after store 7 days under 50 DEG C and 50%RH, be pasted to sheet glass and after store 7 days under 60 DEG C and 90%RH, and be pasted to sheet glass and after store 7 days under 85 DEG C and 50%RH.When described adhesive power drops in described scope, polyurethane-base pressure-sensitive adhesive of the present invention can show extra excellent re-workability.
Polyurethane-base pressure-sensitive adhesive of the present invention preferably has high transparent.When polyurethane-base pressure-sensitive adhesive of the present invention has high transparent, can accurately check etc. under the state on surface pressure-sensitive adhesive being pasted to optical component or electronic component.The mist degree of polyurethane-base pressure-sensitive adhesive of the present invention is preferably less than 5%, and more preferably less than 4%, also more preferably less than 3%, particularly preferably less than 2%, most preferably less than 1%.
Should note, utilize haze meter HM-150 (by (the MURAKAMI COLOR RESEARCH LABORATORY CO. of color technical institute in village according to JIS-K-7136, LTD.) manufacture) mist degree is measured, and calculate based on following formula: mist degree (%)=(Td/Tt) × 100 (Td: diffuse transmittance, Tt: total light transmittance).
<<B. surface protection film >>
Surface protection film of the present invention is the surface protection film of the surface protection being preferred for optical component or electronic component.Surface protection film of the present invention comprises substrate layer and formation of pressure-sensitive adhesive layer and described formation of pressure-sensitive adhesive layer comprises polyurethane-base pressure-sensitive adhesive of the present invention.
Fig. 1 is the schematic sectional view of surface protection film according to the preferred embodiment of the present invention.Surface protection film 10 comprises substrate layer 1 and formation of pressure-sensitive adhesive layer 2.Surface protection film of the present invention can also comprise any other layer of suitable (not shown) as required.
In order to such as form the rolled body that can easily recoil, such as, can by add in substrate layer fatty acid amide, polymine, chain alkyl class additive etc. to substrate layer 1 its on formation of pressure-sensitive adhesive layer 2 is not set surface carry out lift-off processing, or can to substrate layer 1 its on formation of pressure-sensitive adhesive layer 2 is not set surface the coating formed as polysiloxane-based, chain alkyl class or fluorine class stripper by any suitable stripper is set.
The release liner with separability can be pasted to surface protection film of the present invention.
According to application, the thickness of surface protection film of the present invention can be set as any suitable thickness.From the viewpoint of abundant performance effect of the present invention, described thickness is preferably 10 μm ~ 300 μm, more preferably 15 μm ~ 250 μm, also more preferably 20 μm ~ 200 μm, particularly preferably 25 μm ~ 150 μm.
The antistatic property of surface protection film of the present invention is extremely excellent and it is preferably less than 4.0kV relative to the absolute value of the stripping charge voltage of sheet glass; more preferably below 3.5kV; also more preferably below 3.0kV; also more preferably below 2.5kV; also more preferably below 2.0kV, also more preferably below 1.5kV, also more preferably below 1.0kV; particularly preferably below 0.5kV, most preferably below 0.3kV.When stripping charge voltage drops in described scope, the antistatic property of surface protection film of the present invention is extremely excellent.
Surface protection film of the present invention is to the adhesive power of sheet glass; at once initial adhering force after being pasted to sheet glass in it; be preferably below 0.5N/25mm; more preferably 0.005N/25mm ~ 0.5N/25mm; also more preferably 0.005N/25mm ~ 0.4N/25mm; particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described initial adhering force drops in described scope, surface protection film of the present invention has the initial pressure sensitive glueyness of appropriateness and therefore can show extra excellent re-workability.
It should be noted that can the measurement carrying out initial adhering force as described below.Surface protection film is cut into width and is 25mm and length is the evaluation sample of 150mm.By 2.0kg roller being made a round trip under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C, thus the formation of pressure-sensitive adhesive layer surface of evaluation sample is pasted to sheet glass (by Song Langxiaozi Industrial Co., Ltd, trade(brand)name: Micro Slide Glass S), under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C aging 30 minutes subsequently.Thereafter, by under the draw rate of the peel angle of 180 ° and 300mm/ minute, general tensile testing machine (being manufactured by minebea Co., Lt, ProductName: TCM-1kNB) is utilized to carry out peeling off and measure the adhesive power of sample.
Be pasted to sheet glass and after store 7 days under 50 DEG C and 50%RH; the adhesive power of surface protection film of the present invention to sheet glass is preferably below 0.5N/25mm; more preferably 0.005N/25mm ~ 0.5N/25mm; also more preferably 0.005N/25mm ~ 0.4N/25mm; particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described adhesive power drops in described scope, surface protection film of the present invention can show extra excellent re-workability.
It should be noted that the measurement can passing through to carry out described adhesive power as follows: by the method manufacture evaluation sample identical with situation about measuring the initial adhering force of sheet glass; And by the adhesive power measuring sample after 7 days will be being stored under the humidity of described sample at the temperature of 50 DEG C and 50%RH with identical method in the situation measuring initial adhering force.
Be pasted to sheet glass and after store 7 days under 60 DEG C and 90%RH; the adhesive power of surface protection film of the present invention to sheet glass is preferably below 0.5N/25mm; more preferably 0.005N/25mm ~ 0.5N/25mm; also more preferably 0.005N/25mm ~ 0.4N/25mm; particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described adhesive power drops in described scope, surface protection film of the present invention can show extra excellent re-workability.
It should be noted that the measurement can passing through to carry out described adhesive power as follows: by the method manufacture evaluation sample identical with situation about measuring the initial adhering force of sheet glass; And by the adhesive power measuring sample after 7 days will be being stored under the humidity of described sample at the temperature of 60 DEG C and 90%RH with identical method in the situation measuring initial adhering force.
Be pasted to sheet glass and after store 7 days under 85 DEG C and 50%RH; the adhesive power of surface protection film of the present invention to sheet glass is preferably below 0.5N/25mm; more preferably 0.005N/25mm ~ 0.5N/25mm; also more preferably 0.005N/25mm ~ 0.4N/25mm; particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm.When described adhesive power drops in described scope, surface protection film of the present invention can show extra excellent re-workability.
It should be noted that the measurement can passing through to carry out described adhesive power as follows: by the method manufacture evaluation sample identical with situation about measuring the initial adhering force of sheet glass; And by the adhesive power measuring sample after 7 days will be being stored under the humidity of described sample at the temperature of 85 DEG C and 50%RH with identical method in the situation measuring initial adhering force.
Under any one condition following, the adhesive power of surface protection film of the present invention to sheet glass is preferably below 0.5N/25mm, more preferably 0.005N/25mm ~ 0.5N/25mm, also more preferably 0.005N/25mm ~ 0.4N/25mm, particularly preferably 0.005N/25mm ~ 0.3N/25mm, most preferably 0.01N/25mm ~ 0.2N/25mm: after being pasted to sheet glass at once, be pasted to sheet glass and after store 7 days under 50 DEG C and 50%RH, be pasted to sheet glass and after store 7 days under 60 DEG C and 90%RH, and be pasted to sheet glass and after store 7 days under 85 DEG C and 50%RH.When described adhesive power drops in described scope, surface protection film of the present invention can show extra excellent re-workability.
Surface protection film of the present invention preferably has high transparent.When surface protection film of the present invention has high transparent, can accurately check etc. under the state on surface surface protection film being pasted to optical component or electronic component.The mist degree of surface protection film of the present invention is preferably less than 5%, and more preferably less than 4%, also more preferably less than 3%, particularly preferably less than 2%, most preferably less than 1%.It should be noted that the measurement of mist degree is same as described above.
<B-1. formation of pressure-sensitive adhesive layer >
Formation of pressure-sensitive adhesive layer comprises polyurethane-base pressure-sensitive adhesive of the present invention.The content of polyurethane-base pressure-sensitive adhesive of the present invention in formation of pressure-sensitive adhesive layer is preferably 50 % by weight ~ 100 % by weight, more preferably 70 % by weight ~ 100 % by weight, also more preferably 90 % by weight ~ 100 % by weight, particularly preferably 95 % by weight ~ 100 % by weight, most preferably 98 % by weight ~ 100 % by weight.Regulated by the content of polyurethane-base pressure-sensitive adhesive of the present invention in formation of pressure-sensitive adhesive layer to provide adhesive residue to prevent the surface protection film that performance is extremely excellent in described scope.
According to application, any suitable thickness can be used as the thickness of formation of pressure-sensitive adhesive layer.The thickness of formation of pressure-sensitive adhesive layer is preferably 1 μm ~ 100 μm, more preferably 3 μm ~ 50 μm, also more preferably 5 μm ~ 30 μm.
Formation of pressure-sensitive adhesive layer can by any suitable manufacture method manufacture.The example of this manufacture method relates to be applied to as the composition forming formation of pressure-sensitive adhesive layer material on substrate layer to form the method for formation of pressure-sensitive adhesive layer on substrate layer.The example of this coating process comprises roller coat, intaglio plate coating, reverse coating, roller brush, spraying, airblade coating and utilizes the extrusion coated of die applicator.
<B-2. substrate layer >
According to application, any suitable thickness can be used as the thickness of substrate layer.The thickness of substrate layer is preferably 5 μm ~ 300 μm, more preferably 10 μm ~ 250 μm, also more preferably 15 μm ~ 200 μm, particularly preferably 20 μm ~ 150 μm.
Substrate layer can be individual layer or can be two-layer above layered product.Substrate layer can be drawn.
According to application, any suitable material can be used as the material of substrate layer.The example comprises plastics, paper, metallic membrane and non-woven fabrics.Wherein, plastics are preferred.Substrate layer can be made up of a kind of material or can be made up of two or more material.Such as, described layer can be made up of two or more plastics.
The example of plastics comprises polyester resin, polyamide-based resin and polyolefin resin.The example of polyester resin comprises polyethylene terephthalate, polybutylene terephthalate and PEN.The example of polyolefin resin comprises the homopolymer of olefinic monomer and the multipolymer of olefinic monomer.The specific examples of polyolefin resin comprises: homo-polypropylene; Use ethene composition as the propylene copolymers of copolymer composition as block, random or grafting analog copolymer; Reactor directly prepares TPO (reactor TPO); Polyvinyls is as low density, high-density, linea low density or extremely-low density polymkeric substance; With ethene copolymer as ethylene-propylene copolymer, vinyl-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methacrylic acid copolymer or ethylene methyl methacrylate multipolymer.
Substrate layer can comprise any suitable additive as required.The example that can be incorporated into the additive in substrate layer comprises antioxidant, UV light absorber, photostabilizer, static inhibitor, filler and pigment.The kind of the additive that can be incorporated in substrate layer, number and amount can be set suitably according to object.Especially, when the material of substrate layer is plastics, in order to such as prevent deterioration, preferably introduce several additive.From the viewpoint such as improving weathering resistance, the particularly preferably example of additive comprises antioxidant, UV light absorber, photostabilizer and filler.
Any suitable antioxidant can be used as antioxidant.The example of this antioxidant comprises phenol antioxidant, Phosphorus processing thermo-stabilizer, lactone processing thermo-stabilizer, sulphur type thermal stabilizing agent and phenol-phosphorus antioxidants.Relative to the base resin (when substrate layer is blend, resin based on described blend) of substrate layer, the content of antioxidant is preferably less than 1 % by weight, and more preferably less than 0.5 % by weight, also more preferably 0.01 % by weight ~ 0.2 % by weight.
Any suitable UV light absorber can be used as UV light absorber.The example of this UV light absorber comprises Benzotriazole Ultraviolet Stabilizer, triazine-based ultraviolet absorption agent and benzophenone ultraviolet absorption agent.Relative to forming the base resin of substrate layer (when substrate layer is blend, resin based on described blend), the content of UV light absorber is preferably less than 2 % by weight, and more preferably less than 1 % by weight, also more preferably 0.01 % by weight ~ 0.5 % by weight.
Any suitable photostabilizer can be used as photostabilizer.The example of this photostabilizer comprises hindered amine light stabilizer and benzoate light stabilizer.Relative to forming the base resin (when substrate layer is blend, resin based on described blend) of substrate layer, the content of photostabilizer is preferably less than 2 % by weight, and more preferably less than 1 % by weight, also more preferably 0.01 % by weight ~ 0.5 % by weight.
Any suitable filler can be used as filler.The example of this filler comprises mineral filler.The specific examples of mineral filler comprises carbon black, titanium dioxide and zinc oxide.Relative to forming the base resin (when substrate layer is blend, resin based on described blend) of substrate layer, the content of filler is preferably less than 20 % by weight, and more preferably less than 10 % by weight, also more preferably 0.01 % by weight ~ 10 % by weight.
The preferred embodiment of additive also comprises inorganic, the lower molecular weight and high molecular static inhibitor that are intended to give antistatic property as tensio-active agent, inorganic salt, polyvalent alcohol, metallic compound and carbon.Wherein, from the viewpoint polluting and keep pressure sensitive glueyness, high molecular static inhibitor and carbon are preferred.
<B-3. the method > of surface protection film is manufactured
Surface protection film of the present invention can by any suitable method manufacture.This manufacture method can be carried out according to such as following any suitable manufacture method:
(1) relate to by the material for the formation of formation of pressure-sensitive adhesive layer (such as, comprise the composition of polyvalent alcohol (A) and polyfunctional isocyanate compound (B), it is the raw material for polyurethane-base pressure-sensitive adhesive of the present invention) solution or hot melts be applied to method on substrate layer;
(2) according to the method for method (1), relate to described solution or hot melts to be applied on barrier film and by the formation of pressure-sensitive adhesive layer of formation and transfer on substrate layer;
(3) relate to and the material for the formation of formation of pressure-sensitive adhesive layer is expressed on substrate layer also by the cambial method of coating;
(4) relate to and substrate layer and formation of pressure-sensitive adhesive layer are extruded as two-layer above method;
(5) relate to the method utilizing individual layer and formation of pressure-sensitive adhesive layer laminate substrate layer, or utilize the method for two-layer i.e. formation of pressure-sensitive adhesive layer and laminate layers laminate substrate layer; Or
(6) relate to and be formed as the method for two-layer above layered product by formation of pressure-sensitive adhesive layer with for the formation of material such as film or the laminate layers of substrate layer.
<<C. >> is applied
Polyurethane-base pressure-sensitive adhesive of the present invention may be used for any suitable application.Polyurethane-base pressure-sensitive adhesive of the present invention is preferably used as the formation of pressure-sensitive adhesive layer of surface protection film, because the adhesive residue of pressure-sensitive adhesive prevents performance extremely excellent.With such program, surface protection film can be used for suitably the surface protection of optical component or electronic component.The optical component or the electronic component that are pasted with surface protection film of the present invention can repeatedly attach by hand and peel off.
Embodiment
Hereinafter, by embodiment, the present invention is specifically described.But the present invention is never limited to embodiment.It should be noted that test in embodiment etc. and evaluation method as described below.It should be noted that unless otherwise defined, the term " part " in following explanation refers to " weight part ", and unless otherwise defined, the term " % " in following explanation refer to " % by weight ".
< is relative to the measurement > of the stripping charge voltage of sheet glass
Surface protection film is cut into width and is 70mm and length is the sheet of 130mm, and when described there is barrier film, barrier film is peeled off.Thereafter, by 2kg roller is made a round trip, described is crimped on the untreated glass (being manufactured by Song Langxiaozi Co., Ltd., size 1.35mm × 10cm × 10cm) in advance except electricity.Now, surface protection film is in the state of giving prominence to 30cm from glass.Under the environment of the humidity of the temperature and 50%RH with 23 DEG C, gains were left standstill after one day, the end winding support giving prominence to 30cm from glass to be peeled off to sutomatic winding machine under the peeling rate of the peel angle of 150 ° and 10m/ minute.Then, the potential measurement machine (KSD-0103 is manufactured by Kasuga Electric K. K.) be fixed on apart from the position of surface protection film 10cm is utilized to measure stripping charge voltage.Measure under the environment of the humidity of the temperature and 50%RH with 23 DEG C.
< is to the measurement > of the adhesive power of sheet glass
(after being pasted to sheet glass initial adhering force) at once
Surface protection film is cut into width and is 25mm and length is the evaluation sample of 150mm.By 2.0kg roller being made a round trip under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C, thus the formation of pressure-sensitive adhesive layer surface of evaluation sample is pasted to sheet glass (by Song Langxiaozi Industrial Co., Ltd, trade(brand)name: Micro Slide Glass S), under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C aging 30 minutes subsequently.Thereafter, by under the draw rate of the peel angle of 180 ° and 300mm/ minute, general tensile testing machine (being manufactured by minebea Co., Lt, ProductName: TCM-1kNB) is utilized to carry out peeling off and measure the adhesive power of sample.
(being pasted to sheet glass and storing the adhesive power after 7 days under 50 DEG C and 50%RH)
Surface protection film is cut into width and is 25mm and length is the evaluation sample of 150mm.By 2.0kg roller being made a round trip under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C, thus the formation of pressure-sensitive adhesive layer surface of evaluation sample is pasted to sheet glass (by Song Langxiaozi Industrial Co., Ltd, trade(brand)name: Micro Slide Glass S), under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C aging 30 minutes subsequently.Thereafter, sample is stored 7 days under the humidity of the temperature of 50 DEG C and 50%RH.Thereafter, by under the draw rate of the peel angle of 180 ° and 300mm/ minute, general tensile testing machine (being manufactured by minebea Co., Lt, ProductName: TCM-1kNB) is utilized to carry out peeling off and measure the adhesive power of sample.
(being pasted to sheet glass and storing the adhesive power after 7 days under 60 DEG C and 90%RH)
Surface protection film is cut into width and is 25mm and length is the evaluation sample of 150mm.By 2.0kg roller being made a round trip under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C, thus the formation of pressure-sensitive adhesive layer surface of evaluation sample is pasted to sheet glass (by Song Langxiaozi Industrial Co., Ltd, trade(brand)name: Micro Slide Glass S), under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C aging 30 minutes subsequently.Thereafter, sample is stored 7 days under the humidity of the temperature of 60 DEG C and 90%RH.Thereafter, by under the draw rate of the peel angle of 180 ° and 300mm/ minute, general tensile testing machine (being manufactured by minebea Co., Lt, ProductName: TCM-1kNB) is utilized to carry out peeling off and measure the adhesive power of sample.
(being pasted to sheet glass and storing the adhesive power after 7 days under 85 DEG C and 50%RH)
Surface protection film is cut into width and is 25mm and length is the evaluation sample of 150mm.By 2.0kg roller being made a round trip under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C, thus the formation of pressure-sensitive adhesive layer surface of evaluation sample is pasted to sheet glass (by Song Langxiaozi Industrial Co., Ltd, trade(brand)name: Micro Slide Glass S), under the atmosphere of the humidity of the temperature and 50%RH with 23 DEG C aging 30 minutes subsequently.Thereafter, sample is stored 7 days under the humidity of the temperature of 85 DEG C and 50%RH.Thereafter, by under the draw rate of the peel angle of 180 ° and 300mm/ minute, general tensile testing machine (being manufactured by minebea Co., Lt, ProductName: TCM-1kNB) is utilized to carry out peeling off and measure the adhesive power of sample.
[embodiment 1]
Will as the polyvalent alcohol PREMINOL S3011 with three OH bases of 85 weight parts of polyvalent alcohol (A) (by Asahi Glass Co., Ltd (ASAHI GLASS CO., LTD.) manufacture, Mn=10, 000), the polyvalent alcohol SANNIX GP-3000 with three OH bases of 13 weight parts is (by Sanyo Chemical Industries, Ltd. (Sanyo Chemical Industries, Ltd.) manufacture, Mn=3, 000) the polyvalent alcohol SANNIX GP-1000 with three OH bases of and 2 weight parts (is manufactured by Sanyo Chemical Industries, Ltd., Mn=1, 000), as the multifunctional alicyclic isocyanate Compound C ORONATE HX of 18 weight parts of polyfunctional isocyanate compound (B) (by Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry CO., Ltd.) manufacture), the catalyzer of 0.04 weight part is (by chemical Industry Co., Ltd of Japan (NIHON KAGAKU SANGYOCO., LTD.) manufacture, trade(brand)name: Nacem Ferric Iron), as the Irganox 1010 (being manufactured by BASF) of 0.50 weight part of anti-deterioration agent, fatty acid ester (the Wickenol 111 of 30 weight parts, manufactured by Kao Corp (Kao Corporation), trade(brand)name: EXCEPARL IPP, Mn=299), the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines (IL210, by Di-ichi Kogyo Seiyaku Co., Ltd. (Dai-ichi Kogyo Seiyaku CO., Ltd.) manufacture) and mix as the ethyl acetate of 241 weight parts of diluting solvent, then utilize dispersion machine (disper) to carry out stirring to provide polyurethane-base pressure sensitive adhesive compositions.
Dip roll is utilized gained polyurethane-base pressure sensitive adhesive compositions to be applied to base material " Lumirror the S10 " (thickness: 38 μm formed by vibrin, by Dong Li Industrial Co., Ltd (TorayIndustries, Inc.) manufacture) on, make dry its thickness rear become 12 μm, then composition is solidified under the drying temperature of 130 DEG C and the condition of the time of drying of 2 minutes and drying.Thus, base material manufactures the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (1).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (1).
Table 1 illustrates evaluation result.
[embodiment 2]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (2) in the same manner as in example 1, difference is 1-ethyl-3-methylimidazole the amount of two (trimethyl fluoride sulfonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (2).
Table 1 illustrates evaluation result.
[embodiment 3]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (3) in the same manner as in example 1, difference is 1-ethyl-3-methylimidazole the amount of two (trimethyl fluoride sulfonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (3).
Table 1 illustrates evaluation result.
[embodiment 4]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (4) in the same manner as in example 1, difference is 1-ethyl-3-methylimidazole the amount of two (trimethyl fluoride sulfonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (4).
Table 1 illustrates evaluation result.
[embodiment 5]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (5) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-methylimidazole of 0.01 weight part into two (fluorine sulphonyl) imines (AS210 is manufactured by Di-ichi Kogyo Seiyaku Co., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (5).
Table 1 illustrates evaluation result.
[embodiment 6]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (6) in mode in the same manner as in Example 5, difference is 1-ethyl-3-methylimidazole the amount of two (fluorine sulphonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (6).
Table 1 illustrates evaluation result.
[embodiment 7]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (7) in mode in the same manner as in Example 5, difference is 1-ethyl-3-methylimidazole the amount of two (fluorine sulphonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (7).
Table 1 illustrates evaluation result.
[embodiment 8]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (8) in mode in the same manner as in Example 5, difference is 1-ethyl-3-methylimidazole the amount of two (fluorine sulphonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (8).
Table 1 illustrates evaluation result.
[embodiment 9]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (9) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-methylimidazole of 0.01 weight part into seven fluoropropyl sulfonate (EMI-EF31 becomes Co., Ltd. (MitsubishiMaterials Electronic Chemicals CO., Ltd.) to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (9).
Table 2 illustrates evaluation result.
[embodiment 10]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (10) in mode in the same manner as in Example 9, difference is 1-ethyl-3-methylimidazole the amount of seven fluoropropyl sulfonate changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (10).
Table 2 illustrates evaluation result.
[embodiment 11]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (11) in mode in the same manner as in Example 9, difference is 1-ethyl-3-methylimidazole the amount of seven fluoropropyl sulfonate changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (11).
Table 2 illustrates evaluation result.
[embodiment 12]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (12) in mode in the same manner as in Example 9, difference is 1-ethyl-3-methylimidazole the amount of seven fluoropropyl sulfonate changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (12).
Table 2 illustrates evaluation result.
[embodiment 13]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (13) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-methylimidazole of 0.01 weight part into trifluoromethyl sulfonic acid (EMI-EF11 becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (13).
Table 2 illustrates evaluation result.
[embodiment 14]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (14) in the mode identical with embodiment 13, difference is 1-ethyl-3-methylimidazole the amount of trifluoromethyl sulfonic acid changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (14).
Table 2 illustrates evaluation result.
[embodiment 15]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (15) in the mode identical with embodiment 13, difference is 1-ethyl-3-methylimidazole the amount of trifluoromethyl sulfonic acid changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (15).
Table 2 illustrates evaluation result.
[embodiment 16]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (16) in the mode identical with embodiment 13, difference is 1-ethyl-3-methylimidazole the amount of trifluoromethyl sulfonic acid changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (16).
Table 2 illustrates evaluation result.
[embodiment 17]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (17) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-hexyl-3-Methylimidazole of 0.01 weight part into two (fluorine sulphonyl) imines (HMI-FSI becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (17).
Table 3 illustrates evaluation result.
[embodiment 18]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (18) in the mode identical with embodiment 17, difference is 1-hexyl-3-Methylimidazole the amount of two (fluorine sulphonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (18).
Table 3 illustrates evaluation result.
[embodiment 19]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (19) in the mode identical with embodiment 17, difference is 1-hexyl-3-Methylimidazole the amount of two (fluorine sulphonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (19).
Table 3 illustrates evaluation result.
[embodiment 20]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (20) in the mode identical with embodiment 17, difference is 1-hexyl-3-Methylimidazole the amount of two (fluorine sulphonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (20).
Table 3 illustrates evaluation result.
[embodiment 21]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (21) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-picoline of 0.01 weight part into nine fluorine butyl sulfosalts (EtMePy-EF41 becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (21).
Table 3 illustrates evaluation result.
[embodiment 22]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (22) in the mode identical with embodiment 21, difference is 1-ethyl-3-picoline the amount of nine fluorine butyl sulfosalts changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (22).
Table 3 illustrates evaluation result.
[embodiment 23]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (23) in the mode identical with embodiment 21, difference is 1-ethyl-3-picoline the amount of nine fluorine butyl sulfosalts changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (23).
Table 3 illustrates evaluation result.
[embodiment 24]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (24) in the mode identical with embodiment 21, difference is 1-ethyl-3-picoline the amount of nine fluorine butyl sulfosalts changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (24).
Table 3 illustrates evaluation result.
[embodiment 25]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (25) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-picoline of 0.01 weight part into seven fluoropropyl sulfonate (EtMePy-EF31 becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (25).
Table 4 illustrates evaluation result.
[embodiment 26]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (26) in the mode identical with embodiment 25, difference is 1-ethyl-3-picoline the amount of seven fluoropropyl sulfonate changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (26).
Table 4 illustrates evaluation result.
[embodiment 27]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (27) in the mode identical with embodiment 25, difference is 1-ethyl-3-picoline the amount of seven fluoropropyl sulfonate changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (27).
Table 4 illustrates evaluation result.
[embodiment 28]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (28) in the mode identical with embodiment 25, difference is 1-ethyl-3-picoline the amount of seven fluoropropyl sulfonate changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (28).
Table 4 illustrates evaluation result.
[embodiment 29]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (29) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-picoline of 0.01 weight part into pentafluoroethyl group sulfonate (EtMePy-EF21 becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (29).
Table 4 illustrates evaluation result.
[embodiment 30]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (30) in the mode identical with embodiment 29, difference is 1-ethyl-3-picoline the amount of pentafluoroethyl group sulfonate changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (30).
Table 4 illustrates evaluation result.
[embodiment 31]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (31) in the mode identical with embodiment 29, difference is 1-ethyl-3-picoline the amount of pentafluoroethyl group sulfonate changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (31).
Table 4 illustrates evaluation result.
[embodiment 32]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (32) in the mode identical with embodiment 29, difference is 1-ethyl-3-picoline the amount of pentafluoroethyl group sulfonate changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (32).
Table 4 illustrates evaluation result.
[embodiment 33]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (33) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-ethyl-3-picoline of 0.01 weight part into trifluoromethyl sulfonic acid (EtMePy-EF11 becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (33).
Table 5 illustrates evaluation result.
[embodiment 34]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (34) in the mode identical with embodiment 33, difference is 1-ethyl-3-picoline the amount of trifluoromethyl sulfonic acid changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (34).
Table 5 illustrates evaluation result.
[embodiment 35]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (35) in the mode identical with embodiment 33, difference is 1-ethyl-3-picoline the amount of trifluoromethyl sulfonic acid changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (35).
Table 5 illustrates evaluation result.
[embodiment 36]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (36) in the mode identical with embodiment 33, difference is 1-ethyl-3-picoline the amount of trifluoromethyl sulfonic acid changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (36).
Table 5 illustrates evaluation result.
[embodiment 37]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (37) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-butyl-3-picoline of 0.01 weight part into two (trimethyl fluoride sulfonyl) imines (CIL312 is manufactured by Japan Carlit CO., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (37).
Table 5 illustrates evaluation result.
[embodiment 38]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (38) in the mode identical with embodiment 37, difference is 1-butyl-3-picoline the amount of two (trimethyl fluoride sulfonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (38).
Table 5 illustrates evaluation result.
[embodiment 39]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (39) in the mode identical with embodiment 37, difference is 1-butyl-3-picoline the amount of two (trimethyl fluoride sulfonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (39).
Table 5 illustrates evaluation result.
[embodiment 40]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (40) in the mode identical with embodiment 37, difference is 1-butyl-3-picoline the amount of two (trimethyl fluoride sulfonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (40).
Table 5 illustrates evaluation result.
[embodiment 41]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (41) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-butyl-3-picoline of 0.01 weight part into trifluoromethyl sulfonic acid (CIL313 is manufactured by Japan Carlit CO., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (41).
Table 6 illustrates evaluation result.
[embodiment 42]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (42) in the mode identical with embodiment 41, difference is 1-butyl-3-picoline the amount of trifluoromethyl sulfonic acid changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (42).
Table 6 illustrates evaluation result.
[embodiment 43]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (43) in the mode identical with embodiment 41, difference is 1-butyl-3-picoline the amount of trifluoromethyl sulfonic acid changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (43).
Table 6 illustrates evaluation result.
[embodiment 44]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (44) in the mode identical with embodiment 41, difference is 1-butyl-3-picoline the amount of trifluoromethyl sulfonic acid changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (44).
Table 6 illustrates evaluation result.
[embodiment 45]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (45) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-hexyl pyridine of 0.01 weight part into two (fluorine sulphonyl) imines (HxPy-FSI becomes Co., Ltd. to manufacture by Mitsubishi Materials electronization).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (45).
Table 6 illustrates evaluation result.
[embodiment 46]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (46) in the mode identical with embodiment 45, difference is 1-hexyl pyridine the amount of two (fluorine sulphonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (46).
Table 6 illustrates evaluation result.
[embodiment 47]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (47) in the mode identical with embodiment 45, difference is 1-hexyl pyridine the amount of two (fluorine sulphonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (47).
Table 6 illustrates evaluation result.
[embodiment 48]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (48) in the mode identical with embodiment 45, difference is 1-hexyl pyridine the amount of two (fluorine sulphonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (48).
Table 6 illustrates evaluation result.
[embodiment 49]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (49) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-octyl group-4-picoline of 0.01 weight part into two (fluorine sulphonyl) imines (MP403 is manufactured by Di-ichi Kogyo Seiyaku Co., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (49).
Table 7 illustrates evaluation result.
[embodiment 50]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (50) in the mode identical with embodiment 49, difference is 1-octyl group-4-picoline the amount of two (fluorine sulphonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (50).
Table 7 illustrates evaluation result.
[embodiment 51]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (51) in the mode identical with embodiment 49, difference is 1-octyl group-4-picoline the amount of two (fluorine sulphonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (51).
Table 7 illustrates evaluation result.
[embodiment 52]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (52) in the mode identical with embodiment 49, difference is 1-octyl group-4-picoline the amount of two (fluorine sulphonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (52).
Table 7 illustrates evaluation result.
[embodiment 53]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (53) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes trimethylpropylammonium two (trimethyl fluoride sulfonyl) imines (TMPA-TFSI of 0.01 weight part into, manufactured by Toyo Synthetic Industry Co., Ltd. (Toyo GoseiCO., Ltd.)).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (53).
Table 7 illustrates evaluation result.
[embodiment 54]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (54) in the mode identical with embodiment 53, difference is to change the amount of trimethylpropylammonium two (trimethyl fluoride sulfonyl) imines into 0.1 weight part.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (54).
Table 7 illustrates evaluation result.
[embodiment 55]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (55) in the mode identical with embodiment 53, difference is to change the amount of trimethylpropylammonium two (trimethyl fluoride sulfonyl) imines into 1 weight part.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (55).
Table 7 illustrates evaluation result.
[embodiment 56]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (56) in the mode identical with embodiment 53, difference is to change the amount of trimethylpropylammonium two (trimethyl fluoride sulfonyl) imines into 10 weight parts.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (56).
Table 7 illustrates evaluation result.
[embodiment 57]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (57) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-methyl isophthalic acid-propyl pyrrole alkane of 0.01 weight part into two (trimethyl fluoride sulfonyl) imines (IL220 is manufactured by Di-ichi Kogyo Seiyaku Co., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (57).
Table 8 illustrates evaluation result.
[embodiment 58]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (58) in the mode identical with embodiment 57, difference is 1-methyl isophthalic acid-propyl pyrrole alkane the amount of two (trimethyl fluoride sulfonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (58).
Table 8 illustrates evaluation result.
[embodiment 59]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (59) in the mode identical with embodiment 57, difference is 1-methyl isophthalic acid-propyl pyrrole alkane the amount of two (trimethyl fluoride sulfonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (59).
Table 8 illustrates evaluation result.
[embodiment 60]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (60) in the mode identical with embodiment 57, difference is 1-methyl isophthalic acid-propyl pyrrole alkane the amount of two (trimethyl fluoride sulfonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (60).
Table 8 illustrates evaluation result.
[embodiment 61]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (61) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-methyl isophthalic acid-propyl pyrrole alkane of 0.01 weight part into two (fluorine sulphonyl) imines (AS120 is manufactured by Di-ichi Kogyo Seiyaku Co., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (61).
Table 8 illustrates evaluation result.
[embodiment 62]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (62) in the mode identical with embodiment 61, difference is 1-methyl isophthalic acid-propyl pyrrole alkane the amount of two (fluorine sulphonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (62).
Table 8 illustrates evaluation result.
[embodiment 63]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (63) in the mode identical with embodiment 61, difference is 1-methyl isophthalic acid-propyl pyrrole alkane the amount of two (fluorine sulphonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (63).
Table 8 illustrates evaluation result.
[embodiment 64]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (64) in the mode identical with embodiment 61, difference is 1-methyl isophthalic acid-propyl pyrrole alkane the amount of two (fluorine sulphonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (64).
Table 8 illustrates evaluation result.
[embodiment 65]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (65) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-methyl isophthalic acid-propylpiperdine of 0.01 weight part into two (trimethyl fluoride sulfonyl) imines (IL230 is manufactured by Di-ichi Kogyo Seiyaku Co., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (65).
Table 9 illustrates evaluation result.
[embodiment 66]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (66) in the mode identical with embodiment 65, difference is 1-methyl isophthalic acid-propylpiperdine the amount of two (trimethyl fluoride sulfonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (66).
Table 9 illustrates evaluation result.
[embodiment 67]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (67) in the mode identical with embodiment 65, difference is 1-methyl isophthalic acid-propylpiperdine the amount of two (trimethyl fluoride sulfonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (67).
Table 9 illustrates evaluation result.
[embodiment 68]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (68) in the mode identical with embodiment 65, difference is 1-methyl isophthalic acid-propylpiperdine the amount of two (trimethyl fluoride sulfonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (68).
Table 9 illustrates evaluation result.
[embodiment 69]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (69) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes the 1-methyl isophthalic acid-propylpiperdine of 0.01 weight part into two (fluorine sulphonyl) imines (AS 130, is manufactured by Di-ichi Kogyo Seiyaku Co., Ltd.).
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (69).
Table 9 illustrates evaluation result.
[embodiment 70]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (70) in the mode identical with embodiment 69, difference is 1-methyl isophthalic acid-propylpiperdine the amount of two (fluorine sulphonyl) imines changes 0.1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (70).
Table 9 illustrates evaluation result.
[embodiment 71]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (71) in the mode identical with embodiment 69, difference is 1-methyl isophthalic acid-propylpiperdine the amount of two (fluorine sulphonyl) imines changes 1 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (71).
Table 9 illustrates evaluation result.
[embodiment 72]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (72) in the mode identical with embodiment 69, difference is 1-methyl isophthalic acid-propylpiperdine the amount of two (fluorine sulphonyl) imines changes 10 weight parts into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (72).
Table 9 illustrates evaluation result.
[embodiment 73]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (73) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes two (trimethyl fluoride sulfonyl) imine lithium (Li-TFSI is manufactured by Morita Chemical Co., Ltd.) of 0.01 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (73).
Table 10 illustrates evaluation result.
[embodiment 74]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (74) in the mode identical with embodiment 73, difference is to change the amount of two (trimethyl fluoride sulfonyl) imine lithium into 0.1 weight part.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (74).
Table 10 illustrates evaluation result.
[embodiment 75]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (75) in the mode identical with embodiment 73, difference is to change the amount of two (trimethyl fluoride sulfonyl) imine lithium into 1 weight part.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (75).
Table 10 illustrates evaluation result.
[embodiment 76]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (76) in the mode identical with embodiment 73, difference is to change the amount of two (trimethyl fluoride sulfonyl) imine lithium into 10 weight parts.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (76).
Table 10 illustrates evaluation result.
[embodiment 77]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (77) in the same manner as in example 1, difference is the 1-ethyl-3-methylimidazole of 0.01 weight part two (trimethyl fluoride sulfonyl) imines changes two (fluorine sulphonyl) imine lithium (Li-TFSI is manufactured by Morita Chemical Co., Ltd.) of 0.01 weight part into.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (77).
Table 10 illustrates evaluation result.
[embodiment 78]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (78) in the mode identical with embodiment 77, difference is to change the amount of two (fluorine sulphonyl) imine lithium into 0.1 weight part.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (78).
Table 10 illustrates evaluation result.
[embodiment 79]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (79) in the mode identical with embodiment 77, difference is to change the amount of two (fluorine sulphonyl) imine lithium into 1 weight part.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (79).
Table 10 illustrates evaluation result.
[embodiment 80]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (80) in the mode identical with embodiment 77, difference is to change the amount of two (fluorine sulphonyl) imine lithium into 10 weight parts.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (80).
Table 10 illustrates evaluation result.
[embodiment 81]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (81) is manufactured in mode in the same manner as in Example 5, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (81).
Table 11 illustrates evaluation result.
[embodiment 82]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (82) is manufactured in mode in the same manner as in Example 6, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (82).
Table 11 illustrates evaluation result.
[embodiment 83]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (83) is manufactured in mode in the same manner as in Example 7, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (83).
Table 11 illustrates evaluation result.
[embodiment 84]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (84) is manufactured in mode in the same manner as in Example 8, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (84).
Table 11 illustrates evaluation result.
[embodiment 85]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (85) is manufactured in mode in the same manner as in Example 5, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (85).
Table 11 illustrates evaluation result.
[embodiment 86]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (86) is manufactured in mode in the same manner as in Example 6, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (86).
Table 11 illustrates evaluation result.
[embodiment 87]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (87) is manufactured in mode in the same manner as in Example 7, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (87).
Table 11 illustrates evaluation result.
[embodiment 88]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (88) is manufactured in mode in the same manner as in Example 8, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (88).
Table 11 illustrates evaluation result.
[embodiment 89]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (89) is manufactured in mode in the same manner as in Example 5, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (89).
Table 12 illustrates evaluation result.
[embodiment 90]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (90) is manufactured in mode in the same manner as in Example 6, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (90).
Table 12 illustrates evaluation result.
[embodiment 91]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (91) is manufactured in mode in the same manner as in Example 7, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (91).
Table 12 illustrates evaluation result.
[embodiment 92]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (92) is manufactured in mode in the same manner as in Example 8, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the two tip type polyether modified silicon oils (KF-6004 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part are added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (92).
Table 12 illustrates evaluation result.
[embodiment 93]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (93) is manufactured in mode in the same manner as in Example 5, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (93).
Table 12 illustrates evaluation result.
[embodiment 94]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (94) is manufactured in mode in the same manner as in Example 6, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (94).
Table 12 illustrates evaluation result.
[embodiment 95]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (95) is manufactured in mode in the same manner as in Example 7, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (95).
Table 12 illustrates evaluation result.
[embodiment 96]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (96) is manufactured in mode in the same manner as in Example 8, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.001 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (96).
Table 12 illustrates evaluation result.
[embodiment 97]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (97) is manufactured in mode in the same manner as in Example 5, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (97).
Table 13 illustrates evaluation result.
[embodiment 98]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (98) is manufactured in mode in the same manner as in Example 6, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (98).
Table 13 illustrates evaluation result.
[embodiment 99]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (99) is manufactured in mode in the same manner as in Example 7, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (99).
Table 13 illustrates evaluation result.
[embodiment 100]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (100) is manufactured in mode in the same manner as in Example 8, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 0.1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (100).
Table 13 illustrates evaluation result.
[embodiment 101]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (101) is manufactured in mode in the same manner as in Example 5, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (101).
Table 13 illustrates evaluation result.
[embodiment 102]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (102) is manufactured in mode in the same manner as in Example 6, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (102).
Table 13 illustrates evaluation result.
[embodiment 103]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (103) is manufactured in mode in the same manner as in Example 7, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (103).
Table 13 illustrates evaluation result.
[embodiment 104]
On base material, the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (104) is manufactured in mode in the same manner as in Example 8, difference is in the manufacture of polyurethane-base pressure sensitive adhesive compositions, the side chain type polyether modified silicon oil (KF-353 is manufactured by Shin-Etsu Chemial Co., Ltd) of 1 weight part is added in mixture further.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (104).
Table 13 illustrates evaluation result.
[comparative example 1]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (C1) in the same manner as in example 1, difference is not use fatty acid ester and 1-ethyl-3-methylimidazole two (trimethyl fluoride sulfonyl) imines.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (C1).
Table 14 illustrates evaluation result.
[comparative example 2]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (C2) in the same manner as in example 1, difference is not use 1-ethyl-3-methylimidazole two (trimethyl fluoride sulfonyl) imines.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (C2).
Table 14 illustrates evaluation result.
[comparative example 3]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (C3) in the same manner as in example 1, difference is: do not use fatty acid ester and 1-ethyl-3-methylimidazole two (trimethyl fluoride sulfonyl) imines; And use the EMBILIZER OL-1 of 0.08 weight part (being manufactured by Tokyo fine chemistry industry Co., Ltd. (Tokyo Fine Chemical CO., LTD.)) to replace the Nacem Ferric Iron of 0.04 weight part as catalyzer.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (C3).
Table 14 illustrates evaluation result.
[comparative example 4]
On base material, manufacture the formation of pressure-sensitive adhesive layer formed by polyurethane-base pressure-sensitive adhesive (C4) in the same manner as in example 1, difference is: do not use 1-ethyl-3-methylimidazole two (trimethyl fluoride sulfonyl) imines; And use the EMBILIZER OL-1 of 0.08 weight part (being manufactured by Tokyo fine chemistry industry Co., Ltd.) to replace the Nacem Ferric Iron of 0.04 weight part as catalyzer.
Then, a surface has been carried out polysiloxane process, there are 25 μm of thickness, the surface of the polysiloxane process of base material that formed by vibrin is pasted to the surface of formation of pressure-sensitive adhesive layer to provide surface protection film (C4).
Table 14 illustrates evaluation result.
[embodiment 105]
The surface protection film (4) obtained in embodiment 4 is pasted to the polaroid (being manufactured by Nitto Denko Corp, trade(brand)name: " TEG1465DUHC ") as optical component, thus the optical component being pasted with surface protection film is provided.
[embodiment 106]
The surface protection film (8) obtained in embodiment 8 is pasted to the polaroid (being manufactured by Nitto Denko Corp, trade(brand)name: " TEG1465DUHC ") as optical component, thus the optical component being pasted with surface protection film is provided.
[embodiment 107]
The polaroid that the surface protection film (12) obtained in embodiment 12 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 108]
The polaroid that the surface protection film (16) obtained in embodiment 16 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 109]
The polaroid that the surface protection film (20) obtained in embodiment 20 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 110]
The polaroid that the surface protection film (24) obtained in embodiment 24 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 111]
The polaroid that the surface protection film (28) obtained in embodiment 28 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 112]
The polaroid that the surface protection film (32) obtained in embodiment 32 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 113]
The polaroid that the surface protection film (36) obtained in embodiment 36 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 114]
The polaroid that the surface protection film (40) obtained in embodiment 40 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 115]
The polaroid that the surface protection film (44) obtained in embodiment 44 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 116]
The polaroid that the surface protection film (48) obtained in embodiment 48 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 117]
The polaroid that the surface protection film (52) obtained in embodiment 52 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 118]
The polaroid that the surface protection film (56) obtained in embodiment 56 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 119]
The polaroid that the surface protection film (60) obtained in embodiment 60 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 120]
The polaroid that the surface protection film (60) obtained in embodiment 60 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 121]
The polaroid that the surface protection film (64) obtained in embodiment 64 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 122]
The polaroid that the surface protection film (68) obtained in embodiment 68 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 123]
The polaroid that the surface protection film (72) obtained in embodiment 72 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 124]
The polaroid that the surface protection film (76) obtained in embodiment 76 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 125]
The polaroid that the surface protection film (80) obtained in embodiment 80 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 126]
The polaroid that the surface protection film (84) obtained in embodiment 84 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 127]
The polaroid that the surface protection film (88) obtained in embodiment 88 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 128]
The polaroid that the surface protection film (92) obtained in embodiment 92 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 129]
The polaroid that the surface protection film (96) obtained in embodiment 96 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 130]
The polaroid that the surface protection film (100) obtained in embodiment 100 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 131]
The polaroid that the surface protection film (104) obtained in embodiment 104 is pasted to as optical component (is manufactured by Nitto Denko Corp; trade(brand)name: " TEG1465DUHC "), thus the optical component being pasted with surface protection film is provided.
[embodiment 132]
The conducting film that the surface protection film (4) obtained in embodiment 4 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 133]
The conducting film that the surface protection film (8) obtained in embodiment 8 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 134]
The conducting film that the surface protection film (12) obtained in embodiment 12 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 135]
The conducting film that the surface protection film (16) obtained in embodiment 16 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 136]
The conducting film that the surface protection film (20) obtained in embodiment 20 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 137]
The conducting film that the surface protection film (24) obtained in embodiment 24 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 138]
The conducting film that the surface protection film (28) obtained in embodiment 28 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 139]
The conducting film that the surface protection film (32) obtained in embodiment 32 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 140]
The conducting film that the surface protection film (36) obtained in embodiment 36 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 141]
The conducting film that the surface protection film (40) obtained in embodiment 40 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 142]
The conducting film that the surface protection film (44) obtained in embodiment 44 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 143]
The conducting film that the surface protection film (48) obtained in embodiment 48 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 144]
The conducting film that the surface protection film (52) obtained in embodiment 52 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 145]
The conducting film that the surface protection film (56) obtained in embodiment 56 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 146]
The conducting film that the surface protection film (56) obtained in embodiment 56 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 147]
The conducting film that the surface protection film (60) obtained in embodiment 60 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 148]
The conducting film that the surface protection film (64) obtained in embodiment 64 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 149]
The conducting film that the surface protection film (68) obtained in embodiment 68 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 150]
The conducting film that the surface protection film (72) obtained in embodiment 72 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 151]
The conducting film that the surface protection film (76) obtained in embodiment 76 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 152]
The conducting film that the surface protection film (80) obtained in embodiment 80 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 153]
The conducting film that the surface protection film (84) obtained in embodiment 84 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 154]
The conducting film that the surface protection film (88) obtained in embodiment 88 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 155]
The conducting film that the surface protection film (92) obtained in embodiment 92 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 156]
The conducting film that the surface protection film (96) obtained in embodiment 96 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTA V270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 157]
The conducting film that the surface protection film (100) obtained in embodiment 100 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTAV270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
[embodiment 158]
The conducting film that the surface protection film (104) obtained in embodiment 104 is pasted to as electronic component (is manufactured by Nitto Denko Corp; trade(brand)name: " ELECRYSTAV270L-TFMP "), thus the electronic component being pasted with surface protection film is provided.
Polyurethane-base pressure-sensitive adhesive of the present invention may be used for any suitable application.The antistatic property of polyurethane-base pressure-sensitive adhesive of the present invention is extremely excellent and adhesive residue prevents performance and re-workability also excellent.Therefore, preferably described pressure-sensitive adhesive is used as the formation of pressure-sensitive adhesive layer of surface protection film, because described surface protection film can suitably for the surface protection of optical component or electronic component.

Claims (8)

1. a polyurethane-base pressure-sensitive adhesive, comprises polyurethane-based resin, wherein:
The polyurethane-based resin that described polyurethane-based resin comprises the composition solidification by comprising polyvalent alcohol (A) and polyfunctional isocyanate compound (B) and obtains;
Described polyvalent alcohol (A) and the middle equivalence ratio " NCO base/OH yl " between NCO base and OH base of described polyfunctional isocyanate compound (B) are greater than 1.0 and are less than 5.0; And
Described polyurethane-base pressure-sensitive adhesive comprises the ionic liquid containing fluorine organic anion.
2. polyurethane-base pressure-sensitive adhesive according to claim 1, wherein said ionic liquid by described fluorine organic anion and positively charged ion is formed.
3. polyurethane-base pressure-sensitive adhesive according to claim 2, wherein said positively charged ion comprise be selected from nitrogenous positively charged ion, sulfur-bearing positively charged ion and phosphorous cationic at least one.
4. polyurethane-base pressure-sensitive adhesive according to claim 1, wherein said polyvalent alcohol (A) comprises the polyvalent alcohol that number-average molecular weight Mn is 400 ~ 20,000.
5. polyurethane-base pressure-sensitive adhesive according to claim 1, wherein said polyfunctional isocyanate compound (B) is 5 % by weight ~ 60 % by weight relative to the content of described polyvalent alcohol (A).
6. a surface protection film, comprises:
Substrate layer; With
Formation of pressure-sensitive adhesive layer,
Wherein said formation of pressure-sensitive adhesive layer comprises the polyurethane-base pressure-sensitive adhesive any one of Claims 1 to 5.
7. an optical component, comprises the surface protection film according to claim 6 be pasted on it.
8. an electronic component, comprises the surface protection film according to claim 6 be pasted on it.
CN201410659742.5A 2013-11-18 2014-11-18 Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive Pending CN104650792A (en)

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KR20150058003A (en) 2015-05-28

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Application publication date: 20150527