CN110177849A - Adhesive composition, adhesive phase and the optical film with adhesive phase - Google Patents

Adhesive composition, adhesive phase and the optical film with adhesive phase Download PDF

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Publication number
CN110177849A
CN110177849A CN201880006969.6A CN201880006969A CN110177849A CN 110177849 A CN110177849 A CN 110177849A CN 201880006969 A CN201880006969 A CN 201880006969A CN 110177849 A CN110177849 A CN 110177849A
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China
Prior art keywords
methyl
mentioned
weight
adhesive phase
adhesive
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Chinese (zh)
Inventor
藤田雅人
森本有
外山雄祐
天野立巳
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

Present invention offer can be used for also preventing white dot, the adhesive composition of the image display panel purposes of excellent antistatic property, adhesive phase and the optical film with adhesive phase in low temperature environment.Adhesive composition of the invention contains (methyl) acrylate copolymer and fusing point is -5 DEG C of ionic compounds below.

Description

Adhesive composition, adhesive phase and the optical film with adhesive phase
Technical field
The present invention relates to adhesive composition, the adhesive phase formed by above-mentioned adhesive composition and use State the optical film with adhesive phase of adhesive phase.
Background technique
Liquid crystal display device is usually fitted in the two sides of liquid crystal cells via adhesive phase due to its image forming mode Polarizing coating.In addition, the product in the display picture carrying touch panel of liquid crystal display device has obtained functionization.
When manufacturing liquid crystal display device, by mold release film when the above-mentioned polarizing coating with adhesive phase is pasted on liquid crystal cells From with adhesive phase polarizing coating adhesive phase removing, but can due to the mold release film removing and generate electrostatic.It produces in this way Raw electrostatic will affect the orientation of the liquid crystal inside liquid crystal display device, cause unfavorable condition.For example, due to using liquid crystal Electrostatic when showing device and in the case where cause to produce white dot in black display, there are following problems: this can occurs The phenomenon that disappearance for several minutes of white dot, the display characteristic of picture is caused to be deteriorated.
In addition, the above-mentioned polarizing coating with adhesive phase is being pasted on liquid crystal cells when manufacturing liquid crystal display device Later, when carrying out visual examination through backlight, electrostatic will can be generated after the protection film stripping for being located at the surface of polarizing coating, The orientation for causing liquid crystal is chaotic, and then generates white dot in black display.Occurring not disappear for several minutes of the white dot The phenomenon that when, to stop to check, there are problems that productivity is caused to be greatly reduced.In addition, even if be installed on television set etc. it Afterwards, sometimes also due to the electrostatic generated when backlight and polarizing coating rub and generate same white dot.
The generation of electrostatic can for example be inhibited by forming antistatic layer in the outer surface of polarizing coating, but its effect is small, There are problems that fundamentally preventing electrostatic from generating.Therefore, in order to which the essence position generated in electrostatic inhibits its generation, It is required that assigning anti-static function to adhesive phase.As the mode for assigning anti-static function to adhesive phase, it has been proposed that for example Cooperate ionic compound in the adhesive for forming adhesive phase (for example, referring to patent document 1).
Following the description is described in patent document 1: by being used under room temperature in the adhesive for forming adhesive phase as liquid It is used as the ionic compound as antistatic agent for the alkali metal salt of solid under the ionic liquid of body, room temperature, can be made antistatic Property is excellent.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-152235 bulletin
Summary of the invention
Subject to be solved by the invention
But even if in the case where under having used room temperature being the ionic compound of liquid or solid, in low temperature environment In (for example, 0 DEG C or less) there is also do not disappear in the case where producing white dot or until disappear until need for a long time The problem of etc. needing to assign the antistatic property in low temperature environment.In addition, status is in low temperature environment, even if increasing above-mentioned ion The use level of property compound, it is also difficult to obtain sufficient antistatic property.
Therefore, the purpose of the present invention is to provide can be used in low temperature environment capable of also preventing white dot, antistatic Adhesive composition, adhesive phase and the optical film with adhesive phase of the excellent image display panel purposes of property.
The method to solve the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that, utilize following adhesive groups Closing object can solve the above subject, so as to complete the present invention.
That is, adhesive composition of the invention contains (methyl) acrylate copolymer and fusing point is -5 DEG C of ions below Property compound.
In adhesive composition of the invention, conductivity of the preferably above-mentioned ionic compound at 25 DEG C is 10mS/cm More than.
In adhesive composition of the invention, preferably above-mentioned ionic compound is ionic liquid, and above-mentioned ionic liquid is Organic cation-anion salt, above-mentioned anion are bis- (fluorine sulphonyl) imines anion, and/or bis- (trifluoro methylsulfonyl) imines Anion.
Adhesive phase of the invention is formed preferably by above-mentioned adhesive composition.
Optical film with adhesive phase of the invention is preferably formed with above-mentioned adhesive phase in at least side of optical film.
The effect of invention
Adhesive composition of the invention is by containing (methyl) acrylic polymer as basic polymer Also ionic compound can also be made to keep liquid even if in low temperature environment with the ionic compound of specific fusing point simultaneously, Necessary Ion transfer is not easily susceptible to limit for the charging neutrality of electrostatic, can inhibit to remove white caused by electrostatic Spot can obtain the adhesive phase of excellent antistatic property and the optical film with above-mentioned adhesive phase, thus be useful 's.
Specific embodiment
< adhesive composition >
< (methyl) acrylic polymer >
Adhesive composition of the invention contains (methyl) acrylic polymer.Above-mentioned (methyl) acrylic polymer It is base polymer, as long as having adhesiveness to use without particular limitation, usually as monomeric unit, contains (first Base) alkyl acrylate is as principal component.It should be noted that (methyl) acrylate refers to acrylate and/or methyl-prop Olefin(e) acid ester has the same meaning with (methyl) of the invention.
As (methyl) alkyl acrylate for the main framing for constituting above-mentioned (methyl) acrylic polymer, can example go out (methyl) alkyl acrylate that the atomic number of alkyl carbon of straight-chain or branched is 1~18.For example, as abovementioned alkyl, it can It enumerates: methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, hexyl, cyclohexyl, heptyl, 2- ethylhexyl, different pungent Base, nonyl, decyl, isodecyl, dodecyl, different myristyl, lauryl, tridecyl, pentadecyl, cetyl, ten Seven alkyl, octadecyl etc..They can be used alone or are applied in combination.The average carbon atom number of these alkyl is preferably 3~ 9。
Adhesive composition of the invention can be used containing hydroxyl, carboxyl, amino and amide groups isopolarity functional group Monomer is as monomeric unit.(methyl) propylene by using the monomer comprising containing above-mentioned polar functional group as monomeric unit Acids polymers are easy to keep ionic compound within the adhesive layer, ionic compound can be inhibited in adhesive phase The segregation on surface, becomes preferred embodiment.
Hydroxyl monomer can be used in above-mentioned (methyl) acrylic polymer.Hydroxyl monomer is to contain in its structure There are hydroxyl and the compound containing polymerisms unsaturated double-bonds such as (methyl) acryloyl group, vinyl, more preferably uses hydroxyl (methyl) acrylic monomer.It as the concrete example of hydroxyl monomer, can enumerate for example: (methyl) acrylic acid 2- hydroxyl second Ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (first Base) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester etc. (methyl) Hydroxyalkyl acrylates, acrylic acid (4- hydroxymethylcyclohexyl) methyl esters etc..In above-mentioned hydroxyl monomer, from the sight of durability Point consideration, preferably (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 4- hydroxybutyl, particularly preferably (methyl) third Olefin(e) acid 4- hydroxybutyl.
Above-mentioned carboxyl group-containing monomer is in its structure containing carboxyl and containing the polymerization such as (methyl) acryloyl group, vinyl The compound of property unsaturated double-bond.It as the specific example of carboxyl group-containing monomer, can enumerate for example: (methyl) acrylic acid, (first Base) carboxyethyl acrylates, (methyl) acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid, crotonic acid etc..Contain above-mentioned In carboxylic monomer, from the viewpoint of copolymerizable, price and adhesion characteristic (bonding force etc.), preferably acrylic acid.
In above-mentioned (methyl) acrylic polymer, emulsion stability can be used as monomeric unit.List containing amino Body is to contain amino and the compound containing polymerisms unsaturated double-bonds such as (methyl) acryloyl group, vinyl in its structure. It as the specific example of emulsion stability, can enumerate for example: (methyl) acrylate, (methyl) acrylic acid N, N- bis- Methylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc..
In above-mentioned (methyl) acrylic polymer, amide-containing monomer can be used as monomeric unit.Amide containing Base monomer is in its structure containing amide groups and containing polymerisms unsaturated double-bonds such as (methyl) acryloyl group, vinyl Compound.It as the specific example of amide-containing monomer, can enumerate: (methyl) acrylamide, N, N- dimethyl (methyl) third Acrylamide, N, N- diethyl (methyl) acrylamide, n-isopropyl acrylamide, N- methyl (methyl) acrylamide, N- butyl (methyl) acrylamide, N- hexyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- methylol-N- propyl (first Base) acrylamide, amino methyl (methyl) acrylamide, amino-ethyl (methyl) acrylamide, mercapto methyl (methyl) propylene The acrylamide monomers such as amide, mercaptoethyl (methyl) acrylamide；N- (methyl) acryloyl morpholine, N- (methyl) propylene The N- acryloyl group heterocyclic monomers such as acylpiperidine, N- (methyl) acryloyl group pyrrolidines；N-vinyl pyrrolidone, N- ethylene The vinyl lactams containing N- such as base-epsilon-caprolactams class monomer etc..Amide-containing monomer be in terms of meeting durability it is preferred, In amide-containing monomer, the particularly preferably lactams monomer of the vinyl containing N-.
It can also be used in above-mentioned (methyl) acrylic polymer and contain aromatic ring (methyl) acrylate.Containing aromatic ring (methyl) Acrylate is in its structure containing aromatic ring structure and containing the compound of (methyl) acryloyl group.As aromatic ring, can enumerate Phenyl ring, naphthalene nucleus or cyclohexyl biphenyl.It is led containing the white point that aromatic ring (methyl) acrylate meets durability and can improve peripheral portion The display of cause is uneven.As the specific example for containing aromatic ring (methyl) acrylate, it can be mentioned, for example: (methyl) benzyl acrylate, (methyl) phenyl acrylate, o-phenyl phenol (methyl) acrylate, phenoxy group (methyl) acrylate, (methyl) acrylic acid benzene Oxygroup ethyl ester, (methyl) acrylic acid phenoxy-propyl, phenoxy group diethylene glycol (methyl) acrylate, ethylene-oxide-modified nonyl Modified (methyl) propylene of phenol (methyl) acrylate, ethylene-oxide-modified cresols (methyl) acrylate, phenolethylene oxide Acid esters, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyl, (methyl) methoxyethyl benzyl ester, (methyl) acrylic acid benzyl chloride Ester, (methyl) toluene toluene, polystyrene (methyl) acrylate etc. have (methyl) acrylate of phenyl ring；Ethoxy Change betanaphthol acrylate, (methyl) acrylic acid 2- naphthalene ethyl ester, acrylic acid 2- naphthoxy ethyl ester, (methyl) acrylic acid 2- (4- first Oxy-1-naphthoxy) (methyl) acrylate with naphthalene nucleus such as ethyl ester；(methyl) biphenyl acrylate etc. has cyclohexyl biphenyl (methyl) acrylate.Especially from the aspect of adhesion characteristic, durability, contain aromatic ring (methyl) acrylate as above-mentioned, Preferably (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate, particularly preferably (methyl) acrylic acid phenoxy group second Ester.
In the case where adhesive composition contains crosslinking agent, these comonomers become the reflecting point with crosslinking agent.It is special It is not since the reactivity of carboxyl group-containing monomer, hydroxyl monomer and intermolecular cross-linking agent is high, preferably for improving gained Coherency, the heat resistance of adhesive phase.
Above-mentioned (methyl) acrylic polymer contains specified rate in the weight rate of whole monomers (100 weight %) Above-mentioned each monomer is as monomeric unit.The weight rate of above-mentioned (methyl) alkyl acrylate can be set as except above-mentioned (methyl) The surplus of monomer other than alkyl acrylate, specifically, it is preferable that be 65 weight % or more, more preferably 70 weight % with On, further preferably 75~99.9 weight %, particularly preferably 80~99 weight %.By the weight of (methyl) alkyl acrylate It is preferred in terms of ensuring cementability that ratio set, which is measured, as above range.
Above-mentioned (methyl) acrylate copolymer removes above-mentioned (methyl) containing 0.1 weight % or more preferably in whole monomers Monomer other than alkyl acrylate is as monomeric unit, further preferably 0.2~35 weight %, and further preferably 0.5 ~30 weight % particularly preferably contain 1~25 weight %.If the weight of the monomer in addition to above-mentioned (methyl) alkyl acrylate It measures ratio and is lower than 0.1 weight %, then when largely having cooperated the ionic liquid etc. as ionic compound, it some times happens that from Sub- property compound is precipitated in adhesive layer surface, generates the bad orders such as gonorrhoea in low temperature environment or produces in low temperature environment The problem of durabilities such as germ-vesicle, peeling, therefore not preferably.
In above-mentioned (methyl) acrylic polymer, do not needed in addition to above-mentioned monomeric unit particularly containing other Monomeric unit, but in order to improve cementability, heat resistance, can be imported by copolymerization comprising with (methyl) acryloyl group or 1 kind or more comonomer of the polymerizable functional group of the unsaturated double-bonds such as vinyl.
It as the specific example of such comonomer, can enumerate: the list containing anhydride group such as maleic anhydride, itaconic anhydride Body；The caprolactones addition product of acrylic acid；Allyl sulphonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, (methyl) acryloyl The monomers containing sulfonic group such as amine propane sulfonic acid, (methyl) sulfopropyl acrylate；The phosphorous acidic groups such as 2- hydroxylethyl acyl phosphate Monomer etc..
In addition, the example of the monomer as modified purpose, can also enumerate: (methyl) acrylate, (methyl) (methyl) acrylic acid alkylaminoalkyls such as acrylic acid N, N- dimethylamino ethyl ester, (methyl) tbutylaminoethylacrylate Ester；(methyl) alkoxyalkyl acrylates such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate；N- (methyl) acryloyl-oxy methylene succinimide, N- (methyl) acryloyl group -6- oxygroup hexa-methylene succinimide, N- The succinimides class monomers such as eight methylene succinimide of (methyl) acryloyl group -8- oxygroup；N- N-cyclohexylmaleimide, The maleimides monomers such as N- isopropylmaleimide, N- lauryl maleimide, N-phenylmaleimide；N- first Base clothing health acid imide, N- ethyl clothing health acid imide, N- butyl clothing health acid imide, N- octyl clothing health acid imide, N-2- ethylhexyl Clothing health acid imide monomers such as clothing health acid imide, N- cyclohexyl clothing health acid imide, N- lauryl clothing health acid imide etc..
In addition, the vinyl monomers such as vinyl acetate, vinyl propionate also can be used as modified monomer；Propylene The cyanoacrylates monomer such as nitrile, methacrylonitrile；(methyl) glycidyl acrylate etc. contains epoxy group (methyl) propylene Acid esters；Polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy ethyl glycol (methyl) acrylic acid Glycols (methyl) acrylate such as ester, methoxyl group polypropylene glycol (methyl) acrylate；(methyl) tetrahydrofurfuryl acrylate contains (methyl) acrylate monomers such as fluorine (methyl) acrylate, siloxanes (methyl) acrylate, acrylic acid 2- methoxy acrylate Deng.In addition, isoprene, butadiene, isobutene, vinyl ethers etc. can be enumerated.
In addition, the silanes monomer etc. containing silicon atom can be enumerated as the monomer that can be copolymerized than that described above.Make For silanes monomer, it can be mentioned, for example: 3- acryloxypropyl triethoxysilane, vinyltrimethoxysilane, ethylene Ethyl triethoxy silicane alkane, 4- vinyl butyl trimethoxy silane, 4- vinyl butyl triethoxysilane, 8- vinyl octyl Trimethoxy silane, 8- vinyl octyltri-ethoxysilane, 10- Methacryloxydecyl trimethoxy silane, 10- third Alkene acyloxy ruthenium trimethoxysilane, 10- Methacryloxydecyl triethoxysilane, 10- acryloxy decyl Triethoxysilane etc..
In addition, can be used as comonomer: tripropylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) Acrylate, 1,6-hexylene glycols two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, new penta 2 Alcohol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, season penta Tetrol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, oneself Carboxylate of (methyl) acrylic acid such as lactone-modified dipentaerythritol six (methyl) acrylate and polyalcohol etc. has (methyl) 2 or more polyfunctional monomers in the unsaturated double-bonds such as acryloyl group, vinyl, in bones such as polyester, epoxy, carbamates 2 or more in frame in the unsaturated double-bonds such as addition (methyl) acryloyl group, vinyl are as official same as monomer component Polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate made of capable of rolling into a ball etc..
The polymerization ratio of above-mentioned comonomer in above-mentioned (methyl) acrylic polymer is preferably in above-mentioned (methyl) third It is 0~10 weight % or so, more preferably 0~7 weight % or so in whole monomers (100 weight %) of olefin(e) acid quasi polymer, Further preferably 0~5% weight or so.
Above-mentioned (methyl) acrylic polymer can be usually 500,000~3,000,000 it is preferable to use weight average molecular weight (Mw) Polymer.In view of durability, particularly heat resistance, weight average molecular weight (Mw) is more preferably 1,000,000~2,500,000, further excellent It is selected as 1,100,000~2,000,000.It is undesirable from the viewpoint of heat resistance when weight average molecular weight (Mw) is less than 500,000.In addition, When weight average molecular weight (Mw) is greater than 3,000,000, with the tendency that adhesive phase is easy to be hardened, it is easy to happen peeling.It needs to illustrate It is that weight average molecular weight (Mw) by GPC (gel permeation chromatography) by being measured and by the calculated value of polystyrene conversion It finds out.
In addition, for (methyl) acrylic polymer of the invention glass transition temperature (Tg) be preferably 0 DEG C with Under (usually -100 DEG C or more), more preferably -5 DEG C hereinafter, further preferably -10 DEG C or less.In glass transition temperature When higher than 0 DEG C, cohesiveness increases, and mobility reduces, and may cause can not obtain enough bond areas, cannot achieve adherend Fixation.Especially when Tg is -5 DEG C or less, (methyl) acrylic polymer softens, and the movement of ionic compound becomes It is easy, antistatic property improves, therefore preferably.It should be noted that the glass transition temperature of (methyl) acrylic polymer Degree can be adjusted and suitably changing monomer component ready for use, ratio of components to above range.(methyl) third of the invention The measuring method using dynamic viscoelastic device can be used, based on FOX formula in the glass transition temperature of olefin(e) acid quasi polymer Calculated value etc..
The manufacture of such (methyl) acrylic polymer can suitably select polymerisation in solution, bulk polymerization, lotion poly- Manufacturing method well known to conjunction, various free radical polymerizations etc..In addition, obtained (methyl) acrylic polymer can be random total The arbitrary copolymer such as polymers, block copolymer, graft copolymer.It should be noted that in the polar object as emulsion polymerization Matter is easy in the manufacturing method for being adsorbed on the molecular interface of polymer, and ionic compound is consumingly constrained in polymer In, therefore, reduce the effect for eliminating white dot sometimes.
It should be noted that, as polymer solvent, can be used such as ethyl acetate, toluene in polymerisation in solution.As Specific polymerisation in solution example, reaction is that polymerization initiator is added under the inactive gas air-flow such as nitrogen, and usually 50~70 DEG C or so, carry out under 5~30 hours or so reaction conditions.
Polymerization initiator, chain-transferring agent used in free radical polymerization, emulsifier etc. are not particularly limited, it can be appropriate Selection uses.It should be noted that the weight average molecular weight of (methyl) acrylic polymer can be according to polymerization initiator, chain tra nsfer Dosage, the reaction condition of agent and controlled, can according to their type and appropriate adjustment its dosage etc..
< ionic compound >
It is -5 DEG C of ionic compounds below that adhesive composition of the invention, which contains fusing point,.For bonding of the invention For agent composition, by containing the ionic compound with specific fusing point, even if in low temperature environment, ionic compound Also it is able to maintain liquid, necessary Ion transfer is not readily susceptible to limit for the charging neutrality of electrostatic, therefore can press down White dot caused by system removing electrostatic can obtain the adhesive phase of excellent antistatic property and with above-mentioned adhesive The optical film of layer.In addition, the fusing point as above-mentioned ionic compound, preferably -8 DEG C are hereinafter, more preferably -10 DEG C or less.
Conductivity of the above-mentioned ionic compound at 25 DEG C is preferably 10mS/cm or more, more preferably 12mS/cm with On, further preferably 15mS/cm or more.It is above range by (25 DEG C) of conductivity that make above-mentioned ionic compound, it can To speculate that it can also show high conductivity at low temperature, the mobility of ionic compound is high, and antistatic property improves, and becomes Preferred embodiment.
Above-mentioned ionic compound be ionic liquid, above-mentioned ionic liquid is organic cation-anion salt, it is above-mentioned yin from Son is preferably bis- (fluorine sulphonyl) imines anion, and/or bis- (trifluoro methylsulfonyl) imines anion.By making above-mentioned ionicization Conjunction object is ionic liquid, and the high adhesive phase of antistatic effect can be obtained in the case where not damaging adhesion characteristic.By making The detailed reason that can get excellent antistatic property with ionic liquid is still not clear, it is believed that with common alkali metal salt, Ionic solid phase ratio, especially fusing point used in the present invention are the ionic liquid for including in -5 DEG C of ionic compounds below Body is low melting point (fusing point is -5 DEG C or less), therefore is easy to carry out molecular motion, can get excellent antistatic effect.Especially For fusing point ionic liquid (- 5 DEG C of fusing point or less) more lower than room temperature (25 DEG C), even if in low temperature environment or long-term protecting Guan Shi, the precipitation being also less likely to occur in adhesive (composition) can obtain excellent appearance and stable antistatic property. In addition, above-mentioned ionic liquid can easily add and be dispersed or dissolved in adhesive.In addition, not due to above-mentioned ionic liquid With vapour pressure (fixedness), therefore has and sustainably obtain antistatic property without the feature that timely disappears.In addition, The compatibility of ionic liquid and polymer is also excellent, therefore bad order can be inhibited etc..In addition, the case where with regard to ionic solid For, it is easy that segregation (crystal precipitation) occurs in adhesive layer surface, becoming causes bad order (gonorrhoea), durability to reduce The reason of, but these problems will not be generated in the case where ionic liquid, become preferred embodiment.
It should be noted that above-mentioned ionic liquid refer to fusing point be -5 DEG C or less, present liquid fuse salt (it is organic it is positive from Son-anion salt).In addition, " organic cation-anion salt " described in the present invention refers to its cation portion by organic matter structure At organic salt, anion portion can be organic matter, be also possible to inorganic matter.Here " organic cation-anion salt " is no Substance including being referred to as ionic solid.
As the specific example (bracket in indicate fusing point) of above-mentioned ionic liquid, can from above-mentioned cation constituent and yin from Suitably selection uses in the combination of subconstiuent, can enumerate for example: 1- butyl -3- picolineBis- (trifluoro methylsulfonyl) imines Salt (- 70 DEG C), butyl methyl piperidinesBis- (trifluoro methylsulfonyl) inferior amine salts (- 25 DEG C), butyl methyl pyrrolidinesBis- (trifluoros Methylsulfonyl) inferior amine salt (- 18 DEG C), 1- ethyl-3-methylimidazoleBis- (trifluoro methylsulfonyl) inferior amine salts (- 16.2 DEG C), 1- second Base -3- methylimidazoleBis- (fluorine sulphonyl) inferior amine salts (- 12.9 DEG C) particularly preferably use 1- ethyl-3-methylimidazoleIt is double (fluorine sulphonyl) inferior amine salt.Bis- (fluorine sulphonyl) inferior amine salts are since anion molecule is smaller than other ionic liquids, the conduction of charge Speed is fast, and the white dot eradicating efficacy of ratio such as bis- (trifluoro methylsulfonyl) inferior amine salts is good, becomes preferred embodiment.
It should be noted that above-mentioned ionic compound can be used alone, two or more use can also be mixed.
The dosage of the ionic compound contained in adhesive composition of the invention is relative to (methyl) acrylic polymer Closing 100 parts by weight of object is preferably 0.1~20 parts by weight, more preferably 0.5~15 parts by weight, further preferably 1~10 weight Part.When above-mentioned ionic compound is less than 0.1 parts by weight, the improvement effect of antistatic property is insufficient sometimes.On the other hand, exist When above-mentioned ionic compound is more than 20 parts by weight, it some times happens that in precipitation/segregation of ionic compound, low temperature environment The bad orders such as gonorrhoea or durability are insufficient.
It should be noted that other than above-mentioned ionic compound, it can also be in the model for not damaging characteristic of the invention Enclosing can be enumerated for example: ionic surfactant using other ionic compounds as above-mentioned other ionic compounds Agent class, electric conductive polymer, electrically conductive microparticle etc. can assign the material of antistatic property.
< crosslinking agent >
Crosslinking agent can be contained in above-mentioned adhesive composition.As above-mentioned crosslinking agent, can be used organic crosslinking agent, Multi-functional metallo-chelate.As organic crosslinking agent, can enumerate isocyanates crosslinking agent, peroxide crosslinking agent, Epoxies crosslinking agent, imines crosslinking agent etc..Multi-functional metallo-chelate is polyvalent metal and organic compound through covalent bond Chelate made of conjunction or coordination bonding.As polyvalent metal atom, can enumerate Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc..As in the organic compound that covalent bonding or coordination bonding occurs Atom can enumerate oxygen atom etc., as organic compound, can enumerate Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, Ketone compound etc..Wherein, as crosslinking agent, isocyanates crosslinking agent, and/or peroxide crosslinking agent are more preferably used, Isocyanates crosslinking agent and peroxide crosslinking agent is particularly preferably applied in combination.By using isocyanates crosslinking agent, It is contemplated that cohesiveness, removing in durability test prevent, in addition, by using peroxide crosslinking agent, processing Property, re-workability, cross-linked stable, fissility etc. it is excellent, therefore preferably.In addition, being crosslinked by the way that isocyanates is applied in combination Agent and peroxide crosslinking agent simultaneously use antioxidant wherein, can be drawn being effectively inhibited using antioxidant by oxygen While the radical crosslinking risen hinders, efficiency forms the three-dimensional crosslinked network of adhesive phase well.
As above-mentioned isocyanates crosslinking agent, the compound at least two isocyanate group can be used.For example, It is generally used in well known aliphatic polyisocyante, alicyclic polyisocyanates, virtue used in urethane reaction Fragrant race's polyisocyanates etc..
As above-mentioned aliphatic polyisocyante, it can be mentioned, for example: trimethylene diisocyanate, two isocyanide of tetramethylene Acid esters, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanate, 1,3- butylidene two Isocyanates, ten dimethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanate etc..
As above-mentioned alicyclic isocyanate, it can be mentioned, for example: 1,3- cyclopentene diisocyanate, 1,3- hexamethylene two are different Cyanate, 1,4- cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation Xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenation tetramethyl xylylene diisocyanate etc..
As above-mentioned aromatic diisocyanate, it can be mentioned, for example: phenylene diisocyanate, 2,4- toluene di-isocyanate(TDI), 2,6- toluene di-isocyanate(TDI), 2,2 '-methyl diphenylene diisocyanates, 4,4 '-methyl diphenylene diisocyanates, 4,4 '- Toluidine diisocyanate, 4,4 '-diphenyl ether diisocyanates, 4,4 '-biphenyl diisocyanates, 1,5- naphthalene diisocyanate Ester, xylylene diisocyanate etc..
As above-mentioned isocyanates crosslinking agent, can enumerate above-mentioned diisocyanate polymer (dimer, trimer, Pentamer etc.), change with urethane-modified object made of the polyol reactions such as trimethylolpropane, urea-modified object, biuret Property object, allophanate-modified object, isocyanurate-modified object, Carbodiimide-Modified object etc..
In addition, as above-mentioned isocyanates crosslinking agent, preferably as aliphatic polyisocyante and its modifier Aliphatic polyisocyante class compound.Aliphatic polyisocyante class compound compared with other isocyanates crosslinking agents, Cross-linked structure is rich in flexibility, and is easy to mitigate the stress generated along with expansion/contraction of optical film, in durability test It is not susceptible to peel off.As aliphatic polyisocyante class compound, particularly preferably hexamethylene diisocyanate and its change Property object.
As the commercially available product of above-mentioned isocyanates crosslinking agent, it can be mentioned, for example: trade name " Millionate MT ", “Millionate MTL”、“Millionate MR-200”、“Millionate MR-400”、“Coronate L”、 " Coronate HL ", " Coronate HX " [the above are TOSOH Co., Ltd's systems]；Trade name " Takenate D-110N ", “Takenate D-120N”、“Takenate D-140N”、“Takenate D-160N”、“Takenate D-165N”、 " Takenate D-170HN ", " Takenate D-178N ", " Takenate 500 ", " Takenate 600 " [the above are three wells Chemical Co., Ltd. system] etc..These compounds can be used alone, and can also mix two or more use.
As peroxide, as long as generating free radicals reactive species by heating or illumination and making adhesive composition The peroxide that the crosslinking of base polymer carries out, then can be properly used, it is contemplated that operability, stability are, it is preferable to use 1 point The peroxide that clock half life temperature is 80 DEG C~160 DEG C is more preferably 90 DEG C~140 DEG C using 1 minute half life temperature Peroxide.
As above-mentioned peroxide, can enumerate for example: dicetyl peroxydicarbonate two (2- ethylhexyl) ester (declines for 1 minute half Phase temperature: 90.6 DEG C), dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) ester (1 minute half life temperature: 92.1 DEG C), peroxide Change two carbonic acid di-secondary butyl esters (1 minute half life temperature: 92.4 DEG C), new peroxide tert-butyl caprate (1 minute half life temperature: 103.5 DEG C), the tertiary own ester (1 minute half life temperature: 109.1 DEG C) of peroxidating neopentanoic acid, tert-Butyl peroxypivalate (1 minute Half life temperature: 110.3 DEG C), dilauroyl peroxide (1 minute half life temperature: 116.4 DEG C), the positive decoyl (1 of peroxidating two Minute half life temperature: 117.4 DEG C), peroxidating -2 ethyl hexanoic acid 1,1,3,3- tetramethyl butyl ester (1 minute half life temperature: 124.3 DEG C), peroxidating two (4- toluyl) (1 minute half life temperature: 128.2 DEG C), dibenzoyl peroxide (1 minute Half life temperature: 130.0 DEG C), peroxidating tert-butyl isobutyrate (1 minute half life temperature: 136.1 DEG C), bis- (peroxidating of 1,1- Tertiary hexyl) hexamethylene (1 minute half life temperature: 149.2 DEG C) etc..Wherein, especially because cross-linking reaction efficiency is excellent, therefore It is preferable to use dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) esters (1 minute half life temperature: 92.1 DEG C), two laurel of peroxidating Acyl (1 minute half life temperature: 116.4 DEG C), dibenzoyl peroxide (1 minute half life temperature: 130.0 DEG C) etc..
It should be noted that the half-life period of peroxide is the index for indicating the decomposition rate of peroxide, refer to until The residual volume of peroxide reaches the time until half.About for any time obtain half-life period decomposition temperature, appoint Half-life at a temperature of meaning, have in manufacturer's catalogue etc. it is recorded, for example, being recorded in NOF Corp " organic peroxide catalogue the 9th edition (in May, 2003) " etc..
It should be noted that the measuring method as peroxide decomposition amount remaining after reaction treatment, such as can lead to HPLC (high performance liquid chromatography) is crossed to be measured.More specifically, it such as can be proceed as follows: will be viscous after reaction treatment Mixture composite respectively takes out about 0.2g every time, is impregnated in ethyl acetate 10mL, is shaken by oscillator at 25 DEG C with 120rpm After swinging 3 hours and extracting, 3 days are stood at room temperature.Next, addition acetonitrile 10mL, vibrates 30 points at 25 DEG C with 120rpm Clock, and the injection of about 10 μ L of extracting solution obtained from being filtered as molecular filter (0.45 μm) HPLC is analyzed, as anti- Amount of peroxides of answering that treated.
Relative to 100 parts by weight of (methyl) acrylic polymer, the dosage (total amount) of above-mentioned crosslinking agent is preferably 0.01 ~3 parts by weight, more preferably 0.02~2 parts by weight, further preferably 0.03~1 parts by weight.It should be noted that being crosslinked When agent is less than 0.01 parts by weight, there are adhesive phases to become crosslinking deficiency, is unable to satisfy the hidden danger of durability, adhesion characteristic, separately On the one hand, when being more than 3 parts by weight, there are adhesive phases to become really up to the mark, the hidden danger that durability reduces.
In addition, other well known additive can be contained in adhesive composition of the invention, it can be according to the use used Way and powder, the dyestuff, surface for being properly added the polyether compound, colorant, pigment of the polyalkylene glycol such as polypropylene glycol etc. Activating agent, plasticizer, silane coupling agent, tackifier, surface lubricant, levelling agent, softening agent, age resister, antioxidant, light Stabilizer, ultraviolet absorbing agent, polymerization inhibitor, inorganic or organic filler, metal powder or granule, foil-like object etc..In addition, can also To use the redox system of addition reducing agent in controllable range.
< adhesive phase and optical film > with adhesive phase
Adhesive phase of the invention is preferably formed by above-mentioned adhesive composition.It is formed using above-mentioned adhesive composition When above-mentioned adhesive phase, preferably while the dosage to crosslinking agent entirety is adjusted, fully considers crosslinking Treatment temperature, hands over The influence of connection processing time.
Crosslinking Treatment temperature, crosslinking Treatment time can be adjusted according to the crosslinking agent used.Crosslinking Treatment temperature is preferably 170 DEG C or less.
In addition, above-mentioned crosslinking Treatment can carry out at the temperature at which the drying process of adhesive phase, it can also be in drying Crosslinking Treatment process is separately set after process to carry out.
In addition, about the crosslinking Treatment time, it may be considered that productivity, operability are set, but usually 0.2~20 Minute or so, preferably 0.5~10 minute or so.
Optical film with adhesive phase of the invention is preferably formed with above-mentioned adhesive in at least side of optical film.Make Method to form adhesive phase, makes using following method: for example, above-mentioned adhesive composition, which is coated on, have passed through Diaphragm etc. after lift-off processing, after drying and removing polymer solvent etc. and forming adhesive phase, the method that is transferred to optical film； Or above-mentioned adhesive composition is coated on optical film, polymer solvent etc. is dried and removed and forms adhesive on optical film The method etc. of layer.It should be noted that when coating adhesive, suitably can also newly be added in addition to polymer solvent it is a kind of with Upper solvent.
As have passed through the diaphragm after lift-off processing, organosilicon release liner is preferably used.By bonding of the invention Agent composition is coated on that such liner is upper and make it dry and formed in the process of adhesive phase, as keeping adhesive dry Method, can be according to purpose and suitably using suitable method.It is preferred that using the method being thermally dried to above-mentioned coated film. Heat drying temperature is preferably 40 DEG C~200 DEG C, further preferably 50 DEG C~180 DEG C, particularly preferably 70 DEG C~170 DEG C. By the range for keeping heating temperature above-mentioned, the available adhesive with excellent adhesion characteristic.
Drying time can be suitably using the suitable time.Above-mentioned drying time is preferably 5 seconds~20 minutes, further Preferably 5 seconds~10 minutes, particularly preferably 10 seconds~5 minutes.
Furthermore it is possible to optical film surface formed anchor layer, surface-treated layer, or implement sided corona treatment, etc. from Adhesive phase is formed after the various easy bonding processing such as daughter processing.It is easily bonded alternatively, it is also possible to the surface to adhesive phase Processing.
As the forming method of above-mentioned adhesive phase, various methods can be used.It can specifically enumerate for example: rolling method, roller Rubbing method, gravure coating process, reversed rubbing method, roller brush method, spray coating method, dipping rolling method, stick coating method, knife coating, air knife is licked to apply Cloth method, die lip rubbing method, utilizes the methods of extrusion coating methods of die coating machine etc. at curtain coating.
The thickness of above-mentioned adhesive phase is not particularly limited, from the viewpoint of ensuring durability, preferably 5~100 μm, More preferably 5~50 μm, further preferably 10~35 μm.
In addition, the sheet resistance value of above-mentioned adhesive layer surface is preferably 1 × 10 from the viewpoint of antistatic property8~1 ×1010Ω/, more preferably 2 × 108~8 × 109Ω/, further preferably 3 × 108~5 × 109Ω/□。
It, can be until using have passed through at removing before for actual use in the case where the exposure of above-mentioned adhesive phase Piece (diaphragm) after reason protects adhesive phase.
As the constituent material of above-mentioned diaphragm, it can be mentioned, for example: polyethylene, polypropylene, polyethylene terephthalate, What the porous materials such as the plastic foils such as polyester film, paper, cloth, non-woven fabrics, net, foamed sheet, metal foil and their layered product etc. were suitable for Slice substance etc., from surface smoothness it is excellent from the viewpoint of, preferably use plastic foil.
As the plastic foil, as long as the film of above-mentioned adhesive phase can be protected to be not particularly limited, it can be mentioned, for example: Polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, Polyethylene terephthalate film, polybutylene terephthalate (PBT) film, polyurethane film, vinyl-vinyl acetate copolymer Film etc..
The thickness of above-mentioned diaphragm is usually 5~200 μm, and preferably 5~100 μm or so.It can also be as needed using having Machine silicon class, fluorine class, chain alkyl class or fatty acid acyl amine release agent, silicon dioxide powder etc. to above-mentioned diaphragm carry out demoulding and Antifouling process or the antistatic treatment for being coated by type, is mixed into type, vapor deposition type for above-mentioned diaphragm etc..Especially it is possible to pass through The lift-off processings such as organosilicon processing, chain alkyl processing, fluorine processing are suitably carried out to the surface of above-mentioned diaphragm and are further increased Fissility relative to above-mentioned adhesive phase.
It should be noted that the piece that have passed through after lift-off processing used when making the optical film for having adhesive phase can To use directly as the diaphragm of the optical film with adhesive phase, the simplification in terms of process may be implemented.
Hereinafter, being illustrated to the optical film with adhesive phase of the invention.It should be noted that having adhesive phase Optical film successively there is optical film (for example, polarizing coating), adhesive phase.And it can have surface-treated layer, anchor layer.
< optical film >
As above-mentioned optical film, the optics that can be used in the formation of the image display devices such as liquid crystal display device can be used Film, the kind thereof is not particularly limited.For example, polarizing coating can be enumerated as optical film.Polarizing coating is generally used in polarizer One or both sides have the polarizing coating of transparent protective film.
Above-mentioned polarizer is not particularly limited, and various polarizers can be used.As polarizer, it can be mentioned, for example make iodine, two Dichroic substance as color dyestuff is adsorbed in polyvinyl alcohol film, part formalizing polyvinyl alcohol film, ethylene-acetate The hydrophilic macromolecule films such as the partly-hydrolysed film of vinyl ester copolymers class and carry out film obtained from simple tension, polyvinyl alcohol it is de- Polyenoid based oriented film such as dehydrochlorinated products of water process object, polyvinyl chloride etc..Wherein, preferably by polyvinyl alcohol film and iodine Etc. dichroic substances formed polarizer.The thickness of these polarizers is not particularly limited, and usually 80 μm or so or less.
Above-mentioned polyvinyl alcohol film is dyed with iodine and carry out polarizer made of simple tension for example and can pass through by Polyvinyl alcohol film immersion dyes in the aqueous solution of iodine and is stretched to 3~7 times of former length and is made.It can also be impregnated in As needed in the aqueous solution of potassium iodide optionally comprising boric acid, zinc sulfate, zinc chloride etc. etc..Further, it is possible to as needed And polyvinyl alcohol film immersion is washed in water before dyeing.By being washed to polyvinyl alcohol film, in addition to can To wash away other than the dirt of polyvinyl alcohol film surface, antiblocking agent, also having makes polyvinyl alcohol membrane swelling to prevent from contaminating The effect of the unequal unevenness of color.Stretching can carry out after being dyed using iodine, can also be stretched with Edge Coloring side, in addition also It can be dyed after being stretched using iodine.It can also be drawn in the aqueous solution of boric acid, potassium iodide etc. or water-bath It stretches.
In addition, can be used as above-mentioned polarizer with a thickness of 10 μm of slim polarizers below.From the sight of slimming Point considers that the thickness is preferably 1~7 μm.The uneven thickness of such slim polarizer is small, and visibility is excellent, and Change in size is small, therefore excellent in te pins of durability, and then can also realize slimming as the thickness of polarizing coating, in terms of these preferably.
As representative above-mentioned slim polarizer, can enumerate in Japanese Unexamined Patent Application 51-069644 bulletin, Japan Special open 2000-338329 bulletin, WO2010/100917 pamphlet, the specification of PCT/JP2010/001460 or Japan The slim polarizing coating recorded in Patent 2010-269002 specification, Japanese Patent Application 2010-263692 specification.These are thin Type polarizing coating can by include by polyvinyl alcohol resin (hereinafter also referred to PVA resinoid) layer and stretching resin base material with The preparation method of process and the process dyed that the state of laminated body is stretched and obtain.If it is the preparation method, even if then PVA resinoid layer is relatively thin, is supported by being stretched with resin base material, can also be stretched without occurring because stretching causes Fracture a problem that.
It is including the process stretched with the state of laminated body and the process dyed as above-mentioned slim polarizing coating Preparation method in, from can with high magnification is stretched and from the aspect of improving polarization property, preferably pass through WO2010/100917 Number pamphlet, the specification of PCT/JP2010/001460 or Japanese Patent Application 2010-269002 specification, Japanese Patent Application Include the preparation method of the process stretched in boric acid aqueous solution as being recorded in 2010-263692 specification and obtain Slim polarizer, particularly preferably by Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-263692 say What is recorded in bright book includes the process for secondarily stretch in atmosphere before being stretched in boric acid aqueous solution Slim polarizer obtained from preparation method.
As the material for constituting above-mentioned transparent protective film, such as transparency, mechanical strength, thermal stability, moisture can be used The excellent thermoplastic resin such as barrier property, isotropism.As the specific example of such thermoplastic resin, can enumerate: three The celluosic resins such as cellulose acetate, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide, Polyimide resin, polyolefin resin, (methyl) acrylic resin, cyclic polyolefin resin (norbornene resin), poly- virtue Ester resin, polystyrene resin, polyvinyl alcohol resin and their mixture.It should be noted that one for polarizer Face can be bonded transparent protective film by adhesive layer, and for another side, (methyl) acrylic compounds, amino first can be used The thermosetting resin of esters of gallic acid, propenoic methyl carbamate class, epoxies, organic silicon etc. or ultraviolet curing resin conduct Transparent protective film.The additive that can be suitable for containing a kind of any of the above in transparent protective film.As additive, example can be enumerated Such as: ultraviolet absorbing agent, antioxidant, lubricant, plasticizer, release agent, anti-coloring agent, fire retardant, nucleating agent, ionicization Close object, pigment, colorant etc..The content of above-mentioned thermoplastic resin in transparent protective film is preferably 50~100 weight %, more excellent It is selected as 50~99 weight %, further preferably 60~98 weight %, particularly preferably 70~97 weight %.In transparent protective film The content of above-mentioned thermoplastic resin when being 50 weight % or less, exist and be unable to fully show that thermoplastic resin has originally The hidden danger of high transparency etc..
As long as not limited especially for the bonding agent of above-mentioned polarizer and transparent protective film fitting is optically transparent The bonding agent of aqueous, solvent, hot melt class, the various forms of radical-curable, cationic curing type can be used in system, excellent It is selected as aqueous adhesive or radical-curable bonding agent.
In addition, as optical film, it can be mentioned, for example: reflecting plate, anti-transmittance plate, phase difference film are (including 1/2,1/4 etc. wave Piece), vision compensation film, brightness improves film etc. becomes the optics for the optical layer that can be used in the formation of liquid crystal display device etc. Film.They can be used separately as optical film, in addition it is also possible to be laminated in above-mentioned polarizing coating in actual use and use 1 Layer or 2 layers or more.
The optical film that above-mentioned optical layer is laminated on polarizing coating can also be using the manufacture in liquid crystal display device etc. The mode that is successively respectively laminated in journey is formed, but when optical film is made in preparatory stacking, the stabilization with quality Property, the manufacturing process that assembling operation etc. is excellent, can make liquid crystal display device etc. the advantages of improving.Adhesive layer etc. can be used in stacking Appropriate bonding way.When above-mentioned polarizing coating is Nian Jie with other optical layers, their optic axis can be according to the phase of target Potential difference characteristic etc. and be formed as suitable arrangement angles.
Optical film with adhesive phase of the invention can be preferred for the various image display dresses such as liquid crystal display device The formation etc. set.The formation of liquid crystal display device can be carried out based on existing mode.That is, liquid crystal display device can usually lead to It crosses the display panel of liquid crystal cells etc. and optical film with adhesive phase and structures such as lighting system for using as needed It is suitable for assembling and importing driving circuit etc. and is formed at component, in the present invention, of the invention has adhesive phase in addition to using Optical film this point other than, be not particularly limited, can be formed according to existing mode.For liquid crystal cells, can also make With the liquid crystal cells of any types such as such as TN type, STN type, π type, VA type, IPS type etc..
The one or both sides of the display panel of above-mentioned liquid crystal cells etc. can be formed in configured with the optics with adhesive phase The suitable liquid crystal such as the liquid crystal display device of film, the liquid crystal display device for having used backlight or reflecting plate in the illumination system Showing device.At this point, the optical film with adhesive phase of the invention can be set in the side of the display panel of liquid crystal cells etc. Or two sides.In the case where optical film is arranged in two sides, they be may be the same or different.Further, liquid crystal display is being formed When device, 1 layer or 2 layers or more of such as diffusion layer, antiglare layer, antireflection film, protection board, rib can be configured in position The suitable component such as lens array, lens array sheet, light diffusing sheet, backlight.
< anchor layer >
It as anchor layer, can be formed by various conductive agent compositions, as the conductive agent for forming anchor layer, be can be used Electric conductive polymer.
< surface-treated layer >
Surface-treated layer can be set in the side of the not set anchor layer of polarizing coating.Surface-treated layer is in addition to can be set Other than the transparent protective film used in polarizing coating, it can also separately be arranged to the layer different from transparent protective film.As above-mentioned Surface-treated layer can be set: hard conating, non-glare treated layer, anti-reflection layer, anti-sticking layer etc..
As above-mentioned surface-treated layer, preferably hard conating.As the forming material of hard conating, it is, for example, possible to use heat Plastic resin, the material being cured by heat or radioactive ray.It as above-mentioned material, can enumerate: thermohardening type resin, ultraviolet The radiation-curables resins such as line gel-type resin, electronic beam solidified resin.Wherein, it is preferably capable by based on ultraviolet light The curing process of irradiation expeditiously forms the ultraviolet curing resin of curing resin layer with simple process operation.As this A little gel-type resins can be enumerated: polyesters, acrylic compounds, carbamates, amides, organic silicon, epoxies, three The various resins of paracyanogen amine etc., including their monomer, oligomer, polymer etc..It is fast from process velocity, to the heat waste of substrate Hurt it is small from the viewpoint of, particularly preferably radiation-curing type resin, especially ultraviolet curing resin.It is preferable to use purple Outside line gel-type resin is, for example, to have the resin of ultraviolet polymerizing functional group, wherein can enumerate comprising have 2 with The resin of the monomers of upper, particularly acrylic compounds with 3~6 functional groups, oligomer ingredient.In addition, ultraviolet curing Photoepolymerizationinitiater initiater can be combined in type resin.
In addition, non-glare treated layer, the antireflection for improving visibility can be set as above-mentioned surface-treated layer Layer.Furthermore it is possible to which non-glare treated layer, anti-reflection layer are arranged on above-mentioned hard conating.As the constituent material of non-glare treated layer, do not have It is particularly limited to, radiation-curing type resin, thermohardening type resin, thermoplastic resin etc. can be used for example.As antireflection Titanium oxide, zirconium oxide, silica, magnesium fluoride etc. can be used in layer.Multilayer can be set in anti-reflection layer.In addition, as surface treatment Layer, can enumerate anti-sticking layer etc..
Above-mentioned surface-treated layer can be by assigning electric conductivity containing conductive agent.As conductive agent, can be used above-mentioned Ionic compound etc..
Other layers of > of <
It, can also be (inclined in optical film other than above-mentioned each layer in the optical film with adhesive phase of the invention Vibrating diaphragm) setting anchor layer side surface setting adhesive layer or to implement sided corona treatment, corona treatment etc. various easily Bonding processing.
Embodiment
Hereinafter, the present invention is specifically described by Production Example, embodiment, but the present invention is not by these embodiments It limits.It should be noted that part and % in each example are weight basis.The room temperature condition being not particularly limited below is equal It is 25 DEG C.
The theoretical value > of < glass transition temperature (Tg)
The glass transition temperature (Tg) (DEG C) of acrylic polymer obtained in Examples and Comparative Examples is under The literature value stated as the homopolymer based on each monomer glass transition temperature Tg n (DEG C) and found out using following formula.
Formula: 1/ (Tg+273)=Σ [Wn/ (Tgn+273)]
[in formula, Tg (DEG C) indicates that the glass transition temperature of copolymer, Wn (-) indicate the weight percent of each monomer, Tgn (DEG C) indicates that the glass transition temperature of the homopolymer based on each monomer, n indicate the type of each monomer.]
Literature value:
Butyl acrylate (BA): -55 DEG C
Acrylic acid 4- hydroxybutyl (4HBA): -32 DEG C
Acrylic acid (AA): 106 DEG C
Phenoxyethyl acrylate (PEA): -22 DEG C
N-vinyl pyrrolidone (NVP): 54 DEG C
N- acryloyl morpholine (ACMO): 145 DEG C
[embodiment 1]
(production of slim polarizing coating)
In order to make slim polarizing layer, firstly, will form a film on amorphism polyethylene terephthalate (PET) substrate There is the laminated body of 9 μ m-thick polyvinyl alcohol (PVA) layers to form tensile layer by assisting tension in 130 DEG C of draft temperature of atmosphere Stack then generates coloring laminated body by stretching laminated body by dyeing and further passes through 65 DEG C of draft temperature of boric acid water It is stretched in solution and integrally stretches coloring laminated body with amorphism PET base material in a manner of making total stretching ratio reach 5.94 times And form the optical film laminate of the PVA layer comprising 4 μ m-thicks.2 steps in this way stretch, and can be generated and constitute high-performance polarization The optical film laminate comprising 4 μm of thickness of PVA layer of layer, the high-performance polarization layer is formed a film in amorphism PET base material PVA layer PVA molecule have occurred high order orientation and by dyeing and absorption iodine in the form of more iodide ion complex compounds one The polarization layer of high order orientation has occurred on a direction.In turn, in the surface painting polyethylene of the polarization layer of the optical film laminate Alcohols bonding agent and fitting have passed through the tri cellulose acetate membrane of 40 μ m-thicks of saponification process, then remove amorphism PET base Material has made the slim polarizing coating using slim polarization layer.
(preparation of acrylic polymer 1)
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, feed intake containing acrylic acid fourth The monomer mixture of 99 parts by weight of ester (BA), 1 parts by weight of acrylic acid 4- hydroxybutyl (4HBA).Further, relative to above-mentioned list 100 parts by weight of body mixture (solid component), 2, the 2 '-azos two to be fed intake together with ethyl acetate as polymerization initiator are different 0.1 parts by weight of butyronitrile, then nitrogen progress nitrogen displacement is imported while being slowly stirred is maintained at the liquid temperature in flask Near 60 DEG C, 7 hours polymerization reactions have been carried out.Then, ethyl acetate is added in obtained reaction solution, adjusts to solid component Concentration 30%.It is prepared for the solution for the acrylic polymer 1 that glass transition temperature (Tg) is -38 DEG C.
(preparation of acrylic adhesives solution)
Relative to 100 parts by weight of solid component of above-mentioned 1 solution of acrylic polymer, cooperation is used as ionic compound 1- ethyl-3-methylimidazoleBis- (trifluoro methylsulfonyl) inferior amine salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s systems, trade name " ELEXCEL AS-110 ") 6 parts by weight, further cooperate the trimethylolpropane xylylene diisocyanate as crosslinking agent (trade name " TAKENATE D110N ", Mitsui Chemicals, Inc's system) 0.095 parts by weight and dibenzoyl peroxide (commodity Name " NYPER BMT40SV ", NOF Corp's system) 0.3 parts by weight, as thio-alcohol silane coupling agent contain methyl Alkoxysilyl resin (trade name " X-41-1810 ", SHIN-ETSU HANTOTAI's Chemical Co., Ltd. system) 0.2 parts by weight, work with sulfydryl For silane coupling agent (trade name " A-100 ", comprehensive grinding containing acetoacetyl of the silane coupling agent containing acetoacetyl Learn Co. Ltd. system) 0.2 parts by weight and antioxidant (Irganox1010 of BASF AG) 0.3 parts by weight, it is prepared for third Olefin(e) acid class binder solution.
(production of adhesive phase and the polarizing coating with adhesive phase)
Then, by above-mentioned 1 solution coating of acrylic adhesives in poly- pair handled through organic silicon remover The one side of ethylene terephthalate film (diaphragm: Mitsubishi Chemical's polyester film Co. Ltd. system, MRF38), so that viscous after dry Mixture layer with a thickness of 20 μm, drying in 1 minute is carried out at 155 DEG C, forms adhesive phase on the surface of diaphragm.The adhesive Layer is transferred to the face without transparent protective film of above-mentioned polarizing coating, has made the polarizing coating with adhesive phase.
[embodiment 2]
In addition to having cooperated the 1- ethyl-3-methylimidazole as ionic compoundBis- (trifluoro methylsulfonyl) inferior amine salts Other than (Di-ichi Kogyo Seiyaku Co., Ltd.'s system, trade name " ELEXCEL AS-110 ") 2 parts by weight, make similarly to Example 1 The polarizing coating with adhesive phase is made.
[embodiment 3]
(preparation of acrylic polymer 2)
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, feed intake containing acrylic acid fourth 80.3 parts by weight of ester, 16 parts by weight of phenoxyethyl acrylate, 3 parts by weight of n-vinyl-2-pyrrolidone (NVP), acrylic acid The monomer mixture of 0.2 parts by weight, 0.5 parts by weight of acrylic acid 4- hydroxybutyl.Further, relative to above-mentioned monomer mixture (solid component) 100 parts by weight, 2, the 2 '-azos two to be fed intake together with 100 parts by weight of ethyl acetate as polymerization initiator 0.1 parts by weight of isobutyronitrile import nitrogen while being slowly stirred and carry out nitrogen displacement, and then, the liquid temperature in flask is kept 8 hours polymerization reactions are nearby carried out at 55 DEG C, are prepared for the acrylic polymer 2 that glass transition temperature (Tg) is -24 DEG C Solution.
(preparation of acrylic adhesives solution)
Relative to 100 parts by weight of solid component of above-mentioned 2 solution of acrylic polymer, cooperation is used as ionic compound 1- ethyl-3-methylimidazoleBis- (trifluoro methylsulfonyl) inferior amine salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s systems, trade name " ELEXCEL AS-110 ") 6 parts by weight, further cooperate the isocyanate crosslinking (Mitsui Chemicals, Inc as crosslinking agent Society's system, trade name " TAKENATE D-160N ", trimethylolpropane hexamethylene diisocyanate) 0.17 parts by weight, peroxidating Benzoyl (BPO: the NYPER BMT of NOF Corp) 0.25 parts by weight, silane coupling agent (SHIN-ETSU HANTOTAI's chemistry strain formula meeting Society's system: X-41-1810) 0.2 parts by weight, (trade name " A-100 " comprehensive grinds chemical strain to the silane coupling agent containing acetoacetyl Formula commercial firm system) 0.2 parts by weight, it is prepared for acrylic adhesives solution.
[embodiment 4]
In addition to having cooperated the 1- ethyl-3-methylimidazole as ionic compoundBis- (trifluoro methylsulfonyl) inferior amine salts Other than (Di-ichi Kogyo Seiyaku Co., Ltd.'s system, trade name " ELEXCEL AS-110 ") 8 parts by weight, make similarly to Example 2 The polarizing coating with adhesive phase is made.
[embodiment 5]
(preparation of acrylic polymer 3)
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, feed intake butyl acrylate 100 Parts by weight, 7 parts by weight of N- acryloyl morpholine, 3 parts by weight of acrylic acid, 0.3 parts by weight of acrylic acid 2- hydroxybutyl, as polymerization The 2 of initiator, 2 '-azodiisobutyronitrile, 0.1 parts by weight, 200 parts by weight of ethyl acetate, import nitrogen while being slowly stirred Nitrogen displacement is carried out, the liquid temperature in flask is then maintained at 55 DEG C and nearby carries out 8 hours polymerization reactions, vitrifying is prepared for and turns 3 solution of acrylic polymer that temperature (Tg) is -15 DEG C.
(preparation of acrylic adhesives solution)
Relative to 100 parts by weight of solid component of above-mentioned 3 solution of acrylic polymer, cooperation is used as ionic compound 1- ethyl-3-methylimidazoleBis- (trifluoro methylsulfonyl) inferior amine salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s systems, trade name " ELEXCEL AS-110 ") 6 parts by weight, further cooperate the trimethylolpropane by toluene di-isocyanate(TDI) as crosslinking agent Polyisocyanates crosslinking agent made of addition product (TOSOH Co., Ltd's system, trade name " Coronate L ") 0.15 parts by weight, And benzoyl peroxide (BPO: the NYPER BMT of NOF Corp) 0.25 parts by weight, it is prepared for acrylic compounds Binder solution.
[comparative example 1]
In addition to having cooperated the ethyl-methyl pyrrolidines as ionic compoundBis- (trifluoro methylsulfonyl) inferior amine salts (EMPTFSI, Mitsubshi Materials Corp's system, trade name " P1,2N111 ") other than 3 parts by weight, make similarly to Example 3 The polarizing coating with adhesive phase is made.
[comparative example 2]
In addition to having cooperated the 1- octyl -4- picoline as ionic compoundBis- (fluorine sulphonyl) inferior amine salts Other than (MOPyFSI, Di-ichi Kogyo Seiyaku Co., Ltd.'s system, trade name " ELEXCEL AS-804 ") 5 parts by weight, with embodiment 3 The polarizing coating with adhesive phase is similarly made.
[comparative example 3]
In addition to having cooperated bis- (trifluoro methylsulfonyl) imine lithium (LiTFSI, Tokyo chemical conversion industry as ionic compound Co. Ltd. system) 0.7 parts by weight, ethyl-methyl pyrrolidinesBis- (trifluoro methylsulfonyl) inferior amine salt (EMPTFSI, Mitsubishi Materials strain Formula commercial firm system, trade name " P1,2N111 ") other than 1 parts by weight, made similarly to Example 1 with the inclined of adhesive phase Vibrating diaphragm.
[manufacturing method of the surface protection film used when evaluation white dot]
(preparation of acrylic polymer (A))
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, feed intake acrylic acid 2- ethyl Own 100 parts by weight of ester (2EHA), 10 parts by weight of acrylic acid 4- hydroxybutyl (4HBA), 0.02 parts by weight of acrylic acid (AA), conduct The 2 of polymerization initiator, 2 '-azodiisobutyronitrile, 0.2 parts by weight, 157 parts by weight of ethyl acetate, import while being slowly stirred Liquid temperature in flask is maintained at 65 DEG C and nearby carries out 6 hours polymerization reactions, it is molten to be prepared for acrylic polymer (A) by nitrogen Liquid (40 weight %).The glass transition temperature (Tg) of above-mentioned acrylic polymer (A) is -67 DEG C.
(preparation of acrylic adhesives solution)
Above-mentioned acrylic polymer (A) solution (40 weight %) is diluted to 20 weight % with ethyl acetate, it is molten at this Addition uses ethyl acetate that will have alkylene oxides as silicone ingredients in 500 parts by weight of liquid (100 parts by weight of solid component) The organopolysiloxane (trade name " KF-353 ", SHIN-ETSU HANTOTAI's Chemical Co., Ltd. system) of base chain is diluted to 10% 2 parts by weight of solution (0.2 parts by weight of solid component) use ethyl acetate will be sub- as bis- (the trifluoro methylsulfonyls) of the alkali metal salt for becoming antistatic agent Amine lithium (LiN (CF3SO2)2: LiTFSI, Tokyo Chemical Industry Co., Ltd's system) be diluted to 1% 15 parts by weight of solution (solid at Point 0.15 parts by weight), as 3 functional isocyanate compounds, that is, hexamethylene diisocyanate isocyanuric acid ester of crosslinking agent Body (TOSOH Co., Ltd's system, trade name " Coronate HX ") 3.5 parts by weight (1.75 parts by weight of solid component), 2 function isocyanides Ester compound, that is, 1,3- bis- (isocyanatomethyl) hexamethylene (Mitsui Chemicals, Inc's system, trade name " TAKENATE 600 ") 0.3 parts by weight (0.3 parts by weight of solid component), dibutyl tin dilaurate (the 1 weight % second as crosslinking catalyst Acetate solution) 2 parts by weight (0.02 parts by weight of solid component), according to following preparation methods manufacture acrylic acid oligomer 0.5 Parts by weight are mixed, and acrylic adhesives solution is prepared for.
(preparation of acrylic acid oligomer)
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, dropping funel, feed intake toluene 100 parts by weight, methacrylic acid dicyclopentenyl base ester (DCPMA) (trade name " FA-513M ", Hitachi Chemical Co., Ltd. System) 60 parts by weight, 40 parts by weight of methyl methacrylate (MMA) and 3.5 parts by weight of methyl thioglycolate as chain-transferring agent. Then, after 1 hour having been stirred in 70 DEG C, nitrogen atmosphere, 2, the 2 '-azodiisobutyronitriles 0.2 as polymerization initiator are added Parts by weight are reacted 2 hours at 70 DEG C, are then reacted at 80 DEG C 4 hours, are then reacted 1 hour at 90 DEG C, obtained third Olefin(e) acid oligomer.The glass transition temperature (Tg) of above-mentioned acrylic acid oligomer is 144 DEG C.
[production of antistatic treatment film]
By diluting antistatic agent using the mixed solvent being made of 30 parts by weight of water and 70 parts by weight of methanol, (Solvex is public The system of department, MICRO-SOLVER RMd-142, using tin oxide and polyester resin as principal component) 10 parts by weight, be prepared for antistatic Agent solution.
Stick spreader (Mayer bar) is strangled using wheat, and obtained antistatic agent solution is coated on poly terephthalic acid second two It is 1 minute dry at 130 DEG C on alcohol ester (PET) film (thickness: 38 μm), so that solvent is removed, formation antistatic layer (thickness: 0.2 μm), make antistatic treatment film.
[production of surface protection film]
By above-mentioned acrylic adhesives solution coating in the opposite with antistatic treatment face of above-mentioned antistatic treatment film Face heats 2 minutes at 130 DEG C, forms 15 μm of thickness of adhesive phase.Then, organosilicon processing will be implemented on one side The organosilicon process face of polyethylene terephthalate film (25 μm of thickness) is fitted in the surface of above-mentioned adhesive phase, production Surface protection film.
For having the polarizing coating of adhesive phase obtained in above-described embodiment and comparative example, surface electricity below has been carried out Resistance, the relevant evaluation of white dot.Show the results of the evaluation table 3.
The measurement > of the sheet resistance value of < adhesive layer surface
The diaphragm for having the polarizing coating of adhesive phase obtained in Examples and Comparative Examples is peeled, is put in room temperature (25 DEG C) It placed 1 minute, then, the MCP-HT450 manufactured using Mitsubishi Chemical Analytech company under the conditions of setting Determine the sheet resistance value (Ω/) of adhesive layer surface.Wherein, antistatic property is had rated according to sheet resistance value.
From the viewpoint of antistatic property, the sheet resistance value of above-mentioned adhesive layer surface is preferably 1 × 108~1 × 1010 Ω/, more preferably 2 × 108~8 × 109Ω/, further preferably 3 × 108~5 × 109Ω/□。
White extinction time (room temperature (25 DEG C)) > of < liquid crystal display panel
Above-mentioned surface protection film is fitted in obtained in the Examples and Comparative Examples with adhesive phase using hand pressure roller Polarizing coating polarization film surface.Then, be cut into the size of 150mm × 100mm, peel diaphragm, fit in liquid crystal cells and Liquid crystal display panel is made, which is placed on the backlight with 10000cd brightness under room temperature (25 DEG C), with 1m/ seconds Speed generates electrostatic from the above-mentioned surface protection film of polarizing coating sur-face peeling, thus causes the orientation of liquid crystal chaotic.Pass through range estimation And the bad caused undesirable recovery time (second) of display of the orientation is measured, leukasmus point is evaluated.
Show that undesirable recovery time is preferably 10 seconds hereinafter, more preferably 5 seconds or less.It is commented according to benchmark below Valence white dot.It should be noted that in addition to × other than, it is judged as the level that there is no problem in actual use.
◎: restore (disappearance) time less than 5 seconds
Zero: restoring (disappearance) time less than 10 seconds
△: restoring (disappearance) time was 10 seconds more than and less than 30 seconds
×: restoring (disappearance) time is 30 seconds or more
White extinction time (low temperature) > of < liquid crystal display panel
Above-mentioned surface protection film is fitted in obtained in the Examples and Comparative Examples with adhesive phase using hand pressure roller Polarizing coating polarization film surface.Then, be cut into the size of 150mm × 100mm, peel diaphragm, fit in liquid crystal cells and Liquid crystal display panel is made, which is being cooled to -20 DEG C (low temperature) of the large-scale low-temperature testing machine (MG- of ESPEC company manufacture 322) 15 minutes have been stood in.
It is just taking out to after room temperature (25 DEG C), being placed on the panel with the state that surface temperature is -5 DEG C has On the backlight of 10000cd brightness, with 1m/ seconds speed from the above-mentioned surface protection film of polarizing coating sur-face peeling, generate electrostatic, Thus cause the orientation of liquid crystal chaotic.The orientation bad caused display undesirable recovery time is measured by range estimation (second) evaluates leukasmus point.
Show that undesirable recovery time is preferably 10 seconds hereinafter, more preferably 5 seconds or less.It is commented according to benchmark below Valence white dot.It should be noted that in addition to × other than, it is judged as the level that there is no problem in actual use.
◎: restore (disappearance) time less than 5 seconds
Zero: restoring (disappearance) time less than 10 seconds
△: restoring (disappearance) time was 10 seconds more than and less than 30 seconds
×: restoring (disappearance) time is 30 seconds or more
[table 1]
Abbreviation in table 1 and table 2 is as described below.
BA: butyl acrylate
PEA: phenoxyethyl acrylate
NVP:N- vinyl pyrrolidone
AA: acrylic acid
4HBA: acrylic acid 4- hydroxybutyl
ACMO:N- acryloyl morpholine
AS110:1- ethyl-3-methylimidazoleBis- (fluorine sulphonyl) inferior amine salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s systems, commodity Name: ELEXCEL AS-110), ionic liquid (fusing point: -12.9 DEG C)
EMPTFSI: ethyl-methyl pyrrolidinesBis- (trifluoro methylsulfonyl) inferior amine salt (Mitsubshi Materials Corp's systems, commodity Name: P1,2N111), ionic solid (fusing point: 90 DEG C)
MOPyFSI:1- octyl -4- picolineBis- (fluorine sulphonyl) inferior amine salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s systems, quotient The name of an article: ELEXCEL AS-804), ionic liquid (fusing point: -3.1 DEG C)
LiTFSI: bis- (trifluoro methylsulfonyl) imine lithium (Tokyo Chemical Industry Co., Ltd's systems, LiN (CF3SO2)2), alkali gold Belong to salt (fusing point: 232 DEG C)
Note) " E+08 " expression " 1 × 10 in table 38”。
It according to the evaluation result of above-mentioned table 3, is confirmed in whole embodiments: wishing fusing point by using having Ionic compound, can obtain the white dot being able to suppress in low temperature environment, excellent antistatic property with adhesive phase Polarizing coating (optical film).On the other hand, further acknowledged: in a comparative example, due to ionic compound fusing point departing from Desired range, therefore the white dot in low temperature environment can not be inhibited, antistatic property can not be met.
Industrial applicibility
The optical film with adhesive phase formed using adhesive composition disclosed herein can include low temperature ring Broad temperature range including in border assigns antistatic property, therefore can manufacturing process in liquid crystal display device and actual use Temperature range assign the effect that prevents white dot more stable to environmental change.In addition, in electronic component, semiconductor etc. Can break down because of electrostatic or the manufacturing process material of the material of unfavorable condition, protective film use on the way, can also be in broadness Temperature range inhibits electrostatic to generate.In addition, using adhesive disclosed herein as structural elements as grafting material In the case where composition, since generated electrostatic can be discharged, electronic component, the failure of semiconductor and not can be prevented Good situation.

Claims (5)

1. a kind of adhesive composition, contains (methyl) acrylate copolymer and fusing point is -5 DEG C of ionic chemical combination below Object.
2. adhesive composition according to claim 1, wherein conductivity of the ionic compound at 25 DEG C be 10mS/cm or more.
3. adhesive composition according to claim 1 or 2, wherein
The ionic compound is ionic liquid,
The ionic liquid is organic cation-anion salt,
The anion is bis- (fluorine sulphonyl) imines anion, and/or bis- (trifluoro methylsulfonyl) imines anion.
4. a kind of adhesive phase is the layer formed using adhesive composition described in any one of claims 1 to 33.
5. a kind of optical film with adhesive phase is formed with bonding as claimed in claim 4 in at least side of optical film Oxidant layer.
CN201880006969.6A 2017-02-21 2018-02-09 Adhesive composition, adhesive phase and the optical film with adhesive phase Pending CN110177849A (en)

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Application publication date: 20190827