CN106795416A - Polarizer adhesive composition and polarizer bonding sheet - Google Patents

Polarizer adhesive composition and polarizer bonding sheet Download PDF

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Publication number
CN106795416A
CN106795416A CN201580032667.2A CN201580032667A CN106795416A CN 106795416 A CN106795416 A CN 106795416A CN 201580032667 A CN201580032667 A CN 201580032667A CN 106795416 A CN106795416 A CN 106795416A
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CN
China
Prior art keywords
polarizer
composition
adhesive composition
sulfonyl
salt
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Pending
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CN201580032667.2A
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Chinese (zh)
Inventor
山本真之
武藤国昭
柴田俊
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New Oji Paper Co Ltd
Oji Holdings Corp
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Oji Paper Co Ltd
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Publication of CN106795416A publication Critical patent/CN106795416A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Abstract

Problem of the present invention is to provide a kind of polarizer adhesive composition and bonding sheet, and it is the polarizer adhesive composition with antistatic performance, even if in the case where polarizer is directly adhered to, also there is no the decolouring or deterioration of polarizer.The present invention relates to a kind of polarizer adhesive composition, it contains anti-static composition, and above-mentioned anti-static composition is to be dissolved with the composition for possessing the salt with fluorine-based and sulfonyl anion in the plasticizer containing polyether-based in main chain.

Description

Polarizer adhesive composition and polarizer bonding sheet
Technical field
The present invention relates to polarizer adhesive composition and polarizer bonding sheet.In particular to directly attachment In the polarizer adhesive composition and polarizer bonding sheet of polarizer, laminating polarizer and optical component.
Prior art
In the liquid crystal cells of liquid crystal display device (LCD), sometimes must be in display base plate according to image forming method Two sides configuration polarizer, form the adhesive for being pasted on other optical components such as liquid crystal cells in the one side of this polarizer Layer.
In general, polarizer sets on the two sides of the polarizer being made up of dichroism pigments such as polyvinyl alcohol film and iodine It is equipped with transparent protective film.It is weak to there is physical intensity in polarizer, the problems such as being easily broken in the direction of the machine, therefore at least in list Face, it is usually on two sides and is fitted via bond layer above-mentioned transparent protective film.The polarizer that conventional liquid crystal cells are used It is the 3-tier architecture for seizing polarizer on both sides by the arms between 2 triacetyl cellulose (TAC) class diaphragms, or in TAC classes diaphragm and ring Seize the 3-tier architecture of polarizer between olefin polymer (COP) class diaphragm on both sides by the arms.
When by polarizing plate sticking in liquid crystal cells etc., usually using adhesive.Due to polarizer moment can be fixed, Do not need the convenience of drying process etc. when making polarizer cementation, therefore in polarizer one side adhesive is set used as bonding in advance Oxidant layer.
There is generation electrostatic when polarizer is fitted in into liquid crystal cells.Such electrostatic turns into the failure for causing liquid crystal cells Or the foreign matter because powered caused by foreign matter absorption is the reason for snap in, therefore adhesive phase must have antistatic performance.For example, In patent document 1~3, in order that adhesive phase has antistatic performance, ionic compound is typically contained.
In addition, making the optical component of liquid crystal cells also to thin due to the slimming of the touch panels such as smart mobile phone in recent years Typeization develops.Polarizer is no exception, it has been proposed that form the polarizer of diaphragm at least side of polarizer to replace Transparent protective film (patent document 4).In addition, it is proposed that form the polarization of the diaphragm for improving the durability under harsh environment Piece (patent document 5).In addition, for the filming of polarizer, have studied the saturating of side set by the adhesive phase for cancelling polarizer Bright diaphragm, and the polarizer of the structure of adhesive phase is directly set on polarizer.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-100386 publications
Patent document 2：Japanese Unexamined Patent Publication 2013-108031 publications
Patent document 3：Japanese Unexamined Patent Publication 2014-62264 publications
Patent document 4：Japanese Unexamined Patent Publication 2003-185842 publications
Patent document 5：Japanese Unexamined Patent Publication 2010-9027 publications
The content of the invention
Invent problem to be solved
However, the research according to the present inventor etc. shows, cancel polarizer transparent protective film, on polarizer directly In the case that adhesive phase is set, if using the existing adhesive phase with antistatic performance, in the presence of as polarizer The dichroism pigment such as the iodine of polyvinyl alcohol (PVA) institute gas absorption quantity of constitutive requirements occur to decolourize the feelings of (polarizer deterioration) Condition.
Therefore, the present inventor etc. has made intensive studies, its object is to provide a kind of polarizer adhesive composition And bonding sheet, the polarizer adhesive composition is the adhesive composition with antistatic performance, even if directly attached In the case of polarizer, the decolouring or deterioration of polarizer do not occur yet.
Therefore, the present inventor etc. persistently discusses, it is therefore intended that provide a kind of polarizer adhesive composition and bonding sheet, It is the adhesive composition with antistatic performance, even if being attached directly to the situation of polarizer, polarizer does not occur still Decolouring or deterioration.
The technical method of solve problem
The present inventor etc. have investigated reason to solve above-mentioned problem, the result is that having distinguished the decolouring reason of polarizer It is the antistatic agent for assigning antistatic performance contained by adhesive phase.Therefore, the present inventor etc. further grinds with great concentration Study carefully, as a result find, using the antistatic agent with specific composition, antistatic performance can not be damaged by adhesive composition And suppress polarizer decolouring.Specifically, the present inventor etc. has found, by will be molten in the plasticizer containing polyether-based in main chain Solution has the anti-static composition for possessing the salt with fluorine-based and sulfonyl anion stable and is homogeneously dispersed in acrylic acid Class adhesive, is used in fitting for polarizer and optical component, then can not damage antistatic performance and suppress polarizer and take off Color.In addition, the present inventor etc. has found, by using such polarizer adhesive composition, can be thinned polarizer, from And complete the present invention.
Specifically, the present invention has following composition.
[1] a kind of polarizer adhesive composition, it contains anti-static composition, and anti-static composition is in master The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with chain in plasticizer containing polyether-based.
[2] the polarizer adhesive composition as described in [1], wherein, anti-static composition is contained in main chain The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with the polyethers ester plasticizer of polyether-based.
[3] the polarizer adhesive composition as described in [1] or [2], wherein, polyethers ester plasticizer contains following formula (1) at least a kind polyethers ester plasticizer or shown in (2),
Chemical formula 1
Chemical formula 2
In formula (1) and formula (2), m and n is respectively integer, and R represents alkyl.
[4] the polarizer adhesive composition as described in [1], wherein, anti-static composition is contained in main chain The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with the polyethers plasticizer of polyether-based.
[5] the polarizer adhesive composition as described in [4], wherein, polyethers plasticizer is comprising with following formula (11) Polyethers plasticizer,
R1(OCH2CH2)nOR2 (11)
In formula, R1Represent the alkyl of carbon number 1~12, R2The alkyl of hydrogen atom or carbon number 1~12 is represented, n is represented 3~6 integer.
[6] the polarizer adhesive composition as described in [1], wherein, anti-static composition is included：Contain in main chain Have be dissolved with the polyethers ester plasticizer of polyether-based the composition that possesses the salt with fluorine-based and sulfonyl anion and The group for possessing the salt with fluorine-based and sulfonyl anion is dissolved with the polyethers plasticizer containing polyether-based in main chain Compound.
[7] the polarizer adhesive composition as any one of [1]~[6], wherein, polarizer adhesive group The principal component of compound is the adhesive composition for containing substantially no carboxyl.
[8] the polarizer adhesive composition as any one of [1]~[7], wherein, polarizer adhesive group The principal component of compound is acrylic pressure-sensitive adhesive compositions.
[9] the polarizer adhesive composition as described in [7], wherein, acrylic pressure-sensitive adhesive compositions contain (first Base) acrylic copolymer (A) and crosslinking agent (B), (methyl) acrylic copolymer (A) at least makes following (i) to enter with (ii) Row is polymerized and obtains：
I () has the mass % of (methyl) acrylate monomer 60~99.99 of the alkyl of carbon number 1~18,
(ii) have free-radical polymerised unsaturated group and the monomer 0.01 with least one reactive functional groups~ 20 mass %.
[10] the polarizer adhesive composition as described in [8], wherein, reactive functional groups are selected from hydroxyl and amino At least one, the monomer with reactive functional groups contains substantially no carboxyl group-containing monomer.
[11] the polarizer adhesive composition as described in [8] or [9], wherein, crosslinking agent (B) is selected from isocyanates At least a kind in class crosslinking agent, epoxies crosslinking agent and metal-chelating species crosslinking agent.
[12] the polarizer adhesive composition as any one of [8]~[10], wherein, relative to (methyl) third The weight portion of olefin(e) acid analog copolymer (A) 100, the content of anti-static composition is 0.01~30 mass parts.
[13] the polarizer adhesive composition as any one of [1]~[11], wherein, with fluorine-based and sulphonyl The anion of base is selected from double (oroalkane sulfonyl base) imide ionic, three (oroalkane sulfonyl base) methide ions and fluothane Anion in base azochlorosulfonate acid ion.
[14] the polarizer adhesive composition as any one of [1]~[12], wherein, possess with fluorine-based and The salt of the anion of sulfonyl be by least one cation selected from alkali metal, 2 race's elements, transition metal and amphoteric metal with With the salt that fluorine-based and sulfonyl anion is formed.
[15] the polarizer adhesive composition as any one of [1]~[13], wherein, possess with fluorine-based and The salt of the anion of sulfonyl is selected from double (oroalkane sulfonyl base) imido alkali metal salt, three (oroalkane sulfonyl base) methyl Salt in the alkali metal salt of compound and the alkali metal salt of trifluoroalkyl sulfonic acid.
[16] the polarizer adhesive composition as any one of [1]~[14], wherein, polarizer adhesive Composition is used for fit polarizer and optical component.
[17] the polarizer adhesive composition as described in [15], wherein, optical component is liquid crystal cells or touch surface Plate.
[18] a kind of polarizer bonding sheet, it contains the polarizer adhesive group any one of [1]~[16] Compound.
[19] a kind of image display device, it possesses the bonding sheet described at least one [17].
The effect of invention
According to the present invention, it is possible to provide though at least one side in polarizer directly adhere to or stack adhesive composition feelings Under condition, do not damage antistatic performance still and the polarizer adhesive composition of decolouring or the deterioration of polarizer does not occur and rises Polariscope bonding sheet.These polarizer adhesive compositions or bonding sheet are directly adhered to polarizer, use viscous via polarizer Mixture composite or polarizer bonding sheet laminating polarizer and optical component.Therefore, it is capable of achieving the slimming of polarizer.
Brief description of the drawings
The figure of the action effect of the anti-static composition that Fig. 1 is used to illustrate the invention.
Fig. 2 is the structure and existing polarizer for illustrating the polarizer containing polarizer adhesive composition of the invention Structure figure.
Anti-static composition that Fig. 3 is used by embodiment, the extract solution of the bonding sheet containing anti-static composition, The chromatogram of the HPLC (high performance liquid chromatography) of the extract solution of the bonding sheet of anti-static composition is not added.
Symbol description
1 polarizer
10 polarizers
12 diaphragms
20 bonding sheets (polarizer adhesive composition layer)
Specific embodiment
The present invention described further below.The explanation of the constitutive requirements below recorded is based on representational embodiment or specific Example, but the present invention is not limited to such implementation method.In addition, in this specification, the number range for using "~" to represent is Finger includes the numerical value recorded before and after it as lower limit and the scope of higher limit.
(polarizer adhesive composition)
The polarizer adhesive composition of the present invention is attached directly at least one side of polarizer, is for by polarizer The adhesive composition fitted with optical component.Polarizer adhesive composition of the invention contains static electricity resistance combination Thing.Here, anti-static composition is to be dissolved with to possess with fluorine-based and sulphonyl in the plasticizer containing polyether-based in main chain The composition of the salt of the anion of base.Polarizer adhesive composition of the invention is said structure, therefore can make polarizer It is flexibly closely sealed with adhesive phase.In addition, polarizer adhesive composition of the invention is due to can directly paste or be stacked on Polarizer, therefore the slim polarizer for eliminating transparent protective film or protective layer can be made.Thus, even eliminating diaphragm Deng polarizer, under the high temperature or hot and humid environment or repeatedly excellent heat resistance in the environment of heating and cooling, in addition, can The polarizer decolouring suppressed as caused by the transfer of fierce temperature change or adhesive ingredients (predominantly antistatic composition) is (bad Change).
(anti-static composition)
Anti-static composition used in polarizer adhesive composition of the invention, is containing poly- in main chain The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with the plasticizer of ether.That is, static electricity resistance combination In thing, make to possess the salt with fluorine-based and sulfonyl anion and the plasticising containing polyether-based in main chain is scattered in dissolved state In agent.
In addition, the anti-static composition used in polarizer adhesive composition of the invention, is in main chain Dissolved in plasticizer containing polyether-based and possessed selected from least one of alkali metal, 2 race's elements, transition metal and amphoteric metal The composition of the salt of cation.Cation is preferably selected from any one cation in alkali metal and 2 race's elements, more preferably alkali The cation of metal.Wherein, cation is preferably lithium ion.
Here, in polarizer adhesive composition of the invention, as the cation coordination of the counter ion counterionsl gegenions of anion The oxygen atom of the ether in plasticizer, forms complex compound.That is, as the counter ion counterionsl gegenions with fluorine-based and sulfonyl anion The plasticizer containing polyether-based forms the complex ion of lewis acid-alkaline in cation, with main chain.It is used in the present invention anti-quiet Conductive composition is characterised by that containing complex compound the complex compound is by as contending with fluorine-based and sulfonyl anion The oxygen atom of ether of the cation coordination of ion in main chain in the plasticizer containing polyether-based and formed.
The cation for forming complex ion with plasticizer is preferably selected from alkali metal, 2 race's elements, transition metal and amphoteric metal At least one of cation, wherein more preferably lithium ion.That is, the complex compound for being formed preferably lithium polyethers complex compound.
Anti-static composition used in polarizer adhesive composition of the invention is with HPLC (efficient liquid phases Chromatogram) when being analyzed, can detect the peak from complex compound.Anti-static composition or only main chain of the peak in only salt In plasticizer containing polyether-based when be not detected, be derived from the peak of complex compound.
It should be noted that HPLC conditions are as described below.
Post：XBridge C18,4.6 × 250mm of post footpath (WATERS company systems)
Column temperature：30℃
Mobile phase：Acetonitrile/water
Flow velocity：0.8mL/ points
Detection：225nm
In the present invention, by using such anti-static composition, even if being attached directly to by adhesive composition In the case of polarizer, decolourized prevented also from polarizer.In addition, in this specification, so-called " dispersion " refers to possess with fluorine-based And the state that the salt of the anion of sulfonyl disperses or dissolve in plasticizer.As such anti-static composition, can enumerate For example：Sankonol AD2326 (three photochemistry industrial group systems), Sankonol AD2600 (three photochemistry industrial group systems), Sankonol TGR (three photochemistry industrial group systems) etc..
If the existing polarizer adhesive composition containing ionic compound is directly adhered into polarizer, by Poor compatibility in the mobility of ionic compound or with acrylic pressure-sensitive adhesive compositions, thus cation ooze out or Brightness dissipates (blooming), the iodide ion (I with polarizer3-、I5-) false key is formed, cause the decolouring of polarizer.On the other hand, Anti-static composition used in the present invention is due to being dissolved in the increasing high with the compatibility of acrylic pressure-sensitive adhesive compositions Modeling agent in state and disperse, therefore do not cause ooze out or brightness dissipate.And then, the cation of anti-static composition due to plasticising Dosage form therefore with the iodide ion of polarizer does not form chemical bond into the complex ion of lewis acid-alkaline.
The content of anti-static composition is common relative to (methyl) acrylic compounds contained by polarizer adhesive composition The mass parts of polymers 100, preferably 0.01~30 mass parts, more preferably 0.1~10 mass parts.By by anti-static composition Content be set in above range, can play sufficient antistatic performance, and in static electricity resistance combination can be suppressed under low temperature environment A problem that thing is separated out.
(polyethers ester plasticizer)
Anti-static composition is preferably in main chain to be dissolved with the polyethers ester plasticizer containing polyether-based possesses tool There is the composition of the salt of fluorine-based and sulfonyl anion.Polyethers ester plasticizer contains polyether-based and ester bond, is set by entering Fat gap and hinder the rule of resin to be properly oriented.Even if in addition, polyethers ester plasticizer refers in glass transition temperature Hereinafter the polyethers ester plasticizer of noncrystalline state is still kept.Wherein, polyethers ester plasticizer is preferably by following formula (1) or (2) institute The polyethers ester type compound for showing.
Chemical formula 3
Chemical formula 4
In formula (1) and (2), m and n is respectively integer, and R represents alkyl.
Polyethers ester plasticizer viscosity is low and operational good, with low-temperature pliability, with heat-resistant aging, flexibility Balance, non-volatile, non-metastatic, oil resistivity with durability, security (meeting PL) are excellent.
R is preferably the alkyl of carbon number 1~14.For example be preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, Isobutyl group, n-pentyl, n-nonyl, isononyl, positive decyl, positive lauryl etc..
In formula (1) and (2), m is preferably 1~40 integer, and n is preferably 1~20 integer.M and n are more preferably more than 2 Integer.M is particularly preferably more than 2 integer.
The molecular weight of the polyethers ester plasticizer containing polyether-based is preferably 250~2000, more preferably 500 in main chain ~1500.The viscosity (25 DEG C) of polyethers ester plasticizer is preferably 30~600mPas.
(polyethers plasticizer)
Anti-static composition can be dissolved with to possess in the polyethers plasticizer containing polyether-based in main chain to have The composition of the salt of fluorine-based and sulfonyl anion.In addition, anti-static composition can be included：Contain polyethers in main chain Be dissolved with the polyethers ester plasticizer of base possess the salt with fluorine-based and sulfonyl anion composition, contain in main chain Have in the polyethers plasticizer of polyether-based and be dissolved with the composition for possessing the salt with fluorine-based and sulfonyl anion.Here, So-called polyethers plasticizer is preferably polyalkyleneglycol dialkylether compound or polyalkylene shown in following formulas (11) Glycol monoalkyl ether compound.
Chemical formula 5
R1(OCH2CH2)nOR2 (11)
In formula (11), R1Represent the alkyl of carbon number 1~12, R2Represent the alkyl of hydrogen atom or carbon number 1~12, n Represent 3~6 integer.
The polyethers plasticizer is particularly preferably alkyl ether compound.
(other plasticizer)
In addition, can also contain other in addition to above-mentioned polyethers esters or polyethers plasticizer in anti-static composition Plasticizer.As such plasticizer, can enumerate for example：By list or dicarboxylic acids and tool with saturation or unsaturated non-ring alkyl Unsaturated group in the ester that the alcohol for having the non-ring alkyl of carbon number 1~20 is formed, or unsaturated non-ring alkyl is by ring The plasticizer that the ester of oxidation is formed.By using such ester, wetability of the adhesive phase to adherend can be improved, pasted When be not susceptible to bubble and be involved in, while be not susceptible to plasticizer being oozed out from adhesive phase, can be adapted to reduce adherend pollution.
As saturation or undersaturated non-ring alkyl in the list or dicarboxylic acid component for constituting ester, can enumerate for example：Alkyl Or alkylidene, wherein the preferably alkyl or alkylidene of carbon number 1~20, the more preferably alkyl of carbon number 4~18, special Not You Xuanwei carbon number 4~14 alkyl.For such list with saturation or unsaturated non-ring alkyl or dicarboxylic acids Speech, by the acrylic compounds list with the acrylic pressure-sensitive adhesive compositions used with composition polarizer adhesive composition The close carbon number of the carbon number of body, thus good with the compatibility of polarizer adhesive composition, be adapted to hold in In polarizer adhesive composition, therefore can suppress to ooze out.
As monocarboxylic acid and dicarboxylic acids with saturation or undersaturated non-ring alkyl, can enumerate for example：Oxalic acid, the third two The straight-chain aliphatics such as acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid two The monoesters or polyester of carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, undecanoic acid, bay The saturated fatty acids such as acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, crotons Acid, root of Dahurain angelica acid, dodecenoic acid, myristoleic acid (myristoleic acid), palmitin oleic acid, oleic acid, vaccenic acid, cod oil Acid, eicosenoic acid, sinapic acid, tetracosenoic acid, linolenic acid, eicosadienoic acid, two dodecadienoic acids, 18 carbon Trienic acid, pine nut oleic acid, eleostearic acid, eicosatrienoic acid, parinaric acid, arachic acid, eicosatetraenoic acid, 22 carbon Unrighted acids such as tetraenoic acid, elaidic acid, DHA etc..
As the non-ring alkyl of the carbon number 1~20 in the alcohol for constituting ester, can be adapted to use the alkane of carbon number 1~20 Base or alkylidene, especially alkyl, wherein the preferably alkyl of carbon number 4~18, the alkane of particularly preferred carbon number 4~14 Base.Such alcohol with saturation or undersaturated non-ring alkyl, by with constitute polarizer adhesive composition institute The close carbon number of the carbon number of the acrylic monomer of the acrylic pressure-sensitive adhesive compositions for containing, thus used with polarizer The compatibility of adhesive composition is good, is adapted to hold in polarizer adhesive composition, therefore can suppress to ooze out.With structure Carboxylic acid composition into ester compares, and is set to by the carbon number of the alkyl that this is had alcohol composition and constitutes polarizer adhesive The close carbon number of the carbon number of the acrylic monomer of the acrylic pressure-sensitive adhesive compositions of composition, can especially hold Suppression adherend of changing places pollutes.
As such alcohol with non-ring alkyl, can enumerate for example：Methyl alcohol, ethanol, propyl alcohol, butanol, amylalcohol, hexanol, Enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, pentadecanol, cetanol, heptadecanol, octadecyl alcolol, Nonadecanol, the straight chain of arachidic alcohol, branched-chain alcoho.Wherein, butanol, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, the last of the ten Heavenly stems are particularly preferably used Alcohol.
In the present invention, in addition to above-mentioned polyethers ester plasticizer and/or polyethers plasticizer, can also by by above-mentioned single or Dicarboxylic acids is used as plasticizer with the ester that alcohol is formed.As the ester, there can be the skeleton formed by saturation or unsaturated alkyl, Preferably without the ester of the skeleton formed by unsaturated alkyl.Additionally, it is preferred that also making to have by the unsaturated hydrocarbons The unsaturated bond of the ester of the skeleton that base is constituted through epoxidation epoxidised ester.In the middle of the ester, particularly preferably can be used Adipate monoester, decanedioic acid monoesters, epoxidized fat acid monoester.
Can be any one in monoesters or polyester, from easily by solubility parameter (SP as using the ester for plasticizer Value) it is controlled to from the viewpoint of suitable scope, the easily compatibility of raising and polarizer adhesive composition, preferably changed with PS The weight average molecular weight calculated is less than 1000 ester, particularly preferably 300~800 ester.
As plasticizer, the plasticizer that solubility parameter (SP values) is less than 8.5 is preferably used.Wherein, preferably 7.0~ 8.4.The SP values of plasticizer be less than 8.5 when, the excellent compatibility with acrylic pressure-sensitive adhesive compositions, even if therefore with It is pasted with polarizer in the case that the state of polarizer adhesive composition places under the hot and humid environment through long-time, When from polarizer sur-face peeling, still it is difficult to be hazed on polarizer surface.Used as the SP values of plasticizer, generally applicable property ground makes With the plasticizer more than 7.0.In addition, above-mentioned SP values are the Small formulas [P.A.J.Small advocated according to J.Small： J.Appl.Chem., 3,71 (1953)] obtained from calculated value.
Relative to the mass parts of (methyl) acrylic copolymer 100 for constituting acrylic pressure-sensitive adhesive compositions, above-mentioned increasing 0.5~30 mass parts of the preferred addition of modeling agent, more preferably 1~20 mass parts of addition, particularly preferably 1~10 mass parts of addition.If The addition of plasticizer is more than 0.5 mass parts, then in laminating, bubble is easily drained.In addition, if being less than 30 mass parts, it is then Make also to be not easy to be hazed in display surface under hot and humid environment.
(possessing the salt with fluorine-based and sulfonyl anion)
Possess the salt with fluorine-based and sulfonyl anion and be easily dissolved in polyethers ester plasticizer and polyethers plasticising Agent, can improve the salinity in plasticizer.Polarizer adhesive composition is scattered in by by the solution, can make to possess to have The salt of fluorine-based and sulfonyl anion is a large amount of and evenly into polarizer adhesive composition.In polarizer bonding In agent composition, as the oxygen atom ligand of the ether in the cation and plasticizer of the counter ion counterionsl gegenions of anion, complex compound is formed.
The plasticizer solution for possessing the salt with fluorine-based and sulfonyl anion is dissolved, in polarizer adhesive group It is engaged with the plasticity of plasticizer in compound, while antistatic performance is showed, while assigning plasticity.In addition, Plasticizer containing polyether-based in main chain, approaches the solubility parameter (SP values) of polarizer adhesive composition, therefore parent It is excellent with property, do not ooze out.And then, not transfer the pollution, do not rely on humidity, quick-acting is excellent, and persistently has The polarizer adhesive composition of excellent static electricity resistance.It should be noted that the effect above is for polyethers ester plasticizer And it is also identical for polyethers plasticizer.
The plasticizer solution for possessing the salt with fluorine-based and sulfonyl anion is dissolved, in polarizer adhesive group Bonding physical property is kept in compound and static electricity resistance is played.In addition, dissolved possessing the salt with fluorine-based and sulfonyl anion Plasticizer solution, the excellent compatibility with the molecule for constituting polarizer adhesive composition therefore do not ooze Go out, brightness dissipates and transfers the pollution, and does not depend on humidity, quick-acting is excellent, and persistently the polarizer with excellent static electricity resistance is used Adhesive composition.
Double (oroalkane sulfonyl base) imide ionic, three (fluothane are preferably selected from fluorine-based and sulfonyl anion Base sulfonyl) anion in methide ion and fluoroalkyl sulfonic acids ion.
Possesses the salt with fluorine-based and sulfonyl anion, preferably by selected from alkali metal, 2 race's elements, transition metal And the cation and the above-mentioned salt formed with fluorine-based and sulfonyl anion of at least one of amphoteric metal.In addition, tool The standby salt with fluorine-based and sulfonyl anion be particularly preferably double (oroalkane sulfonyl base) imide ionics alkali metal salt, The alkali metal salt of three (oroalkane sulfonyl base) methide ions and the alkali metal salt of fluoroalkyl sulfonic acids ion.Particularly preferably lithium Salt.
The salt formed by above-mentioned anion and cation is numerous, wherein, preferably by double (oroalkane sulfonyl bases) Imide ionic, three (oroalkane sulfonyl base) methide ions and fluoroalkyl sulfonic acids ion are constituted, more preferably selected from double The alkali metal salt and fluoroalkyl sulfonic acids of (oroalkane sulfonyl base) imido alkali metal salt, three (oroalkane sulfonyl base) methides Alkali metal salt in salt.Specifically, preferably double (trifluoromethane sulfonyl group) imide li Li (CF3SO2)2N, double (trifluoros Methane sulfonyl) acid imide potassium K (CF3SO2)2N, double (trifluoromethane sulfonyl group) acid imide sodium Na (CF3SO2)2N, three (fluoroforms Alkane sulfonyl) methylate lithium Li (CF3SO2)3C, three (trifluoromethane sulfonyl group) methoxylation potassium K (CF3SO2)3C, three (fluoroforms Sulfonyl) sodium methylate Na (CF2SO2)3C, trifluoromethayl sulfonic acid lithium Li (CF3SO3), trifluoromethayl sulfonic acid potassium K (CF3SO3), three Fluoromethane sodium sulfonate Na (CF3SO3).Wherein, can enumerate for example：Double (trifluoromethane sulfonyl group) imide lis and three (fluoroforms Alkane sulfonyl) lithium that methylates, trifluoromethayl sulfonic acid lithium.Particularly preferably double (trifluoromethane sulfonyl group) imide lis and fluoroform Alkyl sulfonic acid lithium, by adding these compounds on a small quantity, can further add and play the effect above.
As shown in figure 1, using double (trifluoromethane sulfonyl group) imide lis be dissolved in as salt by diethylene glycol with oneself two State after the polyethers ester plasticizer that is formed of acid, in lithium ion be coordinated in polyethylene glycol in ether oxygen atom state. When adhesive layer is formed with adhesive composition using polarizer, lithium ion is formed with the state that lithium ion is coordinated in ether oxygen atom Dispersed adhesive layer.And, in adhesive layer, lithium ion is in the shape easily moved due to the molecular motion of ether oxygen State.If by outside to this applying electric field, in adhesive layer, lithium ion shown to corresponding Ghandler motion dynamic (ion conveying) from Sub- conductibility.
It is so-called to use double (oroalkane sulfonyl base) imide li Li (CF3SO2)2N is dissolved in the shape of TEG dimethyl ether State, is to be coordinated in Li as the ether of polar group+The state of ion, is scattered in composition with this state.That is, in composition Contain lithium polyethers complex compound.Li+Ion is surrounded by ether oxygen, from (CF3SO2)2N-Depart from ion, in naked state, significantly Contribute to static electricity resistance.Especially lithium salts forms Louis's Acid-Base with the mixture of the plasticizer containing polyether-based in main chain The complex ion of type, the complex compound plays a role as a kind of ionic liquid, is particularly helpful to static electricity resistance.In addition, lithium salts Due to forming the complex ion of lewis acid-alkaline with the plasticizer containing polyether-based in main chain, therefore cannot be with the iodine of polarizer Ion forms chemical bond.Therefore, the decolouring of polarizer is not caused yet.
Relative to the above-mentioned mass parts of plasticizer 100 in main chain containing polyether-based, possess with fluorine-based and sulfonyl The salt of anion preferably comprises 0.1~200 mass parts, more preferably 1~180 mass parts, is even more preferably 5~150 matter Amount part.
Relative to the mass parts of (methyl) acrylic copolymer 100, dissolved possess with it is fluorine-based and sulfonyl it is cloudy from The plasticizer solution of the salt of son preferably comprises 0.01~30 mass parts.Possess with fluorine-based and sulfonyl the moon by that will dissolve The content of the plasticizer solution of the salt of ion is set in above range, can play sufficient antistatic performance.
(polymer-type antistatic agent)
Anti-static composition can also further contain polymer-type antistatic agent.Polymer-type antistatic agent can make to possess Anion it is salt-stabilized.In addition, possessing the salt of anion due to be dissolved in main chain in the plasticizer containing polyether-based State is disperseed, it can thus be assumed that the salt concentrates on the polymer-type for having compatibility with the plasticizer containing polyether-based in main chain preventing At the presence of electrostatic agent, stabilized using both affinity.As such polymer-type antistatic agent, example can be enumerated Such as：Polyether block polyolefin copolymer, poly (oxyalkylene) based co-polymers or epoxy ethane-epoxy propane-pi-allyl glycidyl Copolymer.
Relative to the mass parts of (methyl) acrylic copolymer 100, the matter of polymer-type antistatic agent 0.1~65 is preferably comprised Amount part.
(manufacture method of anti-static composition)
The manufacture method of the anti-static composition used in the present invention includes preparing the operation of salting liquid, and the salt is in As the cation coordination of the counter ion counterionsl gegenions with fluorine-based and sulfonyl anion in main chain the plasticizer containing polyether-based Ether oxygen atom state.In the operation for preparing salting liquid, the plasticizer containing polyether-based will be provided with fluorine in main chain The salt of the anion of base and sulfonyl radiates while rapid dissolving.In the present invention, the plasticising containing polyether-based in main chain Agent is preferably polyethers ester plasticizer and/or polyethers plasticizer, and salting liquid can possess by being added in these plasticizer Salt with fluorine-based and sulfonyl anion is simultaneously stirred etc. and obtains.
(adhesive composition)
The preferred principal component of polarizer adhesive composition is preferably the adhesive composition for containing substantially no carboxyl. Here, the so-called carboxyl that contains substantially no refers to be made in the polymerization that adhesive composition is determined according to JIS K0070 (1992) During the acid number of monomer, its acid number is less than 0.1mgKOH/g.If acid number is less than 0.1mgKOH/g, mean not containing deliberately The carboxyl group-containing monomer of addition.
(acrylic pressure-sensitive adhesive compositions)
The preferred principal component of polarizer adhesive composition is acrylic pressure-sensitive adhesive compositions.So-called acrylic compounds glue Mixture composite contains (methyl) acrylic copolymer and the compound for obtaining is crosslinked via crosslinking agent.In addition, so-called " it is main into Point " refer to relative to adhesive integrally containing more than 50 mass %.
Acrylic pressure-sensitive adhesive compositions contain (methyl) acrylic copolymer (A) and crosslinking agent (B)." acrylic compounds Adhesive composition " is the compound with (methyl) acryloyl group." (methyl) acryloyl group " represents acryloyl group or methyl Acryloyl group.
(methyl) acrylic copolymer (A) is preferably at least polymer obtained from making (i) to be polymerized with (ii)： I () has the mass % of (methyl) acrylate monomer 60~99.99 of the alkyl of carbon number 1~18, (ii) has free radical Polymerism unsaturated group and the mass % of the monomer with least one reactive functional groups 0.01~20.
There is (methyl) acrylate monomer (hereinafter referred to as non-crosslinked property third of the alkyl of carbon number 1~18 as (i) Alkene acrylic monomer), can enumerate for example：(methyl) propylene that the hydrogen atom alkyl substitution of (methyl) acrylic acid carboxyl is obtained Acid esters.The carbon number of the alkyl is preferably 1~18, more preferably 1~8.The alkyl can also have substitution base.As the substitution Base, as long as being free of crosslinkable groups, is not particularly limited, and can enumerate for example：The alkoxies such as methoxyl group, ethyoxyl.As (methyl) acrylate is somebody's turn to do, can specifically be enumerated for example：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene Propyl propionate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid N-butyl, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) third Olefin(e) acid n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) third The positive last of the ten Heavenly stems ester of olefin(e) acid, (methyl) isodecyl acrylate, (methyl) acrylic acid undecyl ester, positive ten diester of (methyl) acrylic acid, (first Base) stearyl acrylate ester, (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid ring Own ester, (methyl) benzyl acrylate.These compounds can be used alone a kind, also can be combined and uses two or more.In addition, in this hair In bright, " (methyl) acrylic acid " refers to including both " acrylic acid " and " methacrylic acid ".In the middle of these, examined from the viewpoint of cementability Consider, preferably n-butyl acrylate, 2-EHA, methyl acrylate.
The amount of the non-crosslinked property acrylic monomer that the polymerization of (methyl) acrylic copolymer (A) is used is preferably 60 ~99.99 mass %, more preferably 65~99.99 mass %.If the non-crosslinked property acrylic monomer that polymerization is used Measure as more than above-mentioned lower limit, then sufficient bonding force can be showed, below above-mentioned higher limit, then can fully be handed over Connection.
(ii) there is free-radical polymerised unsaturated group and the monomer with least one reactive functional groups is (hereinafter referred to as It is cross-linkable monomer), can be acrylic monomer or non-propylene if can be polymerized with non-crosslinked property acrylic monomer Acrylic monomer, preferably acrylic monomer.As reactive functional groups, can enumerate for example：Carboxyl, hydroxyl, amino, epoxy Base, glycidyl etc..
As carboxyl group-containing monomer, can enumerate for example：Acrylic acid, methacrylic acid, butenoic acid, maleic acid, anti-butylene The alpha, beta-unsaturated carboxylic acids such as diacid, itaconicacid, citraconic acid, glutaconate or its acid anhydrides etc..
As hydroxyl monomer, can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxyl fourths (methyl) the dihydroxypropyl alkyl esters such as ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid list (diethylene glycol) ester etc. (methyl) acryliclactones such as (methyl) acrylic acid [(mono-, di- is more) ethylene glycol] ester, (methyl) acrylic acid list caprolactone.
As emulsion stability, can enumerate for example：(methyl) acrylamide, allyl amide, N, N- dimethyl (methyl) Acrylamide, N- butyl (methyl) acrylamide etc..
As monomer containing glycidyl, such as (methyl) Glycidyl Acrylate etc. can be enumerated.
The amount of the cross-linkable monomer that the polymerization of (methyl) acrylic copolymer (A) is used is preferably 0.01~20 matter Measure %, more preferably 0.03~10 mass %, be even more preferably 0.05~10 mass %.If the used bridging property of polymerization The amount of monomer be above-mentioned lower limit more than, then can be full cross-linked；If below above-mentioned higher limit, being then easily controlled bonding force, enter Row is peeled off and recycles the doing over again property of glass also good again.
Peeled off from cohesive, bridging property, polymerism and durability and again and the doing over again property of recycling glass is good From the viewpoint of good, cross-linkable monomer is preferably hydroxyl monomer or emulsion stability.Also by hydroxyl monomer and amino can be contained Combination of monomers is used.As hydroxyl monomer, preferably (methyl) dihydroxypropyl alkyl ester, particularly preferably (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls.As emulsion stability, preferably (methyl) acrylamide, N, N- bis- Methyl (methyl) acrylamide, N- butyl (methyl) acrylamide.
In the case where cross-linkable monomer is carboxyl group-containing monomer, because acidity becomes strong, therefore with tin-doped indium oxide film Or metal film etc. is when there is corrosive film to contact, these erosions are made sometimes.Therefore, from from the viewpoint of preventing corrosivity, The amount of the carboxyl group-containing monomer that the polymerization of (methyl) acrylic copolymer (A) is used it is preferred less than 0.5 mass %, more preferably Less than 0.05 mass %.In addition, the monomer with reactive functional groups preferably contains substantially no carboxyl group-containing monomer.Here, institute Monomer of the meaning with reactive functional groups contains substantially no carboxyl group-containing monomer, refers to be determined according to JIS K0070 (1992) During the acid number of the monomer with reactive functional groups that the polymerization of (methyl) acrylic copolymer (A) is used, its acid number is small In 0.1mgKOH/g.If the acid number of the monomer with reactive functional groups is less than 0.1mgKOH/g, it is believed that it and does not contain The carboxyl group-containing monomer for deliberately adding；If 0.1~1.0mgKOH/g, it is believed that its micro list containing carboxyl containing intentional addition Body.It should be noted that so-called intentional addition, refers to have used carboxyl group-containing monomer as cross-linkable monomer.Using as non- During acrylate (the coming from acrylic acid derivative) of crosslinkable acrylic monomer, although contained in the form of impurity sometimes micro Unreacted acrylic acid, but such situation be not regarded as deliberately addition.
When acid number is determined according to JIS K0070 (1992), for example, proceed as described below measure.
With precision balance in 100ml conical flasks precision weighing sample about 2g or so, be added thereto to ethanol/ether= The mixed solvent 10ml of 1/1 (weight ratio) simultaneously dissolves.Addition ethanolic phenolphthalein solution 1~3 is dripped as indicator in this embodiment again, Be stirred well to sample it is uniform untill.It is titrated with 0.1N potassium hydroxide-ethanol solution, pale red is continued with indicator As neutralization terminal at 30 seconds.By the value according to obtained by using following calculating formulas (1) as the result as sample acid number.
Acid number (mgKOH/g)=[B × f × 5.611]/S (1)
In calculating formula (1), B is the consumption (ml) of 0.1N potassium hydroxide-ethanol solution, and f is 0.1N potassium hydroxide-ethanols The factor of solution, S is the collection capacity (g) of sample.
(methyl) acrylic copolymer (A) can also have beyond non-crosslinked property acrylic monomer and cross-linkable monomer Other monomers.As other monomers, can enumerate for example：(methyl) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinyl Pyrrolidones, vinylpyridine etc..
The amount of other monomers that the polymerization of (methyl) acrylic copolymer (A) is used be preferably 0.1~20 mass %, More preferably 0.5~10 mass %.If the amount of other monomers that polymerization is used is more than above-mentioned lower limit, can be easily adjusted Physical property, if below above-mentioned higher limit, can prevent because of the xanthochromia caused by deterioration.
(weight average molecular weight of (methyl) acrylic copolymer)
The weight average molecular weight of (methyl) acrylic copolymer (A) is preferably 400,000~2,500,000, more preferably 500,000~ 2000000, even more preferably it is 1,000,000~2,000,000, particularly preferred 1,500,000~2,000,000.It is set to by by weight average molecular weight In the range of stating, it can be made to play sufficient cohesive force, durability can be improved.In addition, can suppress to contain polarizer adhesive group The viscosity of the coating fluid of compound increases, and adhesive phase is formed easily by coating.In addition, weight average molecular weight can be used gel to ooze Saturating chromatogram (GPC) is measured, and is the weight average molecular weight for being scaled polystyrene standard (PS).
(crosslinking agent that acrylic pressure-sensitive adhesive compositions are used)
The crosslinking agent (B) used as acrylic pressure-sensitive adhesive compositions, it is preferable to use can with as with reaction The crosslinking agent that the cross-linkable monomer of the monomer of property functional group is reacted.Can enumerate for example：Isocyanates crosslinking agent, epoxies Crosslinking agent,Oxazolines crosslinking agent, aziridines crosslinking agent, metal-chelating species crosslinking agent, the crosslinking of butylated melamines class Agent etc..In these crosslinking agents, due to (methyl) acrylic copolymer (A) can be made easily to be crosslinked, therefore preferred isocyanate class Crosslinking agent, epoxies crosslinking agent, metal-chelator class crosslinking agent.Especially only contain in (methyl) acrylic copolymer (A) In the case that hydroxyl monomer is as cross-linkable monomer, from from the viewpoint of the reactivity of hydroxyl, isocyanates is preferably used Crosslinking agent.
As isocyanates crosslinking agent, can enumerate for example：It is toluene-2,4-diisocyanate, xylene diisocyanate, two different The methylene ester of cyanic acid six, the different Buddhist ketone of two isocyanic acids etc..As epoxies crosslinking agent, can enumerate such as ethylene glycol bisglycidyl ethers, Polyethylene glycol bisglycidyl ethers, propane diols bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, glycerine diepoxy propyl group Ether, neopentyl glycol bisglycidyl ethers, 1,6-HD bisglycidyl ethers, four epoxy dimethylamine phenylenediamines, 1,3- pair (N, N- diepoxy propyl group aminomethyl) it is cyclohexanone, the poly- glycidyl ethers of trimethylolpropane, the poly- glycidyl ethers of two glycerine, poly- sweet The poly- glycidyl ethers of oil, the poly- glycidyl ethers of sorbierite etc..The content of crosslinking agent preferably according to needed for bonding physical property and it is appropriate Selection.In addition, these crosslinking agents can be used alone or use two or more.
Relative to the mass parts of (methyl) acrylic copolymer (A) 100, the friendship that acrylic pressure-sensitive adhesive compositions are used The content of connection agent (B) is preferably 0.001~10 mass parts, more preferably 0.01~5 mass parts.If it is more than above-mentioned lower limit, Foaming can be suppressed, if below above-mentioned higher limit, then can make it have sufficient stress and relax performance.
(additive)
In polarizer adhesive composition of the invention, can also be quiet with anti-containing acrylic pressure-sensitive adhesive compositions Composition beyond conductive composition.For example, beyond acrylic pressure-sensitive adhesive compositions, also can be combined and use polyester resin, ammonia Base resin, epoxy resin, polyurethane resin.
In addition, in polarizer adhesive composition of the invention, optionally can also contain antioxidant, metal erosion The light stabilizers such as preventing agent, tackifier, silane coupler, ultra-violet absorber, hindered amine compound, filler etc. are added Agent.As antioxidant, can enumerate for example：Phenol antioxidant, amine antioxidants, lactone antioxidant, Phosphorus antioxygen Agent, sulphur class antioxidant etc..These antioxidants can independent a kind use, also can be combined use two or more.It is rotten as metal Erosion preventing agent, from from the viewpoint of the raising of the compatibility or effect of adhesive, preferably BTA resinoid.As thickening Agent, can enumerate such as rosin resinoid, terpene resins, terpenephenol resin, benzofuran indene resin, styrene resin, two Toluene resinoid, phenolic resin, Petropols etc..As silane coupler, such as mercaptoalkoxysilane compound can be enumerated (such as sulfydryl substituted alkoxy oligomer etc.) etc..As ultra-violet absorber, can enumerate for example：Benzotriazole compound, Diphenyl ketone compounds, compound in triazine class etc..
Relative to the mass parts of solid constituent 100 of polarizer adhesive composition, the content of these additives is generally excellent Elect 0.01~10 mass parts, more preferably 0.05~5 mass parts, particularly preferred 0.1~3 mass parts as.
(manufacture method of polarizer adhesive composition)
Polarizer adhesive composition makes to possess the salt with fluorine-based and sulfonyl anion to be scattered in and contains propylene Manufactured in the composition of the resin of binding property such as acrylic binder composition.Manufacture method includes：Prepare the operation of salting liquid, institute State salting liquid and dissolved in the plasticizer containing polyether-based in main chain and possess the salt with fluorine-based and sulfonyl anion and form； Salting liquid (the 1st composition) and resin of binding property (the 2nd composition) are kneaded, the operation of composition is formed；Above-mentioned composition is entered one Walk the operation for kneading or mixing with resin of binding property (the 2nd composition).By the kneading of the 1st composition and the 2nd composition, salting liquid is in group Exist or dissolve in the dispersion of microlayer model shape in compound.Then, dissolve in the state in composition with salt, then with resin of binding property the (the 2nd Composition) knead or mix, therefore salt is disperseed in resin of binding property (the 2nd composition) with affine state evenly.
(polarizer bonding sheet)
Polarizer adhesive composition of the invention can form sheet and be made polarizer bonding sheet.Polarizer is used viscous Close after adhesive can be for example dissolved in solvent and coating by piece and manufactured by removing solvent.As coating method, can be from cutter painting Machine, micro- rod coater, Kohler coater, reversion roll-coater, reverse rotating gravure coating machine, Vario gravure coaters, die coating machine, Suitably selected in curtain painting machine etc..If using bonding sheet of the invention, the adhesive coating in the stage that need not fit, back tender Sequence, if lamination polarizer can be bonded with bonding sheet and pressurization between optical thin film and bonding object, therefore it is non- It is often easy.
(thickness of polarizer bonding sheet)
The thickness of the adhesive phase of polarizer bonding sheet of the invention is preferably less than 100 μm, more preferably 5~50 μ m.If below above-mentioned higher limit, then the stress that can fully show adhesive phase relaxes performance.
(bonding sheet of the polarizer with stripping film)
Bonding sheet of the polarizer with stripping film preferably has the knot of the one or two sides that stripping film is located at bonding sheet Structure, the stripping film is provided with remover on base material.For example, the two sides of adhesive phase be provided with stripping film with stripping film Double-sided adhesive sheet can be obtained in the following manner：Adhesive coating solution is provided with the of peeling agent layer in polymeric membrane The stripping aspect of 1 stripping film, after drying, the 2nd stripping film that will be formed by the peeling force peeling agent layer different from the 1st stripping film Stripping aspect fit pressure viscosity in adhesive phase.If the peeling force of the 1st stripping film and the 2nd stripping film is approached, will gently peel off When the stripping film of power side is peeled off, there is the phenomenon that adhesive floats separation from the stripping film of re-release power side.Therefore, weight The peeling force of the stripping film of peeling force side is preferably 0.05N~0.15N, and the peeling force of the stripping film of light peeling force side is preferably 0.01~0.04N.
In addition, now, when the difference of two peeling forces of stripping film is kept, also can formerly by adhesive coating solution extremely After 2nd stripping film, make the 1st stripping film laminating pressure viscosity.The shape of bonding sheet can be sheet, and also rollable is web-like.
(polarizer)
Polarizer adhesive composition of the invention and polarizer bonding sheet, can directly paste (lamination) in being polarized Mirror.Fig. 2 (a) represents polarizer during using polarizer adhesive composition of the invention and bonding sheet.As shown in Fig. 2 (a), Bonding sheet (polarizer adhesive composition layer) 20 is directly adhered to polarizer 10.In addition, bonding sheet (polarizer adhesive Composition layer) 20 also Pasting in the two sides of polarizer 10.
Fig. 2 (b) represents the structure of existing polarizer.In existing polarizer, polarizer is seized on both sides by the arms by diaphragm, is glued Close piece (adhesive layer) and be pasted on diaphragm.Polarizer adhesive composition of the invention and bonding sheet can also be applied to such Structure, effect of the invention can be played when polarizer is directly adhered to as Fig. 2 (a).
Polarizer adhesive composition of the invention and polarizer bonding sheet are used for fit polarizer and the μ of thickness 100 The component of m, preferably more than 1mm.In addition, polarizer adhesive composition of the invention and polarizer bonding sheet are used to fit Polarizer and optical component.As optical component, can enumerate for example：Liquid crystal cells or touch panel etc., can make and possess this hair The image display device of bright bonding sheet.
The polarizer used as polarizer can be used for example, dichroism pigment gas absorption quantity is in polyvinyl alcohol resin The polarizer of the polyvinyl alcohol resin described in film or Japanese Patent Laid-Open 2012-159778.Constitute polarizer Polyvinyl alcohol resin is obtained by by the saponification of polyvinyl acetate esters resin.As polyvinyl acetate esters resin, except Outside polyvinyl acetate as the homopolymers of vinyl acetate, can illustrate vinyl acetate and can with its carry out copolymerization its Copolymer of its monomer etc..As other monomers that copolymerization can be carried out with vinyl acetate, can enumerate for example：Unsaturated carboxylic acid Class, olefines, vinyl ethers, unsaturated sulfonic acid class, the acrylic amide with ammonium etc..The saponification of polyvinyl alcohol resin Degree, usually 85~100 moles of % or so, preferably 98 moles more than %.The polyvinyl alcohol resin also can further be modified, example As can be used by polyvinyl formal that aldehydes was modified or polyvinyl acetaldehyde etc..In addition, the polymerization of polyvinyl alcohol resin Degree is usually 1,000~10,000 or so, preferably 1,500~5,000 or so.
Film obtained from such polyvinyl alcohol resin is carried out into film forming can serve as the raw material film of polarizer.To poly- second The method that enol resinoid carries out film forming is not particularly limited, and can carry out film forming according to known method.By polyvinyl alcohol resin institute The thickness of the raw material film of composition is not particularly limited, and is such as 1~150 μm or so.If considering stretching easness etc., its thickness is excellent Elect more than 3 μm as.
In addition, polarizer can dry to manufacture by following operations and finally：By above-mentioned such polyvinyl alcohol tree Polyvinyl alcohol resin described in adipose membrane or Japanese Patent Laid-Open 2012-159778 carries out the operation of simple tension, will gather Vinyl alcohol resin or film are dyeed with dichroism pigment and are made the operation of dichroism pigment absorption, will adsorb dichroism Operation that the polyvinyl alcohol resin or film of pigment are processed with boric acid aqueous solution and after the treatment of the boric acid aqueous solution The operation washed.
In addition, polarizer has at least one lamination structure of transparent protective film in above-mentioned manufactured polarizer. As the transparent protective film, the diaphragm formed by appropriate transparent resin can be used.Specifically, preferably use by transparent The diaphragm that the excellent polymer such as property or uniform optical characteristics, mechanical strength, heat endurance is formed.As such Ming tree adipose membrane, can be used the cellulose family film such as triacetyl cellulose and diacetyl cellulose, polyethylene terephthalate, poly- The polyesters film such as ethylene isophthalate and polybutylene terephthalate (PBT), poly- (methyl) methyl acrylate and poly- (first Base) the crylic acid resin film such as ethyl acrylate, polycarbonate-based film, polyether sulfone film, polysulfones film, polyimide film, TPO film, polynorbornene class film etc., but it is not limited to this.
Embodiment
Hereinafter, enumerate embodiment and be more particularly described feature of present invention with comparative example.Material shown in following examples, consumption, Ratio, process content, process step etc. can be changed suitably on the premise of present subject matter is not departed from.Therefore, the scope of the invention Not it is defined and is construed to concrete example as shown below.In addition, " part " and " % " in example is in the case of without special instruction, point Wei " mass parts " and " quality % ".
(Production Example 1)
<The preparation of (methyl) acrylic copolymer (A-1)>
To 80 parts of ethyl acetate is added in the reaction vessel for possessing cooling tube, nitrogen ingress pipe, mixer and thermometer, add As 65 parts of the butyl acrylate of monomer, 30 parts of 2-EHA, 5 parts of acrylic acid 2- hydroxy methacrylates, inclosure nitrogen Make it not oxygen-containing, and interior temperature is risen to 55 DEG C.Then, addition is dissolved in 0.06 part of azodiisobutyronitrile (polymerization initiator) The whole amount of solution obtained from 10 parts of ethyl acetate.Then, one side keeping temperature is while be stirred, after stirring 12 hours, Carrying out cooling stops polymerisation.What the utilization GPC of (methyl) acrylic copolymer (A-1) for obtaining was determined is scaled poly- The weight average molecular weight Mw of styrene is 1,500,000.
(measure of the weight average molecular weight of (methyl) acrylic copolymer)
For the weight average molecular weight Mw of (methyl) acrylic copolymer, determined by GPC (gel permeation chromatography) The sample of THF (tetrahydrofuran) is dissolved.
(Production Example 2)
<The preparation of (methyl) acrylic copolymer (A-2)>
To 80 parts of ethyl acetate is added in the reaction vessel for possessing cooling tube, nitrogen ingress pipe, mixer and thermometer, add As 65 parts of the butyl acrylate of monomer, 30 parts of 2-EHA, 5 parts of acrylic acid 2- hydroxy methacrylates, inclosure nitrogen Make it not oxygen-containing, and interior temperature is risen to 45 DEG C.Then, addition is dissolved in 0.04 part of azodiisobutyronitrile (polymerization initiator) The whole amount of solution obtained from 10 parts of ethyl acetate.Then, one side keeping temperature is while be stirred, after stirring 16 hours, Carrying out cooling stops polymerisation.What the utilization GPC of (methyl) acrylic copolymer (A-2) for obtaining was determined is scaled poly- The weight average molecular weight Mw of styrene is 1,800,000.
(Production Example 3)
<The making of polarizer>
Thick 75 μm polyvinyl alcohol film (average degree of polymerization about 2,400,99.9 moles of more than % of saponification degree) is passed through into dry type Stretching simple tension to about 5 times, then keep tense situation under, impregnated in 1 minute in 60 DEG C of pure water, then iodine/KI/ The weight ratio of water for 0.05/5/100 the aqueous solution in 28 DEG C impregnate 60 seconds.Then, in the weight of KI/boric acid/water Than being impregnated 300 seconds in 72 DEG C in the aqueous solution for 8.5/8.5/100.Then cleaned 20 seconds with 26 DEG C of pure water, then in 65 It is dried at DEG C, has obtained iodine gas absorption quantity in the thick 28 μm polarizer of polyvinyl alcohol film.Then, the one of the polarizer Side is coated with epoxies bonding agent, has manufactured thick 40 μm tri acetyl cellulose membrane (TAC) [the Konica Minolta company systems of laminating Make, trade name " KC4UY "] used as the polarizer of transparent protective film, the epoxies bonding agent is relative to 100 parts of water, dissolving Carboxy-modified 3 parts of polyvinyl alcohol [being obtained by Kuraray Co., Ltd, trade name " KL-318 "], and add in the aqueous solution Add and [obtained by Taoka Chemical Industries Co. Ltd., trade name as the daiamid epoxy class additive of water-soluble epoxy resin " Sumirez Resin 650 (30) ", the aqueous solution of solid component concentration 30%] 1.5 parts.
(embodiment 1)
<The preparation of acrylic adhesives solution>
Relative to 100 parts of the solid constituent of (methyl) acrylic copolymer (A-1) obtained by Production Example 1, addition is made It is the XDI (Mitsui Chemicals, Inc.'s system of crosslinking agent：TAKENATE500) 0.1 part and 3- glycidoxypropyl groups Methoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system：KBM-403) 0.1 part, then add in 50 parts of polyethers ester type compound Dissolve double in (mixtures of 1 ︰ 1 of Monocizer (registration mark) W-262 and Polycizer (registration mark) W-230-H) 2.5 parts of the composition of 50 parts of (trifluoromethane sulfonyl group) imide li is diluted to as anti-static composition with ethyl acetate The solution of solid component concentration 15%, is prepared for acrylic adhesives solution.
<The making of bonding sheet>
The binder solution that will be made as described above of spreader is equably coated to be possessed through at polysiloxane-based remover Thick 38 μm polyethylene terephthalate film (seperation film) (prince's F-TEX company systems of the peeling agent layer of reason：38RL-07 (2) surface) so that dried coating weight is 20 μm/m2, dried 3 minutes with 100 DEG C of air circulating type constant temperature ovens, Adhesive phase is formed on the surface of seperation film.Then, being fitted in the adhesive layer surface, (prince F-TEX is public for 38 μm of seperation film Department's system：38RL-07 (L)), bonding sheet has been obtained, the bonding sheet seizes adhesive phase on both sides by the arms by the 1 pair of seperation film differed from peeling force , structure possessing seperation film/adhesive phase/seperation film.The bonding sheet enters under conditions of 23 DEG C, relative humidity 50% Row maintenance 7 days.
<The making of the polarizer with adhesive phase>
The seperation film of the peeling agent layer for possessing lighter peeling force of bonding sheet is peeled off, the polarization obtained by Production Example 3 The polarizing layer side of the polarizer of piece directly transfers (attachment) adhesive phase, has made the polarizer with adhesive phase.
(embodiment 2)
<The preparation of acrylic adhesives solution>
Relative to 100 parts of the solid constituent of (methyl) acrylic copolymer (A-2) obtained by Production Example 2, addition is made It is the XDI (Mitsui Chemicals, Inc.'s system of crosslinking agent：TAKENATE500) 0.1 part and 3- glycidoxypropyl groups Methoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system：KBM-403) 0.1 part, then add in 50 parts of polyethers ester type compound Dissolve double in (mixtures of 1 ︰ 1 of Monocizer (registration mark) W-262 and Polycizer (registration mark) W-230-H) 1.8 parts of the composition of 50 parts of (trifluoromethane sulfonyl group) imide li is diluted to as anti-static composition with ethyl acetate The solution of solid component concentration 15%, is prepared for acrylic adhesives solution.
<The making of bonding sheet>
Bonding sheet has been made similarly to Example 1.
<The making of the polarizer with adhesive phase>
The polarizer with adhesive phase has been made similarly to Example 1.
(embodiment 11)
<The preparation of acrylic adhesives solution>
Relative to 100 parts of the solid constituent of (methyl) acrylic copolymer (A-1) obtained by Production Example 1, addition is made It is the XDI (Mitsui Chemicals, Inc.'s system of crosslinking agent：TAKENATE500) 0.1 part and 3- glycidoxypropyl groups Methoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system：KBM-403) 0.1 part, then add in PAG (two/mono-) alkyl ether 2.5 parts of the composition that double 50 parts of (trifluoromethane sulfonyl group) imide lis have been dissolved in 50 parts of compound is combined as static electricity resistance Thing, the solution of solid component concentration 15% is diluted to ethyl acetate, is prepared for acrylic adhesives solution.
<The making of bonding sheet>
The binder solution that will be made as described above of spreader is equably coated to be possessed through at polysiloxane-based remover Thick 38 μm polyethylene terephthalate film (seperation film) (prince's F-TEX company systems of the peeling agent layer of reason：38RL-07 (2) surface), is dried 3 minutes with 100 DEG C of air circulating type constant temperature ovens so that dried coating weight is 20 μm/m2, The surface of seperation film forms adhesive phase.Then, fitted 38 μm of seperation film (prince F-TEX companies in the adhesive layer surface System：38RL-07 (L)), obtained 1 pair of seperation film by being differed from peeling force seize on both sides by the arms adhesive phase, possess seperation film/ The bonding sheet of the structure of adhesive phase/seperation film.The bonding sheet carries out maintenance 7 days under conditions of 23 DEG C, relative humidity 50%.
<The making of the polarizer with adhesive phase>
The seperation film of the peeling agent layer for possessing lighter peeling force of bonding sheet is peeled off, the polarization obtained by Production Example 3 The polarizing layer side of the polarizer of piece directly transfers (attachment) adhesive phase, has made the polarizer with adhesive phase.
(comparative example 1)
<The preparation of acrylic adhesives solution>
Except using as the N- hexyl -4- picolines of ionic solidHexafluorophosphoric acid ester (being solid at 25 DEG C) To replace embodiment 1 to be used in 50 parts of (Monocizer (registration mark) W-262 and Polycizer of polyethers ester type compound The mixtures of 1 ︰ 1 of (registration mark) W-230-H) in dissolved the composition of double 50 parts of (trifluoromethane sulfonyl group) imide lis with Outward, acrylic adhesives solution has been obtained similarly to Example 1.
<The making of bonding sheet>
Bonding sheet has been made similarly to Example 1.
<The making of the polarizer with adhesive phase>
The polarizer with adhesive phase has been made similarly to Example 1.
(comparative example 2)
<The preparation of acrylic adhesives solution>
Except using as the epoxy ammonium trifluoromethayl sulfonic acid ester (being liquid at 25 DEG C) of ionic solid To replace embodiment 1 to be used in 50 parts of (Monocizer (registration mark) W-262 and Polycizer of polyethers ester type compound The mixtures of 1 ︰ 1 of (registration mark) W-230-H) in dissolved the composition of double 50 parts of (trifluoromethane sulfonyl group) imide lis with Outward, acrylic adhesives solution has been obtained similarly to Example 1.
<The making of bonding sheet>
Bonding sheet has been made similarly to Example 1.
<The making of the polarizer with adhesive phase>
The polarizer with adhesive phase has been made similarly to Example 1.
(reference example 1)
<The preparation of acrylic adhesives solution>
Except being not added with that embodiment 1 used in 50 parts of (Monocizer (registration mark) W- of polyethers ester type compound 262 with the mixtures of 1 ︰ 1 of Polycizer (registration mark) W-230-H) in dissolved double (trifluoromethane sulfonyl group) imide lis Beyond 50 parts of composition, acrylic adhesives solution has been obtained similarly to Example 1.
<The making of bonding sheet>
Bonding sheet has been made similarly to Example 1.
<The making of the polarizer with adhesive phase>
The polarizer with adhesive phase has been made similarly to Example 1.
(evaluation)
<The measure of sheet resistance value>
After severing is peeled off for the seperation film of the polarizer with adhesive phase of 100mm × 100mm, surveyed using resistance value Determine device (Mitsubishi Chemical Ind's system：Hiresta-UP, MCP-HT450) determine adhesive surface sheet resistance value (Ω/).
<The evaluation of polarizer durability>
After the seperation film of the polarizer with adhesive phase is peeled off, adhesive face is pasted on the alkali-free of thick 0.7mm Glass (Corning Incorporated's system：EAGLE XG) one side, made optical laminates.Then, carry out 50 DEG C, 0.5MPa, 20 minutes Autoclave process, made the optical laminates for making the polarizer with adhesive phase be sealed at glass completely.By above-mentioned system The optical laminates constant temperature and humidity cabinet of work is processed 500 hours under 85 DEG C (heat resistant test), to visually observe the light after experiment Learn laminated body.
(metewand)
○：Do not observe the cosmetic variation float, peel off, foaming etc. completely.
△：The cosmetic variation such as slightly float, peel off, foaming.
×：Substantially observe and the cosmetic variation such as float, peel off, foaming.
<The evaluation of optical durability (transmission tone)>
After the seperation film of the polarizer with adhesive phase is peeled off, adhesive face is pasted on the alkali-free of thick 0.7mm Glass (Corning Incorporated's system：EAGLE XG) one side, made optical laminates.Then, carry out 50 DEG C, 0.5MPa, 20 minutes Autoclave process, made and the polarizer with adhesive phase be sealed at the optical laminates of glass completely.By above-mentioned system The optical laminates constant temperature and humidity cabinet of work is under 60 DEG C, relative humidity 90% (hot resistance test) with initial stage, 100 hours, 240 Hour, the transmission tone b values for being processed and being determined each process time for 500 hours.Determine and use spectrocolorimeter (Japan's electricity Color company system：SE6000).The variation delta b values of the transmission tone before and after experiment are calculated using the measured value.
Initial value before measured value-experiment after Δ b values=experiment
<The evaluation of optical durability (780nm transmissivities)>
After the seperation film of the polarizer with adhesive phase is peeled off, adhesive face is pasted on the alkali-free of thick 0.7mm Glass (Corning Incorporated's system：EAGLE XG) one side, made optical laminates.Then, carry out 50 DEG C, 0.5MPa, 20 minutes Autoclave process, made and the polarizer with adhesive phase be sealed at the optical laminates of glass completely.By above-mentioned system The optical laminates constant temperature and humidity cabinet of work is under 60 DEG C, relative humidity 90% (hot resistance test) with initial stage, 100 hours, 240 Hour, processed within 500 hours, determine the transmissivity T ⊥ of the 780nm of each process time.Determine system and use sub-ray spectrometer (island Tianjin manufacturing company system：Solidspec-3700).The change of the 780nm transmissivities before and after experiment is calculated using the measured value Amount Δ T ⊥.
Δ T ⊥=(measured value after treatment)-(initial value)
<The measure of degree of polarization>
After the seperation film of the polarizer with adhesive phase is peeled off, adhesive face is pasted on the alkali-free of thick 0.7mm Glass (Corning Incorporated's system：EAGLE XG) one side, made optical laminates.Then, carry out 50 DEG C, 0.5MPa, 20 minutes Autoclave process, made and the polarizer with adhesive phase be sealed at the optical laminates of glass completely.By above-mentioned system The optical laminates of work were processed under 60 DEG C, relative humidity 90% (hot resistance test) with initial stage, 100 hours, using point Photothermal spectroscopic analyzer (Japanese light splitting company system：The degree of polarization of the polarizer after V-7100) determining before processing and processing 100 hours, calculates Go out variation delta Py.
Δ Py=(measured value after treatment)-(initial values)
(observing by the naked eye confirmation color change)
After the seperation film of the polarizer with adhesive phase is peeled off, adhesive face is pasted on the alkali-free of thick 0.7mm Glass (Corning Incorporated's system：EAGLE XG) one side, made optical laminates.Then, carry out 50 DEG C, 0.5MPa, 20 minutes Autoclave process, made and the polarizer with adhesive phase be sealed at the optical laminates of glass completely.By above-mentioned system The optical laminates constant temperature and humidity cabinet of work is processed 500 hours under 60 DEG C, relative humidity 90% (hot resistance test), by meat Eye observation confirmation whether there is color change.
<The analysis (peak of the detection from complex compound) of the anti-static composition in bonding sheet>
The bonding sheet 0.2g addition acetonitrile 15ml made to embodiment etc., carries out ultrasonic treatment 30 minutes, Ran Houjing Put 1 day (pre-treatment).Carry out concentration it is solid after, be dissolved in 1ml acetonitriles and the sample after being filtered with 0.45 μm of filter as Sample is determined, HPLC (high performance liquid chromatography) analyses are carried out.HPLC (high performance liquid chromatography) is analyzed using what WATERS was manufactured System：Separations Module2696, using Photodiode Array Detector 996 as detector.In addition, The detailed conditions of HPLC analyses are as described below.
Post：XBridge C18,4.6 × 250mm of post footpath (WATERS company systems)
Column temperature：30℃
Mobile phase：Acetonitrile/water
Flow velocity：0.8mL/ points
Detection：225nm
Above evaluation result is shown in table 1.
As shown in Table 1, in embodiment in addition to polarizer durability, optical durability is also excellent.That is, for embodiment For, though under high temperature, high humidity environment place for a long time, still colour less, light transmission it is high.
On the other hand understand, for comparative example, optical durability is poor.For especially for comparative example 1 and 2, partially Piece durability of shaking is also bad, is deteriorated as the function of polarizer.
In addition, Fig. 3 is the anti-static composition containing complex compound from by top, contains static electricity resistance obtained by embodiment The extract solution of the bonding sheet of composition, do not add anti-static composition bonding sheet extract (reference example 1) HPLC it is (high Effect liquid phase chromatogram) analysis result.As shown in the chromatogram of the extract solution of the bonding sheet containing anti-static composition in stage casing, from adding Added anti-static composition bonding sheet extract solution in detect complex compound peak within 15.0 minutes in retention time.

Claims (19)

1. a kind of polarizer adhesive composition, it contains anti-static composition, and the anti-static composition is in master The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with chain in plasticizer containing polyether-based.
2. polarizer adhesive composition as claimed in claim 1, wherein, the anti-static composition is in main chain The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with polyethers ester plasticizer containing polyether-based.
3. polarizer adhesive composition as claimed in claim 2, wherein, the polyethers ester plasticizer contains following formula (1) at least a kind polyethers ester plasticizer or shown in (2),
In formula (1) and formula (2), m and n is respectively integer, and R represents alkyl.
4. polarizer adhesive composition as claimed in claim 1, wherein, the anti-static composition is in main chain The composition for possessing the salt with fluorine-based and sulfonyl anion is dissolved with polyethers plasticizer containing polyether-based.
5. polarizer adhesive composition as claimed in claim 4, wherein, the polyethers plasticizer is comprising having following formula (11) polyethers plasticizer,
R1(OCH2CH2)nOR2 (11)
In formula, R1Represent the alkyl of carbon number 1~12, R2The alkyl of hydrogen atom or carbon number 1~12 is represented, n represents 3~6 Integer.
6. polarizer adhesive composition as claimed in claim 1, wherein, the anti-static composition is included：In master The combination for possessing the salt with fluorine-based and sulfonyl anion is dissolved with chain in polyethers ester plasticizer containing polyether-based Thing and being dissolved with the polyethers plasticizer containing polyether-based in main chain possesses with fluorine-based and sulfonyl anion The composition of salt.
7. the polarizer adhesive composition as any one of claim 1~6, wherein, the polarizer bonding The principal component of agent composition is the adhesive composition for containing substantially no carboxyl.
8. the polarizer adhesive composition as any one of claim 1~7, wherein, the polarizer bonding The principal component of agent composition is acrylic pressure-sensitive adhesive compositions.
9. polarizer adhesive composition as claimed in claim 8, wherein, the acrylic pressure-sensitive adhesive compositions contain (methyl) acrylic copolymer (A) and crosslinking agent (B), (methyl) acrylic copolymer (A) at least make following (i) with (ii) it is polymerized and is obtained：
I () has the mass % of (methyl) acrylate monomer 60~99.99 of the alkyl of carbon number 1~18,
(ii) there is free-radical polymerised unsaturated group and the matter of monomer 0.01~20 with least one reactive functional groups Amount %.
10. polarizer adhesive composition as claimed in claim 9, wherein, the reactive functional groups be selected from hydroxyl and At least one of amino, the monomer with reactive functional groups contains substantially no carboxyl group-containing monomer.
The 11. polarizer adhesive composition as described in claim 9 or 10, wherein, the crosslinking agent (B) is selected from isocyanide At least a kind in esters of gallic acid crosslinking agent, epoxies crosslinking agent and metal-chelating species crosslinking agent.
The 12. polarizer adhesive composition as any one of claim 9~11, wherein, relative to (the first Base) mass parts of acrylic copolymer (A) 100, the content of the anti-static composition is 0.01~30 mass parts.
The 13. polarizer adhesive composition as any one of claim 1~12, wherein, it is described with fluorine-based and The anion of sulfonyl be selected from double (oroalkane sulfonyl base) imide ionics, three (oroalkane sulfonyl base) methide ions and Anion in fluoroalkyl sulfonic acids ion.
The 14. polarizer adhesive composition as any one of claim 1~13, wherein, it is described to possess with fluorine The salt of the anion of base and sulfonyl be by selected from alkali metal, 2 race's elements, transition metal and amphoteric metal at least one sun from It is sub with the salt formed with fluorine-based and sulfonyl anion.
The 15. polarizer adhesive composition as any one of claim 1~14, wherein, it is described to possess with fluorine The salt of the anion of base and sulfonyl is selected from double (oroalkane sulfonyl base) imido alkali metal salt, three (oroalkane sulfonyl bases) Salt in the alkali metal salt of methide and the alkali metal salt of trifluoroalkyl sulfonic acid.
The 16. polarizer adhesive composition as any one of claim 1~15, wherein, the polarizer is used viscous Mixture composite is used for fit polarizer and optical component.
17. polarizer adhesive compositions as claimed in claim 16, wherein, the optical component is liquid crystal cells or touches Touch panel.
A kind of 18. polarizer bonding sheets, its polarizer for containing any one of claim 1~17 is combined with adhesive Thing.
A kind of 19. image display devices, it possesses the bonding sheet described at least one claim 18.
CN201580032667.2A 2014-06-18 2015-06-16 Polarizer adhesive composition and polarizer bonding sheet Pending CN106795416A (en)

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