CN106795407B - Polarizing film adhesive composition, bonding sheet, polarizing film and laminated body with adhesive phase - Google Patents
Polarizing film adhesive composition, bonding sheet, polarizing film and laminated body with adhesive phase Download PDFInfo
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- CN106795407B CN106795407B CN201580054308.7A CN201580054308A CN106795407B CN 106795407 B CN106795407 B CN 106795407B CN 201580054308 A CN201580054308 A CN 201580054308A CN 106795407 B CN106795407 B CN 106795407B
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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
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- 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
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Abstract
It is excellent and have the polarizing film adhesive composition of the adhesive phase of durability under high temperature and humidity that the present invention provides a kind of antistatic performance that is capable of forming.The polarizing film adhesive composition contains: (A) includes 41 mass % or more as being selected from N with (methyl) acrylic polymer, (B) crosslinking agent and (C) anion obtained by the polymerization of the polymerizable monomer of polyoxyalkylenes or (methyl) acrylate (a1) of alkoxyalkyl, bis- (fluorine sulphonyl) imines of N- and bis- (trifluoro methylsulfonyl) imines of N, N-, cation are the ionic compound of organic cation and fusing point at 25 DEG C or more.
Description
Technical field
The present invention relates to polarizing film adhesive composition, bonding sheet, polarizing films and laminated body with adhesive phase.
Background technique
In recent years, liquid crystal cell vehicle-mounted, outdoor instrument with or display, the television set etc. of PC on use
Way constantly expands, and use environment also becomes very harsh therewith.Liquid crystal cell has liquid crystal material by two pieces of substrates (such as glass
Plate) clamped by structure, polarizing film is adhered to the surface of the substrate via adhesive phase.It is therefore desirable to described adhesive layer
Also there is the durability under high temperature and humidity heat.
When manufacturing liquid crystal cell, polarizing film is usually stained with the cover film that lift-off processing is crossed in single side with adhesive phase
It is pasted on polarizing film under state, then, removes cover film and keep adhesive phase exposed, then be attached on substrate.At this point, by
Electrostatic is generated in the insulating properties of cover film or polarizing film height, can generate and upset the bad shadows such as liquid crystal aligning, damage electronic component
It rings.
It is therefore desirable to which polarizing film adhesive phase also has antistatic performance, as the polarizing film with antistatic performance
With adhesive phase, the technology made to be formed in the adhesive composition of adhesive phase containing ionic compound is reported.
For example, described in patent document 1 containing the acrylic resin as obtained by specific (methyl) acrylic ester polymerization,
It is with organic cation and at room temperature the adhesive composition of the ionic compound of solid and crosslinking agent.In patent document 2
Describe the ionic compound containing fusing point at 50 DEG C or more, the matrix polymer with 0 DEG C of glass transition temperature below
Adhesive composition.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2010-66756 bulletin
Patent document 2: Japanese Patent Laid-Open 2009-19162 bulletin
Summary of the invention
The technical problems to be solved by the invention
Polarizing film usually has the protective film for protecting polarizer (Japanese: polarisation) mostly.Adhesive phase and institute
Protective film is stated to connect and formed.However, the research of people according to the present invention, finds under hygrothermal environment, by institute in adhesive phase
Comprising ionic compound, it is long-term that the component of polymer generation hydrolysis for constituting the protective film, corrosion polarizing film etc. can be generated
The problem of reliability.Further, since extensiveization of the further filming use scope of component in recent years, it is desirable that than so far
Until long term test it is harsher under conditions of the above problem does not also occur.
Technical problem to be solved by the present invention lies in offer, to be capable of forming antistatic performance excellent and have high temperature and humidity
The polarizing film adhesive composition of the adhesive phase of lower durability, the bonding with the adhesive phase formed by above-mentioned composition
Piece, the polarizing film with adhesive phase with above-mentioned adhesive phase and the laminated body with above-mentioned adhesive phase.
Technical scheme applied to solve the technical problem
The present inventor has made intensive studies to solve above-mentioned technical problem.As a result, it has been found that specific quantity will be contained
(methyl) acrylic polymer, crosslinking agent and specific ion as obtained by the polymerizable monomer of specific (methyl) acrylate
Under the occasion for closing object, it is able to solve above-mentioned technical problem, so as to complete the present invention.
The present invention [1] for example, below~[6].
[1] a kind of polarizing film adhesive composition, contains:
It (A) include 41 mass % or more by (methyl) acrylate (a1) with polyoxyalkylenes or alkoxyalkyl
Polymerizable monomer polymerization obtained by (methyl) acrylic polymer,
(B) crosslinking agent and
(C) anion is selected from N, and bis- (fluorine sulphonyl) imines of N- and bis- (trifluoro methylsulfonyl) imines of N, N-, cation are organic
Cation and ionic compound of the fusing point at 25 DEG C or more.
[2] the polarizing film adhesive composition as described in [1], wherein also contain silane coupling agent (D).
[3] the polarizing film adhesive composition as described in [1] or [2], wherein in ionic compound (C), it is organic sun from
Son is the tetraalkylammonium cation indicated with formula (c-1),
In formula (c-1), R1、R2、R3And R4It is separately alkyl.
[4] a kind of polarizing film bonding sheet has the polarizing film adhesive group as described in any one of [1]~[3]
Close the adhesive phase that object is formed.
[5] a kind of polarizing film with adhesive phase, with polarizing film and in at least one side of the polarizing film by
[1] adhesive phase that polarizing film described in any one of~[3] is formed with adhesive composition.
[6] a kind of laminated body, wherein polarizing film has the protective film of polarizer and configuration on the polarizer,
The laminated body is combined by the polarizer, the protective film, the polarizing film described in any one of [1]~[3] with adhesive
The adhesive phase and glass substrate that object is formed are laminated in this order.
The effect of invention
By means of the invention it is possible to which it is excellent and have the inclined of the adhesive phase of durability under high temperature and humidity to form antistatic performance
Shake piece adhesive composition, the bonding sheet with the adhesive phase formed by above-mentioned composition, with above-mentioned adhesive phase
Polarizing film with adhesive phase and the laminated body with above-mentioned adhesive phase.
Specific embodiment
In the following, to polarizing film adhesive composition of the invention, polarizing film bonding sheet, with the polarization of adhesive phase
Piece and laminated body are illustrated.Hereinafter, polarizing film of the invention is also referred to as " adhesive group with adhesive composition
Close object ", polarizing film of the invention is also referred to as " bonding sheet " with bonding sheet.
Acrylic acid and methacrylic acid are referred to as in this specification and are denoted as " (methyl) acrylic acid ".
[polarizing film adhesive composition]
Polarizing film adhesive composition of the invention contains (methyl) acrylic polymer (A) as described below, hands over
Join agent (B) and ionic compound (C).Above-mentioned adhesive composition can also contain silane coupling agent (D) as needed, or also
Organic solvent (E) can be contained.
[(methyl) acrylic compounds polymers (A)]
(methyl) acrylic polymer (A) is comprising having polyoxyalkylenes or alkoxyalkyl (methyl) acrylic acid
The polymer of the polymerizable monomer of ester (a1), is polymerize by above-mentioned polymer monomer and is obtained.(methyl) acrylic polymer as a result,
(A) preferably there is the structural unit from (a1).
It both can be only with polyoxyalkylenes or alkoxyalkyl (methyl) acrylic acid as above-mentioned polymerizable monomer
Ester (a1) can also also include selected from without polyoxyalkylenes, alkoxyalkyl and crosslinking while comprising above-mentioned (a1)
Any (methyl) acrylate (a2), monomer (a3) and other monomers (a4) containing crosslinkable groups in property group
At least one of.For example, can enumerate comprising above-mentioned (a1)~(a3) and according to necessary also comprising the polymerism list of above-mentioned (a4)
Body.
Here, the crosslinkable groups are to refer to import to (methyl) acrylic polymer (A) to be handed over by crosslinking agent (B)
The group for joining obtained crosslinking points, can enumerate hydroxyl, carboxyl etc..
Hereinafter, described (methyl) acrylate (a1) is also referred to as " monomer (a1) ", (methyl) acrylate (a2)
Also referred to as " monomer (a2) ", the monomer (a3) containing crosslinkable groups are also referred to as " monomer (a3) ", and other monomers (a4) are also referred to as
" monomer (a4) ".
" monomer (a1) "
Monomer (a1) is with polyoxyalkylenes or alkoxyalkyl (methyl) acrylate.Monomer (a1) is preferably not
(methyl) acrylate containing crosslinkable groups.
Monomer (a1) can for example be indicated with formula (a-1).
CH2=CR1-COOR2···(a-1)
R1For hydrogen atom or methyl, R2For the group indicated with formula (g-1).
-(R3O)nR4···(g-1)
R3For alkylidene, R4For alkyl, the integer that n is 1 or more.The carbon number of alkylidene is usually 1~10, and preferably 1~5.
The carbon number of alkyl is usually 1~10, and preferably 1~4.N is preferably 1~20, and more preferably 1~4, further preferably 1~2.
As monomer (a1), it is more that such as (methyl) alkyl acrylate oxygroup alkyl ester, single (methyl) alkyl acrylate oxygroup can be enumerated
Alkylene glycols ester.
As (methyl) alkyl acrylate oxygroup alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) third can be enumerated
Olefin(e) acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) propylene
Sour 3- ethyoxyl propyl ester, (methyl) acrylic acid 4- methoxybutyl, (methyl) acrylic acid 4- Ethoxybutyl.
As the more alkylene glycols esters of list (methyl) alkyl acrylate oxygroup, for example single (methyl) methoxyethyl two can be enumerated
Glycol ester, list (methyl) methoxyethyl dipropylene glycol ester, single (methyl) ethioxy triglycol ester, single (first
Base) ethioxy binaryglycol ester, single (methyl) methoxyethyl triglycol ester.
As monomer (a1), from the viewpoint of reactivity, the R of preferred formula (a-1) in above-mentioned substance2For alkoxyalkyl
(methyl) alkoxyalkyl acrylate.
Monomer (a1) both can be used alone one kind, it is possible to use two or more.
In the 100 mass % of polymerizable monomer of formation (methyl) acrylic polymer (A), the dosage of monomer (a1) exists
41 mass % or more, preferably more than 50 mass %, more preferably 60~99.3 mass %.
If the dosage of monomer (a1) is more than 41 mass %, by viscous containing (methyl) acrylic polymer (A)
The adhesive phase that mixture composite is formed show it is highly polar, and to the adaptation of polarizing film and substrate (especially glass plate) etc.
It is excellent.Therefore, even if in the case where high temperature, height are damp and hot, adhesive phase will not occur from tilting, the peeling on polarizing film or substrate etc.
Deng being capable of forming the adhesive phase of excellent in te pins of durability.Further, since the excellent adhesion with substrate, therefore doing over again property (リ ワ ー
Network) well, so that adhesive phase is not susceptible to the adherency to piercing tip (beating Chi order I sword), surrounding polarizing film etc., operation
Property is excellent.If the dosage of monomer (a1) is more than 50 mass %, said effect is more significant.If the dosage of monomer (a1)
Within the above range, then (methyl) acrylic polymer (A) and the compatibility of ionic compound (C) described below are good, energy
Enough inhibit the exudation of ionic compound (C).
" monomer (a2) "
Monomer (a2) is without (methyl) third any in polyoxyalkylenes, alkoxyalkyl and crosslinkable groups
Olefin(e) acid ester.(methyl) acrylic polymer (A) preferably has the structural unit from (a2).
Monomer (a2) can for example be indicated with formula (a-2).
CH2=CR5-COOR6···(a-2)
R5For hydrogen atom or methyl, R6To have without any in polyoxyalkylenes, alkoxyalkyl and crosslinking group
Machine group.
As R6Represented organic group can enumerate the ester ring types group such as alkyl, naphthenic base, aryl, aralkyl, fragrant oxygen
The aminoalkyl etc. that base alkyl, N- monoalkyl replace.The carbon number of alkyl is usually 1~24.The carbon of the ester ring types group such as naphthenic base
Number is usually 3~15.The carbon number of aryl is usually 6~10.The alkylidene and carbon number that aralkyl is usually 1~6 by carbon number be 6~
10 aryl is constituted.The aryl that the oxyalkylene group and carbon number that aryloxy alkyl is usually 1~6 by carbon number are 6~10 is constituted.N- is mono-
The carbon number of alkyl-substituted aminoalkyl is usually 1~12.
As monomer (a2), such as (methyl) alkyl acrylate, (methyl) acrylate base ester etc. can be enumerated and contained
(methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid aralkyl ester, (methyl) propylene of ester ring type group
(methyl) acrylate of sour aryloxy group alkyl base ester, the aminoalkyl replaced containing N- monoalkyl.
As (methyl) alkyl acrylate, such as (methyl) acrylate methyl esters, (methyl) acrylic acid second can be enumerated
Ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) propylene N-butyl, (methyl) isobutyl acrylate,
(methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, the positive heptyl ester of (methyl) acrylic acid,
(methyl) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl of (methyl) acrylic acid
Ester, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid 11
Arrcostab, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) acrylic acid isooctadecane base
Ester.
(methyl) acrylate, (methyl) acrylic acid as (methyl) acrylate base ester etc. containing ester ring type group
Aryl ester and (methyl) acrylic acid aralkyl ester can enumerate such as (methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid
Piece ester, (methyl) phenyl acrylate, (methyl) benzyl acrylate.
As (methyl) acrylic acid aryloxy group alkyl base ester, such as (methyl) acrylic acid phenoxy group methyl esters, (methyl) can be enumerated
Acrylic acid 2- phenoxy ethyl, (methyl) acrylic acid 2- toloxyl ethyl ester, (methyl) acrylic acid xylyloxy methyl esters, (first
Base) acrylic acid naphthoxy methyl esters.
As (methyl) acrylate of the aminoalkyl replaced containing N- monoalkyl, such as (methyl) acrylic acid can be enumerated
Monomethylaminoethylester, (methyl) acrylic acid list ethylamino ethyl ester, (methyl) acrylic acid mono-methyl amino propyl ester, (methyl) third
Olefin(e) acid list ethylamino propyl ester.
Monomer (a2) both can be used alone one kind, it is possible to use two or more.
In the 100 mass % of polymerizable monomer of formation (methyl) acrylic polymer (A), the dosage of monomer (a2) is excellent
Choosing is less than 59 mass %, more preferably 0.2~49.9 mass %, further preferably 0.5~39.8 mass %.
" monomer (a3) "
Monomer (a3) is the monomer containing crosslinkable groups.(methyl) acrylic polymer (A) can also have from
(a3) structural unit.
As the polymerizable monomer of composition (methyl) acrylic polymer (A), can be come by using monomer (a3) to (first
Base) acrylic polymer (A) imports and is crosslinked obtained crosslinking points by crosslinking agent (B).
Monomer (a3) can for example be indicated with formula (a-3).
CH2=CR7-COOR8···(a-3)
R7For hydrogen atom or methyl, R8For the organic group with crosslinkable groups.It, can example as the crosslinkable groups
Lift hydroxyl, carboxyl etc..
As R8Represented organic group can enumerate the aliphatic group that the hydroxyalkyl, carboxyl that carbon number is 1~12 replace
Deng.
As monomer (a3), such as (methyl) acrylate containing hydroxyl, (methyl) propylene containing carboxyl can be enumerated
Acid esters.
As (methyl) acrylate containing hydroxyl, (methyl) acrylic acid hydroxy alkyl ester etc., such as (methyl) can be enumerated
Acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl acrylate, (methyl) acrylic acid 4- hydroxy butyl ester, (methyl) acrylic acid 6- hydroxyl oneself
Ester, (methyl) acrylic acid 8- hydroxyl monooctyl ester.
As (methyl) acrylate containing carboxyl, such as (methyl) β-acryloxypropionic acid, (methyl) third can be enumerated
Olefin(e) acid 5- carboxylic pentyl ester.
Alkene unsaturated carboxylic acid can be also enumerated other than the compound indicated with formula (a-3) as monomer (a3).Make
For alkene unsaturated carboxylic acid, such as (methyl) acrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid can be enumerated.
Monomer (a3) both can be used alone one kind, it is possible to use two or more.
In the 100 mass % of polymerizable monomer of formation (methyl) acrylic polymer (A), from by appropriately crosslinked
From the viewpoint of showing durability and stress relaxation properties, the dosage of monomer (a3) is preferably greater than 0 mass % and in 15 matter
% is measured hereinafter, more preferably 0.1~10 mass %, further preferably 0.2~5 mass %.
" monomer (a4) "
(methyl) acrylic polymer (A) can also have the structural unit from (a4).
It as monomer (a4), can enumerate for example: the enesters class such as vinyl acetate, vinyl propionate；Ethylene, propylene, isobutyl
The olefines such as alkene；The haloalkenes hydro carbons such as vinyl chloride, vinylidene chloride；The styrene monomers such as styrene, α-methylstyrene；Fourth two
The diene-based monomers such as alkene, isoprene, chlorobutadiene；The nitrile monomers such as (methyl) acrylonitrile；Monomer containing amide groups.
As the monomer containing amide groups, can enumerate for example: (methyl) acrylamide, N- methyl (methyl) acrylamide,
The N- monoalkyls such as N- ethyl (methyl) acrylamide, N- propyl (methyl) acrylamide, N- hexyl (methyl) acrylamide replace
Acrylamide；N, N- dimethylacrylamide, N, the acryloyl that N, the N- dialkyl group such as N- dimethylmethacryl amide replace
Amine.
Monomer (a4) both can be used alone one kind, it is possible to use two or more.
" manufacturing condition of (methyl) acrylic polymer (A) "
(methyl) acrylic polymer (A) can be for example, by solution polymerization process, mass polymerization, emulsion polymerization, outstanding
Well known polymerization manufactures floating polymerization etc. so far, wherein it is preferred that solution polymerization process.Specifically, being by polymer solvent, gathering
Conjunction property monomer is packed into reaction vessel, and polymerization initiator, reacting initial temperature setting are added under the inert gas atmospheres such as nitrogen
It is usual 40~100 DEG C, preferably 50~80 DEG C, reaction system is made to maintain the temperature of usual 50~90 DEG C, preferably 60~90 DEG C
Lower reaction 4~20 hours.
As polymerization initiator, such as azo-initiator, peroxide type polymerization initiator can be enumerated.
As azo-initiator, such as 2 can be enumerated, 2 '-azodiisobutyronitriles, 2,2 '-azos two (methoxyl group -2 4-,
4- methyl pentane nitrile), 2,2 '-azos two (2- cyclopropyl propionitrile), 2,2 '-azos two (2,4- methyl pentane nitrile), 2,2 '-azos
Two (2- methylbutyronitriles), 1,1 '-azos two (hexamethylene -1- nitrile), 2- (carbamoyl azo) isobutyronitrile, 2- phenylazo -4-
Methoxyl group -2,4- methyl pentane nitrile, two acidified 2,2 '-azos two (2- amidine propane), 2,2 '-azo, two (N, the N methylene of '-two
Base NSC 18620), 2,2 '-azos two [2- methyl-N- (2- ethoxy)-propionamide], 2,2 '-azo, two (isobutyramides) two hydration
Object, 4,4 '-azos two (4- cyanopentanoic acid), 2,2 '-azos two (2- cyano propyl alcohol), (the 2- methyl of dimethyl -2,2 '-azo two
Propionic ester), the azo-compounds such as 2,2 '-azos two [2- methyl-N- (2- ethoxy) propionamide].
As peroxide type polymerization initiator, such as tert-butyl hydroperoxide, cumyl hydroperoxide, peroxide can be enumerated
Change diisopropylbenzene (DIPB), benzoyl peroxide, lauroyl peroxide, peroxidating hexanoyl, di-isopropyl peroxydicarbonate, peroxidating two
Two 2- ethylhexyl of carbonic acid, tert-Butyl peroxypivalate, 2,2- bis- (peroxidating 4,4- di-t-butyl cyclohexyl) propane, 2,2-
Two (bis- tert-amylcyclohexyl of peroxidating 4,4-) propane, 2,2- bis- (bis- t-octyl cyclohexyl of peroxidating 4,4-) propane, 2,2- bis-
(bis- α of peroxidating 4,4--cumyl cyclohexyl) propane, 2,2- bis- (peroxidating 4,4- di-t-butyl cyclohexyl) butane, bis- (mistake of 2,2-
Aoxidize bis- t-octyl cyclohexyl of 4,4-) butane.
Polymerization initiator can be used alone one kind, it is possible to use two or more.
Also it is not limited in polymerization and repeatedly adds polymerization initiator.
Relative to 100 mass parts of polymerizable monomer of formation (methyl) acrylic polymer (A), usually 0.001
~5 mass parts, the amount preferably within the scope of 0.005~3 mass parts use polymerization initiator.In addition, in above-mentioned polymerization reaction,
Addition polymerization initiator, chain-transferring agent, polymerizable monomer, polymer solvent can also suitably be added.
As the polymer solvent for polymerisation in solution, can enumerate for example: benzene,toluene,xylene etc. is aromatic hydrocarbon；Positive penta
The aliphatic hydrocarbons such as alkane, n-hexane, normal heptane, normal octane；The ester ring types hydro carbons such as pentamethylene, hexamethylene, cycloheptane, cyclooctane；
Diethyl ether, diisopropyl ether, 1,2- dimethoxy-ethane, butyl oxide, tetrahydrofuran, dioxanes (dioxane), methyl phenyl ethers anisole, benzene second
The ethers such as ether, diphenyl ether；The halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2- dichloroethanes, chlorobenzene；Ethyl acetate, propyl acetate,
The esters such as butyl acetate, methyl propionate；The ketones such as acetone, methyl ethyl ketone, diethyl ketone, methylisobutylketone, cyclohexanone；N, N- dimethyl
The amides such as formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone；The nitriles such as acetonitrile, benzonitrile；Dimethyl sulfoxide, ring
The sulfoxide types such as fourth sulfone.
Polymer solvent both can be used alone one kind, it is possible to use two or more.
" physical property and content of (methyl) acrylic polymer (A) "
(methyl) acrylic polymer (A) is the Weight-average molecular measured for example, by gel permeation chromatography (GPC method)
Measure (Mw) in terms of polystyrene scaled value usually 400,000 or more, preferably 450,000~2,000,000, more preferably 600,000~1,800,000,
Further preferably 800,000~1,800,000 polymer (A-1).If Mw is more than above-mentioned lower limit value, in the resistance to of adhesive phase
It is preferred on this aspect of long property.If Mw in above-mentioned upper limit value hereinafter, if on this aspect of the coating of adhesive composition be excellent
Choosing.
The molecular weight distribution (weight average molecular weight (Mw)/number-average molecular weight (Mn)) that polymer (A-1) is measured by GPC method is logical
It is often 2~60, preferably 3~45, more preferably 3~20.If Mw/Mn is more than above-mentioned lower limit value, to substrate or partially
It is preferred that vibration piece etc., which shows on this aspect of adaptation,.If Mw/Mn in above-mentioned upper limit value hereinafter, if in excellent heat resistance and guarantor
It is preferred for holding on this aspect of durability.
(methyl) acrylic polymer (A) can be only made of above-mentioned polymer (A-1).In addition, (methyl) acrylic acid
Quasi polymer (A) is also possible to the admixture of the polymer (A-2) of above-mentioned polymer (A-1) and low molecular weight.If using upper
Admixture is stated, then is preferred improving wetability and improving on this aspect of stress retentivity.
Relative to 100 mass parts of above-mentioned polymer (A-1), the content of the polymer (A-2) of low molecular weight is preferably in 50 matter
Part is measured hereinafter, more preferably below the mass 40, further preferably 1~30 mass parts.
The Mw that the polymer (A-2) of low molecular weight is measured by GPC method in terms of polystyrene scaled value usually 50,000 with
Under, preferably 1000~50,000, more preferably 2000~20,000.
The glass transition temperature (Tg) of (methyl) acrylic polymer (A) can come for example, by differential scanning calorimeter
Measurement, in addition, can be by the monomeric unit and its content ratio for constituting the copolymer according to the calculating of Fox formula.For example, can be according to
The glass transition temperature (Tg) acquired by Fox formula reaches usually -70~10 DEG C, preferably -60~0 DEG C of condition synthesizes
(methyl) acrylic polymer (A).Example can be used in the glass transition temperature for the homopolymer being made of in Fox formula each monomer
Such as documented number in " polymer handbook (Polymer Handbook) " fourth edition (Wiley-Interscience 2003)
Value.
[crosslinking agent (B)]
Adhesive composition of the invention has crosslinking agent (B).Crosslinking agent (B) is according to can be to (methyl) acrylic
The crosslinkable groups that object (A) imports suitably select, and such as isocyanate compound, epoxide, metal-chelating can be used
Object.
It is crosslinked (methyl) acrylic polymer (A) by crosslinking agent (B), it is (netted poly- to be capable of forming crosslinked whereby
Close object), obtain the adhesive phase of excellent heat resistance.
Crosslinking agent (B) both can be used alone one kind, it is possible to use two or more.
In adhesive composition of the invention, the content of crosslinking agent (B) is fitted according to (methyl) acrylic polymer (A)
Work as selection, is 0.01~25 mass parts preferably with respect to above-mentioned 100 mass parts of (methyl) acrylic polymer (A).More preferably
, the content of crosslinking agent (B) (methyl) acrylic polymer (A-1) Mw under 800,000 or more occasion for 0.01~
3 mass parts are 5~25 mass parts under 400,000 occasions more than and less than 800,000 in Mw.
The crosslinking agent (B) in above range is blended under 800,000 or more occasion by the Mw at (A-1), by adhesive group
It closes the adhesive phase that object is formed and shows stress relaxation properties, can obtain substantially resistant to hot.Moreover, flexibility, adaptation
It is excellent.The crosslinking agent (B) in above range is admixed under 400,000 occasions more than and less than 800,000 by the Mw at (A-1), by
Adhesive composition formed adhesive phase due to adhesive phase cohesive force and can obtain substantially resistant to hot.Moreover, bonding
Layer is inhibited from the exudation of substrate or substrate or to the adherency of piercing tip, surrounding polarizing film etc., and workability is excellent.
As isocyanate compound, usually using isocyanates chemical combination of the isocyanates radix 2 or more in a molecule
Object, isocyanates radix is preferably 2~8 in a molecule, and more preferably 3~6.If isocyanates radix is within the above range,
It is then viscous on (methyl) acrylic polymer (A) and this aspect of the cross-linking reaction efficiency of isocyanate compound and in holding
It is preferred on this aspect of the flexibility of mixture.
The diisocyanate cpd for being 2 as isocyanates radix in a molecule can enumerate for example aliphatic two isocyanides
Acid esters, alicyclic diisocyanate, aromatic diisocyanates.As aliphatic vulcabond, ethylene isocyanic acid can be enumerated
Ester, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2- methyl-1,5- pentane two
Isocyanates, 3- methyl-1, the carbon numbers such as 5- pentane diisocyanate, 2,2,4- trimethyl -1,6- hexamethylene diisocyanate
For 4~30 aliphatic vulcabond.As alicyclic diisocyanate, isophorone diisocyanate, cyclopenta can be enumerated
Diisocyanate, cyclohexyl diisocyanate hydrogenate sub- xylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenation two
The alicyclic diisocyanate that the carbon numbers such as phenylmethane diisocyanate, hydrogenation tetramethyl Asia xylene diisocyanate are 7~30.
As aromatic diisocyanates, such as phenylene vulcabond, toluene di-isocyanate(TDI), sub- dimethylbenzene diisocyanate can be enumerated
The carbon numbers such as ester, naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate
For 8~30 aromatic diisocyanates
As isocyanate compound of the isocyanates radix 3 or more in a molecule, the poly- isocyanide of such as aromatics can be enumerated
Acid esters, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate.Specifically, 2,4,6- triisocyanate toluene, 1,3 can be enumerated,
5- triisocyanate benzene, 4,4 ', 4 "-triphenylmethane triisocyanates.
In addition, above-mentioned isocyanic acid of such as isocyanates radix 2 or 3 or more can be enumerated as isocyanate compound
The polymers (such as dimer or tripolymer, biuret body, isocyanuric acid ester body) of ester compounds, derivative (such as polyalcohol
With the addition reaction product of diisocyanate cpds more than two molecules), polymer.As polynary in said derivative
Alcohol, low molecular weight polyols can enumerate the alcohol of the ternary such as trimethylolpropane, glycerine, pentaerythrite or more；Macromolecule
Weight polyalcohol can enumerate such as polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, poly- isoamyl two
Alkene polyalcohol.
Such isocyanate compound can enumerate the tripolymer of such as '-diphenylmethane diisocyanate, polymethylene polyphenyl
Biuret body or isocyanuric acid ester body, three hydroxyls of base polyisocyanate, hexamethylene diisocyanate or toluene di-isocyanate(TDI)
Reaction product (such as toluene di-isocyanate(TDI) or the Asia of methylpropane and toluene di-isocyanate(TDI) or sub- xylene diisocyanate
Three molecule addition products of xylene diisocyanate), the reaction product (example of trimethylolpropane and hexamethylene diisocyanate
Such as three molecule addition products of hexamethylene diisocyanate), polyethers polyisocyanate, polyester polyisocyanate.
, can be on this aspect can be improved curing property and resistance to light leakage in isocyanate compound, preferred trimethylolpropane
With reaction product (Japanese polyurethane Co., Ltd. (Japanese Port リ ウ レ of toluene di-isocyanate(TDI) or sub- xylene diisocyanate
タ Application society) the CORONATE L (U ロ ネ ー ト L) of manufacture, Soken Chemical & Engineering Co., Ltd.'s manufacture TD-75 etc.), hexa-methylene two
The isocyanuric acid ester body of isocyanates or toluene di-isocyanate(TDI) be (Asahi Chemical Industry Co., Ltd (industry society, Asahi Chemical Industry) manufacture
TSE-100, Japanese polyurethane Co., Ltd. manufacture 2050 etc.).
As epoxide, the compound in molecule with more than two epoxy groups can be enumerated, such as second two can be enumerated
Alcohol diglycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6- oneself
Glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, diamines diglycidyl
Amine (ジ ア ミ Application グ リ シ ジ Le ア ミ Application), N, N, N ', N '-four glycidyl group m-xylene diamine, 1,3- are bis-, and (N, N- bis- shrinks
Glyceryl amino methyl).As commercial product, the E-5CM of such as Soken Chemical & Engineering Co., Ltd. manufacture can be enumerated, comprehensive grind chemical strain
The E-5XM of formula commercial firm manufacture.
As metallo-chelate, can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate to aluminium, iron, copper, zinc,
Compound made of the polyvalent metal coordinations such as tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium.Specifically, aluminium isopropoxide, secondary can be enumerated
Butyric acid aluminium, acetoacetate aluminium ethide diisopropyl ester, tri ethylacetoacetate aluminium, praseodynium aluminium.
[ionic compound (C)]
Adhesive composition of the invention is by being selected from N, bis- (fluorine sulphonyl) imines of N- and bis- (trifluoro methylsulfonyl) imines of N, N-
Anion and organic cation constitute, and the ionic compound (C) containing fusing point at 25 DEG C or more.
Adhesive composition can reduce the adhesive formed by adhesive composition by containing ionic compound (C)
The sheet resistance value of layer, obtains the adhesive phase with antistatic performance.
In addition, the polarizing film for being pasted with described adhesive layer usually has the protective film for protecting polarizer mostly,
As the protective film, the cellulose membranes such as tri acetyl cellulose, polycarbonate membrane, poly (ether sulfone) film etc. can be enumerated, it is particularly common
Be the cellulose membranes such as tri acetyl cellulose.
Hitherto known ionic compound is the ionic compound that hydrolysis can occur with tri acetyl cellulose mostly,
And then hardly with tri acetyl cellulose hydrolysis occurs for the ionic compound (C).Due to this point, even if described
The adhesive phase for containing the ionic compound (C) is attached on protective film, also there is no concern that described adhesive layer is in hygrothermal environment
Under can generate corrosion to the protective film, therefore the excellent polarizing film with adhesive phase of long-term reliability can be obtained.
Anion included in ionic compound (C) is selected from N, bis- (fluorine sulphonyl) the imines ((FSO of N-2)2N-) and N, N- it is bis-
(trifluoro methylsulfonyl) imines ((CF3SO2)2N-)。
As organic cation included in ionic compound (C), can enumerate such as pyridylium, piperidines sun from
Son, pyrrolidonium cation, pyrroles's cation moiety, the cation with pyrrole ring, glyoxaline cation, tetrahydropyrimidine cation,
Dihydro-pyrimidin cation, pyrazoles cation, dihydropyazolo cationic (ピ ラ ゾ リ ニ ウ system カ チ オ Application), alkylammonium sun from
Son, alkyl sulfonium cation, alkylphosphines cation and their derivative.As the cation with pyrrole ring, pyrrole can be enumerated
Cough up cation, indoles cation, carbazole cation etc..As derivative, it can enumerate and have on the ring for constituting the organic cation
There is the cation etc. of one or more alkyl, the carbon number of the alkyl is usually 1~12.
Wherein, optimizing alkyl ammonium cation, the tetraalkylammonium cation especially indicated with formula (c-1) are more preferred.
In formula (c-1), R1、R2、R3And R4It is separately alkyl.
Preferably, R1It is the alkyl that carbon number is 1~18, R2~R4It is the alkyl that carbon number is 1~8.From obtaining humidity resistance more
From the point of view of adding excellent adhesive phase, it is further preferred that R1It is the alkyl that carbon number is 1~14, R2~R4Be carbon number be 1~6
Alkyl, it is further preferred that, R1It is the alkyl that carbon number is 1~10, R2~R4It is the alkyl that carbon number is 1~6.It is preferred that R1、R2、
R3And R4Represented alkyl is all alkyl.In addition, being presented from (methyl) acrylic polymer (A) and ionic compound (C)
Out from the point of view of appropriate intermiscibility, the carbon number of alkyl is advisable within the above range.By showing appropriate intermiscibility,
While showing the good antistatic performance at initial stage, it is suppressed that continue at any time and occur because exudation caused by antistatic
Performance deterioration is deteriorated with the adaptation of clung body.Moreover, humidity resistance is excellent.
As the tetraalkylammonium cation indicated with formula (c-1), tetramethylammonium cation, tetraethyl ammonium sun can be enumerated
Ion, tetrabutyl ammonium cation, tetrahexyl ammonium cation, trimethyldecylammonium ammonium cation, triethyl methyl ammonium cation, three fourths
Ylmethyl ammonium cation, tributyl ethyl ammonium cations, dodecyl trimethyl ammonium cation etc..
The fusing point of ionic compound (C) is at 25 DEG C or more, preferably at 25 DEG C more than or lower than 60 DEG C, particularly preferably at 27 DEG C
More than or lower than 50 DEG C.The ionic compound (C) of fusing point within the above range is affine with (methyl) acrylic polymer (A)
Property it is good, and be able to suppress it is long-term keeping when ionic compound (C) from adhesive phase ooze out.Fusing point can be for example, by differential scanning warm
It measures fixed (DSC), measured in the method recorded in embodiment.
As ionic compound (C), specifically, it is preferable that bis- (trifluoro methylsulfonyl) imines of tributyl-methyl phosphonium ammonium, positive 12
Bis- (fluorine sulphonyl) imines of alkyl trimethyl ammonium.
From the viewpoint of durability, the content of the ionic compound (C) in adhesive composition of the invention relative to
100 mass parts of (methyl) acrylic polymer (A) be typically larger than 0 mass parts and 15 below the mass, preferably 0.1~10
Mass parts, further preferably 0.1~8 mass parts.
[silane coupling agent (D)]
Adhesive composition of the invention can also contain silane coupling agent (D) other than above compound.By using
Silane coupling agent (D) makes the substrates strong bond such as adhesive phase and glass plate, helps to prevent polarizing film under high humid and warm environment
It is peeling-off.
As silane coupling agent (D), can enumerate for example: vinyltrimethoxysilane, vinyltriethoxysilane, 3-
Methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methyl-prop
Alkene methyl diethoxy silane, 3- methacryloxypropyl etc. contain polymerism insatiable hunger
With the silane coupling agent of group；3- glycidoxypropyltrime,hoxysilane, 3- epoxy propoxy propyl triethoxysilane,
3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl diethoxy silane, 2- (3,4- epoxy
Cyclohexyl) silane coupling agent containing epoxy group such as ethyl trimethoxy silane；3- TSL 8330,3- amino
Propyl-triethoxysilicane, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- amino
Hydroxypropyl methyl dimethoxysilane, 3- triethoxysilyl-N- (1,3- dimethyl-butylidene) propyl amine, N- phenyl -3-
The silane coupling agent containing amino such as TSL 8330；The silicon containing halogen such as 3- r-chloropropyl trimethoxyl silane
Alkane coupling agent.
The content of silane coupling agent (D) in polarizing film adhesive composition of the invention is relative to (methyl) acrylic acid
100 mass parts of quasi polymer (A) are usually 0~1 mass parts, preferably 0.01~1 mass parts, more preferably 0.05~0.5 matter
Measure part.
[organic solvent (E)]
Adhesive composition of the invention preferably comprises organic solvent (E) to adjust its coating.As organic molten
Agent can enumerate the polymer solvent illustrated in " manufacturing condition of (methyl) acrylic polymer (A) " column.For example, can will wrap
Polymer solution containing (methyl) acrylic polymer (A) and polymer solvent is mixed with crosslinking agent (B), ionic compound (C)
Carry out modulating adhesive composition.In adhesive composition of the invention, the content of organic solvent is usually 50~90 mass %, excellent
It is selected as 60~90 mass %.
In addition, " solid component " in this specification refers in ingredient contained in adhesive composition have in addition to above-mentioned
Whole components other than solvent (E), " solid component concentration " refer to above-mentioned solid component relative to 100 matter of adhesive composition
Measure the ratio of %.
[additive]
Adhesive composition of the invention in addition to the above ingredients, can also contain within the scope of the effect of the invention
Have selected from antioxidant, light stabilizer, preventing metal corrosion agent, tackifier, plasticizer, crosslinking accelerator, surfactant, above-mentioned
One or more of (A) (methyl) acrylic polymer other than and agent (リ ワ ー Network drug of doing over again).
[modulation of polarizing film adhesive composition]
Polarizing film adhesive composition of the invention can be by the method well known to so far to (methyl) acrylic polymer
Object (A), crosslinking agent (B), ionic compound (C) and other ingredients that are as needed and using are closed to be mixed to modulate.It can
It enumerates for example to obtained comprising (methyl) acrylic polymer (A) when synthesis (methyl) acrylic polymer (A)
Polymer solution in blend crosslinking agent (B), ionic compound (C) and other ingredients for using as needed.
Described adhesive composition is to the durability under the adaptation and high-temperature high-humidity of glass substrate or polarizing film etc.
It is excellent, it is thus possible to suitable for being bonded for polarizing film and glass substrate.
[adhesive phase]
Adhesive phase of the invention is formed by above-mentioned adhesive with composition.Described adhesive layer can be above-mentioned viscous by carrying out
Cross-linking reaction in mixture composite obtains, specifically can be by making (methyl) acrylic polymer (A) with crosslinking agent (B)
Crosslinking is to obtain.
The formation condition of adhesive phase is for example as described below.Adhesive composition of the invention is coated on supporting mass,
Temperature is different according to solvent type, but usually 50~150 DEG C, preferably carried out at 60~100 DEG C usually 1~10 minute,
Drying in preferably 2~7 minutes and remove solvent, formed film.The film thickness of dry coating is usually 5~75 μm, preferably 10
~50 μm.
Adhesive phase is preferably formed under the following conditions.Adhesive composition of the invention is coated on supporting mass,
After pasting cover film on the film formed under above-mentioned condition, at usual 5~60 DEG C, preferably 15~40 DEG C and usual 30~70%
It is conserved in the environment of RH, preferably 40~70%RH usual 3 days or more, preferably 7~10 days.If in cooking conditions as described above
Under be crosslinked, then crosslinked (network polymers) can be efficiently formed.
As the coating method of adhesive composition, well known method can be used, such as pass through spin-coating method, cutter painting method, roller
Coating, stick coating method, scraper coating, die coating method, gravure coating method form the coating drying means of specific thickness.
It as supporting mass and cover film, can enumerate for example: the polyester films such as polyethylene terephthalate (PET)；Poly- second
The plastic foil of the polyolefin films such as alkene, polypropylene, vinyl-vinyl acetate copolymer etc..
The adhesive phase formed by adhesive composition of the invention is from inhibiting polarizing film distortion, cohesiveness, bonding force, again
From the viewpoint of fissility, gel fraction is preferably 20~98 mass %, further preferably 30~98 mass %, further
Preferably 35~95 mass %.
In addition, the sheet resistance value of described adhesive layer preferably existsHereinafter, more preferably existingWith
Under, particularly preferablyThe resistance of sheet resistance value indication adhesive layer surface, the smaller electricity of numerical value
Hinder it is smaller, display antistatic performance it is excellent.Sheet resistance value can be measured by the method for embodiment record.
Adhesive phase of the invention with the above-mentioned adhesive composition constituted by forming, therefore even if than 60 DEG C/90
Excellent durability is also showed under the conditions of the damp and hot promotion of DEG C 85 DEG C RH harsher/90%RH.
[polarizing film bonding sheet]
Polarizing film of the invention has the adhesive phase formed by above-mentioned polarizing film adhesive composition with bonding sheet.Make
For bonding sheet, the double-sided adhesive sheet for example only with above-mentioned adhesive phase can be enumerated, there is substrate and be formed on substrate two sides
Above-mentioned adhesive phase double-sided adhesive sheet, with the single side of substrate and the above-mentioned adhesive phase being formed in substrate one side bond
Piece and these bonding sheets are pasted with the viscous of the cover film by lift-off processing on the face of adhesive phase not contacted with substrate
Close piece.
It as substrate and cover film, can enumerate for example: the polyester films such as polyethylene terephthalate (PET)；Polyethylene,
The plastic foil of the polyolefin films such as polypropylene, vinyl-vinyl acetate copolymer etc..
The formation condition or gel fraction of adhesive phase are identical as documented condition in [adhesive phase] column.
The film thickness of adhesive phase is usually 5~75 μm, preferably 10~50 μm from the viewpoint of maintaining bond properties.Base
The film thickness of material and cover film is not particularly limited, but usually 10~125 μm, preferably 25~75 μm.
[polarizing film and laminated body with adhesive phase]
Polarizing film with adhesive phase of the invention have polarizing film and in at least one side of above-mentioned polarizing film by this
The adhesive phase that invention polarizing film is formed with adhesive composition.In addition, " polarizing film " is in this specification to include " polarizing coating "
Meaning use.
As polarizing film, well known polarizing film so far can be used, can enumerate for example with polarizer and configuration described
The polarizing film of polarizer protective film on the single or double of polarizer.
As polarizer, can enumerate it for example after containing polarized component in the film for making to be made of polyvinyl alcohol resin
Stretched film obtained from stretching.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, poly- second can be enumerated
Enol acetal, ethylene vinyl acetate copolymer it is saponified.As polarized component, such as iodine or dichroism dye can be enumerated
Material.
As polarizer protective film, can enumerate such as the acetyl group as tri acetyl cellulose, diacetyl cellulose
Film, the polycarbonate membrane, poly (ether sulfone) film of the celluloses such as cellulose composition.In the present invention, use cellulose membrane as polarizer
Protective film, even if under the occasion that adhesive phase connects with the cellulose membrane and is formed, long-term reliability, specifically wet-heat resisting
Property is also excellent.
The thickness of polarizing film is usually 30~250 μm, and preferably 50~200 μm.
It is not particularly limited, can be enumerated using direct stick coating method etc. inclined in the method that polarizing film surface forms adhesive phase
The method that makes it dry and cure after being coated with above-mentioned adhesive composition on vibration piece surface, by polarizing film bonding sheet of the invention
Possessed adhesive phase is transferred to the method for curing it behind polarizing film surface.Dry and cooking conditions or gel fraction etc. with
Documented condition is identical in [adhesive phase] column.
The thickness for being formed in the adhesive phase on polarizing film is usually 5~75 μm in terms of dry film thickness, preferably 10~50 μ
m.In addition, adhesive phase is formed in at least one side of polarizing film, adhesive phase can be enumerated and be only formed in polarizing film single side
On form, adhesive phase be formed in the form on polarizing film two sides.
Further, it is also possible to which being laminated on above-mentioned polarizing film has it such as antiglare layer, phase separation layer, angle of visibility improve layer
The layer of its function.
By the base that the polarizing film of the invention with adhesive phase obtained in the manner described above is arranged in liquid crystal cell
Liquid crystal cell is manufactured in plate surface.Here liquid crystal cell has liquid crystal layer construction clamped by two pieces of substrates.
For example, following laminated body can be manufactured, wherein the polarizing film has polarizer and configuration in the polarizer
On protective film, the laminated body by the polarizer, the protective film, by polarizing film of the invention adhesive composition shape
At adhesive phase and glass substrate be laminated in this order.
As the substrate with liquid crystal cell, the glass plate such as alkali-free glass plate can be enumerated.The thickness of substrate preferably exists
5mm is hereinafter, more preferably 0.05~2mm.
[embodiment]
More specific description is carried out to the present invention below based on embodiment, but the present invention is not limited to these embodiments.With
In the record of lower embodiment etc., unless otherwise instructed, " part " expression " mass parts ".
[evaluation of ionic compound]
2g water and 2g ionic compound are added into polypropylene bottle, the testing liquid that concentration is 50 mass % is made.
0.25g (40 μm of thickness, 40mm × 120mm) tri acetyl cellulose film (TAC film, Konica beauty are put into the testing liquid
Can be up to the K-10 of Co., Ltd. (U ニ カ ミ ノ Le タ (strain)) manufacture), make its dipping.By above-mentioned polypropylene bottle in temperature
85 DEG C, stand 300 hours in the environment of humidity 85% after, acquire above-mentioned testing liquid, utilize high-speed liquid chromatography (strain formula
The manufacture of Shimadzu Seisakusho Ltd., commercial firm) acetic acid concentration in solution is analyzed.The results are shown in tables 1.
Ionic compound used in above-mentioned evaluation is as described below.In addition, the fusing point of ionic compound is by showing that difference is swept
Calorimetry (DSC) is retouched between -20 DEG C~400 DEG C and is measured with 10 DEG C of heating rate per minute.
[table 1]
Table 1
As shown in table 1, in ionic compound (C3) and (C4), acetic acid concentration in solution is high, it is thus regarded that TAC film into
Hydrolysis is gone.And in ionic compound (C1) and (C2), the acetic acid concentration in solution is low, it is thus regarded that the hydrolysis of TAC film into
Stroke degree is low.Especially in ionic compound (C1), acetic acid concentration in solution with referring to water it is almost the same.
[GPC]
For (methyl) acrylic polymer (A), weight is acquired by gel permeation chromatography (GPC) method, with following conditions
Average molecular weight (Mw) and number-average molecular weight (Mn).
Measurement device: HLC-8320GPC (TOSOH Co., Ltd (Dong ソ ー (strain)) manufacture)
The composition of GPC column: four pedestal (all being manufactured by TOSOH Co., Ltd) below
(1) TSKgel HxL-H (guard column)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
Flow velocity: 1.0 ml/mins
Column temperature: 40 DEG C
Sample solution concentration: 1.5% (w/v) (being diluted with tetrahydrofuran)
Mobile phase solvent: tetrahydrofuran
It is converted into standard polystyren
[synthesis example A1]
90 parts of acrylic acid are added into the reaction unit for having blender, reflux cooler, thermometer and nitrogen ingress pipe
2- methoxy acrylate, 6.5 parts of n-butyl acrylates, 3 parts of acrylic acid 2- hydroxyl ethyl esters, 0.5 part of acrylamide and 100 parts of ethyl acetate
Solvent is warming up to 80 DEG C while importing nitrogen.Then, 0.1 part of 2,2 '-azodiisobutyronitriles are added, in nitrogen atmosphere
Under in 80 DEG C carry out 6 hours polymerization reactions.After reaction, it is diluted with ethyl acetate, obtained solid component concentration is
The polymer solution of 30 mass %.The Mw of obtained (methyl) acrylic polymer A1 is 1,000,000, Mw/Mn 7.5.
[synthesis example A2 and A3]
Be changed in table 2 other than documented content in addition to by polymerizable monomer used in polymerization reaction, according to
The identical mode of synthesis example A1 is synthesized, and is made comprising (methyl) acrylic polymer A2 or A3 and solid component concentration is
The polymer solution of 30 mass %.As a result it is shown in table 2.
[synthesis example A4]
It is molten that 100 parts of toluene are added into the reaction unit for having blender, reflux cooler, thermometer and nitrogen ingress pipe
Liquid is warming up to 90 DEG C while importing nitrogen.Then, 2 hours 80 parts of acrylic acid 2- methoxyl groups that drip of dropping funel are utilized
Ethyl ester, 20 parts of n-butyl acrylates, 2 part 2,2 '-azodiisobutyronitriles add 1 part 2,2 '-azodiisobutyronitriles, in nitrogen
In the polymerization reaction of 90 DEG C of progress 6 hours under atmosphere.After reaction, be diluted with ethyl acetate, be made comprising toluene and
The mixed solution and solid component concentration of ethyl acetate are the polymer solution of 30 mass %.Obtained (methyl) acrylic compounds
The Mw of polymer A4-2 is 5,000, Mw/Mn 2.1.
Then, to 100 parts comprising according to (methyl) acrylic polymer A4- made from mode identical with synthesis example A1
1 and solid component concentration be 10 parts are added in the polymer solution of 30 mass % comprising (methyl) acrylic polymer A4-2 and
Solid component concentration is the polymer solution of 30 mass %, and the polymer solution that solid component concentration is 30 mass % is made.
[synthesis example A5]
In addition to polymerizable monomer used in polymerization reaction is changed to documented content in table 2 and mixes 0.15 part
It other than 2,2 '-azodiisobutyronitriles, is synthesized according to mode identical with synthesis example A1, being made includes (methyl) acrylic compounds
The polymer solution that polymer A5 and solid component concentration are 30 mass %.As a result it is shown in table 2.
[synthesis example A6 and A7]
In addition to polymerizable monomer used in polymerization reaction is changed to documented content in table 2 and is made and polymerism
The blended amount for the ethyl acetate that monomer is added together is to be synthesized other than 200 parts according to mode identical with synthesis example A1, is made
Obtain the polymer solution that comprising (methyl) acrylic polymer A6 or A7 and solid component concentration is 25 mass %.As a result it is shown in
Table 2.
[table 2]
Table 2
[embodiment 1]
(1) adjusting of adhesive composition
To (methyl) acrylic polymer solution obtained in synthesis example A1 (solid component concentration is 30 mass %), make
(solid component concentration is 75 matter to " the CORONATE L " manufactured for (B1): Nippon Polyurethane Industry Co., Ltd. of crosslinking agent (B)
Measure %), as (C1): (n-C of ionic compound (C)4H9)3(CH3)N+(CF3SO2)2N- and letter as silane coupling agent (D)
" KBM-403 " of more chemical industry Co., Ltd. (SHIN-ETSU HANTOTAI's chemical industry (strain)) manufacture is mixed, and adhesive composition is obtained.
The ratio of each ingredient is, relative to polymer included in (methyl) acrylic polymer solution obtained in synthesis example A1
100 parts of A1, (B1) are 0.4 part, and (C1) is 2.0 parts, the amount (being all solid component value above) that (D) is 0.2 part.
(2) production of bonding sheet
After defoaming, with scraper in the polyethylene terephthalate film (PET Jing Guo lift-off processing under 25 DEG C of liquid temperature
Film) on be coated with the adhesive composition that is obtained by above-mentioned (1), it is 3 minutes dry at 90 DEG C, forms dry film thickness as 20 μm of painting
Film.The PET film Jing Guo lift-off processing is further bonded on the reverse side of the adhesive surface of the above-mentioned PET film of film, 23 DEG C/50%
After standing 7 days under RH environment and being cured, obtain with clamped by two pieces of PET films with a thickness of the viscous of 20 μm of adhesive phase
Close piece.
(3) production of the polarizing film with adhesive phase
After defoaming, with scraper in the polyethylene terephthalate film (PET Jing Guo lift-off processing under 25 DEG C of liquid temperature
Film) on be coated with the adhesive composition that is obtained by above-mentioned (1), it is 3 minutes dry at 90 DEG C, obtain with dry film thickness being 20 μm
Film bonding sheet.Make sheet above and polarizing film (thickness: 110 μm, layer structure: tri acetyl cellulose film/polyvinyl alcohol
Film/tri acetyl cellulose film) it is bonded in a manner of making above-mentioned film connect with polarizing film, under conditions of 23 DEG C/50%RH
Stand after being cured within 7 days, obtain having PET film and with a thickness of 20 μm adhesive phase and polarizing film with adhesive phase
Polarizing film.
[embodiment 2~10, comparative example 1~3]
In addition to by embodiment 1 blending composition be changed in table 3 other than documented content, according to 1 phase of embodiment
Same mode obtains adhesive composition, bonding sheet and the polarizing film with adhesive phase.
In addition, each material in table 3 is as follows.
Crosslinking agent (B)
B1: the trimethylolpropane adduct of toluene di-isocyanate(TDI)
(Nippon Polyurethane Industry Co., Ltd.'s manufacture, CORONATE L, solid component concentration are 75 mass %)
B2: the trimethylolpropane adduct of sub- xylene diisocyanate
(Soken Chemical & Engineering Co., Ltd.'s manufacture, TD-75, solid component concentration are 75 mass %)
B3: epoxies crosslinking agent (Soken Chemical & Engineering Co., Ltd.'s manufacture, E-5CM, solid component concentration are 5 mass %)
Ionic compound (C)
It is identical as ionic compound C1~C4 used in above-mentioned [evaluation of ionic compound].
Silane coupling agent (D)
D:3- glycidoxypropyltrime,hoxysilane
(Shin-Etsu Chemial Co., Ltd's manufacture, KBM-403)
[evaluation]
[gel fraction]
It is placed in sample bottle, is added from the bonding sheet acquisition about 0.1g adhesive phase obtained by embodiment comparative example
It shakes after 30mL ethyl acetate 4 hours, then the content of the sample bottle was carried out with 200 purposes stainless steel metal mesh
Filter measures dry weight after carrying out drying in 2 hours to the residue on metal mesh at 100 DEG C.Bonding is found out using following formula
The gel fraction of agent.
Gel fraction (%)=(dry weight/adhesive acquires weight) × 100 (%)
[sheet resistance value]
Bonding sheet obtained in embodiment comparative example is cut into the size of 100mm × 100mm, test piece.It will
PET film is removed from bonding sheet, clamps adhesive phase with circular surface electrode and rear electrode.Apply 100V voltage, measurement
Sheet resistance value after 60 seconds.In addition, measurement utilizes double rings electrode method (the double リ Application on the basis of JIS K6911 (nineteen ninety-five)
グ electrode method) Lai Jinhang, the measurement of sheet resistance value used R8252 digital electrometer (Co., Ltd. ADC ((strain) エ ー デ ィ
ー シ ー) manufacture).
[measurement of bonding force]
By the polarizing film with adhesive phase obtained by embodiment comparative example (by PET film/adhesive phase/polarizing film structure
At laminated body) cut into the size of 70mm × 25mm, test film is made.PET film is removed from test film, it will with laminating roll
The laminated body being made of adhesive phase/polarizing film be bonded in a manner of making adhesive phase connect with alkali glass plate with a thickness of
On the single side of the alkali glass plate of 2mm.Obtained laminated body is kept in adjusting the autoclave to 50 DEG C/5 atmospheric pressure
20 minutes.Then, it is placed 2 hours or more under 23 DEG C/50%RH environment, further along the alkali glass plate table relative to clung body
The peel angle in face is that polarizing film end is pullled with the peeling rate of 300 mm/mins in 180 DEG C of direction, and measurement is viscous
(peel strength) with joint efforts.
[durability test]
By the polarizing film with adhesive phase obtained by embodiment comparative example (by PET film/adhesive phase/polarizing film structure
At laminated body) cut into the size of 150mm × 250mm, test film is made.PET film is removed from test film, uses laminating roll
The laminated body being made of adhesive phase/polarizing film is bonded in a manner of making adhesive phase connect with alkali-free glass plate with a thickness of
On the single side of the alkali metal-free glass plate of 2mm.By obtained laminated body in adjusting the autoclave to 50 DEG C/5 atmospheric pressure
It is kept for 20 minutes, breadboard is made.Two pieces of identical breadboards are made.By above-mentioned breadboard under conditions of temperature is 85 DEG C
(heat resistance) or temperature are that (humidity resistance) is placed 500 hours under conditions of 85 DEG C/humidity is 90%RH.With following benchmark pair
The open defects such as the foaming of the autoadhesion oxidant layer of above-mentioned breadboard, the cracking of above-mentioned breadboard, the removing of adhesive phase carry out
It visually observes and evaluates.
(benchmark)
AA: open defect occurring area is 0%
BB: open defect occurring area is greater than 0% and less than 3%
CC: open defect occurring area is 3% more than and less than 5%
DD: open defect occurring area is 5% or more
[table 3]
Claims (6)
1. a kind of polarizing film adhesive composition, contains:
(A) (methyl) propylene as obtained by the polymerizable monomer polymerization of (methyl) acrylate (a1) comprising 41 mass % or more
Acids polymers；(methyl) acrylate (a1) be (methyl) alkyl acrylate oxygroup alkyl ester,
(B) crosslinking agent and
(C) anion is selected from N, bis- (fluorine sulphonyl) imines of N- and bis- (trifluoro methylsulfonyl) imines of N, N-, cation for it is organic it is positive from
Son and ionic compound of the fusing point at 25 DEG C or more.
2. polarizing film adhesive composition as described in claim 1, which is characterized in that also contain silane coupling agent (D).
3. polarizing film adhesive composition as claimed in claim 1 or 2, which is characterized in that in ionic compound (C), have
Machine cation is the tetraalkylammonium cation indicated with formula (c-1),
In formula (c-1), R1、R2、R3And R4It is separately alkyl.
4. a kind of polarizing film bonding sheet has and is combined by polarizing film according to any one of claims 1 to 3 with adhesive
The adhesive phase that object is formed.
5. a kind of polarizing film with adhesive phase is wanted with polarizing film and in at least one side of the polarizing film by right
The adhesive phase that polarizing film described in asking any one of 1~3 is formed with adhesive composition.
6. a kind of laminated body, which is characterized in that polarizing film has the protective film of polarizer and configuration on the polarizer,
The adhesive phase and glass that the laminated body is formed by the polarizer, the protective film, polarizing film adhesive composition
Glass substrate is laminated in this order；
The polarizing film adhesive composition contains:
(A) by the poly- of (methyl) acrylate (a1) with polyoxyalkylenes or alkoxyalkyl comprising 41 mass % or more
(methyl) acrylic polymer obtained by conjunction property monomer polymerization,
(B) crosslinking agent and
(C) anion is selected from N, bis- (fluorine sulphonyl) imines of N- and bis- (trifluoro methylsulfonyl) imines of N, N-, cation for it is organic it is positive from
Son and ionic compound of the fusing point at 25 DEG C or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-209833 | 2014-10-14 | ||
| JP2014209833 | 2014-10-14 | ||
| PCT/JP2015/076160 WO2016059926A1 (en) | 2014-10-14 | 2015-09-15 | Adhesive composition for polarizing plates, adhesive sheet, polarizing plate with adhesive layer, and laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106795407A CN106795407A (en) | 2017-05-31 |
| CN106795407B true CN106795407B (en) | 2019-03-01 |
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| CN201580054308.7A Active CN106795407B (en) | 2014-10-14 | 2015-09-15 | Polarizing film adhesive composition, bonding sheet, polarizing film and laminated body with adhesive phase |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6499193B2 (en) |
| KR (1) | KR102217610B1 (en) |
| CN (1) | CN106795407B (en) |
| TW (1) | TWI688626B (en) |
| WO (1) | WO2016059926A1 (en) |
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| JP6521896B2 (en) * | 2016-04-25 | 2019-05-29 | 藤森工業株式会社 | Pressure sensitive adhesive composition and antistatic surface protective film |
| JP2017200975A (en) * | 2016-05-06 | 2017-11-09 | 王子ホールディングス株式会社 | Adhesive sheet and laminate |
| WO2018008712A1 (en) * | 2016-07-08 | 2018-01-11 | 日東電工株式会社 | Adhesive composition, adhesive layer, optical film provided with adhesive layer, image display panel, and liquid crystal display |
| KR102186080B1 (en) * | 2017-06-27 | 2020-12-03 | 주식회사 엘지화학 | Adhesive composition, protective film and polarizing plate comprising adhesive layer comprising the same and display device comprising the same |
| CN110997320A (en) * | 2017-08-10 | 2020-04-10 | 综研化学株式会社 | Laminate and touch panel |
| EP3714017A2 (en) * | 2017-11-21 | 2020-09-30 | Nitto Denko Corporation | Basic ionic liquids compositions and elements including the same |
| KR102152295B1 (en) * | 2018-09-04 | 2020-09-04 | (주)이녹스첨단소재 | Adhesive sheet for display and display comprising the same |
| JP7291474B2 (en) * | 2018-12-04 | 2023-06-15 | 三星エスディアイ株式会社 | OPTICAL FILM ADHESIVE, ADHESIVE LAYER, OPTICAL MEMBER, AND IMAGE DISPLAY DEVICE |
| WO2020136762A1 (en) * | 2018-12-26 | 2020-07-02 | 日東電工株式会社 | Adhesive composition for optical films, adhesive layer for optical films, and optical film with adhesive layer |
| TWI828646B (en) * | 2018-12-26 | 2024-01-11 | 日商日東電工股份有限公司 | Adhesive compositions for optical films, adhesive layers for optical films, and optical films with adhesive layers |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
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2015
- 2015-09-15 JP JP2016554019A patent/JP6499193B2/en active Active
- 2015-09-15 KR KR1020177000619A patent/KR102217610B1/en active IP Right Grant
- 2015-09-15 WO PCT/JP2015/076160 patent/WO2016059926A1/en active Application Filing
- 2015-09-15 CN CN201580054308.7A patent/CN106795407B/en active Active
- 2015-09-25 TW TW104131785A patent/TWI688626B/en active
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201617427A (en) | 2016-05-16 |
| JP6499193B2 (en) | 2019-04-10 |
| CN106795407A (en) | 2017-05-31 |
| TWI688626B (en) | 2020-03-21 |
| KR20170069191A (en) | 2017-06-20 |
| KR102217610B1 (en) | 2021-02-19 |
| WO2016059926A1 (en) | 2016-04-21 |
| JPWO2016059926A1 (en) | 2017-07-27 |
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