CN107148586A - Polarizer adhesive composition and the polarizer with adhesive phase - Google Patents
Polarizer adhesive composition and the polarizer with adhesive phase Download PDFInfo
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- CN107148586A CN107148586A CN201580057978.4A CN201580057978A CN107148586A CN 107148586 A CN107148586 A CN 107148586A CN 201580057978 A CN201580057978 A CN 201580057978A CN 107148586 A CN107148586 A CN 107148586A
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- polarizer
- adhesive phase
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
Abstract
The present invention provides one kind and can be formed and can suppress the polarizer adhesive composition of liquid crystal cell warpage (bending) and the adhesive phase of excellent in te pins of durability, the structure that at least one party that described adhesive layer is applicable in the polarizer diaphragm that is generally formed on polarizer two sides is removed.The polarizer adhesive composition is used to be formed the adhesive phase directly connected with polarizer, and the polarizer adhesive composition contains：By (methyl) acrylic copolymer obtained comprising 30 mass % less than alkyl methacrylate (a1) of the glass transition temperature less than 30 DEG C, the 10 mass % of 90 mass % homopolymer less than the monomer component copolymerization of alkyl methacrylate (a2) of the glass transition temperature more than 30 DEG C and the monomer (a3) containing cross-linking functional group more than 0 mass % and in below 10 mass % of 70 mass % homopolymer, and (B) crosslinking agent.
Description
Technical field
Polarizer the present invention relates to polarizer adhesive composition and with adhesive phase etc..
Background technology
Liquid crystal cell have liquid crystal layer by two pieces of substrates (for example：Glass plate) clamped by construction.Constitute liquid crystal cell
On substrate surface polarizer is pasted with via adhesive phase.So far, in order to improve the mechanical property and optical durability of polarizer,
It is typically employed in the polarizer diaphragm of stacking tri acetyl cellulose etc. on the polarizer two sides with polarization function
Structure.
In recent years, with the slimming and the slimming of polarizer of liquid crystal cell, liquid crystal is brilliant under hot and humid thermal environment
The warpage of born of the same parents turns into a big problem.The reason for occurring warpage as liquid crystal cell, can enumerate answering for for example conventional adhesive phase
Power relaxation properties are low, it is impossible to fully relax the stress produced by the thermal contraction of polarizer (change in size).
On the other hand, for the slimming requirement of polarizer, attempt to save the polarization member to be formed on polarizer two sides
Part diaphragm.However, the polarizer of no polarization element protection film due to adhesive phase is directly contacted with polarizer and in height
Not only can easily occur liquid as the thermal contraction of polarizer is over the binder layer by big stress under warm high humid and warm environment
The warpage of Jingjing born of the same parents, is also easy to a problem that fracture, stripping of polarizer for occurring adhesive phase.
A kind of adhesive is recorded in patent document 1, it is included is had by the ester group end containing 19~99.5 mass %
(methyl) acrylic polymer that the monomer component copolymerization of (methyl) alkyl acrylate of the branched alkyl groups of carbon number 10~24 is obtained
Compound.However, it not should be particularly mentioned that on saving polarizer diaphragm, adhesive phase being directly layered in into polarizer
On occasion under above-mentioned warpage issues.
A kind of adhesion type with polarizer and the adhesive phase being arranged on the polarizer is recorded in patent document 2 inclined
Shake piece, and the polarizer, which has, only there is transparent protective film, described adhesive layer to be arranged on no institute on the one side of polarizer
State the composition on the polarizer of transparent protective film side.It not should be particularly mentioned that produces with the saving for transparent protective film
The warpage issues of raw liquid crystal cell.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 2012-246477 publications
Patent document 2：Japanese Patent Laid-Open 2012-247574 publications
The content of the invention
The technical problems to be solved by the invention
The technical problems to be solved by the invention are to provide one kind and can be formed that liquid crystal cell warpage (bending) can be suppressed
And the polarizer adhesive composition of the adhesive phase of excellent in te pins of durability, described adhesive layer is applicable to be generally formed in partially
The structure that at least one party in the polarizer diaphragm on element two sides that shakes is removed.
Solve the technical scheme that technical problem is used
The present inventor has made intensive studies to solve above-mentioned technical problem.As a result find using specific (methyl)
Under the occasion of acrylic copolymer and use crosslinking agent, can be formed can suppress liquid crystal cell warpage (bending) and durability
Excellent adhesive phase.
That is, the inventors discovered that, can be solved by using the polarizer adhesive composition with following specific composition
Certainly above-mentioned technical problem, so as to complete invention.
The present invention is, for example, following [1]~[5].
[1] a kind of polarizer adhesive composition, it is used to form the adhesive phase directly connected with polarizer, institute
Polarizer adhesive composition is stated to contain：(A) by including glass of the 30 mass % less than 90 mass % homopolymer
Change the homopolymer of alkyl methacrylate (a1) of the transition temperature less than -30 DEG C, 10 mass % less than 70 mass %
Alkyl methacrylate (a2) of the glass transition temperature more than -30 DEG C and more than 0 mass % and 10 mass % with
Under the monomer (a3) containing cross-linking functional group obtained (methyl) acrylic copolymer of monomer component copolymerization, and (B)
Crosslinking agent.
[2] a kind of polarizer adhesive phase, it is formed as the adhesive composition described in above-mentioned [1].
[3] the polarizer adhesive phase described in above-mentioned [2], its storage modulus at 23 DEG C is in more than 0.10MPa, 85
Storage modulus at DEG C is designated as G' in below 0.05MPa, and by the storage modulus at T DEG C of temperatureT, by the energy storage mould at T+1 DEG C
Amount is designated as G'T+1When, temperature T always meets G' when in the range of 23~50 DEG CT/G'T+1＜ 1.07.
[4] a kind of polarizer bonding sheet, it has the adhesive phase described in above-mentioned [2] or [3].
[5] a kind of polarizer with adhesive phase, it is above-mentioned at least one side of polarizer with being directly layered in
[2] or the adhesive phase described in [3].
The effect of invention
Pass through the present invention, it is possible to provide one kind, which can be formed, can suppress the viscous of liquid crystal cell warpage (bending) and excellent in te pins of durability
The polarizer adhesive composition of mixture layer, described adhesive layer is applicable to be generally formed in inclined on polarizer two sides
The structure that at least one party in element protection film that shakes is removed.Used in addition, may also provide the polarizer formed by the composition
Adhesive phase, the polarizer with described adhesive layer are with bonding sheet and with described adhesive layer with adhesive phase
Polarizer.
Embodiment
Below, to the present invention polarizer adhesive composition, polarizer adhesive phase, polarizer bonding sheet with
And the polarizer with adhesive phase is illustrated.Hereinafter, the polarizer adhesive composition of the present invention, polarizer are used viscous
Mixture layer and polarizer are also referred to as " adhesive composition ", " adhesive phase " and " bonding sheet " with bonding sheet.
[polarizer adhesive composition]
The polarizer adhesive composition of the present invention contains (methyl) acrylic copolymer (A) being described below
With crosslinking agent (B).Above-mentioned composition can also contain in silane coupler (C) and antistatic agent (D) at least as needed
One kind, can also contain organic solvent (E).
[(methyl) acrylic copolymer (A)]
(methyl) acrylic copolymer (A) is the glass less than 90 mass % homopolymer comprising 30 mass %
Change alkyl methacrylate (a1) of the transition temperature (Tg) less than -30 DEG C, 10 mass % equal less than 70 mass %'s
Alkyl methacrylate (a2) of the glass transition temperature (Tg) of polymers more than -30 DEG C and more than 0 mass % and 10
The copolymer of the monomer component of below the quality % monomer (a3) containing cross-linking functional group, is obtained by above-mentioned monomer component copolymerization
Arrive.Above-mentioned copolymer (A) generally has the construction unit from alkyl methacrylate (a1), from methacrylate
The construction unit of ester (a2) and the construction unit from the monomer (a3) containing cross-linking functional group.
Acrylic acid and methacrylic acid are referred to as in this specification and are denoted as " (methyl) acrylic acid ".In addition, by polymer
Included in the construction unit from certain monomer A be denoted as " monomer A units ".In addition, above-mentioned (a1), (a2) and (a3) also distinguishes
Referred to as " monomer (a1) ", " monomer (a2) " and " monomer (a3) ".
The glass transition temperature (Tg) of the homopolymer of (methyl) alkyl acrylate can be used《Polymer handbook
(Polymer Handbook)》Described numerical value in fourth edition (Wiley-Interscience 2003).
《Alkyl methacrylate (a1)》
Monomer (a1) is that the Tg of homopolymer is less than -30 DEG C of alkyl methacrylate.The Tg of homopolymer is -80~-40
DEG C the monomer be preferred, the Tg of homopolymer is preferred for -70~-50 DEG C of the monomer.
The copolymer (A) that monomer (a1) copolymerization by using the Tg by homopolymer less than -30 DEG C is obtained, can be assigned viscous
Mixture layer is with appropriate stress relaxation properties.
As monomer (a1), it can enumerate for example with CH2=C (CH3)-COOR1The Tg of homopolymer is low in the compound of expression
In -30 DEG C of compound.In formula, R1For the alkyl of carbon number 6~18.The carbon number of the alkyl is preferably 6~14, can be obtained from presence
Consider to this point with the tendency for the hydrophobic adhesive phase that can prevent moisture intrusion polarizer, more preferably 8~14.
As monomer (a1), such as EHMA (- 45 DEG C), isodecyl methacrylate (- 41 can be enumerated
DEG C), lauryl methacrylate (- 65 DEG C), methacrylic acid tetradecane base ester (- 72 DEG C).Numerical value in bracket is represented
The Tg of the homopolymer of each monomer.
If using (methyl) propylene of the construction unit containing the alkyl methacrylate low Tg from homopolymer
Acid copolymer, then can assign adhesive phase with appropriate stress relaxation properties.In addition, if the use of alkyl being the first of long-chain
Base alkyl acrylate, then can also assign adhesive phase with hydrophobicity in addition to stress relaxation properties.For example, by using
, there is the storage modulus at available 85 DEG C in below 0.05MPa and there is flexibility simultaneously in the monomer (a1) with chain alkyl
Tendency with the hydrophobic adhesive phase that can prevent moisture intrusion polarizer.
Monomer (a1) both can be used alone one kind, it is possible to use two or more.
In the mass % of monomer component 100 for forming copolymer (A), the consumption of monomer (a1) 30 mass % less than
90 mass %, preferably 30~70 mass %, more preferably 30~50 mass %.If the consumption of monomer (a1) is in above range
It is interior, then the storage modulus of gained adhesive phase can adjusted to following ranges to this point (flexibility and the balance of hard)
On be preferred.
《Alkyl methacrylate (a2)》
Monomer (a2) is alkyl methacrylates of the Tg of homopolymer more than -30 DEG C.The Tg of homopolymer is -30~30
DEG C the monomer be preferred, the Tg of homopolymer is preferred for -20~0 DEG C of the monomer.
The copolymer (A) obtained by using monomer (a2) copolymerization of the Tg by homopolymer more than -30 DEG C, can be assigned
Adhesive phase is with appropriate processability.
As monomer (a2), it can enumerate for example with CH2=C (CH3)-COOR2In the compound of expression the Tg of homopolymer-
More than 30 DEG C of compound.In formula, R2For the alkyl of carbon number 1~18.The carbon number of the alkyl is preferably 1~8, can be obtained from presence
Consider to this point with the tendency for the hydrophobic adhesive phase that can prevent moisture intrusion polarizer, more preferably 4~8.
As monomer (a2), such as methyl methacrylate (105 DEG C), EMA (65 DEG C), first can be enumerated
Base propyl acrylate (35 DEG C), isopropyl methacrylate (81 DEG C), Tert-butyl Methacrylate (118 DEG C), methacrylic acid
N-butyl (20 DEG C), Isobutyl methacrylate (48 DEG C), pentylmethacrylate (- 5 DEG C), hexyl methacrylate (- 5
DEG C), 2-Propenoic acid, 2-methyl-, octyl ester (- 20 DEG C), 2-Ethylhexyl Methacrylate (- 10 DEG C), methacrylic acid cetyl ester (15
℃).Numerical value in bracket represents the Tg of the homopolymer of each monomer.
If using (methyl) propylene of the construction unit containing the alkyl methacrylate high Tg from homopolymer
Acid copolymer, then can assign adhesive phase with appropriate processability.In addition, if the use of alkyl being the metering system of long-chain
Acid alkyl ester, then can also assign adhesive phase with hydrophobicity in addition to processability.For example, by using with chain alkyl
Monomer (a2), there is storage modulus at available 23 DEG C in more than 0.10MPa and for hard and with moisture can be prevented
Invade the tendency of the hydrophobic adhesive phase of polarizer.
Monomer (a2) both can be used alone one kind, it is possible to use two or more.
In the mass % of monomer component 100 for forming copolymer (A), the consumption of monomer (a2) 10 mass % less than
70 mass %, preferably 30~65 mass %, more preferably 40~60 mass %.If the consumption of monomer (a2) is in above range
It is interior, then the storage modulus of gained adhesive phase can adjusted to following ranges to this point (flexibility and the balance of hard)
On be preferred.
If, there is the elevated tendency of storage modulus of adhesive phase in the use ratio increase of monomer (a2), if single
The use ratio of body (a2) reduces, then the tendency that there is the storage modulus reduction of adhesive phase.
In the present invention, the alkyl methacrylate (a1) and above-mentioned Tg due to above-mentioned Tg less than -30 DEG C are more than -30 DEG C
Alkyl methacrylate (a2) be copolymerized, with Tg less than -30 DEG C of alkyl acrylate and Tg more than -30 DEG C third
The occasion that olefin(e) acid Arrcostab is copolymerized is compared, and is excellent keeping hydrophobicity to show on binder performance this aspect simultaneously
Different.
《Monomer (a3) containing cross-linking functional group》
The monomer component for forming copolymer (A) is also included with the cross-linking functional group's that can be reacted with crosslinking agent (B)
Monomer, i.e. also include the monomer (a3) containing cross-linking functional group.
As monomer (a3), such as hydroxyl monomer can be enumerated, containing acid-based monomers, emulsion stability, amide-containing list
Body, nitrogenous system's heterocyclic monomer, cyano-containing monomer.As the acidic group in this specification, such as carboxyl, anhydride group, phosphoric acid can be enumerated
Base, sulfate.
As hydroxyl monomer, (methyl) acrylate of such as hydroxyl can be enumerated, specifically, can be enumerated (methyl)
Acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 3- hydroxypropyl acrylates, (methyl) acrylic acid 4- hydroxy butyl esters, (methyl) acrylic acid 6- hydroxyls oneself
(methyl) hydroxyalkyl acrylates such as ester, (methyl) acrylic acid 8- hydroxyl monooctyl esters.The carbon number of hydroxyalkyl in (methyl) hydroxyalkyl acrylate
Usually 2~8, preferably 2~6.
As carboxyl group-containing monomer, it can enumerate for example：(methyl) β-acryloxypropionic acid, (methyl) acrylic acid 5- carboxylics penta
(the first containing carboxyl such as ester, succinic acid list (methyl) acryloyloxyethyl ester, list (methyl) acrylic acid ω-carboxyl pla-pcl
Base) acrylate；Acrylic acid, methacrylic acid, itaconic acid, butenoic acid, fumaric acid, maleic acid., can as monomer containing anhydride group
Enumerate such as maleic anhydride, itaconic anhydride.As phosphorous acid-based monomers, (methyl) third on side chain with phosphate can be enumerated
Alkene acrylic monomer, as sulfur-bearing acid-based monomers, can enumerate (methyl) acrylic monomer on side chain with sulfate.
As emulsion stability, such as (methyl) acrylate, (methyl) acrylic acid diethyl can be enumerated
(methyl) acrylate containing amino such as base amino ethyl ester.As amide-containing monomer, can enumerate such as (methyl) acrylamide,
N- methyl (methyl) acrylamide, N- ethyls (methyl) acrylamide, N- propyl group (methyl) acrylamide, N- hexyls (methyl) third
Acrylamide.As nitrogenous system's heterocyclic monomer, such as vinyl pyrrolidone, acryloyl morpholine, caprolactam can be enumerated.
As cyano-containing monomer, such as cyano group (methyl) acrylate, (methyl) acrylonitrile can be enumerated.
As monomer (a3), from from the viewpoint of the bridging property of crosslinking agent (B), being preferably selected from hydroxyl monomer (still
The monomer with carboxyl is excluded from hydroxyl monomer) and at least one of carboxyl group-containing monomer, more preferably hydroxyl monomer.
Monomer (a3) both can be used alone one kind, it is possible to use two or more.
In the mass % of monomer component 100 for forming copolymer (A), the consumption of monomer (a3) is more than 0 mass % and in 10 matter
Measure below %, more preferably preferably 2~8 mass %, 4~6 mass %.If the consumption of monomer (a3) is in the above-mentioned upper limit
Value is following, then the crosslink density formed by copolymer (A) and crosslinking agent (B) will not become too high, can obtain stress and relax spy
The excellent adhesive phase of property.If the consumption of monomer (a3) can be effectively formed cross-linked structure more than above-mentioned lower limit,
Obtain the adhesive phase at normal temperatures with appropriate intensity.
《Other monomers》
As the monomer component for forming copolymer (A), example is it is also possible to use in the range of copolymer (A) physical property is not damaged
Such as alkyl acrylate, (methyl) alkyl acrylate epoxide alkyl ester, single (methyl) alkyl acrylate epoxide many alkylene glycols esters (ア Le Us
キ シ Port リ ア Le キ レ Application グ リ コ ー Le モ ノ (メ タ) ア Network リ レ ー ト), (methyl) containing ester ring type group or aromatic ring
Other (methyl) acrylate such as acrylate.That is, described copolymer (A), which can also have, comes from other (methyl) acrylic acid
The construction unit of ester.
Alkyl acrylate can such as formula：CH2=CH-COOR3Represent.In formula, R3For the alkyl of carbon number 1~18.Can example
Citing such as acrylate methyl esters, ethyl acrylate, n-propyl, isopropyl acrylate, propylene N-butyl, i-butyl
Ester, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-EHA, 2-ethyl hexyl acrylate,
Isooctyl acrylate monomer, acrylic acid nonyl ester, decyl acrylate, acrylic acid hendecane base ester, dodecylacrylate, acrylic acid ten
Eight Arrcostabs, acrylic acid isooctadecane base ester.
As (methyl) alkyl acrylate epoxide alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) third can be enumerated
Olefin(e) acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 3- methoxyl groups propyl ester, (methyl) propylene
Sour 3- ethyoxyls propyl ester, (methyl) acrylic acid 4- methoxybutyls, (methyl) acrylic acid 4- Ethoxybutyls.
As many alkylene glycols esters of list (methyl) alkyl acrylate epoxide, for example single (methyl) methoxyethyl two can be enumerated
Glycol ester, list (methyl) methoxyethyl DPG ester, single (methyl) ethioxy triglycol ester, single (first
Base) ethioxy binaryglycol ester, singly (methyl) methoxyethyl triglycol ester.
As (methyl) acrylate containing ester ring type group or aromatic ring, such as (methyl) acrylate can be enumerated
Ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate.
In addition, as the monomer component for forming copolymer (A), may be used also in the range of copolymer (A) physical property is not damaged
Use the co-polymerized monomer such as styrene monomer, vinyl acetate.That is, described copolymer (A) can also have from described
The construction unit of co-polymerized monomer.
As styrene monomer, it can enumerate for example：Styrene, methyl styrene, dimethyl styrene, trimethyl first
The ring-alkylated styrenes such as styrene, propylstyrene, butylstyrene, hexyl styrene, heptyl styrene, octyl styrene；Fluorine
The halogenated styrenes such as styrene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethene；Nitrostyrolene, acetylbenzene
Ethene, methoxy styrene.
Other monomers can be used alone one kind, it is possible to use two or more.
In the mass % of monomer component 100 for forming copolymer (A), above-mentioned other monomer (such as other (methyl) acrylic acid
Ester, co-polymerized monomer) total consumption be preferably 0~10 mass %, more preferably 0~5 mass %.
《The manufacturing condition of (methyl) acrylic copolymer (A)》
The manufacturing condition of (methyl) acrylic copolymer (A) is not particularly limited, and can come for example, by solution polymerization process
Manufacture.Specifically, it is to load polymer solvent and monomer component in reaction vessel, is added under the inert gas atmospheres such as nitrogen
Polymerization initiator, reacting initial temperature is set as usual 40~100 DEG C, preferably 50~80 DEG C, reaction system is maintained generally
Reacted 4~20 hours at a temperature of 50~90 DEG C, preferably 70~90 DEG C.
Copolymer (A) can be obtained for example, by making the monomer component copolymerization comprising above-mentioned monomer (a1)~(a3), both may be used
To be random copolymer or block copolymer.Wherein, random copolymer is preferred.
As the polymer solvent for polymerisation in solution, it 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 type hydro carbons such as pentamethylene, hexamethylene, cycloheptane, cyclooctane；
Diethyl ether, diisopropyl ether, 1,2- dimethoxy-ethanes, 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, MEK, diethyl ketone, methylisobutylketone, cyclohexanone；N, N- dimethyl
The amide-types such as formamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE；The nitriles such as acetonitrile, benzonitrile；Dimethyl sulfoxide, ring
Sulfoxide types such as fourth sulfone etc..These polymer solvents can be used alone one kind, it is possible to use two or more.
As the polymerization initiator used in polymerisation in solution, such as azo-initiator, peroxide can be enumerated and drawn
Send out agent.Specifically, the azo-compounds such as 2,2'- azodiisobutyronitriles, benzoyl peroxide, lauroyl peroxide etc. can be enumerated
Peroxide.Wherein, preferred azo-compound.As azo-compound, such as 2,2'- azodiisobutyronitriles, 2,2'- can be enumerated
Azo two (4- methoxyl group -2,4- methyl pentane nitriles), 2,2'- azos two (2- cyclopropyl propionitrile), (2,4- bis- of 2,2'- azos two
Methyl valeronitrile), 2,2'- azos two (2- methylbutyronitriles), 1,1'- azos two (hexamethylene -1- nitriles), 2- (carbamoyl azo) it is different
Butyronitrile, 2- phenylazo -4- methoxyl group -2,4- methyl pentane nitriles, two acidified 2,2'- azos two (2- amidine propanes), 2,2'-
Azo two (N, N'- dimethyleneisobutylamidine), 2,2'- azos two [2- methyl-N- (2- ethoxys)-propionamide], 2,2'- azos
Two (isobutyramide) dihydrates, 4,4'- azos two (4- cyanopentanoic acids), 2,2'- azos two (2- cyano group propyl alcohol), dimethyl-
2,2'- azos two (2 Methylpropionic acid ester).These polymerization initiators can be used alone one kind, it is possible to use two or more.
Polymerization initiator is relative to the mass parts of monomer component 100 for forming (methyl) acrylic copolymer (A), with usual
Amount in the range of 0.01~5 mass parts, preferably 0.1~3 mass parts is used.In addition, in above-mentioned polymerisation, can also be appropriate
Additional addition polymerization initiator, chain-transferring agent, monomer component, polymer solvent.
《The physical property and content of (methyl) acrylic copolymer (A)》
The weight average molecular weight (Mw) that (methyl) acrylic copolymer (A) is determined by gel permeation chromatography (GPC) method with
Polystyrene scaled value meter is usually 400,000~1,800,000, preferably 600,000~1,400,000, more preferably 800,000~1,000,000.Pass through
Using Mw within the above range and with above-mentioned monomeric unit copolymer (A), easily obtain bonding force balance (storage modulus
(G'1) and (G'2) balance), formed with suitable for coating viscosity adhesive composition.
The molecular weight distribution (Mw/Mn) that (methyl) acrylic copolymer (A) is determined by GPC method generally below 15,
Preferably 2~10, more preferably 4~8.
The glass transition temperature (Tg) of (methyl) acrylic copolymer (A) can be by for example constituting the monomer of the copolymer
Unit and its content ratio are calculated according to Fox formula.For example, can and with the glass transition temperature (Tg) of homopolymer in above-mentioned model
Interior monomer (a1) and (a2) is enclosed, and so that the glass transition temperature (Tg) tried to achieve according to Fox formula is usually -70~-20
DEG C, be preferably that -60~-30 DEG C of condition synthesizes (methyl) acrylic copolymer (A).By using with such glass
Change (methyl) acrylic copolymer (A) of transition temperature (Tg), stress relaxation properties and excellent in te pins of durability can be obtained and normal
The excellent adhesive composition of cohesive under temperature.
Fox formula：
1/Tg=(W1/Tg1)+(W2/Tg2)+……+(Wm/Tgm)
W1+W2+……+Wm=1
In formula, Tg is the glass transition temperature (unit of (methyl) acrylic copolymer (A)：K), Tg1、Tg2、……、
TgmFor the glass transition temperature (unit for the homopolymer being made up of each monomer：K), W1、W2、……、WmFor from each monomer
Weight fraction in the above-mentioned copolymer (A) of construction unit.As the weight fraction of the construction unit from each monomer, it can be used
Ingredient proportion of each single phase for whole monomers when copolymer is synthesized.
The glass transition temperature for the homopolymer being made up of in above-mentioned Fox formula each monomer can be used for example《Polymer hand
Volume》Described numerical value in fourth edition (Wiley-Interscience 2003).
In the adhesive composition of the present invention, the content of (methyl) acrylic copolymer (A) is in the composition except organic
It is usually 60~99.99 mass %, more preferably 70~99.95 mass %, spy in the mass % of solid constituent 100 beyond solvent
You Xuanwei not 80~99.90 mass %.If the content of (methyl) acrylic copolymer (A) is within the above range, can
The balance of the performance as adhesive is obtained, and adhesion characteristic is excellent.
[crosslinking agent (B)]
The adhesive composition of the present invention also contains crosslinking agent (B).
Crosslinking agent (B) as long as can have with (methyl) acrylic copolymer (A) come from contain bridging property official
The composition that the cross-linking functional group for the monomer (a3) that can be rolled into a ball crosslinks reaction is just not particularly limited, and can enumerate such as isocyanic acid
Ester compounds (B1), metallo-chelate (B2), epoxide (B3).
Crosslinking agent (B) can be used alone one kind, it is possible to use two or more.
In the adhesive composition of the present invention, the content of crosslinking agent (B) is relative to (methyl) acrylic copolymer (A)
100 mass parts are usually 0.01~5 mass parts, more preferably 0.05~2.5 mass parts, more preferably 0.1~1 mass
Part.If the content is within the above range, the balance of durability and stress relaxation properties is easily obtained, thus preferably.
《Isocyanate compound (B1)》
As isocyanate compound (B1), usually using isocyanation esterification of the isocyanates radix more than 2 in 1 molecule
Compound.By being crosslinked (methyl) acrylic copolymer (A) by isocyanate compound (B1), crosslinked (net can be formed
Shaped polymer).
The isocyanates radix of isocyanate compound (B1) is generally more than 2, preferably 2~8, more preferably 3
~6.If isocyanates radix is within the above range, in (methyl) acrylic copolymer (A) and isocyanate compound
(B1) it is preferred on this aspect of cross-linking reaction efficiency and keeping on this aspect of the flexibility of adhesive phase.
As the diisocyanate cpd that isocyanates radix in 1 molecule is 2, for example aliphatic two isocyanic acid can be enumerated
Ester, alicyclic diisocyanate, aromatic diisocyanates.As aliphatic vulcabond, can enumerate ethylidene diisocyanate,
Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2- methyl isophthalic acids, 5- pentanes two are different
Cyanate, 3- methyl isophthalic acids, the carbon number such as 5- pentane diisocyanates, 2,2,4- trimethyl -1,6- hexamethylene diisocyanates are 4
~30 aliphatic vulcabond.As alicyclic diisocyanate, IPDI, cyclopenta two can be enumerated different
Cyanate, cyclohexyl diisocyanate, the sub- XDI of hydrogenation, hydrogenated toluene diisocyanate, hydrogenation hexichol first
The alicyclic diisocyanate that the carbon numbers such as alkane diisocyanate, the sub- XDI of hydrogenation tetramethyl are 7~30.As
Aromatic diisocyanates, can enumerate for example phenylene vulcabond, toluene di-isocyanate(TDI), sub- XDI,
The carbon numbers such as naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate are 8
~30 aromatic diisocyanates
As isocyanate compound of the isocyanates radix more than 3 in 1 molecule, such as aromatics polyisocyanate can be enumerated
Ester, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate.Specifically, 2,4,6- triisocyanate toluene, 1,3,5- can be enumerated
Triisocyanate benzene, 4,4', 4 "-triphenylmethane triisocyanate.
In addition, as isocyanate compound (B1), can enumerate such as isocyanates radix 2 or more than 3 it is above-mentioned different
Polymer (such as dimer or tripolymer, biuret body, isocyanuric acid ester body), the derivative of cyanate esters are (such as more
The addition reaction product of diisocyanate cpd more than first alcohol and 2 molecules), polymer.As many in said derivative
First alcohol, low molecular weight polyols can enumerate the alcohol more than ternary such as trimethylolpropane, glycerine, pentaerythrite；High score
Sub- weight polyalcohol can enumerate such as PPG, PEPA, acrylic polyol, polybutadiene polyol, poly- isoamyl
Diene polyol.
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 PIC, hexamethylene diisocyanate or toluene di-isocyanate(TDI)
Methylpropane and toluene di-isocyanate(TDI) or reaction product (such as toluene di-isocyanate(TDI) or Asia of sub- XDI
Three molecule addition products of XDI), the reaction product (example of trimethylolpropane and hexamethylene diisocyanate
As hexamethylene diisocyanate three molecule addition products), polyethers PIC, polyester PIC.
In isocyanate compound (B1), on it can carry good curing performance this aspect, preferably trimethylolpropane and toluene two
The L- of reaction product (Soken Chemical ＆ Engineering Co., Ltd. (Integrated are ground chemical (strain)) manufacture of isocyanates or sub- XDI
45, TD-75 etc. of Soken Chemical ＆ Engineering Co., Ltd.'s manufacture), the isocyanide urea of hexamethylene diisocyanate or toluene di-isocyanate(TDI)
Acid esters body (TSE-100, Nippon Polyurethane Industry Co., Ltd. (the Japanese Port リ of Asahi Kasei Corporation's (Asahi Chemical Industry (strain)) manufacture
ウ レ タ Application industry (strain)) manufacture 2050 etc.).
Isocyanate compound (B1) can be used alone one kind, it is possible to use two or more.
《Metallo-chelate (B2)》
As metallo-chelate (B2), can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate to aluminium, iron, copper,
The compound of the polyvalent metal coordinations such as zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium.
Wherein, particularly preferred aluminium chelate compound (M-12AT of Soken Chemical ＆ Engineering Co., Ltd.'s manufacture etc.).Specifically, it can enumerate
Aluminium isopropoxide, secondary butyric acid aluminium, acetoacetate aluminium ethide diisopropyl ester, tri ethylacetoacetate aluminium, praseodynium aluminium.
Metallo-chelate (B2) can be used alone one kind, it is possible to use two or more.
Metallo-chelate (B2) makes (methyl) acrylic copolymer (A) be crosslinked (quasi-crosslink) by coordinate bond.Using
Under occasion of the metallo-chelate (B2) as crosslinking agent (B), in room temperature, the crosslinking is maintained, and polymer plays cohesion
Property, and a part for the crosslinking is released in high temperature, adhesive phase shows more excellent flexibility.
《Epoxide (B3)》
As epoxide (B3), usually using epoxide of the 1 molecule epoxy group number more than 2.It can enumerate
Such as ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, glycerine three-glycidyl
Ether, 1,3- couples of (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N', N'- four glycidyl groups m-xylene diamine, N,
N, N', N'- four glycidyl group aminophenyl methane, triglycidyl isocyanurate, a N, N- diglycidyl amino
Phenyl glycidyl ether, N, N- diglycidyls toluidines, N, N- diglycidylanilines.
[silane coupler (C)]
The polarizer of present invention adhesive composition preferably also contains silane coupler (C).Silane coupler (C) makes to glue
The clung body strong bond such as mixture layer and glass plate, helps to prevent the stripping under high humid and warm environment.
As silane coupler (C), it can enumerate for example：Vinyltrimethoxy silane, VTES, first
The silane couplers containing polymerism unsaturated group such as base acryloxypropyl trimethoxy silane；3- glycidoxies third
Base trimethoxy silane, 3- glycidoxypropyl groups triethoxysilane, 3- glycidoxypropyls dimethoxysilane,
3- glycidoxypropyls diethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane etc. contain epoxy
The silane coupler of base；3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s,
The silane couplers containing amino such as N- (2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes；3- chloros propyl group three
The silane coupler containing halogen such as methoxy silane.
In the adhesive composition of the present invention, the content of silane coupler (C) is relative to (methyl) acrylic copolymer
(A) 100 mass parts are generally below 1 mass parts, preferably 0.01~1 mass parts, more preferably 0.05~0.5 mass
Part.If content is within the above range, with prevent under high humid and warm environment polarizer to peel off or hot environment under it is silane coupled
The tendency that agent (C) is oozed out.
[antistatic agent (D)]
It can be used to for example reduce the sheet resistance value of the adhesive phase formed by the adhesive composition of the present invention
Antistatic agent (D).As antistatic agent (D), such as surfactant, ionic compound, electric conductive polymer can be enumerated.
As surfactant, it can enumerate for example：Quaternary ammonium salt, amidoquat salt, pyridine salt, with primary amino radical~
The cationic surface active agent of the cationic groups such as tertiary amino；With sulphonate-base, sulfuric ester alkali, phosphate alkali etc.
The anionic surfactant of anionic group；Alkyl betaines bases, alkyl imidazole betaines, alkyl amine
The amphoteric surfactantes such as class, amino acid sulfuric acid ester；Fatty acid glycerine esters, sorbitan fatty acid ester class, polyoxy second
Allylic alkylation amine, polyoxyethylene alkyl amine fatty acid ester, N- ethoxy-N-2- hydroxyalkyls amine, alkyl diethanolamide class
Deng nonionic surface active agent.
In addition, surfactant can also enumerate the reactive emulsifier with polymerizable group, it is also possible to use makes containing upper
State polymer types of surfactants obtained from the monomer component molecular weight of surfactant or reactive emulsifier.
Ionic compound is made up of cationic moiety and anionicsite, and (23 DEG C/50%RH) can be in solid-state at room temperature
Any of or liquid.
The cationic moiety for constituting ionic compound both can be any in inorganic cationoid or organic cationoid
Person or both.Inorganic cationoid preferred as alkali ion and alkaline-earth metal ion, more preferably excellent electrostatic prevention property
Li+、Na+And K+.As organic cationoid, can enumerate for example pyridylium, piperidines cation, pyrrolidonium cation,
Pyrroles's cation moiety, pyrroles's cation, glyoxaline cation, tetrahydropyrimidine cation, dihydro-pyrimidin cation, pyrazoles cation,
Dihydropyazolo cation (ピ ラ ゾ リ ニ ウ system カ チ オ Application), tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl
Phosphine cation and their derivative.
As constitute ionic compound anionicsite, as long as can with cationic moiety ionic bonding and formed from
The material of sub- compound is not particularly limited.Specifically, F can be enumerated-、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、
PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-(CF3SO2)
(CF3CO)N-.Wherein, the anion containing fluorine atom because the ionic compound of low melting point can be provided and it is preferred that, particularly preferably
(F2SO2)2N-(CF3SO2)2N-。
The preferred bis-trifluoromethylsulfoandimide lithium of ionic compound, double difluoro sulfimide lithiums, three (trifyl) first
Alkane lithium, bis-trifluoromethylsulfoandimide potassium, double difluoro sulfimide potassium, 1- ethylpyridines hexafluorophosphate, 1- butyl-pyridinium hexafluoros
Phosphate, 1- hexyl -4- picolines hexafluorophosphate, 1- octyl group -4- picolines hexafluorophosphate, 1- octyl group -4- methyl
Pyridine difluoro sulfimide, 1- octyl group -4- picolines bis-trifluoromethylsulfoandimide, (N, N- diethyl-N- methyl-N- (2- first
Epoxide ethyl) ammonium tetrafluoroborate, N, N- diethyl-N- methyl-N- (2- methoxy ethyls) ammonium bis-trifluoromethylsulfoandimide, 1-
Octylpyridinium fluorine thionyl imide (1- オ Network チ Le ピ リ ジ ニ ウ system Off Le オ ロ ス ホ ニ ウ system イ ミ De), 1- octyl group -3- first
Yl pyridines, trifluoro thionyl imide (ト リ Off Le オ ロ ス Le ホ ニ ウ system イ ミ De).
As electric conductive polymer, such as polythiophene, polyaniline, polypyrrole and their derivative can be enumerated.
In the adhesive composition of the present invention, the content of antistatic agent (D) is relative to (methyl) acrylic copolymer (A)
100 mass parts are generally below 3 mass parts, preferably 0.01~3 mass parts, more preferably 0.05~2.5 mass parts.
[organic solvent (E)]
The adhesive composition of the present invention preferably comprises organic solvent (E) to adjust its coating.Organic solvent can
Enumerate the polymer solvent illustrated in the column of (methyl) acrylic copolymer (A) one.For example, can be by containing for being obtained in above-mentioned copolymerization
The polymer solution of (methyl) acrylic copolymer (A) and polymer solvent carrys out modulating adhesive with crosslinking agent (B) mixing and combined
Thing.In the adhesive composition of the present invention, the content of organic solvent (E) is usually 50~90 mass %, preferably 60~85 matter
Measure %.
In addition, " solid constituent " in this specification refers to have in composition contained in adhesive composition except above-mentioned
Whole compositions beyond machine solvent (E), " solid component concentration " refers to above-mentioned solid constituent relative to the matter of adhesive composition 100
Measure % ratio.
[additive]
The adhesive composition of the present invention in the range of effect of the present invention is not damaged, may be used also in addition to mentioned component
Containing beyond antioxidant, light stabilizer, preventing metal corrosion agent, tackifier, plasticizer, crosslinking accelerator, above-mentioned (A)
(methyl) acrylic polymer and agent (リ ワ ー Network drug of doing over again) one or both of more than.
[modulation of polarizer adhesive composition]
The present invention adhesive composition can by using known method so far to (methyl) acrylic copolymer (A) with
Crosslinking agent (B) and the other compositions used as needed are mixed to modulate.It can enumerate for example to synthesis (methyl) third
Crosslinking agent (B) is blended in the polymer solution containing the polymer obtained by when olefin(e) acid analog copolymer (A) and as needed
And the other compositions used.
The adhesive composition of the present invention is applied to constitute fit purposes of the substrate with polarizer of liquid crystal cell.Especially
It is under thickness as low as 0.05~1.0mm or so the occasion of the glass plate of the liquid crystal cell of composition slimming, to be also suitable
In fit purposes of the substrate with polarizer.
The gel fraction of adhesive formed by the adhesive composition of the present invention is preferably in more than 40 mass %, more preferably
For 50~80 mass %, more preferably 55~70 mass %.Above-mentioned gel fraction is the bar for example recorded according to embodiment
Part is measured obtained numerical value to the adhesive gathered.
[polarizer adhesive phase]
The polarizer of the present invention is formed with adhesive phase by above-mentioned adhesive composition.By using the adhesive of the present invention
Composition, can form the adhesive phase with following storage modulus characteristic.
Storage modulus (G'1) at 23 DEG C of the adhesive phase of the present invention is preferably in more than 0.10MPa, more preferably 0.10
~0.20MPa, particularly preferably 0.10~0.15MPa；Storage modulus (G'2) at 85 DEG C is more excellent preferably in below 0.05MPa
Elect 0.01~0.04MPa, particularly preferably 0.01~0.03MPa as.
Storage modulus of the adhesive phase of the present invention at T DEG C of temperature is designated as G'T, at T+1 DEG C storage modulus note
For G'T+1When, temperature T preferably always meets G' when in the range of 23~50 DEG CT/G'T+1＜ 1.07, more preferably always meets 1
≤G'T/G'T+1≤1.06。
Above-mentioned storage modulus is that it is about 1.0mm's to make thickness for example, by above-mentioned adhesive phase is mutually repeatedly fitted
Layered product, by the value calculated to the dynamic viscoelastic spectrogram that the layered product is measured.
Storage modulus (G'1) at 23 DEG C causes the hard under the normal temperature of the adhesive phase of the present invention within the above range
Excellent, processability is improved.For example, when being cut to adhesive phase, can prevent adhesive attachment from cutting on blade
Or adhesive phase wire drawing the problems such as.
Storage modulus (G'2) at 85 DEG C causes the adhesive phase of the present invention to have in high temperature environments within the above range
Sufficient flexibility, it is thus possible to fully relax the stress produced by the thermal contraction of polarizer (change in size).Therefore, i.e.,
Make exposure in high temperature environments, can also mitigate the warpage of clung body, and be not susceptible to the fracture of adhesive phase, adhesive phase from
Stripping on polarizer.
G' is always met in the range of 23~50 DEG CT/G'T+1＜ 1.07 means the modulus change in the temperature range
It is small, deformation and the extrusion of adhesive phase can be suppressed.
By the adhesive phase that is formed of adhesive composition of the present invention from suppression polarizer distortion, cohesiveness, bonding force, again
From the viewpoint of fissility, gel fraction is preferably in more than 40 mass %, more preferably 50~80 mass %, more preferably
55~70 mass %.If gel fraction is within the above range, adhesive phase shows excellent durability.
The adhesive phase of the present invention can be obtained for example, by carrying out the cross-linking reaction in above-mentioned adhesive composition, specifically
It is to obtain by using crosslinking agent (B) (methyl) acrylic copolymer (A) crosslinking.
The formation condition of adhesive phase is for example as described below.The adhesive composition of the present invention is coated on supporting mass,
Temperature is different according to solvent species, but generally 50~150 DEG C, preferably at 60~100 DEG C carry out be usually 1~10 minute,
The drying of preferably 2~7 minutes and remove solvent, formed film.The thickness of dry coating is usually 5~75 μm, preferably 10
~50 μm.
Adhesive phase is preferably formed under the following conditions.The adhesive composition of the present invention is coated on supporting mass,
On the film formed under above-mentioned condition after stickup cover layer, at usual 5~60 DEG C, preferably 15~40 DEG C and usual 30~70%
Conserved in the environment of RH, preferably 40~70%RH usual more than 3 days, preferably 7~10 days.If in cooking conditions as described above
It is lower to be crosslinked, then crosslinked (network polymers) can be efficiently formed.
As the coating method of adhesive composition, known method can be used, for example, passes through spin-coating method, cutter painting method, roller
Coating, stick coating method, scraper coating, die coating method, gravure coating method etc. form the coating drying means of specific thickness.
As supporting mass and cover layer, it 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..
[polarizer bonding sheet]
The polarizer of the present invention has the adhesive phase formed by above-mentioned adhesive composition with bonding sheet.It is used as bonding
Piece, can enumerate for example only the double-sided adhesive sheet with above-mentioned adhesive phase, with base material and be formed at above-mentioned on base material two sides
The double-sided adhesive sheet of adhesive phase, the one side bonding sheet with base material and the above-mentioned adhesive phase being formed in base material one side, with
And these bonding sheets are pasted with the bonding sheet of the cover layer by lift-off processing on the face not contacted with base material of adhesive phase.
As base material and cover layer, it 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 of adhesive phase is identical with condition described in [polarizer adhesive phase] column.
The thickness of adhesive phase is usually 5~75 μm, preferably 10~50 μm from the viewpoint of bond properties is maintained.Base
The thickness of material and cover layer is not particularly limited, but usually 10~125 μm, preferably 25~75 μm.
[polarizer with adhesive phase]
The present invention the polarizer with adhesive phase have directly be layered at least one side of polarizer by this hair
The adhesive phase of bright adhesive composition formation.In addition, in this specification, " polarizer " is made with the implication comprising " polarizing coating "
With.
As polarizer, polarizing coating known so far can be used.Can enumerate for example polarizer in itself, with polarizer
With the multilayer film of polarizer diaphragm of the configuration on polarizer.In the present invention, due to above-mentioned adhesive phase with polarization
The mode that element directly connects is configured, can enumerate only on the one side of polarizer configure polarizer diaphragm composition, partially
Shake and do not configure the composition of polarizer diaphragm on element two sides.
As polarizer, it can enumerate and contain it in the film for for example making to be made up of polyvinyl alcohol resin after polarized component
Stretched film obtained from stretching.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, poly- second can be enumerated
Ketene acetal, EVAc it is saponified.As polarized component, such as iodine or dichroism dye can be enumerated
Material.
As polarizer diaphragm, the film being for example made up of thermoplastic resin can be enumerated., can example as thermoplastic resin
Citing such as tri acetyl cellulose celluosic resin, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, gather
Amide resin, polyimide resin, vistanex, (methyl) acrylic resin, cyclic polyolefin resin (borneol alkenes tree
Fat), polyarylate resin, polystyrene resin, polyvinyl alcohol resin and the two or more mixing in these resins
Thing.
The thickness of polarizer is usually 10~200 μm, preferably 50~100 μm.In the present invention, it can save to be formed inclined
The polarizer diaphragm shaken on element, it is thus possible to be thinned polarizer.
In the present invention, above-mentioned adhesive phase is formed in the way of directly connecting with polarizer.Glued as the band of the present invention
The polarizer of mixture layer, can enumerate for example following composition：Polarizer diaphragm, polarizer and above-mentioned adhesive phase layer successively
Folded composition；What above-mentioned adhesive phase, polarizer diaphragm, polarizer and above-mentioned adhesive phase were stacked gradually
Constitute；The composition that above-mentioned adhesive phase, polarizer and above-mentioned adhesive phase are stacked gradually.In these compositions, bonding
Above-mentioned cover layer is can also configure in oxidant layer as outermost layer.
The method for forming adhesive phase on polarizer surface is not particularly limited, and can enumerate and be existed using direct stick coating method etc.
The method for making it dry and cure after above-mentioned adhesive composition is coated with polarizer surface, the polarizer of the present invention is used and glued
The adhesive phase that closing piece has is transferred to the method for curing it behind polarizer surface.Dry and cooking conditions or gel point
Several scope etc. is identical with condition described in [polarizer adhesive phase] column.
The thickness of adhesive phase is usually 5~75 μm, preferably 10~50 μm in terms of dry film thickness.In addition, adhesive phase
Connect at least one side of polarizer with polarizer and formed, adhesive phase can be enumerated and be only formed at polarizer
Form, adhesive phase on one side are formed at the form on polarizer two sides.
Furthermore it is also possible to which such as protective layer, antiglare layer, phase separation layer, angle of visibility are laminated on above-mentioned polarizer improves layer
Deng the layer with other functions.
By the base that the polarizer of the invention with adhesive phase obtained in the manner described above is arranged on to liquid crystal cell
Liquid crystal cell is manufactured in plate surface.Here liquid crystal cell has liquid crystal layer by the construction clamped by two pieces of substrates.
Substrate with liquid crystal cell can enumerate such as glass plate.The thickness of substrate is usually 0.05~3mm, is preferably
0.2~1mm.In the present invention, by using above-mentioned adhesive composition, it is directly laminated even in adhesive phase in polarizer
On occasion under, can also suppress the warpage of polarizer and substrate.Therefore, above-mentioned adhesive composition is small even in substrate thickness
Occasion under (for example：Below 1mm, preferably 0.2~1mm), it can also be suitably used for fitting for polarizer and substrate.
[embodiment]
Below, more specific description is carried out to the present invention based on embodiment, but the invention is not restricted to these embodiments.Below
In the record of embodiment etc., unless otherwise instructed, " part " expression " mass parts ".
[GPC]
For (methyl) acrylic copolymer, weight is obtained by gel permeation chromatography (GPC method), with following conditions equal
Molecular weight (Mw) and number-average molecular weight (Mn).
Determine device：HLC-8320GPC (TOSOH Co., Ltd (East ソ ー (strain)) is produced)
The composition of GPC posts：Following 4 pedestals (all being produced by TOSOH Co., Ltd)
(1) TSKgel HxL-H (guard column)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
Flow velocity：1.0 ml/min
Column temperature：40℃
Sample solution concentration：1.5% (w/v) (being diluted with tetrahydrofuran)
Mobile phase solvent：Tetrahydrofuran
Polystyrene standard converts
[synthesis example 1]
39 parts of methyl-props are added into the reaction unit for possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe
Olefin(e) acid dodecyl ester, 56 parts of 2-Ethylhexyl Methacrylates, 5 parts of HEMAs and 100 parts of ethyl acetate
Solvent, imports nitrogen while being warming up to 80 DEG C.Then, 0.1 part of 2,2'- azodiisobutyronitrile is added, in nitrogen atmosphere
In the polymerisation that 6 hours are carried out at 80 DEG C.After reaction terminates, it is diluted with ethyl acetate, obtained solid component concentration is
30 mass % polymer solution.Resulting (methyl) acrylic copolymer A1 weight average molecular weight (Mw) is 910,000, point
Son amount distribution (Mw/Mn) is 6.2.
[synthesis example 2~5]
In addition to monomer component used in by polymerisation is changed to content described in table 1, according to conjunction
Synthesized into the identical mode of example 1, the polymer solution that solid component concentration is 30 mass % is made.As a result it is shown in table 1.
[table 1]
[embodiment 1]
(1) modulation of adhesive composition
By the polymer solution obtained in synthesis example 1 (solid component concentration is 30 mass %), relative to institute in the solution
100 parts of (methyl) the acrylic copolymer A1 (solid constituent amount) contained is 0.2 part (solid constituent amount) as isocyanic acid
" TD-75 " (solid constituent is 75 mass %, ethyl acetate solution) of Soken Chemical ＆ Engineering Co., Ltd.'s manufacture of ester compounds and 0.2
" KBM-403 " (solid that part manufactures as Shin-Etsu Chemial Co., Ltd's (SHIN-ETSU HANTOTAI's chemical industry (strain)) of silane coupler
Composition is 100 mass %) mixed, obtain adhesive composition.
(2) making of bonding sheet
In the polyethylene terephthalate film (PET film) Jing Guo lift-off processing, the adhesive that above-mentioned (1) is obtained
Scraper for coating is used after composition froth breaking, is dried 3 minutes at 90 DEG C, the film that dry film thickness is 20 μm is formed.In the upper of film
The PET film fitted again by lift-off processing on the reverse side for the sticking veneer for stating PET film, stands to enter for 7 days under 23 DEG C/50%RH environment
After row curing, obtain with by bonding sheet of the thickness clamped by 2 pieces of PET films for 20 μm of adhesive phase.
(3) making of the polarizer with adhesive phase
In the polyethylene terephthalate film (PET film) Jing Guo lift-off processing, the adhesive that above-mentioned (1) is obtained
Scraper for coating is used after composition froth breaking, is dried 3 minutes at 90 DEG C, the sheet material for 20 μm of film with dry film thickness is formed.
So that the coated surface of the sheet material with by the polyvinyl alcohol film as polarizer and the triacetyl as polarizer diaphragm
The mode that the polyvinyl alcohol film one side for the double-deck polarizer for constituting (thickness is 60 μm) that cellulose membrane is constituted connects is fitted,
Stand under conditions of the 23 DEG C/50%RH after being cured within 7 days, it is 20 μm of adhesive phase, inclined to obtain with PET film, thickness
Shake the polarizer with adhesive phase of element and polarizer diaphragm.
[embodiment 2, comparative example 1~3]
Except the polymer solution in embodiment 1 is changed to obtain in synthesis example 2 polymer solution, will blend and constitute
Be changed in table 2 beyond described content, obtain according to the same manner as in Example 1 adhesive composition, bonding sheet and
Polarizer with adhesive phase.
[evaluation]
[gel fraction]
The adhesive that about 0.1g is gathered in the bonding sheet obtained from embodiment comparative example is placed in sample bottle, is added
Shake 4 hours, the content of the sample bottle was carried out with 200 purposes stainless steel wire netting after 30mL ethyl acetate then
Filter, dry weight is determined after the drying for carrying out 2 hours to the residue on wire netting at 100 DEG C.Bonding is obtained according to following formula
The gel fraction of agent.
Gel fraction (%)=(dry weight/adhesive collection weight) × 100 (%)
[storage modulus]
In the bonding sheet that will be obtained in embodiment comparative example thickness for 20 μm adhesive phase 23 DEG C/50%RH ring
Mutually repeatedly laminating, is handled 20 minutes in the autoclave of 50 DEG C/5 atmospheric pressure under border, and the adhesive that thickness is 1.0mm is made
Layer." the Physica MCR300 ", according to dynamic based on JIS K7244 manufactured by using Anton Paar company (Anton Paar)
State determination of viscoelasticity method (condition be temperature range -40~160 DEG C, 3.67 DEG C/min of programming rate, frequency 1Hz) is determined
The thickness for 1.0mm adhesive phase viscoplasticity spectrogram, temperature be 23 DEG C and 85 DEG C at storage modulus, 23~50 DEG C
In the range of G'T/G'T+1Maximum.
[measure of bonding force]
By obtained in embodiment comparative example with adhesive phase polarizer (by PET film/adhesive phase/polarizer/
The layered product that polarizer diaphragm is constituted) 70mm × 25mm size is cut into, test film is made.By PET film from test film
It is upper peel off, with laminating roll by the layered product being made up of adhesive phase/polarizer/polarizer diaphragm so that adhesive phase with
The mode that glass plate connects is conformed on the one side for the glass plate that thickness is 2mm.By resulting layered product adjust to 50 DEG C/
Kept for 20 minutes in the autoclave of 5 atmospheric pressure.Then, after being placed 1 hour under 23 DEG C/50%RH environment, along relative
Polarizer end is pullled with the speed of 300 mm/mins for 90 ° of direction in glass pane surface, bonding force (stripping is determined
From intensity).
[moisture-vapor transmission]
Moisture-vapor transmission is determined with the following methods according to JIS Z0208.According to in " making of (2) bonding sheet " column
Described method identical method makes the bonding sheet for 50 μm of adhesive phase with thickness.By PET film from the bonding sheet
It is upper to peel off, non-woven fabrics (resulting layered product be referred to as " sheet material A ") of being fitted on the two sides of adhesive phase, matching moisture vapor transmission cup
Diameter is cut.To 10g calcium chloride is added in moisture vapor transmission cup (internal diameter is 60mm), set the sheet material A cut out, rubber washer,
Cover plate, is fixed with fixture.Under the conditions of 40 DEG C/90%RH constant temperature and humidity, input is provided with sheet material A etc. moisture vapor transmission cup, and 24 is small
When after take out moisture vapor transmission cup, the weight to moisture vapor transmission cup is weighed (initial weight).Moisture vapor transmission cup after weighing is put back to 40 DEG C/90%
Under conditions of RH, weighed every 24 hours.When the scope that quality at every 24 hours is increased up within 5%, by most
Mass change amount afterwards, measuring interval calculate moisture-vapor transmission using following formula.
Moisture-vapor transmission [grams m2/ day]=240 × M/T × S
M：Experiment proceeds to the last mass incremental (mg) for weighing interval twice
T：Experiment proceeds to last weighing interlude (hour) twice
S：Transmission area (cm2)
[endurancing (experiment of heat resistance humidity resistance)]
By obtained in embodiment comparative example with adhesive phase polarizer (by PET film/adhesive phase/polarizer/
The layered product that polarizer diaphragm is constituted) 150mm × 250mm size is cut into, test film is made.By PET film from experiment
On piece peel off, with laminating roll by the layered product being made up of adhesive phase/polarizer/polarizer diaphragm so that adhesive phase
The mode connected with glass plate is conformed on the one side for the glass plate that thickness is 0.5mm.By resulting layered product adjust to
Kept for 20 minutes in the autoclave of 50 DEG C/5 atmospheric pressure, breadboard is made.Two pieces of identical breadboards are made.By above-mentioned experiment
Plate is that (heat resistance) or temperature are that 60 DEG C/humidity is that (humidity resistance) is placed under conditions of 90%RH under conditions of 80 DEG C in temperature
500 hours, observation evaluation is carried out to foaming, the generation for tilting and peeling off according to following benchmark.
AA：Not it was observed that the bad order situation such as foaming, tilting, stripping
BB：It was observed that the bad order situation such as a small amount of foaming, tilting, stripping
CC：It was observed that the bad order situation such as obvious foaming, tilting, stripping
[warpage (bending) experiment]
By obtained in embodiment comparative example with adhesive phase polarizer (by PET film/adhesive phase/polarizer/
The layered product that polarizer diaphragm is constituted) size of 35mm × 400mm (stretching direction of principal axis) is cut into, test film is made.Will
PET film is peeled off from test film, the layered product that will be made up of with laminating roll adhesive phase/polarizer/polarizer diaphragm
Thickness is conformed in the way of adhesive phase is connected with glass plate as on the one side of 0.7mm 40mm × 410mm glass plate.
After resulting layered product is placed 24 hours under 23 DEG C/50%RH environment, kept for 72 hours in 60 DEG C of stove.Will
Unilateral end is fixed on metope perpendicular to the ground, and the amount tilted with ruler to opposite side extremities is measured.According to
Lower benchmark is observed warpage (bending).
AA：The tilting of end is in below 3mm
BB：The tilting of end is more than 3mm and less than 5mm
CC：The tilting of end is in more than 5mm
[processability (cutting property)]
The bonding that will be obtained using Thomson bicker with 50mm × 50mm Thomson blade in embodiment comparative example
Piece cuts into 30 pieces.Shape after cutting immediately to end is observed, by paste-extruded or end ulceration at one in 30 pieces, viscous
Also unobserved situation is determined as AA to the defect of mixture layer, it will be observed that the situation of drawbacks described above is determined as CC.
[bonding morphotropism]
10 pieces of stacking cuts into the polarizer with adhesive phase obtained in 100mm × 100mm embodiment comparative example,
Impose and placed 24 hours after 1kg heavy burden thereon, the extrusion of adhesive phase is visually observed according to following benchmark.
AA：Not it was observed that adhesive phase is extruded
BB：It was observed that a small amount of adhesive phase extrusion
CC：It was observed that obvious adhesive phase extrusion
[table 2]
As a result, as formed (methyl) acrylic copolymer monomer, (1) as shown in the Examples, with above-mentioned spy
In example of the certainty ratio using monomer (a1) and monomer (a2), durability, warpage suppress, processability and bonding non-deformable are excellent
Different, (2) are durable in example not with above-mentioned special ratios using monomer (a1) and monomer (a2) as shown in comparative example 1,2
Property, warpage suppress, processability or bonding non-deformable it is poor, (3) as shown in comparative example 3, without using alkyl methacrylate
And use in the example of alkyl acrylate, moisture-vapor transmission height (hydrophobicity is low), the humidity resistance of adhesive or warpage suppression
System is poor.
Claims (5)
1. a kind of polarizer adhesive composition, it is used to form the adhesive phase directly connected with polarizer, described inclined
The piece adhesive composition that shakes contains：
(A) by including glass transition temperature first less than -30 DEG C of the 30 mass % less than 90 mass % homopolymer
Base alkyl acrylate (a1), 10 mass % less than 70 mass % homopolymer glass transition temperature at -30 DEG C
More than alkyl methacrylate (a2) and contain cross-linking functional group's more than 0 mass % and in below 10 mass %
(methyl) acrylic copolymer that the monomer component copolymerization of monomer (a3) is obtained, and
(B) crosslinking agent.
2. a kind of polarizer adhesive phase, it is formed as the adhesive composition described in claim 1.
3. polarizer adhesive phase as claimed in claim 2, it is characterised in that
Storage modulus at 23 DEG C in more than 0.10MPa,
Storage modulus at 85 DEG C in below 0.05MPa, and
Storage modulus at T DEG C of temperature is designated as G'T, the storage modulus at T+1 DEG C is designated as G'T+1When, temperature T is at 23~50 DEG C
In the range of when always meet G'T/G'T+1＜ 1.07.
4. a kind of polarizer bonding sheet, it has the adhesive phase described in Claims 2 or 3.
5. a kind of polarizer with adhesive phase, it has the claim 2 being directly layered at least one side of polarizer
Or the adhesive phase described in 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-224411 | 2014-11-04 | ||
| JP2014224411 | 2014-11-04 | ||
| PCT/JP2015/078304 WO2016072199A1 (en) | 2014-11-04 | 2015-10-06 | Adhesive composition for polarizing plates and polarizing plate having adhesive layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107148586A true CN107148586A (en) | 2017-09-08 |
Family
ID=55908927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580057978.4A Pending CN107148586A (en) | 2014-11-04 | 2015-10-06 | Polarizer adhesive composition and the polarizer with adhesive phase |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2016072199A1 (en) |
| KR (1) | KR20170082517A (en) |
| CN (1) | CN107148586A (en) |
| TW (1) | TW201621017A (en) |
| WO (1) | WO2016072199A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895522A (en) * | 2022-11-18 | 2023-04-04 | 江西塔益莱高分子材料有限公司 | Adhesive applied to polaroid interlayer and polaroid with same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7007100B2 (en) * | 2017-04-10 | 2022-02-10 | 綜研化学株式会社 | Adhesive composition and adhesive sheet |
| JP7253533B2 (en) * | 2018-03-27 | 2023-04-06 | 綜研化学株式会社 | Adhesive tape |
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|---|---|---|---|---|
| JP2008291071A (en) * | 2007-05-23 | 2008-12-04 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition and stacked body |
| JP2010048889A (en) * | 2008-08-19 | 2010-03-04 | Sumitomo Chemical Co Ltd | Method for producing retardation film |
| CN101688098A (en) * | 2007-07-11 | 2010-03-31 | 综研化学株式会社 | Pressure-sensitive adhesive composition for polarizing plates and polarizing plate having pressure-sensitive adhesive layer |
| JP2010187316A (en) * | 2009-02-13 | 2010-08-26 | Mitsubishi Electric Corp | Automated meter reading wireless system and wireless communication terminal device used therefor |
| JP2012128099A (en) * | 2010-12-14 | 2012-07-05 | Saiden Chemical Industry Co Ltd | Polarizing plate with adhesive layer and method for manufacturing the same |
| CN103492516A (en) * | 2011-05-02 | 2014-01-01 | 日东电工株式会社 | Adhesive, adhesive layer, and adhesive sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05297220A (en) * | 1992-04-20 | 1993-11-12 | Nippon Synthetic Chem Ind Co Ltd:The | Elliptically polarizing plate |
| JP6102331B2 (en) * | 2013-02-22 | 2017-03-29 | 大日本印刷株式会社 | Retardation film with adhesive layer and optical member using the same |
-
2015
- 2015-10-06 JP JP2016557507A patent/JPWO2016072199A1/en active Pending
- 2015-10-06 CN CN201580057978.4A patent/CN107148586A/en active Pending
- 2015-10-06 KR KR1020177011075A patent/KR20170082517A/en not_active Application Discontinuation
- 2015-10-06 WO PCT/JP2015/078304 patent/WO2016072199A1/en active Application Filing
- 2015-10-28 TW TW104135383A patent/TW201621017A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008291071A (en) * | 2007-05-23 | 2008-12-04 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition and stacked body |
| CN101688098A (en) * | 2007-07-11 | 2010-03-31 | 综研化学株式会社 | Pressure-sensitive adhesive composition for polarizing plates and polarizing plate having pressure-sensitive adhesive layer |
| JP2010048889A (en) * | 2008-08-19 | 2010-03-04 | Sumitomo Chemical Co Ltd | Method for producing retardation film |
| JP2010187316A (en) * | 2009-02-13 | 2010-08-26 | Mitsubishi Electric Corp | Automated meter reading wireless system and wireless communication terminal device used therefor |
| JP2012128099A (en) * | 2010-12-14 | 2012-07-05 | Saiden Chemical Industry Co Ltd | Polarizing plate with adhesive layer and method for manufacturing the same |
| CN103492516A (en) * | 2011-05-02 | 2014-01-01 | 日东电工株式会社 | Adhesive, adhesive layer, and adhesive sheet |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895522A (en) * | 2022-11-18 | 2023-04-04 | 江西塔益莱高分子材料有限公司 | Adhesive applied to polaroid interlayer and polaroid with same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016072199A1 (en) | 2016-05-12 |
| JPWO2016072199A1 (en) | 2017-08-31 |
| KR20170082517A (en) | 2017-07-14 |
| TW201621017A (en) | 2016-06-16 |
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