CN102333838A - Acrylic adhesive, adhesive sheet for polarizing film that uses the same, and adhesive polarizing film - Google Patents
Acrylic adhesive, adhesive sheet for polarizing film that uses the same, and adhesive polarizing film Download PDFInfo
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- CN102333838A CN102333838A CN2010800095783A CN201080009578A CN102333838A CN 102333838 A CN102333838 A CN 102333838A CN 2010800095783 A CN2010800095783 A CN 2010800095783A CN 201080009578 A CN201080009578 A CN 201080009578A CN 102333838 A CN102333838 A CN 102333838A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
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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
-
- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
Abstract
Disclosed is an acrylic adhesive that features superior durability and light leakage prevention, even under harsh ambient use conditions. Said acrylic adhesive contains constituents (A) through (C): (A) an acrylic polymer obtained by copolymerizing the following monomers: (a-1) a (meth)acrylic acid ester, (a-2) a monomer containing an aromatic ring, and (a-3) a monomer containing a functional group, wherein the content of the monomer (a-2) is 3-50% by mass with respect to the total quantity of the monomers (a-1) and (a-2), (B) a polyfunctional isocyanate compound (C) an aromatic ring-containing spacer compound with an isocyanate group-reactive functional group, wherein the equivalence ratio of the isocyanate group-reactive functional groups in constituent (C) with respect to the isocyanate groups in constituent (B) is 0.01-0.60, and the photoelastic coefficient of the adhesive layer formed thereby is not less than 100 10-12 m2/N and not more than 1000 10-12 m2/N.
Description
Technical field
The present invention relates to a kind of tackiness agent, in more detail, relate to and a kind ofly can reduce double refraction through the control photoelastic coefficient with optical compensation function, thus acrylic adhesives that prevents light leak effectively and the polarizing film that uses this acrylic adhesives.
Background technology
Liquid crystal cell has liquid crystal material and is clamped in two structures between the substrate, and on this substrate surface, is fitted with Polarizer through binder layer.In recent years; Liquid crystal cell enlarges in purposes such as the indicating meter of vehicle boarded usefulness, outdoor gauger usefulness, PC, televisors, owing to accompany therewith, it is too harsh that environment for use also becomes; Therefore, the high-durability that requires employed tackiness agent to have can not to peel off or float etc.
In addition, under this too harsh environment for use, because the internal stress that produces in the Polarizer, the optical transmission rate will change, and be easy to generate light leak thereby become.For example; Though in the liquid crystal cell of TN pattern; Polarizer is configured with the mode that becomes 45 °/135 ° cross-polarized light state, but because the internal stress that produces in the Polarizer, thereby produce periphery that expose, the so-called frame light leakage phenomena of light from picture.Particularly be accompanied by the maximization of indicating meter in recent years, the problem that is declined to become of the display quality that causes owing to above-mentioned light leak.
In order to address the above problem; A kind of following technology is disclosed; Promptly; The isocyanates linking agent acrylate adhesive this, that have the linking agent of positive intrinsic degree of birefringence that contains just like have aromatic ring through use; Or use contain the monomer that for example has aromatic rings such as phenyl ring etc., have the monomer of positive intrinsic degree of birefringence and a tackiness agent of the multipolymer of acrylic ester monomer separately with negative intrinsic degree of birefringence, thereby the double refraction of adjustment tackiness agent and prevent the technology (special permission document 1 and 2) of light leak.
But; Because under general situation; Therefore the positive bigger structure of intrinsic double refraction has the higher molecular structure of planarity, and demonstrates higher crystallinity, when comprising the linking agent higher naphthalene structure of this planarity etc., that have higher positive intrinsic degree of birefringence with the excessive interpolation of degree of eliminating the light leakage; To worsen with the compatible of binder polymer, thus exist cause that the albefaction of filming, bounding force descend or with days through peeling off of producing etc.In addition; Even in monomeric copolymerization; A large amount of when having the monomer of positive intrinsic degree of birefringence when using; Thereby also will there be copolymerization property variation operation property deterioration or owing to the rising of the second-order transition temperature of binder polymer causes the hardening of filming, thereby cause the possibility of the decline of bounding force.
TP formerly
Patent documentation
Special permission document 1: TOHKEMY 2008-144125 communique
Special permission document 2: TOHKEMY 2008-144126 communique
Summary of the invention
Invent problem to be solved
Therefore, problem of the present invention is, even provide a kind of under hot and humid condition, also possesses the high-durability that can not peel off or float etc., and can when keeping excellent adhesion performance, prevent the tackiness agent of light leak effectively.
The inventor has carried out deep investigation in order to solve above-mentioned problem; The result finds; Form and polyfunctional isocyanate's cooperation etc. through the monomer in the acrylic polymers; The photoelastic coefficient of the tackiness agent after crosslinked is adjusted to is in certain scope,, thereby can access high-durability and excellent bond properties again through using the compartmentation compound (spacer compound) with the isocyanic ester radical reaction; And reduce the double refraction that produces owing to inner stress significantly, thereby accomplished the present invention.
Promptly; The present invention is a kind of acrylic adhesives, contains following compositions (A) to (C), wherein; (A) following acrylic polymers; That is, the monomer, (a-3) that following monomer (a-1) (methyl) propenoate, (a-2) are contained aromatic ring contain the monomer copolymerization of functional group and obtain, and monomer (a-2) is 3～50 quality % with respect to the content of monomer (a-1) and total amount (a-2); (B) polyfunctional isocyanate's compound; (C) has the compartmentation compound that contains aromatic ring of NCO reactive functional groups; Acrylic adhesives is characterised in that; NCO reactive functional groups in the composition (C) is 0.01～0.60 with respect to the equivalence ratio of the NCO in the composition (B), and the photoelastic coefficient of the binder layer that forms thus is 100 * 10
-12m
2/ N is above and 1000 * 10
-12m
2Below/the N.
In addition, the present invention is that a kind of polarizing film is used adhesive sheet, and it forms through the binder layer that is formed by aforesaid propylene acids tackiness agent is set at least one face of supporting mass.
And the present invention is a kind of adhesion type polarizing film, and it forms through the binder layer that is formed by aforesaid propylene acids tackiness agent is set at least one face of polarizing film.
Acrylic adhesives of the present invention can reduce the double refraction that causes owing to the internal stress that produces in the Polarizer, thereby has prevented light leak effectively.In addition,, also can not peel off or float etc., thereby weather resistance be also excellent even under hot and humid environment.
Embodiment
The acrylic polymers of the employed composition of tackiness agent of the present invention (A) contains the monomer of aromatic ring and monomer copolymerization that monomer (a-3) contains functional group obtains to major general's monomer (a-1) (methyl) propenoate, monomer (a-2).
As (methyl) propenoate of monomer (a-1), can illustration go out alkyl acrylate, alkyl methacrylate, vinylformic acid alcoxyl base ester, methylacrylic acid alkoxy ester, vinylformic acid alkylene diol ester, methylacrylic acid alkylene glycol ester etc.
As alkyl acrylate, can enumerate out methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, the just own ester of vinylformic acid, the positive heptyl ester of vinylformic acid, vinylformic acid n-octyl, ethyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, dodecylacrylate, IBOA, cyclohexyl acrylate etc.
As alkyl methacrylate, can enumerate out TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methylacrylic acid, methacrylic tert-butyl acrylate, methylacrylic acid n-pentyl ester, methacrylic isoamyl valerate, the just own ester of methylacrylic acid, the positive heptyl ester of methylacrylic acid, n octyl methacrylate, methylacrylic acid-2-ethylhexyl, nonyl methacrylate, decyl-octyl methacrylate, dodecylacrylate, isobornyl methacrylate, cyclohexyl methacrylate etc.
As vinylformic acid alcoxyl base ester, can illustration go out vinylformic acid-2-methoxyl group ethyl ester, vinylformic acid-2-ethoxy ethyl ester, vinylformic acid-2-methoxyl group propyl ester, vinylformic acid-3-methoxyl group propyl ester, vinylformic acid-2-methoxyl group butyl ester, vinylformic acid-4-methoxyl group butyl ester etc.
As the methylacrylic acid alkoxy ester, can illustration go out methylacrylic acid-2-methoxyl group ethyl ester, methylacrylic acid-2-ethoxy ethyl ester, methylacrylic acid-2-methoxyl group propyl ester, methylacrylic acid-3-methoxyl group propyl ester, methylacrylic acid-2-methoxyl group butyl ester, methylacrylic acid-4-methoxyl group butyl ester etc.
As vinylformic acid alkylene diol ester, can enumerate out vinylformic acid glycol ester, polyalkylene glycol acrylate ester, vinylformic acid propylene glycol ester, vinylformic acid W 166 ester etc.
As methylacrylic acid alkylene glycol ester, can enumerate out methacrylic acid glycol ester, methylacrylic acid macrogol ester, methacrylic acid propylene glycol ester, methylacrylic acid W 166 ester etc.
Wherein, When preferred use in whole monomers (a-1) be more than the 60 quality % (below; Only with " % " expression) the alkyl acrylate of carbonatoms 4～8; When more preferably being used for the alkyl acrylate of the above carbonatoms 4～8 of 80 quality %, then copolymerization property is good, thereby the bounding force of resulting tackiness agent and snappiness are more excellent.Particularly can preferably use n-butyl acrylate, ethyl acrylate.
As the monomer that contains aromatic ring of above-mentioned monomer (a-2), can illustration go out methacrylic acid aryl esters such as aryl acrylates such as benzyl acrylate, vinylformic acid phenoxy ethyl, phenyl acrylate, vinylformic acid naphthalene ester or benzyl methacrylate, methylacrylic acid phenoxy ethyl, phenyl methacrylate, methylacrylic acid naphthalene ester etc.
In the composition of composition (A), content above-mentioned relatively monomer (a-1) and total amount (a-2), monomer (a-1) is 50～97%, the content of monomer (a-2) is 3～50%.More preferably, (a-1) content is 50～90%, the content of (a-2) is 10～50%.In addition, in that only to use aromatic ring be monocyclic monomer with as monomer (a-2) time, the content of monomer (a-2) is 5～50%, more preferably 15～50%.On the other hand, only use aromatic ring as the heterocyclic monomer with as monomer (a-2) time, the content of monomer (a-2) is 3～30%, more preferably 10～30%.And; And to use aromatic ring be monocyclic monomer and during as the heterocyclic monomer; The aggregate value that preferably content of relative monomer (a-1) and the content total amount, monocyclic monomers (a-2) and heterocyclic monomer multiply by between the value that obtains after 1.67 is adjusted to; Be in 3～50% the scope, further be preferably in 10～50% the scope of being adjusted to.
As the monomer that contains functional group of above-mentioned monomer (a-3), can illustration go out to contain carboxyl monomer, contain hydroxyl monomer, contain amino monomer, contain carboxamido-group monomer, contain the monomer of epoxy group(ing) etc.
As the monomer that contains carboxyl, can illustration go out vinylformic acid, methylacrylic acid, senecioate-carboxyl ethyl ester, methylacrylic acid-β-carboxyl ethyl ester, vinylformic acid-5-carboxyl pentyl ester, mono succinate acryloxy ethyl ester, mono succinate methacryloxy ethyl ester, ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates, methylene-succinic acid, Ba Dousuan, fumaric acid, toxilic acid etc.
As the monomer that contains hydroxyl, can illustration go out vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacrylate, vinylformic acid-2-hydroxypropyl acrylate, methylacrylic acid-2-hydroxypropyl acrylate, vinylformic acid-3-hydroxypropyl acrylate, methylacrylic acid-3-hydroxypropyl acrylate, vinylformic acid-4-hydroxy butyl ester, methylacrylic acid-4-hydroxy butyl ester, 2-hydroxy-3-chloropropyl acrylate, methylacrylic acid 2-hydroxyl-3-chlorine propyl ester, vinylformic acid-2-hydroxyl-3-phenoxy propyl ester, methylacrylic acid-2-hydroxyl-3-phenoxy propyl ester etc.
As containing amino monomer, can illustration go out vinylformic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, vinylformic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate etc.
As the monomer that contains carboxamido-group, can illustration go out acrylic amide, USAF RH-1, N hydroxymethyl acrylamide, N-methylol methacrylamide etc.
As the monomer that contains epoxy group(ing), can illustration go out vinylformic acid glycidyl ether, methyl propenoic acid glycidyl ether, acrylic acid-2-ethyl glycidyl ether, methylacrylic acid-2-glycidyl ether etc.
Because this contains the monomer (a-3) of functional group; As after composition (B) the polyfunctional isocyanate compound stated cross-linking set and play a role; Therefore in above-mentioned substance, as cross-linking set, be preferably the reactive good monomer that contains carboxyl, contain the monomer of hydroxyl; Particularly, be preferably the monomer that contain hydroxyl reactive higher with composition (B).And, to improve reactive purpose of NCO and hydroxyl, can contain the monomeric while of hydroxyl in use, and with the monomer that contains carboxyl.
Relatively add up to the monomer (a-1) and the monomer (a-2) of 100 mass parts (below, only represent with " part "), above-mentioned monomer (a-3) preferably uses 1～30 part.In addition, the content of the monomer (a-3) in whole monomers of constituent (A) is preferably 0.1～15%.As monomer (a-3), the preferred content when using the monomer contain hydroxyl is 1～10% with respect to whole formation monomers of composition (A), and the preferred content when using the monomer that contains carboxyl is 0.1～5%.Even when also using the monomer that contains hydroxyl and containing the monomer of carboxyl, also preferably be made as same content respectively.
In composition (A), except that above-mentioned monomer (a-1) to (a-3), can cooperate can with the monomer (a-4) of their copolymerization.As such monomer, can illustration go out vinyl acetate between to for plastic, vinylbenzene, alpha-methyl styrene, allyl acetate, vinyl cyanide etc.Monomer (a-4) is preferably, and monomer (a-1) and monomer (a-2) with respect to adding up to 100 parts cooperate 0～10 part.
Though the acrylic polymers of composition (A) can be through known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerizations; Above-mentioned monomer (a-1)～(a-3) is obtained with (a-4) copolymerization of using as required; But wherein; Solution polymerization and can reduce impurity because the adjusting of molecular weight is easier to, thereby preferred.
The acrylic polymers of the composition that obtains thus (A) is preferably, and weight-average molecular weight (Mw) is 600,000～3,000,000.When weight-average molecular weight less than 600,000 the time, the weather resistance when damp and hot will descend, thus peel off sometimes or float, the adhesive residue when reprocessing, and greater than 3,000,000 o'clock, operation property worsens sometimes.In addition, in this manual, weight-average molecular weight (Mw) is the weight-average molecular weight of being measured through the gel permeation chromatography of putting down in writing among the embodiment (GPC) with the polystyrene standard conversion.
In addition, the acrylic polymers of composition (A) is preferably, and second-order transition temperature is below 0 ℃, more preferably below-20 ℃.When second-order transition temperature is higher than 0 ℃, the adaptation of resulting tackiness agent and base material or the snappiness of binder layer will descend, thereby peeling off or float from base material taken place sometimes.In addition, in this manual, second-order transition temperature is the value of being calculated by following FOX formula.
(FOX formula)
1/Tg＝Wa/Tga+Wb/Tgb+…
Tg: the second-order transition temperature of multipolymer
Tga, Tgb ...: monomer a, monomer b ... The second-order transition temperature of homopolymer
Wa, Wb ...: monomer a, monomer b ... Wt ratio
It is crosslinked that the polyfunctional isocyanate of the employed composition of tackiness agent of the present invention (B) has crosslinked composition (A) acrylic polymers, and the function of adjustment photoelastic coefficient.As this polyfunctional isocyanate; Can enumerate out the isocyanate-monomer of toluenediisocyanate, chlorine phenylene vulcabond, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, eylylene diisocyanate, diphenylmethanediisocyanate, hydrogenant diphenylmethanediisocyanate etc. and make polyvalent alcohol addition such as these isocyanate-monomers and TriMethylolPropane(TMP) and polyalcohol modified isocyanate compound or isocyanate compound, biuret type compound and carry out isocyanic ester addition reaction, the carbamate prepolymer type with polyether glycol or polyester polyol, acrylic polyol, polybutadiene polyol, TR 301 polyvalent alcohol etc.; Wherein, Polyalcohol modified isocyanate compound, with after state the compartmentation compound that contains aromatic ring with NCO reactive functional groups reactive good of composition (C); And the acrylic polymers of composition (A) is orientated easily, thereby is preferably using aspect the control photoelastic coefficient.
Composition (B) is preferably, and the composition with respect to 100 parts (A) acrylic polymers uses 0.1～10 part.
The compartmentation compound that contains aromatic ring with NCO reactive functional groups of the employed composition of tackiness agent of the present invention (C) (below be sometimes referred to as " the compartmentation compound that contains aromatic ring "); With polyfunctional isocyanate's compound reaction of composition (B), and has the function that makes acrylic polymers orientation and adjustment photoelastic coefficient easily.
The compartmentation compound that this contains aromatic ring is the compartmentation compound that contains NCO reactive functional groups such as aromatic ring and the above hydroxyl of two senses, amino, carboxyl, carboxamido-group, compound that particularly can be below the illustration.
By two represented functional glycol of following formula 1～30, that is, 2,3-pyridine glycol (formula 1), N; N '-two (salicylidene)-1,3-tn (formula 2), 2-phenyl-1, ammediol (formula 3), N, N '-two (salicylidene)-1; 4-tetramethylenediamine (formula 4), N, N '-two (salicylidene)-1,6-hexanediamine (formula 5), N, N '-two (salicylidene) quadrol (formula 6), N; N '-two salicyl-1,2-phenylenediamine (formula 7), 3-phenoxy-1,2-Ucar 35 (formula 8), 4-benzyloxy-1,3 butylene glycol (formula 9), 2-benzyloxy-1; Ammediol (formula 10), 4,4 '-'-biphenyl diphenol (formula 11), 2,2 '-'-biphenyl diphenol (formula 12), phenyl Resorcinol (formula 13), 2,2 '-dihydroxyl-4-methoxy benzophenone (formula 14), 1; 3-dihydroxy naphthlene (formula 15), 1,4-dihydroxy naphthlene (formula 16), 1,5-dihydroxy naphthlene (formula 17), 1,6-dihydroxy naphthlene (formula 18), 1; 7-dihydroxy naphthlene (formula 19), 2,3-dihydroxy naphthlene (formula 20), 2,7 dihydroxy naphthalene (formula 21), 1,4-xylyl alcohol (formula 22), diethylstilbestrol (formula 23), 2; 2 '-dihydroxyl ditan (formula 24), 2,6-dihydroxyl quinoline (formula 25), 2,3-dihydroxyl quinoxaline (formula 26), 2,2 '-dihydroxybiphenyl ether (formula 27), 2; 5-dihydroxyl-1,4-benzophenone (formula 28), two (4-hydroxy phenyl) thioether (formula 29), 2,6-pyridine dimethanol (formula 30) etc.;
[Chemical formula 1]
By two represented sense diamines of following formula 31～61, that is, and (±)-1,2-diphenyl ethylene diamine (formula 31), (11R, 12R)-9,10-dihydro-9; 10-ethylene anthracene-11,12-diamines (formula 32), (11R, 12R)-9,10-dihydro-9,10-ethylene anthracene-11,12-diamines (formula 33), 4; 5-dimethyl--1,2-phenylenediamine (formula 34), (1R, 2R)-(+)-1,2-diphenyl ethylene diamine (formula 35), (1R, 2R)-1,2-two (2; 4, the 6-trimethylphenyl) quadrol (formula 36), (1R, 2R)-1, two (4-p-methoxy-phenyl) quadrols (formula 37) of 2-, (1S, 2S)-(-)-1,2-diphenyl ethylene diamine (formula 38), 1; 3-phenylenediamine (formula 39), 1,4-phenylenediamine (formula 40), 1,2-phenylenediamine (formula 41), N, N '-diacetyl-1,4-phenylenediamine (formula 42), N, N '-phenylbenzene-1; 4-phenylenediamine (formula 43), N, N '-diphenyl ethylene diamine (formula 44), (1S, 2S)-1, two (2,4, the 6-trimethylphenyl) quadrols (formula 45), 2 of 2-; 3,5,6-tetrafluoro-1,4-phenylenediamine (formula 46), 2,3,5; 6-tetramethyl--1,4-phenylenediamine (formula 47), 2,4,5,6-tetrafluoro-1,3-phenylenediamine (formula 48), 2; 4,5-three fluoro-1,3-phenylenediamine (formula 49), 2,4,6-trimethylammonium-1,3-phenylenediamine (formula 50), 2; 5-dimethyl--1,4-phenylenediamine (formula 51), m-xylene diamine (formula 52), N, N '-two (2-amino-benzene methylene radical) quadrol (formula 53), N, N '-two-2-naphthyl-1,4-phenylenediamine (formula 54), N; N '-two-sec.-butyl-1,4-phenylenediamine (formula 55), N-benzyl quadrol (formula 56), N-phenylethylenediamine (formula 57), p dimethylamine's (formula 58), 2,7 diamin of luorene (formula 59), 2,6-diamino-pyridine (formula 60), 3,6-diamino-carbazole (formula 61) etc.;
[Chemical formula 2]
[Chemical formula 2-1]
By the represented dicarboxylicacid of following formula 62～79, that is, 2, dipicolimic acid 2 (formula 62), 2; 5-pyridine dicarboxylic acid (formula 63), 2,3-pyridine dicarboxylic acid (formula 64), 3,5-pyridine dicarboxylic acid (formula 65), m-phthalic acid (formula 66), 2; 3-pyrazine dicarboxylicacid (formula 67), terephthalic acid (formula 68), phthalic acid (formula 69), 2,6-naphthalene dicarboxylic acids (formula 70), 1,4-naphthalene dicarboxylic acids (formula 71), 2; 2 '-diphenyl dicarboxylic acid (formula 72), 2,2 '-two pyridines-4,4 '-dicarboxylicacid (formula 73), 4; 4 '-diphenyl dicarboxylic acid (formula 74), 4,4 '-stilbenedicarboxylicacid acid (formula 75), anthraquinone-2,3-dicarboxylicacid (formula 76), nitrogen benzide-3; 3 '-dicarboxylicacid (formula 77), nitrogen benzide-4,4 '-dicarboxylicacid (formula 78), benzophenone-4,4 '-dicarboxylicacid (formula 79) etc.;
[chemical formula 3]
The polyfunctional compound who representes by following formula, that is, and pyridine-2, the diamide compound of 3-diformamide (formula 80), phthalamide (formula 81) etc.; The carboxylic acid amide of terephthalic acid monoamide (formula 82), phthalamic acid (formula 83) etc.; The aminocarboxylic acid of 4-(amino methyl) phenylformic acid (formula 84) etc.; The hydroxynaphthoic acid of 6-hydroxyl-2-naphthoic acid (formula 85) etc.; The aminophenol compound of 2-amino-4-phenylphenol (formula 86) etc.; The aniline compound of 4 '-hydroxyacetanilide (formula 87), 3 '-hydroxyacetanilide (formula 88), 4 '-amino acetanilide (formula 89), 3 '-amino acetanilide (formula 90) etc.; 3 functional alcohol of Phloroglucinol monomethyl ether (formula 91) etc.; 3 functional carboxylic acid of trimesic acid (formula 92) etc.; 5-hydroxyl m-phthalic acid (formula 93), 2,6-resorcylic acid (formula 94), 3,5-methyl dihydroxy benzoate (formula 95) etc.;
[chemical formula 4]
[chemical formula 4-1]
In these compounds, for the orientation of controlling polymers effectively, thereby preferred two functional compounds through using two so functional compounds, thereby become good to the consistency of acrylate resin with to the solvability of general organic solvent.Especially preferably have the compartmentation compound of the higher aromatic ring of planarity, preferably use 4,4 '-'-biphenyl diphenol, P-pHENYLENE dI AMINE.
Orientation from controlling polymers; And set out in the aspect of keeping its orientation; Composition (C) preferably fits in; NCO reactive functional groups in the composition (C) reaches 0.01～0.6 with respect to the equivalence ratio (NCO in the NCO reactive functional groups/composition (B) in the composition (C)) of the NCO in the composition (B), and more preferably 0.10～0.50.When less than 0.01 the time, the orientation of controlling polymers effectively then, in addition, when greater than 0.6 the time, then since with polyfunctional isocyanate (B) thus the reaction of NCO cause isocyanic ester can't be introduced crosslinking structure effectively sometimes.That is, composition (C) plays a role as crosslinked obstruction factor sometimes, thereby causes the decline of cross-linking efficiency.
In addition, preferably also in acrylic adhesives of the present invention, cooperate silane coupling agent.As silane coupling agent, can illustration 3-glycidyl propyl trimethoxy silicane etc.
Composition with respect to 100 parts (A), when the use level of silane coupling agent is 0.1～10 part, because the balance of glass adaptation and re-workability becomes well, thereby preferably.
In addition, in acrylic adhesives of the present invention, in the scope of not damaging effect of the present invention, as required, can also cooperate any composition of giving fusible resin etc.
The preparation of acrylic adhesives of the present invention is, through mix according to usual method mentioned component (A) to (C) be added as required become to assign to carry out arbitrarily.
Acrylic adhesives of the present invention does, the photoelastic coefficient of it is the crosslinked and binder layer that forms is at 100m
2/ N is above and 1000 * 10
-12m
2Below/the N, preferably 150～600 * 10
-12m
2Tackiness agent in the scope of/N.In addition, in this manual, photoelastic coefficient is the measured value that obtains through the method for putting down in writing among the embodiment.
According to usual method, behind the acrylic adhesives that obtains in the above described manner of coating at least one face on the supporting mass, carry out drying, crosslinking Treatment and form binder layer, can obtain polarizing film of the present invention thus and use adhesive sheet.As supporting mass, can use polyethylene terephthalate etc.The thickness of binder layer is generally 5～100 μ m, preferably is about 10～50 μ m.
In addition, through the binder layer that is formed by aforesaid propylene acids tackiness agent is set, thereby can access adhesion type polarizing film of the present invention at least one face of polarizing film.As the method that binder layer is set on polarizing film; Both can on polarizing film, directly be coated with aforesaid propylene acids tackiness agent; And carry out drying, crosslinking Treatment and form tackiness agent, also can be on polarizing film with the binder layer transfer printing that forms on adhesive sheet at above-mentioned polarizing film.The thickness of the binder layer that on polarizing film, is provided with is generally 5～100 μ m, preferably is about 10～50 μ m.In addition, as polarizing film used in the present invention, can also range upon range of layer with other function, particularly, comprise elliptical polarized light film, phase-contrast film etc.
Though display format as the liquid crystal cell that uses the adhesion type polarizing film of the present invention that obtains in the above described manner; Be not specially limited; But, can preferably use TN (Twisted Nematic: twisted-nematic) pattern, STN (Super Twisted Nematic: supertwist is to row) pattern in order to bring into play the effect that prevents light leak better.
The adhesion type polarizing film of the application of the invention can reduce the generation of the light leak under hot and humid condition significantly, thinks that it the reasons are as follows.
Promptly; Through acrylic polymers is added polyfunctional isocyanate's compound and has the multifunctional compartmentation compound that has reactive functional group with NCO; And make them crosslinked, thereby can obtain having in the structure after crosslinked the acrylate cross linked resin of the crosslinking structure that comprises multifunctional spacer structure.
Think to have following effect by this multifunctional spacer structure, that is, the binder polymer optical anisotropy is given in (1), and (2) are improved the orientation from the polyurea structure body of polyfunctional isocyanate's compound (B).
Promptly; Through acrylic polymers being added simultaneously polyfunctional isocyanate's compound and multifunctional compartmentation compound; Or under the condition that polyfunctional isocyanate's compound exists; Add multifunctional compartmentation compound, thus the reaction of the reaction of acrylic polymers and polyfunctional isocyanate's compound and polyfunctional isocyanate's compound and multifunctional compartmentation compound carry out simultaneously, combine through isocyanate compound and compartmentation compound between the acrylic polymers chain thus.Through such structure, acrylic polymers orientation and be endowed optical anisotropy.In addition, through with after the polyurea structure stated introduce the bound fraction between the acrylic polymers chain, thereby further improved the whole optical anisotropy (above-mentioned (1)) of tackiness agent.
In addition, polyfunctional isocyanate's compound reacts through the moisture that comprises in the tackiness agent or the moisture that in aging, is absorbed etc., thereby generates polyurea structure.With isocyanic ester have reactive compartmentation compound have with the polyureas that generated in residual isocyanic ester radical reaction, thereby the effect (above-mentioned (2)) that the orientation of polyurea structure body is improved.
Embodiment
Then, enumerate embodiment and the present invention will be described in further detail, but the present invention does not receive any restriction of these embodiment.
Make example 1
The preparation of acrylic polymers:
In the reaction unit that possesses stirrer, reflux cooler, TM and nitrogen ingress pipe; Add 73 parts of n-butyl acrylates (BA), 25 parts of benzyl acrylates (BzA), 2 parts of 2-Hydroxy ethyl acrylates (2HEA) and 150 parts of vinyl acetic monomers; And add 0.2 part of Diisopropyl azodicarboxylate (AIBN); In stream of nitrogen gas; With 68 ℃ of polymerizations 8 hours, thereby obtain the solution of the acrylic polymers A-1 of weight-average molecular weight (Mw) 1,100,000, MWD (weight-average molecular weight (Mw)/number-average molecular weight (Mn)) 35.In addition, Mw and Mn are obtained by following measuring method.
(measuring method of Mw and Mn)
Through the gel permeation chromatography (GPC) of following condition, and obtain weight-average molecular weight (Mw) and the number-average molecular weight (Mn) that converts with polystyrene standard.
< GPC condition determination >
Device: HLC-8120 (Tosoh (strain) production)
Chromatographic column: G7000HXL (Tosoh (strain) production)
GMHXL (Tosoh (strain) production)
G2500HXL (Tosoh (strain) production)
Sample concentration: 1.5mg/ml
Mobile phase solvent: THF
Flow velocity: 1.0ml/min
Column temperature: 40 ℃
Make example 2
Except the composition with comonomer replaces with 88 parts of BA, 10 parts of BzA, 2 parts the 2HEA, other are with to make example 1 identical, and obtain the solution of acrylic polymers A-2.The Mw of this polymkeric substance is 1,100,000, MWD (Mw/Mn) is 35.
Make example 3
Except the composition with comonomer replaces with 23 parts of BA, 75 parts of BzA, 2 parts the 2HEA, other are with to make example 1 identical, and obtain the solution of acrylic polymers A-3.The Mw of this polymkeric substance is 1,100,000, MWD (Mw/Mn) is 35.
Embodiment 1
The preparation of adhesion type polarizing film:
(preparation of acrylic adhesives)
To 100 parts through making the solids component of the example 1 acrylic polymers A-1 solution that obtains; The tolylene diisocyanate (CORONATE L: Japanese Polyurethane industry (strain) company produces), 0.056 part 4 that add 2 parts of TriMethylolPropane(TMP) additions; 4 '-'-biphenyl diphenol and 0.2 part of 3-glycidyl propyl group methoxy silane are also mixed, thereby obtain acrylic adhesives solution.
(making of adhesion type polarizing film)
The resulting acrylic adhesives solution of coating on the polyethylene terephthalate after the silicone coated (PET) film, so that its thickness reaches 25 μ m, and in 80 ℃ drying machine dry 2 minutes.Then, polarizing film is fitted on the dry face, and under 23 ℃, the condition of 65%RH, leaves standstill 7, thereby obtain the adhesion type polarizing film.
Embodiment 2～5 and comparative example 1～8
Except shown in below table 1, replacing acrylic polymers and polyfunctional isocyanate's compound like this, containing the compartmentation compound of aromatic ring, other are identical with embodiment 1, and obtain acrylic adhesives solution.In addition, use resulting acrylic adhesives solution and to obtain the adhesion type polarizing film with embodiment 1 identical mode.The NCO equivalent is meant in the table, and the NCO reactive functional groups of compartmentation compound that contains aromatic ring is with respect to the equivalence ratio of the NCO of polyfunctional isocyanate's compound.
[table 1]
Test Example 1
About by embodiment 1～5 and comparative example 1～8 resulting acrylic adhesives, measure gel ratio, bounding force, photoelastic coefficient through following method.The result is shown in table 2.
(gel ratio)
Coating acrylic adhesives solution on the PET film after the silicone coated of thickness 38 μ m, so that its dried thickness reaches 25 μ m, and in 80 ℃ drying machine dry 2 minutes.Then, make the PET of thickness 38 μ m film adhered on dry face, and under 23 ℃, the condition of 65%RH, leave standstill 7, thereby obtain adhesive sheet.
With resulting adhesive sheet severing is that 50mm * 50mm size is processed test film, peels binder layer from test film, and measures the initial weight of binder layer.This binder layer of dipping in the 100g vinyl acetic monomer, and at room temperature placed 24 hours.Then, filter with 200 mesh filter screens, with 80 ℃ with dry 2 hours of remaining composition residual on the mesh and carry out weighing.According to initial weight and remaining composition weight and go out the gel ratio through computes.
Gel ratio (%)=100 * (remaining composition weight/initial weight)
(bounding force)
Coating acrylic adhesives solution on the PET film after the silicone coated of thickness 38 μ m, so that its dried thickness reaches 25 μ m, and in 80 ℃ drying machine dry 2 minutes.Then, make the PET of thickness 38 μ m film adhered on dry face, and under 23 ℃, the condition of 65%RH, leave standstill 7, thereby obtain adhesive sheet.
With resulting adhesive sheet severing is that wide 25mm * long 150mm processes test film.Patch test sheet on non-alkali glass.To pulling an end of test films and power when beginning to peel off is measured to 180 ° of directions with the speed that peels of 300mm/min.
(photoelastic coefficient)
Coating acrylic adhesives solution on the PET film after the silicone coated of thickness 38 μ m, so that its dried thickness reaches 50 μ m, and in 80 ℃ drying machine dry 2 minutes.Then, make the PET after the silicone coated film adhered on dry face, and under 23 ℃, the condition of 65%RH, leave standstill 7, thereby obtain adhesive sheet.
Resulting adhesive sheet is built up to thickness 1000 μ m, and process 2cm * 5cm quadrate test film.Under 25 ℃, the environment of 50%RH, use ellipsometer M-220 (Japanese beam split company produce), and in the scope of 0～10N, apply tensile stress, and measure the photoelastic coefficient of 600nm by made test film two end portions.
[table 2]
Test Example 2
About by embodiment 1～5 and the adhesion type polarizing film that comparative example 1～8 obtains, estimate weather resistance through following method, and measure brightness.The result is shown in table 3.
(weather resistance)
< thermotolerance and humidity resistance >
With the severing of adhesion type polarizing film is 15 inches sizes (233mm * 309mm), and use laminating roll that it is attached on the single face of non-alkali glass plate of thickness 0.5mm.After the attaching, use autoclave (tremble former make produce) to carry out pressure treatment, use plate thereby obtain testing with 0.5MPa, 50 ℃, 20 minutes condition.To place 500 hours with the plate that this kind mode obtains, and peel off, float through visual observation, and following commentary valency benchmark estimated 85 ℃/condition dry, 60 ℃/90%RH.
[benchmark]
Zero: do not have to find the bad order that peel off or float etc.
△: confirm as the bad order that peeling off is arranged slightly or float etc.
*: confirmed to peel off and/or float
< cold cycling weather resistance >
The thermal shock device TSA-71L-A that uses ESPEC Co., Ltd. to produce; To the plate that obtains in the above described manner carry out repeatedly 200 times with-40 ℃ following 30 minutes, 80 ℃ following 30 minutes be 1 round-robin cold cycling; The viewing optics member has or not foaming, floats, peels off, and with following benchmark evaluation.
[benchmark]
Zero: the bad order that does not foam, floats, peels off etc.
△: confirm as the bad order that foaming is arranged slightly, float, peel off etc.
*: confirmed foaming, floated, peeled off (mensuration of brightness)
With the severing of adhesion type polarizing film is 15 inches sizes (233mm * 309mm), and attach (45 °) respectively on the surface of the non-alkali glass of thickness 0.5mm with the mode that forms the cross-polarized light state.After the attaching, use autoclave (tremble former make produce) to carry out pressure treatment, use plate thereby obtain testing with 0.5MPa, 50 ℃, 20 minutes condition.Resulting test is installed with the Polarizer exchange of plate and display monitor BENQ PF01G.85 ℃/after environment dry or 60 ℃/90%RH is placed 200 hours respectively with this display controller down, transferred cold 2 hours at the environment of 25 ℃ * 50%RH, in the darkroom, be connected again and be made as whole pictures demonstration black with PC.The display monitor that shows black about these whole pictures; (Hyland company produces, RISA-COLOR/CD8) and near the brightness (La, Lb, Lc, Ld) in the zone of the diameter 1cm the center on each limit and the regional brightness (L of diameter 1cm of watch-dog middle body to use nitometer
Center) measure, and obtain light leak property (Δ L) through following formula.As long as the more little expression light leak of Δ L is few more, usually less than 4.0, then can be used for using as liquid-crystal display.
ΔL＝(La+Lb+Lc+Ld)/4-L
center
[table 3]
The weather resistance of the tackiness agent that in acrylic polymers of the present invention, adds polyfunctional isocyanate's compound and multifunctional compartmentation compound and obtain is good and light leak is also less.Relative therewith, in the comparative example that does not add multifunctional compartmentation compound 1,5,6,, also can only adjust light leak property a little even change the addition of isocyanate compound, can't obtain the superperformance as the application.In addition, in the comparative example that has added the compartmentation compound that does not have aromatic ring 2,3,4, also can't obtain good anti-light leak property.And; Isocyanate compound equivalent is being added in the comparative example 8 of compartmentation compound of the present invention; Because thereby isocyanate compound and the reaction of compartmentation compound can't be crosslinked effectively with polymkeric substance; Therefore in damp and hot, cold cycling, be confirmed to be bad order, and anti-light leak property is also insufficient.In addition, in acrylic polymers, make in the comparative example 7 of the monomer copolymerization that contains aromatic ring more than the specified quantitative, relatively poor, the anti-light leak property of weather resistance is also relatively poor.
On the industry maybe the property used
Acrylic adhesives of the present invention has excellent weather resistance, and through the control photoelastic coefficient, and reduce owing to the double refraction that internal stress caused, thereby can prevent light leak effectively.Therefore, can be suitable as the tackiness agent that polarizing film uses and utilize.
Claims (9)
1. an acrylic adhesives contains following compositions (A) to (C),
(A) following acrylic polymers, that is, and with following monomer
(a-1) (methyl) propenoate
(a-2) contain the monomer of aromatic ring
(a-3) contain the monomer of functional group
Copolymerization and obtaining, and monomer (a-2) is 3～50 quality % with respect to the content of monomer (a-1) and total amount (a-2);
(B) polyfunctional isocyanate's compound;
(C) have the compartmentation compound that contains aromatic ring of NCO reactive functional groups,
It is characterized in that,
NCO reactive functional groups in the composition (C) is 0.01～0.60 with respect to the equivalence ratio of the NCO in the composition (B), and the photoelastic coefficient of the binder layer that forms thus is 100 * 10
-12m
2/ N is above and 1000 * 10
-12m
2Below/the N.
2. acrylic adhesives as claimed in claim 1, wherein,
Monomer (a-1) for be selected from (methyl) alkyl acrylate, (methyl) vinylformic acid alcoxyl base ester and (methyl) vinylformic acid aklylene glycol more than a kind or 2 kinds.
3. according to claim 1 or claim 2 acrylic adhesives, wherein,
Monomer (a-1) is with respect to whole monomers (a-1), to contain the monomer of the alkyl acrylate of the above carbonatoms 4～8 of 60 quality %.
4. like any described acrylic adhesives in the claim 1～3, wherein,
Monomer (a-2) for be selected from (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid phenoxy ethyl, (methyl) phenyl acrylate and (methyl) vinylformic acid naphthyl ester more than a kind or 2 kinds.
5. like any described acrylic adhesives in the claim 1～4, wherein,
Monomer (a-3) is for containing the monomer of hydroxyl.
6. like any described acrylic adhesives in the claim 1～5, wherein,
Composition (B) is polyalcohol modified isocyanate compound.
7. a polarizing film is used adhesive sheet, and it forms through the binder layer that is formed by any described acrylic adhesives in the claim 1～6 is set at least one face of supporting mass.
8. adhesion type polarizing film, it forms through the binder layer that is formed by any described acrylic adhesives in the claim 1～6 is set at least one face of polarizing film.
9. adhesion type polarizing film as claimed in claim 8, it is used for the liquid crystal cell that display format is twisted nematic mode or supertwist nematic-mode.
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|---|---|---|---|
| JP2009-045289 | 2009-02-27 | ||
| JP2009045289A JP5531190B2 (en) | 2009-02-27 | 2009-02-27 | Acrylic adhesive, adhesive sheet for polarizing film and adhesive polarizing film using the same |
| PCT/JP2010/051483 WO2010098182A1 (en) | 2009-02-27 | 2010-02-03 | Acrylic adhesive, adhesive sheet for polarizing film that uses the same, and adhesive polarizing film |
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| CN102333838A true CN102333838A (en) | 2012-01-25 |
| CN102333838B CN102333838B (en) | 2014-01-08 |
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Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5531190B2 (en) |
| KR (1) | KR20110131173A (en) |
| CN (1) | CN102333838B (en) |
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| JP2005053976A (en) * | 2003-08-06 | 2005-03-03 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for lowly polar film |
| JP2007138057A (en) * | 2005-11-21 | 2007-06-07 | Soken Chem & Eng Co Ltd | Adhesive composition for optical film and adhesive sheet, and optical member using the same |
| CN101283069A (en) * | 2005-10-18 | 2008-10-08 | 日东电工株式会社 | Adhesive composition, adhesive layer, method for producing the layer, and optical member with adhesive |
| CN101292180A (en) * | 2005-10-21 | 2008-10-22 | 日东电工株式会社 | Polarizing plate with optical compensation layer and image display using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5591477B2 (en) * | 2008-03-13 | 2014-09-17 | 日東電工株式会社 | Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, transparent conductive laminate, touch panel, and image display device |
-
2009
- 2009-02-27 JP JP2009045289A patent/JP5531190B2/en active Active
-
2010
- 2010-02-03 WO PCT/JP2010/051483 patent/WO2010098182A1/en active Application Filing
- 2010-02-03 CN CN201080009578.3A patent/CN102333838B/en not_active Expired - Fee Related
- 2010-02-03 KR KR1020117018310A patent/KR20110131173A/en not_active Application Discontinuation
- 2010-02-10 TW TW099104169A patent/TW201040237A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005053976A (en) * | 2003-08-06 | 2005-03-03 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for lowly polar film |
| CN101283069A (en) * | 2005-10-18 | 2008-10-08 | 日东电工株式会社 | Adhesive composition, adhesive layer, method for producing the layer, and optical member with adhesive |
| CN101292180A (en) * | 2005-10-21 | 2008-10-22 | 日东电工株式会社 | Polarizing plate with optical compensation layer and image display using same |
| JP2007138057A (en) * | 2005-11-21 | 2007-06-07 | Soken Chem & Eng Co Ltd | Adhesive composition for optical film and adhesive sheet, and optical member using the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812580A (en) * | 2012-12-27 | 2015-07-29 | 日东新兴有限公司 | Insulating paper for oil-immersed motors |
| US9931812B2 (en) | 2012-12-27 | 2018-04-03 | Nitto Shinko Corporation | Insulating paper for oil-immersed motors |
| CN104812580B (en) * | 2012-12-27 | 2018-07-06 | 日东新兴有限公司 | Submersible motor insulating paper |
| CN103980844A (en) * | 2013-02-13 | 2014-08-13 | 琳得科株式会社 | Pressure sensitive adhesion composition, pressure sensitive adhesive and pressure sensitive adhesion sheet |
| CN104303083A (en) * | 2013-05-14 | 2015-01-21 | Lg化学株式会社 | Polarizing plate |
| CN107924009A (en) * | 2015-08-18 | 2018-04-17 | 综研化学株式会社 | Polarizer adhesive phase and adhesive composition |
| CN107924009B (en) * | 2015-08-18 | 2020-09-04 | 综研化学株式会社 | Adhesive layer for polarizing plate and adhesive composition |
| 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 |
|---|---|
| JP5531190B2 (en) | 2014-06-25 |
| TW201040237A (en) | 2010-11-16 |
| WO2010098182A1 (en) | 2010-09-02 |
| CN102333838B (en) | 2014-01-08 |
| KR20110131173A (en) | 2011-12-06 |
| JP2010196000A (en) | 2010-09-09 |
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