CN102333838B - 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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- CN102333838B CN102333838B CN201080009578.3A CN201080009578A CN102333838B CN 102333838 B CN102333838 B CN 102333838B CN 201080009578 A CN201080009578 A CN 201080009578A CN 102333838 B CN102333838 B CN 102333838B
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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
- 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
-
- 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
-
- 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
-
- 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 with optical compensation function, in more detail, relate to and a kind ofly can reduce double refraction by controlling photoelastic coefficient, thereby effectively prevent the acrylic adhesives of light leak and use the polarizing film of this acrylic adhesives.
Background technology
Liquid crystal cell has liquid crystal material and is clamped in two structures between substrate, and is fitted with Polarizer by binder layer on this substrate surface.In recent years, liquid crystal cell enlarges in purposes such as the indicating meter of vehicle boarded use, outdoor gauger use, PC, televisors, and owing to accompanying therewith, it is too harsh that environment for use also becomes, therefore, the tackiness agent that requires to use has the high-durability that can not peel off or float etc.
In addition, under this too harsh environment for use, due to the internal stress produced in Polarizer, the optical transmission rate will change, thereby become, easily produce light leak.For example, although in the liquid crystal cell of TN pattern, Polarizer is configured in the mode that becomes the cross-polarized light state of 45 °/135 °, but, due to the internal stress produced in Polarizer, thereby produce, light is that expose from the periphery of picture, so-called frame light leakage phenomena.Particularly be accompanied by the maximization of indicating meter in recent years, the problem that is declined to become of the display quality caused due to above-mentioned light leak.
In order to address the above problem, a kind of following technology is disclosed,, contain, acrylate adhesive that there is the linking agent of positive intrinsic degree of birefringence this just like the isocyanates linking agent with aromatic ring by use, or use and to contain the tackiness agent with the multipolymer of the acrylic ester monomer with negative intrinsic degree of birefringence such as the monomer with the aromatic ring such as phenyl ring etc., monomer that there is separately positive intrinsic degree of birefringence, thereby adjust the double refraction of tackiness agent and prevent the technology (Patent Document 1 and 2) of light leak.
But, due in the situation that general, the positive larger structure of intrinsic double refraction has the molecular structure that planarity is higher, and demonstrate higher crystallinity, therefore when the excessive interpolation of degree to eliminate the light leakage comprises linking agent naphthalene structure that this planarity is higher etc., that have higher positive intrinsic degree of birefringence, with the compatible of binder polymer, will worsen, thus exist cause that the albefaction of filming, bounding force descend or with days through peeling off of producing etc.In addition, even in the copolymerization of monomer, a large amount of while thering is the monomer of positive intrinsic degree of birefringence when using, thereby also will exist copolymerizable variation workability to worsen or because 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.
Technical literature formerly
Patent documentation
Patent Document 1: TOHKEMY 2008-144125 communique
Patent 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 good bond properties, effectively prevent the tackiness agent of light leak.
The inventor has carried out deep investigation in order to solve above-mentioned problem, found that, cooperation by the monomer composition in acrylic polymers and polyfunctional isocyanate etc., the photoelastic coefficient of the tackiness agent after crosslinked is adjusted in certain scope, again by the compartmentation compound (spacer compound) of use and isocyanic ester radical reaction, thereby can access high-durability and excellent bond properties, and reduce significantly the double refraction produced due to inner stress, thereby completed the present invention.
; the present invention is a kind of acrylic adhesives; contain following compositions (A) to (C); wherein; (A) following acrylic polymers; that is, the monomer that following monomer (a-1) (methyl) acrylate, (a-2) are contained to aromatic ring, the monomer copolymerization that (a-3) contains functional group and obtain, and the content of monomer (a-2) is 3～50 quality % with respect to monomer (a-1) and total amount (a-2); (B) polyfunctional isocyanate's compound; (C) there is the compartmentation compound that contains aromatic ring of isocyanate group reactive functional groups, acrylic adhesives is characterised in that, isocyanate group reactive functional groups in composition (C) is 0.01～0.60 with respect to the equivalence ratio of the isocyanate group in composition (B), and the photoelastic coefficient of the binder layer formed by described acrylic adhesives is 100 * 10
-12m
2/ N is above and 1000 * 10
-12m
2below/N.
In addition, the present invention is a kind of polarizing film adhesive sheet, and it forms by the binder layer 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, it forms by the binder layer 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 caused due to the internal stress produced in Polarizer, thereby has effectively prevented light leak.In addition, even under hot and humid environment, also can not peel off or float etc., thereby weather resistance be also excellent.
Embodiment
The acrylic polymers of the composition that tackiness agent of the present invention is used (A), the monomer copolymerization that the monomer that contains aromatic ring to major general's monomer (a-1) (methyl) acrylate, monomer (a-2) and monomer (a-3) contain functional group obtains.
As (methyl) acrylate of monomer (a-1), can exemplify alkyl acrylate, alkyl methacrylate, vinylformic acid alcoxyl base ester, methacrylic acid alkoxy ester, vinylformic acid alkylene diol ester, methacrylic acid alkylene glycol ester etc.
As alkyl acrylate, can list 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, isobornyl acrylate, cyclohexyl acrylate etc.
As alkyl methacrylate, can list methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, the positive heptyl ester of methacrylic acid, n octyl methacrylate, methacrylic acid-2-ethylhexyl, nonyl methacrylate, decyl-octyl methacrylate, dodecylacrylate, isobornyl methacrylate, cyclohexyl methacrylate etc.
As vinylformic acid alcoxyl base ester, can exemplify 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 methacrylic acid alkoxy ester, can exemplify methacrylic acid-2-methoxyl group ethyl ester, methacrylic acid-2-ethoxy ethyl ester, methacrylic acid-2-methoxyl group propyl ester, methacrylic acid-3-methoxyl group propyl ester, methacrylic acid-2-methoxyl group butyl ester, methacrylic acid-4-methoxyl group butyl ester etc.
As vinylformic acid alkylene diol ester, can list vinylformic acid glycol ester, polyalkylene glycol acrylate ester, vinylformic acid propylene glycol ester, vinylformic acid polypropylene glycol ester etc.
As methacrylic acid alkylene glycol ester, can list methacrylic acid glycol ester, methacrylic acid macrogol ester, methacrylic acid propylene glycol ester, methacrylic acid polypropylene glycol ester etc.
Wherein, when preferred use, in whole monomers (a-1), be more than 60 quality % (below, only with " % ", mean) the alkyl acrylate of carbonatoms 4～8, more preferably use while being the alkyl acrylate of the above carbonatoms 4～8 of 80 quality %, copolymerizable 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 exemplify methacrylic acid aryl esters such as the aryl acrylates such as benzyl acrylate, vinylformic acid phenoxy ethyl, phenyl acrylate, vinylformic acid naphthalene ester or benzyl methacrylate, methacrylic acid phenoxy ethyl, phenyl methacrylate, methacrylic acid naphthalene ester etc.
In the composition of composition (A), content relatively above-mentioned 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, content (a-1) is 50～90%, the content of (a-2) is 10～50%.In addition, when only using monomer that aromatic ring is monocycle to using as monomer (a-2), the content of monomer (a-2) is 5～50%, more preferably 15～50%.On the other hand, when only using monomer that aromatic ring is heterocycle to using as monomer (a-2), the content of monomer (a-2) is 3～30%, more preferably 10～30%.And, and the monomer that is monocycle with aromatic ring and while being the monomer of heterocycle, the aggregate value preferably content of relative monomer (a-1) and content total amount (a-2), monocyclic monomers and heterocyclic monomer is multiplied by between the value obtained after 1.67 is adjusted to, in 3～50% scope, more preferably be adjusted in 10～50% scope.
As the monomer that contains functional group of above-mentioned monomer (a-3), can exemplify the monomer, the monomer that contains hydroxyl that contain carboxyl, contain amino monomer, the monomer that contains amide group, the monomer that contains epoxy group(ing) etc.
As the monomer that contains carboxyl, can exemplify vinylformic acid, methacrylic acid, senecioate-carboxyl ethyl ester, methacrylic 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, β-crotonic acid, fumaric acid, toxilic acid etc.
As the monomer that contains hydroxyl, can exemplify vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxypropyl acrylate, vinylformic acid-3-hydroxypropyl acrylate, methacrylic acid-3-hydroxypropyl acrylate, vinylformic acid-4-hydroxy butyl ester, methacrylic acid-4-hydroxy butyl ester, 2-hydroxy-3-chloropropyl acrylate, methacrylic acid 2-hydroxyl-3-chlorine propyl ester, vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, methacrylic acid-2-hydroxyl-3-phenoxy group propyl ester etc.
As containing amino monomer, can exemplify vinylformic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, vinylformic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate etc.
As the monomer that contains amide group, can exemplify acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide etc.
As the monomer that contains epoxy group(ing), can exemplify vinylformic acid glycidyl ether, methyl propenoic acid glycidyl ether, acrylic acid-2-ethyl glycidyl ether, methacrylic acid-2-glycidyl ether etc.
Due to this monomer that contains functional group (a-3), as the cross-linking set of composition described later (B) polyfunctional isocyanate compound and play a role, therefore in above-mentioned substance, as cross-linking set, be preferably the reactive good monomer that contains carboxyl, the monomer that contains hydroxyl, particularly, be preferably the monomer that contain hydroxyl reactive higher with composition (B).And, to improve reactive purpose of isocyanate group and hydroxyl, in the monomer that can contain hydroxyl in use, and with the monomer that contains carboxyl.
Relatively add up to monomer (a-1) and the monomer (a-2) of 100 mass parts (below, only with " part " expression), above-mentioned monomer (a-3) is preferably used 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 while using the monomer contain hydroxyl, be 1～10% with respect to whole formation monomers of composition (A), and the preferred content while using the monomer that contains carboxyl is 0.1～5%.Even when also using the monomer that contains hydroxyl and the monomer that contains carboxyl, also preferably be made as respectively same content.
In composition (A), except above-mentioned monomer (a-1) to (a-3), can coordinate can with the monomer (a-4) of their copolymerization.As such monomer, can exemplify 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, coordinate 0～10 part.
Although the acrylic polymers of composition (A) can be by known polymerization processs such as solution polymerization, emulsion polymerization, suspension polymerizations, (a-4) copolymerization that makes above-mentioned monomer (a-1)～(a-3) and use as required and obtaining, but wherein, solution polymerization is because the adjusting of molecular weight is easier to, and can reduce impurity, thereby preferably.
The acrylic polymers of the composition obtained thus (A) is preferably, and weight-average molecular weight (Mw) is 600,000～3,000,000.When weight-average molecular weight is less than 600,000, weather resistance when damp and hot will descend, thus peel off sometimes or float, the adhesive residue while reprocessing, and be greater than at 3,000,000 o'clock, workability worsens sometimes.In addition, in this manual, weight-average molecular weight (Mw) is the weight-average molecular weight converted with polystyrene standard that the gel permeation chromatography (GPC) by putting down in writing in embodiment is measured.
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, during higher than 0 ℃, the adaptation of resulting tackiness agent and base material or the snappiness of binder layer will descend, thereby peeling off or floating from base material occurs 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 ... weight ratio
It is crosslinked that the polyfunctional isocyanate of the composition that tackiness agent of the present invention is used (B) has crosslinking component (A) acrylic polymers, and adjust the function of photoelastic coefficient.As this polyfunctional isocyanate, can list toluenediisocyanate, the chlorine phenylene vulcabond, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, eylylene diisocyanate, diphenylmethanediisocyanate, the isocyanate-monomer of the diphenylmethanediisocyanate of hydrogenation etc. and make the polyvalent alcohol addition such as these isocyanate-monomers and TriMethylolPropane(TMP) and must polyalcohol modified isocyanate compound or isocyanate compound, biuret type compound, and with polyether glycol or polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyvalent alcohol etc. carries out addition reaction, the isocyanic ester of carbamate prepolymer type, wherein, polyalcohol modified isocyanate compound, good with the reactivity of the compartmentation compound that contains aromatic ring with isocyanate group reactive functional groups of aftermentioned composition (C), and the acrylic polymers of composition (A) easily is orientated, thus preferably using controlling aspect photoelastic coefficient.
Composition (B) is preferably, and the composition with respect to 100 parts (A) acrylic polymers, used 0.1～10 part.
The compartmentation compound that contains aromatic ring with isocyanate group reactive functional groups of the composition that tackiness agent of the present invention is used (C) (below be sometimes referred to as " the compartmentation compound that contains aromatic ring "), react with polyfunctional isocyanate's compound of composition (B), and there is the function that easily makes the acrylic polymers orientation and adjust photoelastic coefficient.
The compartmentation compound that this contains aromatic ring, be the compartmentation compound that contains the isocyanate group reactive functional groups such as aromatic ring and the above hydroxyl of two senses, amino, carboxyl, amide group, particularly can the following compound of illustration.
Represented two functional glycol by following formula 1～30, that is, and 2,3-pyridine glycol (formula 1), N, N '-bis-(salicylidene)-1,3-propylene diamine (formula 2), PPD (formula 3), N, N '-bis-(salicylidene)-Putriscine (formula 4), N, N '-bis-(salicylidene)-1,6-hexanediamine (formula 5), N, N '-bis-(salicylidene) quadrol (formula 6), N, N '-bis-salicyl-1,2-phenylenediamine (formula 7), 3-phenoxy group-1,2-PD (formula 8), 4-benzyloxy-1,3 butylene glycol (formula 9), 2-benzyloxy-1,3-PD (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), Isosorbide-5-Nitrae-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), Isosorbide-5-Nitrae-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-Isosorbide-5-Nitrae-benzophenone (formula 28), two (4-hydroxy phenyl) thioether (formula 29), 2,6-pyridine dimethanol (formula 30) etc.,
[Chemical formula 1]
The represented two sense diamines by 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, two (2,4, the 6-trimethylphenyl) quadrols (formula 36) of 2-, (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), Isosorbide-5-Nitrae-phenylenediamine (formula 40), 1,2-phenylenediamine (formula 41), N, N '-diacetyl-Isosorbide-5-Nitrae-phenylenediamine (formula 42), N, N '-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine (formula 43), N, N '-diphenyl ethylene diamine (formula 44), (1S, 2S)-1, two (2,4, the 6-trimethylphenyl) quadrols (formula 45) of 2-, 2,3,5,6-tetrafluoro-Isosorbide-5-Nitrae-phenylenediamine (formula 46), 2,3,5,6-tetramethyl--Isosorbide-5-Nitrae-phenylenediamine (formula 47), 2,4,5,6-tetrafluoro-1,3-phenylenediamine (formula 48), 2,4,5-tri-is fluoro-1,3-phenylenediamine (formula 49), 2,4,6-trimethylammonium-1,3-phenylenediamine (formula 50), 2,5-dimethyl-Isosorbide-5-Nitrae-phenylenediamine (formula 51), m-xylene diamine (formula 52), N, N '-bis-(2-amino-benzene methylene radical) quadrol (formula 53), N, N '-bis--2-naphthyl-Isosorbide-5-Nitrae-phenylenediamine (formula 54), N, N '-bis--sec-butyl-Isosorbide-5-Nitrae-phenylenediamine (formula 55), N-benzyl quadrol (formula 56), N-phenylethylenediamine (formula 57), p dimethylamine's (formula 58), 2,7 diamin of luorene (formula 59), DAP (formula 60), 3,6-diamino carbazole (formula 61) etc.,
[Chemical formula 2]
[Chemical formula 2-1]
By the represented dicarboxylic acid of following formula 62～79, , 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 dicarboxylic acid (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 '-bis-pyridines-4, 4 '-dicarboxylic acid (formula 73), 4, 4 '-diphenyl dicarboxylic acid (formula 74), 4, 4 '-stilbenedicarboxylicacid acid (formula 75), anthraquinone-2, 3-dicarboxylic acid (formula 76), nitrogen benzide-3, 3 '-dicarboxylic acid (formula 77), nitrogen benzide-4, 4 '-dicarboxylic acid (formula 78), benzophenone-4, 4 '-dicarboxylic acid (formula 79) etc.,
[chemical formula 3]
The polyfunctional compound who is meaned 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-Hydroxy-2-naphthoic acid (formula 85) etc.; The aminophenol compound of 2-amino-4-phenyl phenol (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-Hydroxy M Phthalic Acid (formula 93), 2,6-DHBA (formula 94), 3,5-methyl dihydroxy benzoate (formula 95) etc.;
[chemical formula 4]
[chemical formula 4-1]
In these compounds, in order effectively to control the orientation of polymkeric substance, thereby the preferred compound of two senses by using the compound of two such senses, thereby becomes good to the consistency of acrylate resin with to the solvability of general organic solvent.Particularly preferably there is the compartmentation compound of the aromatic ring that planarity is higher, preferably use 4,4 '-'-biphenyl diphenol, P-pHENYLENE dI AMINE.
From controlling the orientation of polymkeric substance, and set out in the aspect that maintains its orientation, composition (C) preferably fits in, isocyanate group reactive functional groups in composition (C) reaches 0.01～0.6 with respect to the equivalence ratio (isocyanate group in the isocyanate group reactive functional groups/composition (B) in composition (C)) of the isocyanate group in composition (B), and more preferably 0.10～0.50.When being less than 0.01, can't effectively control the orientation of polymkeric substance, in addition, when being greater than 0.6, due to polyfunctional isocyanate (B) thus reacting of isocyanate group cause isocyanic ester can't effectively be introduced crosslinking structure 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, coordinate 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 coordinate any composition of giving fusible resin etc.
The preparation of acrylic adhesives of the present invention is, by according to usual method, mix mentioned component (A) to (C) be added as required become to assign to carry out arbitrarily.
Acrylic adhesives of the present invention is, the photoelastic coefficient of cross-linking and the binder layer that forms is at 100m
2/ N is above and 1000 * 10
-12m
2below/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 the method by putting down in writing in embodiment obtains.
According to usual method, at least one face on supporting mass after the acrylic adhesives that obtains in the above described manner of coating, carry out drying, crosslinking Treatment and form binder layer, can obtain thus polarizing film adhesive sheet of the present invention.As supporting mass, can use polyethylene terephthalate etc.The thickness of binder layer, be generally 5～100 μ m, preferably be about 10～50 μ m.
In addition, by the binder layer formed by aforesaid propylene acids tackiness agent is set at least one face of polarizing film, thereby can access adhesion type polarizing film of the present invention.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 will with the binder layer formed on adhesive sheet, be transferred on polarizing film at above-mentioned polarizing film.The thickness of the binder layer arranged on polarizing film 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 the stacked layer with other function, particularly, comprise elliptical polarized light film, phase-contrast film etc.
Although the display format as the liquid crystal cell that uses the adhesion type polarizing film of the present invention obtained in the above described manner, be not specially limited, but, in order to bring into play better the effect that prevents light leak, can preferably use TN (Twisted Nematic: twisted-nematic) pattern, STN (Super Twisted Nematic: supertwist is to row) pattern.
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 be the reasons are as follows.
; by acrylic polymers is added polyfunctional isocyanate's compound and has the multifunctional compartmentation compound that has reactive functional group with isocyanate group; and make them crosslinked, thereby can obtain in the structure after crosslinked having the acrylate cross linked resin of the crosslinking structure that comprises multifunctional spacer structure.
Think and have following effect by this multifunctional spacer structure, that is, (1) gives the binder polymer optical anisotropy, and (2) make to improve from the orientation of the polyurea structure body of polyfunctional isocyanate's compound (B).
; by acrylic polymers is added to polyfunctional isocyanate's compound and multifunctional compartmentation compound simultaneously; or under the condition existed at polyfunctional isocyanate's compound; add multifunctional compartmentation compound; thereby acrylic polymers and polyfunctional isocyanate's compound react and polyfunctional isocyanate's compound carries out with reacting simultaneously of multifunctional compartmentation compound, thus between the acrylic polymers chain by isocyanate compound and compartmentation compound and combination.By such structure, acrylic polymers orientation and be endowed optical anisotropy.In addition, by polyurea structure described later is introduced to the bound fraction between the acrylic polymers chain, thereby further improved the optical anisotropy (above-mentioned (1)) of tackiness agent integral body.
In addition, polyfunctional isocyanate's compound reacts by the moisture that comprises in tackiness agent or at aging middle absorbed moisture etc., thereby generates polyurea structure.With isocyanic ester have reactive compartmentation compound have with generated polyureas 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 is not subject to any restriction of these embodiment.
Production Example 1
The preparation of acrylic polymers:
In the reaction unit that possesses stirrer, reflux cooler, thermometer 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, molecular weight distribution (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)
By the gel permeation chromatography (GPC) of following condition, and obtain weight-average molecular weight (Mw) and the number-average molecular weight (Mn) converted 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: tetrahydrofuran (THF)
Flow velocity: 1.0ml/min
Column temperature: 40 ℃
Production Example 2
Except the composition by comonomer replaces with 88 parts of BA, 10 parts of BzA, 2 parts of 2HEA, other are identical with Production Example 1, and obtain the solution of acrylic polymers A-2.The Mw of this polymkeric substance is 1,100,000, molecular weight distribution (Mw/Mn) is 35.
Production Example 3
Except the composition by comonomer replaces with 23 parts of BA, 75 parts of BzA, 2 parts of 2HEA, other are identical with Production Example 1, and obtain the solution of acrylic polymers A-3.The Mw of this polymkeric substance is 1,100,000, molecular weight distribution (Mw/Mn) is 35.
Embodiment 1
The preparation of adhesion type polarizing film:
(preparation of acrylic adhesives)
Solids component to 100 parts of acrylic polymers A-1 solution that obtain by Production Example 1, 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 polyethylene terephthalate after silicone coated (PET) film, so that its thickness reaches 25 μ m, and in the drying machine of 80 ℃ dry 2 minutes.Then, polarizing film is fitted on dry face, and under 23 ℃, the condition of 65%RH standing 7 days, thereby the adhesion type polarizing film obtained.
Embodiment 2～5 and comparative example 1～8
Except the compartmentation compound of replacing so as described in Table 1 acrylic polymers and polyfunctional isocyanate's compound, containing aromatic ring, other are identical with embodiment 1, and obtain acrylic adhesives solution.In addition, use resulting acrylic adhesives solution and obtain the adhesion type polarizing film in the mode identical with embodiment 1.In table, the NCO equivalent refers to, the isocyanate group reactive functional groups of the compartmentation compound that contains aromatic ring is with respect to the equivalence ratio of the isocyanate group of polyfunctional isocyanate's compound.
[table 1]
Test example 1
About by embodiment 1～5 and the resulting acrylic adhesives of comparative example 1～8, by following method, measure gel ratio, bounding force, photoelastic coefficient.Show the result in table 2.
(gel ratio)
Coating acrylic adhesives solution on PET film after the silicone coated of thickness 38 μ m, so that its dried thickness reaches 25 μ m, and in the drying machine of 80 ℃ 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 standing 7 days, thereby adhesive sheet obtained.
Be that 50mm * 50mm size is made test film by resulting adhesive sheet severing, peel binder layer from test film, and measure the initial weight of binder layer.This binder layer of dipping in the 100g vinyl acetic monomer, and at room temperature place 24 hours.Then, with 200 mesh filter screens, filter, with 80 ℃ by dry 2 hours of remaining composition residual on mesh and carry out weighing.According to initial weight and remaining composition weight and calculate the gel ratio by following formula.
Gel ratio (%)=100 * (remaining composition weight/initial weight)
(bounding force)
Coating acrylic adhesives solution on PET film after the silicone coated of thickness 38 μ m, so that its dried thickness reaches 25 μ m, and in the drying machine of 80 ℃ 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 standing 7 days, thereby adhesive sheet obtained.
By resulting adhesive sheet severing, be that wide 25mm * long 150mm makes test film.Patch test sheet on non-alkali glass.The power when speed that peels with 300mm/min is started to peel off to an end of 180 ° of directions pulling test films is measured.
(photoelastic coefficient)
Coating acrylic adhesives solution on PET film after the silicone coated of thickness 38 μ m, so that its dried thickness reaches 50 μ m, and in the drying machine of 80 ℃ dry 2 minutes.Then, make the PET after silicone coated film adhered on dry face, and under 23 ℃, the condition of 65%RH standing 7 days, thereby adhesive sheet obtained.
Resulting adhesive sheet is built up to thickness 1000 μ m, and make the test film that 2cm * 5cm is square.Under 25 ℃, the environment of 50%RH, use ellipsometer M-220 (Japanese light splitting company produce), and apply tensile stress by made test film two end portions in the scope of 0～10N, and measure the photoelastic coefficient of 600nm.
[table 2]
Test example 2
About the adhesion type polarizing film obtained by embodiment 1～5 and comparative example 1～8, estimate weather resistance by following method, and measure brightness.Show the result in table 3.
(weather resistance)
<thermotolerance and humidity resistance >
Be 15 inches sizes (233mm * 309mm) by the severing of adhesion type polarizing film, and use laminating roll that it is attached on the single face of non-alkali glass plate of thickness 0.5mm.After attaching, use autoclave (the former making of chestnut is produced) to carry out pressure treatment with 0.5MPa, the condition of 50 ℃, 20 minutes, thereby obtain testing, use plate.Place 500 hours at 85 ℃/plate that condition dry, 60 ℃/90%RH will obtain in this way, peel off, float by visual observation, and following commentary valency benchmark is estimated.
[benchmark]
Zero: there is no to find the bad order that peel off or float etc.
△: confirm as the bad order that peeling off is slightly arranged 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, the plate obtained is in the above described manner carried out take for 200 times-40 ℃ of lower 30 minutes, 80 ℃ lower 30 minutes cold cycling as 1 circulation repeatedly, 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 slightly arranged, float, peel off etc.
*: confirmed foaming, floated, peeled off (mensuration of brightness)
Be 15 inches sizes (233mm * 309mm) by the severing of adhesion type polarizing film, and attach respectively (45 °) on the surface of the non-alkali glass of thickness 0.5mm in the mode that forms the cross-polarized light state.After attaching, use autoclave (the former making of chestnut is produced) to carry out pressure treatment with 0.5MPa, the condition of 50 ℃, 20 minutes, thereby obtain testing, use plate.Resulting test is installed with the Polarizer exchange of plate and display monitor BENQ PF01G.After under the environment of 85 ℃/dry or 60 ℃/90%RH, this display controller being placed respectively to 200 hours, let cool 2 hours under the environment of 25 ℃ * 50%RH, then be connected with PC in darkroom and be made as whole picture disply black.Display monitor about these whole picture disply black, (Hyland company produces, RISA-COLOR/CD8) and to the brightness (L in the diameter 1cm zone of near the brightness (La, Lb, Lc, Ld) in the diameter 1cm zone Ge Bian center and watch-dog middle body to use luminance meter
center) measured, and obtain light leak (Δ L) by following formula.The less expression light leak of Δ L is fewer, usually only is less than 4.0, 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 adds polyfunctional isocyanate's compound and multifunctional compartmentation compound and obtain in acrylic polymers of the present invention is good and light leak is also less.On the other hand, in the comparative example 1,5,6 that does not add multifunctional compartmentation compound, even change the addition of isocyanate compound, also light leak can only be adjusted a little, the superperformance as the application can't be obtained.In addition, in the comparative example 2,3,4 that has added the compartmentation compound that does not there is aromatic ring, also can't obtain good anti-light leak.And, in isocyanate compound equivalent has been added to the comparative example 8 of compartmentation compound of the present invention, thereby due to isocyanate compound reacts with the compartmentation compound can't polymkeric substance is effectively crosslinked, therefore be confirmed to be bad order in damp and hot, cold cycling, and anti-light leak is also insufficient.In addition, in acrylic polymers, make in the comparative example 7 of the monomer copolymerization that contains aromatic ring more than specified quantitative, poor, the anti-light leak of weather resistance is also poor.
On industry may the property used
Acrylic adhesives of the present invention has excellent weather resistance, and by controlling photoelastic coefficient, and reduce the double refraction caused due to internal stress, thus can effectively prevent light leak.Therefore, can be suitable as the tackiness agent that polarizing film uses and utilize.
Claims (6)
1. an acrylic adhesives, contain following compositions (A) to (C),
(A) following acrylic polymers, that is, and by following monomer
(a-1) (methyl) acrylate
(a-2) monomer that contains aromatic ring
(a-3) monomer copolymerization that contains functional group and obtaining, and the content of monomer (a-2) is 3～50 quality % with respect to monomer (a-1) and total amount (a-2);
(B) polyfunctional isocyanate's compound;
(C) the compartmentation compound that contains aromatic ring, it contains any one the above isocyanate group reactive functional groups in aromatic ring and the above hydroxyl of two senses, amino, carboxyl, amide group,
It is characterized in that,
Isocyanate group reactive functional groups in composition (C) is 0.01～0.60 with respect to the equivalence ratio of the isocyanate group in composition (B), and the photoelastic coefficient of the binder layer formed by described acrylic adhesives is 100 * 10
-12m
2/ N is above and 1000 * 10
-12m
2below/N,
Monomer (a-1) is for being selected from one kind or two or more in (methyl) alkyl acrylate, (methyl) vinylformic acid alcoxyl base ester and (methyl) vinylformic acid aklylene glycol,
Monomer (a-2) is for being selected from one kind or two or more in (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid phenoxy ethyl, (methyl) phenyl acrylate and (methyl) vinylformic acid naphthyl ester,
Monomer (a-3) is a kind or 2 kinds in the monomer that is selected from the monomer that contains carboxyl and contains hydroxyl.
2. acrylic adhesives as claimed in claim 1, wherein,
Monomer (a-1) is, with respect to whole monomers (a-1), and the monomer of the alkyl acrylate that contains the above carbonatoms 4～8 of 60 quality %.
3. acrylic adhesives as claimed in claim 1, wherein,
Composition (B) is polyalcohol modified isocyanate compound.
4. a polarizing film adhesive sheet, it forms by the binder layer formed by the described acrylic adhesives of any one in claim 1～3 is set at least one face of supporting mass.
5. an adhesion type polarizing film, it forms by the binder layer formed by the described acrylic adhesives of any one in claim 1～3 is set at least one face of polarizing film.
6. adhesion type polarizing film as claimed in claim 5, its liquid crystal cell that is twisted nematic mode or supertwist nematic-mode for display format.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009045289A JP5531190B2 (en) | 2009-02-27 | 2009-02-27 | Acrylic adhesive, adhesive sheet for polarizing film and adhesive polarizing film using the same |
| JP2009-045289 | 2009-02-27 | ||
| 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 CN102333838A (en) | 2012-01-25 |
| CN102333838B true CN102333838B (en) | 2014-01-08 |
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| JP (1) | JP5531190B2 (en) |
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| JP6097474B2 (en) * | 2010-12-13 | 2017-03-15 | 日東電工株式会社 | Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, pressure-sensitive adhesive optical film, and image display device |
| JP5003849B1 (en) * | 2011-03-31 | 2012-08-15 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition for laminated sheet and back surface protective sheet for solar cell |
| JP2013178507A (en) * | 2012-02-03 | 2013-09-09 | Fujifilm Corp | Polarizing plate and liquid crystal display device using the same |
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| JP6196781B2 (en) * | 2013-02-13 | 2017-09-13 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| KR101408712B1 (en) * | 2013-05-14 | 2014-06-17 | 주식회사 엘지화학 | Polarizing plate |
| JP2016020442A (en) * | 2014-07-15 | 2016-02-04 | 昭和電工株式会社 | Composition for transparent adhesive sheet, and transparent adhesive sheet |
| JP6644971B2 (en) * | 2014-08-06 | 2020-02-12 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6886401B2 (en) * | 2015-08-18 | 2021-06-16 | 綜研化学株式会社 | Adhesive layer and adhesive composition for polarizing plates |
| KR102047288B1 (en) | 2015-12-10 | 2019-11-21 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| JP6290466B2 (en) * | 2017-01-25 | 2018-03-07 | リンテック株式会社 | Adhesive sheet |
| CN115362233A (en) * | 2020-03-24 | 2022-11-18 | 日东电工株式会社 | Interlayer sheet, interlayer sheet with release liner, and optical laminate |
| KR20220153087A (en) * | 2020-03-24 | 2022-11-17 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
| 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 |
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| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4521520B2 (en) * | 2003-08-06 | 2010-08-11 | 綜研化学株式会社 | Adhesive for low polarity film |
| JP3997271B2 (en) * | 2005-11-21 | 2007-10-24 | 綜研化学株式会社 | Optical film pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet, and optical member using the same |
| 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 CN CN201080009578.3A patent/CN102333838B/en not_active Expired - Fee Related
- 2010-02-03 WO PCT/JP2010/051483 patent/WO2010098182A1/en active Application Filing
- 2010-02-03 KR KR1020117018310A patent/KR20110131173A/en not_active Application Discontinuation
- 2010-02-10 TW TW099104169A patent/TW201040237A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2005-53976A 2005.03.03 |
| JP特开2007-138057A 2007.06.07 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102333838A (en) | 2012-01-25 |
| KR20110131173A (en) | 2011-12-06 |
| TW201040237A (en) | 2010-11-16 |
| WO2010098182A1 (en) | 2010-09-02 |
| JP5531190B2 (en) | 2014-06-25 |
| JP2010196000A (en) | 2010-09-09 |
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