CN106010385B - Optical film and liquid crystal display device with adhesive phase - Google Patents

Optical film and liquid crystal display device with adhesive phase Download PDF

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Publication number
CN106010385B
CN106010385B CN201610187176.1A CN201610187176A CN106010385B CN 106010385 B CN106010385 B CN 106010385B CN 201610187176 A CN201610187176 A CN 201610187176A CN 106010385 B CN106010385 B CN 106010385B
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methyl
adhesive phase
optical film
substituent group
weight
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CN106010385A (en
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浅津悠司
韩银九
柳智熙
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Abstract

The present invention provides a kind of optical film with adhesive phase, it includes optical films and adhesive phase, described adhesive is laminated on optical film layer by layer, by containing 100 parts by weight of (methyl) acrylic resin (A), isocyanates system crosslinking agent (B) 0.08~2.5 parts by weight, silane compound (C), and the adhesive composition of the defined ionic compound (D) indicated with formula (I) is constituted, (methyl) acrylic resin (A) contains the Component units of the alkyl acrylate (a1) from the glass transition temperature of homopolymer lower than 0 DEG C, and from homopolymer glass transition temperature be 0 DEG C or more alkyl acrylate (a2) Component units, and there is single peak in the range of weight average molecular weight 1000~2,500,000 on the elution curve of GPC , the present invention also provides the liquid crystal display devices comprising the optical film.

Description

Optical film and liquid crystal display device with adhesive phase
Technical field
The present invention relates to the optical film with adhesive phase and include the liquid crystal display device of the optical film.
Background technique
Made so that polarization plates made of fitting transparent resin film are laminated in the one or both sides of polarizing film as the optical film of representative It is widely used to constitute the optical component of the image display devices such as liquid crystal display device.The optical film of polarization plates etc passes through It is often pressed from both sides across adhesive phase and to be bonded use with other components (such as liquid crystal cells in liquid crystal display device etc.) and (such as join According to Japanese Unexamined Patent Publication 2010-229321 bulletin).Therefore, as optical film, it is known to be previously provided with adhesive in one face The optical film with adhesive phase of layer.In addition, in order to assign anti-static electricity interference, it is also known that have within the adhesive layer containing from The optical film of sub- property compound.
Summary of the invention
In recent years, liquid crystal display device is extended to using smart phone and panel type terminal, vehicle-mounted navigation system as generation The mobile device purposes with touch panel function of table.Adhesive phase is had in such touch input formula liquid crystal display device Optical film also its adhesive phase is for example pressed from both sides sometimes across resin layer or is directly contact configured at for example by metal line On the metal layer of composition.However, in the metal layer and the adhesive phase group containing ionic compound that will be made of metal material In the composition of conjunction, under hot and humid environment having metal layer, there is a situation where corrode.In corrosion, since spot corrosion is in gold Belong to layer thickness it is thin in the case where or metal layer when being metal line in the case where its line width, metal layer can be run through, therefore outstanding It becomes problem.
In addition, requiring durability generally, for the optical film with adhesive phase for constituting liquid crystal display device etc.. That is, the adhesive phase being fitted into liquid crystal display device etc. is placed in sometimes under high temperature or hot and humid environment, or it is placed in repeatedly In the environment of high temperature and low temperature, and the optical film for having adhesive phase, it is desirable that even if under these circumstances, can also inhibit Adhesive phase and the tilting in the interface for the optical component for being bonded it fall off, the not good situations such as the foaming of adhesive phase, in addition, Optical characteristics is also required not deteriorate.
The object of the present invention is to provide the burn into durability for the metal layer that can inhibit metal wiring layer etc is also excellent The different optical film with adhesive phase and the liquid crystal display device comprising the optical film.
The present invention provides the optical film with adhesive phase and the liquid crystal display dress comprising the optical film as shown below It sets and adhesive composition.
[1] a kind of optical film with adhesive phase it includes optical film and is laminated in viscous on its at least one face Mixture layer,
Described adhesive layer is by containing (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), silane chemical combination The adhesive composition of object (C) and ionic compound (D) is constituted,
(methyl) acrylic resin (A) is containing the glass transition temperature from homopolymer lower than 0 DEG C Component units of alkyl acrylate (a1) and be 0 DEG C or more of acrylic acid from the glass transition temperature of homopolymer The Component units of Arrcostab (a2) and weight average molecular weight 1000~2,500,000 on the elution curve of gel permeation chromatography There is (methyl) acrylic resin at single peak in range,
The content of isocyanates system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A) For 0.08~2.5 parts by weight,
The ionic compound (D) is the ionic compound indicated with following formula (I):
[changing 1]
In formula, R1~R8It each independently represents hydrogen atom, the alkyl that can have substituent group, can have substituent group Alkenyl, the alkynyl that can have substituent group, the aryl that can have substituent group or the heterocycle that can have substituent group, R1~R4 Ring, R can also be formed between adjacent substituent group5~R8Ring can also be formed between adjacent substituent group.
[2] according to the optical film with adhesive phase recorded in [1], wherein the ionic compound (D) it is negative from Son is the borate anion indicated with following formula (II):
[changing 2]
In formula, R9~R13It each independently represents hydrogen atom, the alkyl that can have substituent group, can have substituent group Alkenyl, the alkynyl that can have substituent group, the aryl that can have substituent group, the heterocycle or halogen that can have substituent group Atom can also form ring between adjacent substituent group.
[3] according to the optical film with adhesive phase recorded in [1] or [2], wherein the ionic compound (D) Anion be four (pentafluorophenyl group) borate anions.
[4] optical film with adhesive phase recorded according to any one of [1]~[3], wherein the ionic chemical combination The anion of object (D) is four (pentafluorophenyl group) borate anions, and cation is with former containing nitrogen comprising unsaturated bond The heterocycle structure of son.
[5] optical film with adhesive phase recorded according to any one of [1]~[4], wherein the ionic chemical combination The anion of object (D) is four (pentafluorophenyl group) borate anions, and cation is the pyridine indicated with following formula (III) Cation:
[changing 3]
In formula, R14~R19It each independently represents hydrogen atom, the alkyl that can have substituent group, can have substituent group Alkenyl, can have substituent group alkynyl, can have substituent group aryl, can have substituent group heterocycle, hydroxyl, Ether, carboxyl, carbonyl or halogen atom can also form ring between adjacent substituent group.
[6] optical film with adhesive phase recorded according to any one of [1]~[5], wherein (methyl) propylene Acid system resin (A) contains the Component units from the monomer with hydroxyl.
[7] optical film with adhesive phase recorded according to any one of [1]~[6], wherein (methyl) propylene The weight average molecular weight of acid system resin (A) is 500,000~2,500,000.
[8] optical film with adhesive phase recorded according to any one of [1]~[7], wherein described adhesive combination Object contains substantially no peroxide.
[9] optical film with adhesive phase recorded according to any one of [1]~[8], wherein described adhesive combination Object contains substantially no three azole compounds.
[10] optical film with adhesive phase recorded according to any one of [1]~[9], wherein (methyl) third Olefin(e) acid system resin (A) contains substantially no the Component units from methacrylate ester monomer.
[11] optical film with adhesive phase recorded according to any one of [1]~[10], wherein the optical film packet Containing the polarizing film by being constituted by the polyvinyl alcohol resin of iodine staining,
Described adhesive layer is directly laminated on the polarizing film.
[12] a kind of liquid crystal display device, it includes the optics with adhesive phase that any one of [1]~[11] are recorded Film.
[13] a kind of adhesive composition, contain (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), Silane compound (C) and ionic compound (D),
(methyl) acrylic resin (A) is containing the glass transition temperature from homopolymer lower than 0 DEG C Component units of alkyl acrylate (a1) and be 0 DEG C or more of acrylic acid from the glass transition temperature of homopolymer The Component units of Arrcostab (a2) and weight average molecular weight 1000~2,500,000 on the elution curve of gel permeation chromatography There is (methyl) acrylic resin at single peak in range,
The content of isocyanates system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A) For 0.08~2.5 parts by weight,
The ionic compound (D) is the ionic compound indicated with following formula (I):
[changing 4]
In formula, R1~R8It each independently represents hydrogen atom, the alkyl that can have substituent group, can have substituent group Alkenyl, the alkynyl that can have substituent group, the aryl that can have substituent group or the heterocycle that can have substituent group, R1~R4 Ring, R can also be formed between adjacent substituent group5~R8Ring can also be formed between adjacent substituent group.
Described adhesive composition is used to form the adhesive phase of stacking on the metal layer.
According to the present invention it is possible to provide the burn into durability for being able to suppress the metal layer contiguously configured with adhesive phase Also the excellent optical film with adhesive phase and the liquid crystal display device comprising the optical film.
Detailed description of the invention
Fig. 1 is the constructed profile for indicating an example of the optical film with adhesive phase of the invention.
Fig. 2 is the constructed profile of an example for indicating that the layer of polarization plates is constituted.
Fig. 3 is another constructed profile for indicating the layer of polarization plates and constituting.
Fig. 4 is the constructed profile of an example for indicating that the layer of optical laminate is constituted.
Fig. 5 is another constructed profile for indicating the layer of optical laminate and constituting.
Fig. 6 is another constructed profile for indicating the layer of optical laminate and constituting.
Fig. 7 is another constructed profile for indicating the layer of optical laminate and constituting.
Fig. 8 is another constructed profile for indicating the layer of optical laminate and constituting.
Specific embodiment
< has the optical film > of adhesive phase
Fig. 1 is the constructed profile for indicating an example of the optical film with adhesive phase of the invention.This hair as shown in Figure 1 The bright optical film 1 with adhesive phase includes optical film 10 and the adhesive phase 20 being laminated on its at least one face.Bonding Oxidant layer 20 is usually directly laminated in the surface of optical film 10.
Optical film 10 either single layer structure optical film, be also possible to the optical film of multilayered structure.Adhesive phase 20 By containing (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), silane compound (C) and ionic chemical combination The adhesive composition of object (D) is constituted.The adhesive composition can also be also containing other ingredients." (first in this specification Base) acrylic acid " refer at least one party in acrylic acid and methacrylic acid.For " (methyl) acrylate " or " (first Base) acryloyl group " etc. it is also identical.
(1) optical film
The optical film 10 that optical film 1 with adhesive phase has, which can be, can be packed into the images such as liquid crystal display device The various optical films (film with optical characteristics) of display device.Optical film 10 either single layer structure optical film, can also To be the optical film of multilayered structure.The concrete example of the optical film of single layer structure further includes phase difference film, bright other than polarizing film Degree improves the optical functionals films such as film, antiglare film, antireflection film, diffusion barrier, condensing film.The concrete example of the optical film of multilayered structure Including polarization plates, phase plate.So-called polarization plates, which refer to, in this specification is laminated with resin film at least one surface layer of polarizing film Or the component of resin layer.So-called phase plate refers to and is laminated with resin film or resin layer at least one surface layer of phase difference film Component.Optical film 10 is preferably polarization plates, polarizer, phase difference board or phase difference film, more preferably polarization plates or polarizing film.
(1-1) polarization plates
Fig. 2 and Fig. 3 is the constructed profile for the example for indicating that the layer of polarization plates is constituted.Polarization plates 10a shown in Fig. 2 is Polarization plates are protected in the folded single side for being fitted with the first resin film 3 of a surface layer of polarizing film 2, polarization plates 10b shown in Fig. 3 is Also in the folded two-sided protection polarization plates for being fitted with the second resin film 4 of another surface layer of polarizing film 2.First, second resin film 3,4 It can press from both sides and be bonded across gluing oxidant layer (not shown) or adhesive phase with polarizing film 2.Polarization plates 10a, 10b also may include One, the other films or layer other than the second resin film 3,4.
Polarizing film 2 be the rectilinearly polarized light having Xi Shous with the vibration plane parallel with its absorption axis, transmission have and suction The film of the property of the rectilinearly polarized light of orthogonal (parallel with the axis of homology) vibration plane of axis is received, can be used for example makes dichroism color Film obtained by element is adsorbed in polyvinyl alcohol resin film and is orientated.As dichroism pigment, iodine can be used, dichroism has engine dyeing Material.
Polyvinyl alcohol resin can be obtained by by polyvinyl acetate system resin saponification.As polyvinyl acetate It is resin, other than as the polyvinyl acetate of the homopolymer of vinyl acetate, can also enumerate can be with vinyl acetate Monomer and the copolymer of vinyl acetate of ester copolymerization etc..As can be enumerated not with the monomer of vinyl acetate copolymerization Saturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, (methyl) acrylamide with ammonium etc..
The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of %, preferably 98 moles of % or more.Polyvinyl alcohol It is that resin can also be modified, such as the polyvinyl formal or polyvinyl acetal being modified by aldehydes also can be used Deng.The average degree of polymerization of polyvinyl alcohol resin is usually 1000~10000, and preferably 1500~5000.Polyethenol series tree The average degree of polymerization of rouge can be found out according to JIS K 6726.
Usually used using the raw material film of film obtained by being film-made polyvinyl alcohol resin as polarizing film 2.Polyvinyl alcohol It is that resin can use well known method film.The thickness of raw material film is usually 1~150 μm, if also considering the appearance of stretching Yi Du etc., then preferably 10 μm or more.
Polarizing film 2 can for example manufacture as follows, that is, implement the process being uniaxially stretched to raw material film, use dichroism pigment Film is dyed and is allowed to adsorb the process of the dichroism pigment, with the process of boric acid aqueous solution process film and water is carried out to film The process washed, is finally dried and is manufactured.The thickness of polarizing film 2 is usually 1~30 μm, from the optical film for having adhesive phase From the viewpoint of 1 filming, preferably 20 μm hereinafter, more preferably 15 μm hereinafter, further preferably 10 μm or less.
Polarizing film 2 made of making dichroism pigment be adsorbed in polyvinyl alcohol resin film and be orientated can use following side Method 1 obtains, that is, uses the independent film of polyvinyl alcohol resin film as raw material film, and is uniaxially stretched processing to film implementation And the dyeing processing of dichroism pigment can also be obtained in addition to this using method 2, that is, contain polyethylene to base material film coating The coating fluid (aqueous solution etc.) of alcohol system resin, be allowed to it is dry obtain the base material film with polyvinyl alcohol resin layer after, by it It being uniaxially stretched together with base material film, the dyeing for implementing dichroism pigment to the polyvinyl alcohol resin layer after stretching is handled, Then removing removes base material film.As base material film, it can be used and include and aftermentioned first, second resin film 3,4 can be constituted The identical thermoplastic resin of thermoplastic resin film, preferably comprising the polyester based resins such as polyethylene terephthalate, The cyclic polyolefins hydrocarbon system such as the cellulose-based resins such as polycarbonate-based resin, triacetyl cellulose, norbornene resin resin gathers The film of phenylethylene resin series etc..According to the above method 2, it is easy the polarizing film 2 of production film, is also easy such as 7 μm of thickness of production Polarizing film 2 below.
First, second resin film 3,4 can be each independently comprising with translucency, preferably optically transparent Thermoplastic resin, such as chain polyolefin-based resins (polyethylene-based resin, polypropylene-based resin), cyclic polyolefin hydrocarbon system resin The polyolefin-based resins of (norbornene resin etc.) etc；Cellulose-based resin (cellulose esters system resin etc.)；Polyester tree Rouge (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT) etc.)；It is polycarbonate-based Resin；(methyl) acrylic resin；Polystyrene resin；Polyether-ether-ketone system resin；Polysulfones system resin or their mixing The film of object, copolymer etc..Wherein, the first, second resin film 3,4 is preferably respectively by being selected from cyclic polyolefin hydrocarbon system resin, poly- carbonic acid Resin in ester system resin, cellulose-based resin, polyester based resin and (methyl) acrylic resin is constituted, more preferably by Resin in cellulose-based resin and cyclic polyolefin hydrocarbon system resin is constituted.
As chain polyolefin-based resins, other than the homopolymer of the chain olefins such as polyvinyl resin, acrylic resin, The copolymer comprising chain olefin of more than two kinds can also be enumerated.
It includes with norbornene, tetracyclododecen (alias: dimethano eight that cyclic polyolefin hydrocarbon system resin, which is as polymerized unit, Hydrogen naphthalene) or they derivative be typical example cyclic olefin resin general name.If enumerating cyclic polyolefin hydrocarbon system resin Concrete example, then be the open loop (co) polymer and its hydride of cyclic olefin, the addition polymer of cyclic olefin, cyclic olefin Insatiable hunger is used with the chain olefin of ethylene, propylene etc or the copolymer of the aromatic compound with vinyl and by them With carboxylic acid or derivatives thereof the modification (co) polymer being modified etc..Wherein, it is preferable to use having used drop ice as cyclic olefin The norbornene resin of the orbornene-baseds monomer such as piece alkene or condensed ring orbornene-based monomer.
Cellulose-based resin is preferably cellulose esters system resin, i.e. the partially or completely carboxylate etc. of cellulose, such as can With acetic acid esters, propionic ester, butyrate, their mixed ester etc. for enumerating cellulose.Wherein, it is preferable to use triacetyl cellulose, Diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc..
Polyester based resin is the resin having other than ester bond, above-mentioned cellulose esters system resin, usually includes polynary carboxylic The resin of acid or derivatives thereof and the condensation polymer of polyalcohol.The concrete example of polyester based resin includes polyethylene terephthalate Ester, polybutylene terephthalate (PBT), polyethylene naphthalate, polybutylene naphthalate, poly terephthalic acid third Diol ester, polytrimethylene naphthalate, polycyclohexylene's diformazan alcohol ester, poly- naphthalenedicarboxylic acid cyclohexanedimethanol Ester.
Polycarbonate-based resin is the polyester formed by carbonic acid and glycol or bis-phenol.Wherein, from heat resistance, weatherability and resistance to From the viewpoint of acidity, it is preferable to use with the aromatic copolycarbonate of diphenyl alkane in strand.As polycarbonate, It may be exemplified out by bis- (4- hydroxy phenyl) propane (alias bisphenol-A) of 2,2-, 2,2- bis- (4- hydroxy phenyl) butane, 1, Bis- (4- hydroxy phenyl) iso-butanes of 1- bis(4-hydroxyphenyl)cyclohexane, 1,1-, bis- (4- hydroxy phenyl) ethane of 1,1- Etc bis-phenol derived from polycarbonate.
(methyl) acrylic resin that the first, second resin film 3,4 can be constituted can be from metering system (such as this composition unit containing the 50 weight % or more) polymer of the Component units of acid esters as main body, preferably at it It is upper to be copolymerized the copolymer for having other copolymer compositions.(methyl) acrylic resin also may include of more than two kinds from methyl The Component units of acrylate.As methacrylate, methyl methacrylate, ethyl methacrylate, first can be enumerated The C of the methacrylic acids such as base butyl acrylate1~C4Arrcostab.
As acrylate can be enumerated with the copolymer composition of methacrylate copolymers.Acrylate is preferably The C of the acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-EHA1~C8Arrcostab.Other The concrete example of copolymer composition can enumerate the unsaturated acids such as (methyl) acrylic acid；Styrene, halogenated styrenes, Alpha-Methyl benzene The aromatic ethenyl compounds such as ethylene, vinyltoluene；The vinyl cyanide compounds such as (methyl) acrylonitrile；Maleic anhydride, lemon The unsaturated acid anhydrides such as health acid anhydrides；Unsaturated acyls imines such as phenyl maleimide, N-cyclohexylmaleimide etc. has in the molecule There is the compound other than 1 polymerism carbon-to-carbon double bond, acrylate.It can also will be poly- with 2 or more in the molecule The compound of conjunction property carbon-to-carbon double bond is used as copolymer composition.Copolymer composition can both be used only a kind, also can be used together 2 kinds More than.
From the aspect of the durability that film can be improved, (methyl) acrylic resin can also be in high polymer main chain With ring structure.Ring structure is preferably the heterocycle structures such as cyclic acid anhydride structure, cyclic imide structure, lactone ring structure.As The concrete example of cyclic acid anhydride structure can enumerate glutaric anhydride structure, succinic anhydride structure, the tool as cyclic imide structure Body example can enumerate glutarimide structure, succimide structure, as the concrete example of lactone ring structure, can enumerate fourth Lactone ring structure, valerolactone ring structure.
Consider from the viewpoints such as the film formation property of film, the impact resistance of film are made, (methyl) acrylic resin can also contain Acrylic rubber particle.So-called acrylic rubber particle is particle as an essential component with elastomeric polymer, the bullet Property polymer using acrylate as main body, can enumerate substantially only comprising the elastomeric polymer single layer structure particle, Using elastomeric polymer as the particle of the multilayered structure of 1 layer.As the example of elastomeric polymer, can enumerate with alkyl acrylate Base ester is as principal component and has been copolymerized the crosslinking elastomeric copolymer of other vinyl monomers and cross-linkable monomer that can be copolymerized therewith Object.As the alkyl acrylate for the principal component for becoming elastomeric polymer, for example, methyl acrylate, acrylic acid second The C of the acrylic acid such as ester, butyl acrylate, 2-EHA1~C8Arrcostab.The carbon atom number of alkyl be preferably 4 with On.
As can with other vinyl monomers of alkyl acrylate copolymer, can enumerate in the molecule have 1 it is poly- More specifically the compound of conjunction property carbon-to-carbon double bond can enumerate the methacrylate, benzene of methyl methacrylate etc The vinyl cyanide compound etc. of the aromatic ethenyl compound of ethylene etc, (methyl) acrylonitrile etc.As bridging property list Body, the compound that can enumerate the bridging property at least two polymerism carbon-to-carbon double bond in the molecule more specifically can With enumerate the polyalcohols such as ethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate (methyl) acrylate, The alkenyl esters, divinylbenzene etc. of (methyl) allyl acrylate etc. (methyl) acrylic acid.
The content of acrylic rubber particle is relative to 100 parts by weight of (methyl) acrylic resin, preferably 5 parts by weight More than, it is more than more preferably 10 parts by weight.If the content of acrylic rubber particle is too many, the surface hardness of film is reduced, In addition, may be decreased in the case where film is implemented and is surface-treated to the solvent resistance of the organic solvent in surface treating agent.Cause And the content of acrylic rubber particle is relative to 100 parts by weight of (methyl) acrylic resin, usually 80 parts by weight with Under, below preferably 60 parts by weight.
First, second resin film 3,4 can contain the common additive in technical field of the invention.The tool of additive Body example is for example including ultraviolet absorbing agent, infrared absorbent, organic based dye, pigment, inorganic system's pigment, antioxidant, anti- Electrostatic interference agent, surfactant, lubricant, dispersing agent, heat stabilizer etc..
As ultraviolet absorbing agent, salicylate compounds, benzophenone cpd, benzotriazole chemical combination can be enumerated Object, triaizine compounds, (methyl) acrylic acid cyano ester compound, nickel complex etc..
First, second resin film 3,4 can be the film being not stretched or appointing by the film of uniaxial or biaxial stretching respectively It anticipates one kind.It is biaxial stretch-formed either along 2 draw directions simultaneously stretched while it is biaxial stretch-formed, can also along provide Direction is stretched gradually biaxial stretch-formed along other direction after stretching.First resin film 3 and/or the second resin film 4 can be with It is the protective film for undertaking the effect of protection polarizing film 2, is also possible to have both optical function as aftermentioned phase difference film Protective film.Phase difference film is to show optically anisotropic optical film.For example, can be by including above-mentioned thermoplastic resin Film stretched and (be stretched uniaxially or biaxially) or formed liquid crystal layer etc. on the thermoplastic resin film and be made and assigned The phase difference film of arbitrary phase difference value is given.
First resin film 3 and the second resin film 4 either the film being made of identical thermoplastic resin, be also possible to by The film that thermoplastic resin different from each other is constituted.First resin film 3 and the second resin film 4 the presence or absence of thickness, additive or its Type, phase difference characteristics etc. both may be the same or different.
First resin film 3 and/or the second resin film 4 can also be in its outer surfaces (surface with 2 opposite side of polarizing film) Have the surface-treated layers such as hard conating, antiglare layer, anti-reflection layer, light diffusion layer, anti-static electricity interference layer, stain-proofing layer, conductive layer (to apply Coating).
The thickness of first resin film 3 and the second resin film 4 is usually 1~150 μm respectively, preferably 5~100 μm, more excellent It is selected as 5~60 μm.The thickness is also possible to 50 μm hereinafter, even 30 μm or less.Reduce the thickness of the first, second resin film 3,4 Degree, is conducive to the filming of the optical film 1 with adhesive phase and the optical laminate comprising the optical film 1, and then is conducive to The filming of liquid crystal display device comprising optical film 1 or optical laminate with adhesive phase.
For towards polarization plates middle-size and small-size as smart phone, panel type terminal, from filming It is required that consider, as the first resin film 3 and/or the second resin film 4 commonly using 30 μm of thickness thin resin films below, and this Kind polarization plates inhibit the power of the convergent force of polarizing film 2 weak, and durability is easy insufficient.According to the present invention, even if will be such inclined In the case that vibration plate is as 10 use of optical film, the optical film with adhesive phase with good durability can also be provided 1 and the optical laminate comprising the optical film 1.It is so-called with the optical film 1 of adhesive phase and the durability of optical laminate Refer to following property, that is, such as under high temperature environment, under hot and humid environment, repeatedly in the environment of high temperature and low temperature, can With inhibit the tilting in the interface of adhesive phase 20 and optical component adjacent thereto or fall off, the foaming of adhesive phase 20 etc. no Good situation.
In addition, from the viewpoint of the filming of polarization plates, only in polarizing film 2 as polarization plates 10a shown in Fig. 2 The composition for configuring resin film on one side is advantageous composition.Bonding usually is directly fitted in another face of polarizing film 2 in this case Oxidant layer 20 and become the optical film 1 (referring to Fig. 4) with adhesive phase.In the case where the polarization plates of such composition, because of bonding Ionic compound contained in oxidant layer 20 and make under hot and humid environment polarization plates optical property reduce the problem of become It is especially apparent.According to the present invention, even if can also provide has using such polarization plates as in the case where 10 use of optical film The optical film 1 and packet with adhesive phase of good optical durability (property that the deterioration of optical characteristics can be inhibited) Optical laminate containing the optical film 1.
First, second resin film 3,4, which can be pressed from both sides, to be bonded across gluing oxidant layer or adhesive phase with polarizing film 2.As formation Water system adhesive or active energy ray-curable adhesive can be used in the adhesive of gluing oxidant layer.
As water system adhesive, the adhesive comprising polyvinyl alcohol resin aqueous solution, water system two-liquid type ammonia can be enumerated Carbamate system emulsion adhesive etc..Wherein, it is suitble to use the water system adhesive comprising polyvinyl alcohol resin aqueous solution.As Polyvinyl alcohol resin, in addition to the polyvinyl acetate progress saponification process to the homopolymer as vinyl acetate can be used Obtained by other than alcotex, can also use to vinyl acetate and can be copolymerized therewith other monomers copolymer Carry out polyvinyl alcohol based copolymer or the modified polyvinylalcohol system for being modified their hydroxylic moiety obtained by saponification process Polymer etc..Water system adhesive can contain aldehyde compound, epoxy compounds, melamine based compound, methylol chemical combination The crosslinking agents such as object, isocyanate compound, amine compounds, multivalent metal salt.
Using water system adhesive, after being bonded polarizing film 2 with the first, second resin film 3,4, in order to remove The preferred implementation of water contained in water system adhesive is gone to be allowed to dry process.It can also be arranged after drying process for example 20 The curing step that~45 DEG C or so of temperature is cured.
Above-mentioned so-called active energy ray-curable adhesive refers to because irradiation ultraviolet light or electron beam isoreactivity energy are penetrated Line and cured adhesive, for example, the solidification compound containing polymerizable compound and Photoepolymerizationinitiater initiater, containing Solidification compound, solidification compound containing binder resin and photoreactivity crosslinking agent for having light reactive resin etc.. Preferably ultra-violet solidified adhesive.As polymerizable compound, photo-curable epoxy monomer, photo-curable can be enumerated Photopolymerization monomers such as (methyl) acrylic monomer, photo-curable carbamate system monomer or from optical polymerism list The oligomer of body.As Photoepolymerizationinitiater initiater, generated due to can enumerating containing the irradiation because of active energy beam Neutral radical, Radical anion, radical cation isoreactivity center substance Photoepolymerizationinitiater initiater.As containing polymerizable compound And the active energy ray-curable adhesive of Photoepolymerizationinitiater initiater it is preferable to use containing photo-curable epoxy monomer and The solidification compound of light cationic polymerization initiator polymerize containing photo-curable (methyl) acrylic monomer and optical free radical The mixture of the solidification compound of initiator or these solidification compounds.
Using active energy ray-curable adhesive, by polarizing film 2 and the first, second resin film 3, After 4 fittings, process is dried as needed, then carries out making active energy ray-curable by irradiating active energy beam The property cured curing process of adhesive.The light source of active energy beam is not particularly limited, however it is preferred that below wavelength 400nm Ultraviolet light with luminous distribution, specifically, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, super-pressure can be used Mercury vapor lamp, chemical lamp, black light lamp, microwave-excitation mercury vapor lamp, metal halide lamp etc..
It, can be to the fitting of their at least any one party when polarizing film 2 to be bonded with the first, second resin film 3,4 Implement the processing of the surface activations such as saponification process, sided corona treatment, corona treatment in face.Resin is bonded on the two sides of polarizing film 2 For the adhesive that is bonded these resin films either adhesive of the same race, is also possible to glue not of the same race in the case where film Stick.
Polarization plates 10a, 10b can be also comprising other films or layer.Its concrete example is other than aftermentioned phase difference film, also It can be the adhesive phase other than brightness raising film, antiglare film, antireflection film, diffusion barrier, condensing film, adhesive phase 20, coat Layer, protective film etc..Protective film is for protecting the surface of the optical films such as polarization plates 10 to use from the purpose damaged or polluted Film, it is common practice to after the optical film 1 for having adhesive phase is fitted on such as metal layer 30, be stripped removing.
Protective film is usually made of the adhesive phase of base material film and stacking thereon.Base material film can by thermoplastic resin, Such as the polyolefin-based resins such as polyethylene-based resin, polypropylene-based resin；Polyethylene terephthalate or poly- naphthalenedicarboxylic acid The polyester based resins such as glycol ester；Polycarbonate-based resin；(methyl) acrylic resin etc. is constituted.
(1-2) phase plate
Phase difference film contained in phase plate is as described above, be to show optically anisotropic optical film, as can Can be to thermoplastic resin and example comprising being illustrated above for the phase difference film in the first, second resin film 3,4 Such as polyvinyl alcohol resin, polyarylate system resin, polyimides system resins, polyether sulfone system resin, polyvinylidene fluoride/poly- methyl Methyl acrylate system resin, liquid crystal polyester system resin, ethylene-acetidin copolymer saponification material, polyvinyl chloride resin etc. Resin film be stretched as 1.01~6 times or so obtained by stretched film.Wherein, preferably to polycarbonate-based resin film or cyclic annular alkene Drawing obtained by hydrocarbon system resin film, (methyl) acrylic resin film or cellulose-based resin film are stretched uniaxially or biaxially Stretch film.In addition, in the present specification, zero-lag film, which is also contained in phase difference film, (but can also be used as protective film use.). In addition to this, uniaxiality phase difference film, wide viewing angle phase difference film, low modulus of photoelasticity phase difference film etc. will can also be referred to as Film is used as phase difference film.
So-called zero-lag film, refers to phase difference value R in faceeAnd thickness direction phase difference value RthAll for -15~15nm's Film.The phase difference film can be adapted for the liquid crystal display device of IPS mode.Phase difference value R in faceeAnd thickness direction phase difference value RthIt is more preferably all -5~5nm it is preferred that being all -10~10nm.Phase difference value R in face described hereineAnd thickness direction phase Potential difference value RthValue when being wavelength 590nm.
Phase difference value R in faceeAnd thickness direction phase difference value RthIt is defined by the formula respectively:
Re=(nx- ny)×d
Rth=((nx+ny)/2-nz〕×d
In formula, nxIt is the refractive index of the slow-axis direction (x-axis direction) in film surface, nyIt is the fast axis direction in film surface (in face The y-axis direction orthogonal with x-axis) refractive index, nzIt is the refractive index in film thickness direction (perpendicular to the z-axis direction of film surface), d is film Thickness.
As zero-lag film, can be used for example comprising cellulose-based resin, chain polyolefin-based resins and cyclic polyolefin The resin of the polyolefin-based resins such as hydrocarbon system resin, PET series resin or (methyl) acrylic resin Film.Especially because the control of phase difference value is easy, acquisition is also easy, therefore it is preferable to use cellulose-based resins, polyolefin Resin or (methyl) acrylic resin.
In addition, embodying optically anisotropic film using the coating of liquid crystal compounds, orientation, using inorganic laminated The coating of compound can also be used as phase difference film use to embody optically anisotropic film.As such phase difference film, There is the phase difference film referred to as temperature compensating type phase difference film, in addition, also by JX days mine days Shi Nengyuan (strain) with " NH film " Trade name sale is incited somebody to action by film obtained by rod shaped liquid crystal tilted alignment, by Fujiphoto (strain) with what the trade name of " WV film " was sold Film obtained by disc-like liquid crystal tilted alignment, the complete biaxial orientation sold by Sumitomo Chemical (strain) with the trade name of " VAC film " The film of type, the film of biaxially oriented version equally sold by Sumitomo Chemical (strain) with the trade name of " new VAC film " etc..
The resin film for being laminated at least one face of phase difference film for example can be above-mentioned protective film.
(2) adhesive phase
The adhesive phase 20 at least one face of optical film 10 is laminated in by containing (methyl) acrylic resin (A), different The adhesive composition of cyanate system crosslinking agent (B), silane compound (C) and ionic compound (D) is constituted.The bonding (methyl) acrylic resin (A) is be lower than 0 DEG C containing the glass transition temperature from homopolymer third in agent composition Component units of olefin(e) acid Arrcostab (a1) and be 0 DEG C or more of alkyl acrylate from the glass transition temperature of homopolymer The Component units of base ester (a2) and weight average molecular weight 1000~2,500,000 on the elution curve of gel permeation chromatography (GPC) Range in single peak (methyl) acrylic resin.The content of isocyanates system crosslinking agent (B) is relative to (first Base) acrylic resin (A) 100 parts by weight be 0.08~2.5 parts by weight.
Ionic compound (D) is the ionic compound indicated with following formula (I):
[changing 5]
In formula, R1~R8It each independently represents hydrogen atom, the alkyl that can have substituent group, can have substituent group Alkenyl, the alkynyl that can have substituent group, the aryl that can have substituent group or the heterocycle that can have substituent group, R5~R8 Ring can also be formed between adjacent substituent group.
According to the adhesive phase 20 being made of above-mentioned adhesive composition, even if including adhesive phase 20 to be configured at In the case where in the substrate of the composition of metal layer, the corrosion of the metal layer can also be inhibited, furthermore it is possible to improve with adhesive The optical film 1 of layer and the durability of the optical laminate comprising the optical film 1.In addition, being combined according to by above-mentioned adhesive The adhesive phase 20 that object is constituted, even the optical film 1 with adhesive phase and the optical laminate comprising the optical film 1 Adhesive phase 20 is mounted directly on composition made of on polarizing film 2, can also show good optical durability.Hereinafter, Also the property of the corrosion of metal layer will can be inhibited to be referred to as " resistance to metal protection ".
The thickness of adhesive phase 20 is usually 2~40 μm, from the optical film 1 with adhesive phase and includes the optics The re-workability (リ ワ ー Network of the durability of the optical laminate of film 1 and the optical film 1 with adhesive phase) etc. viewpoints examine Consider, preferably 5~30 μm, more preferably 10~25 μm.In addition, if adhesive phase 20 with a thickness of 10 μm or more, bond Oxidant layer 20 becomes well the tracing ability of the change in size of optical film 10, if it is 25 μm hereinafter, then re-workability becomes good It is good.
Adhesive phase 20 is preferably the storage elastic modulus that 0.1~5MPa is shown in 23~80 DEG C of temperature range Layer.The optical film 1 with adhesive phase and the optics stacking comprising the optical film 1 can be more efficiently improved as a result, The durability of body.So-called " storage elastic modulus of 0.1~5MPa is shown in 23~80 DEG C of temperature range ", refers at this At the arbitrary temperature of range, storage elastic modulus is all the value in above range.Since storage elastic modulus is usually with temperature Degree is increased and is gradually reduced, so if 23 DEG C and 80 DEG C of storage elastic modulus both falls within above range, then it can be in the model The storage elastic modulus in above range is shown at a temperature of enclosing.The storage elastic modulus of adhesive phase 20 can be used commercially available Determination of viscoelasticity device, such as REOMETRIC corporation determination of viscoelasticity device " DYNAMIC ANALYZER RDAII " Measurement.
(2-1) (methyl) acrylic resin (A)
Be using the Component units from (methyl) acrylic monomer as principal component (preferably comprise 50 weight % with On) polymer or copolymer.The concrete example of (methyl) acrylic monomer is having for (methyl) alkyl acrylate etc The monomer of (methyl) acryloyl group, (methyl) acrylic resin (A) are containing the glass transition temperature from homopolymer The Component units of alkyl acrylate (a1) of the Tg lower than 0 DEG C and the alkyl acrylate for being 0 DEG C or more from the Tg of homopolymer The resin of the Component units of base ester (a2).It is possible thereby to improve optical film 1 with adhesive phase and comprising the optical film 1 Optical laminate resistance to metal protection and durability.The Tg of the homopolymer of alkyl acrylate can for example be used The literature value of POLYMER HANDBOOK (Wiley-Interscience) etc..
The concrete example of alkyl acrylate (a1) is including ethyl acrylate, acrylic acid just and isopropyl ester, acrylic acid are just and different Butyl ester, acrylic acid n-pentyl ester, acrylic acid just and the positive heptyl ester of dissident's ester, acrylic acid, acrylic acid just and different monooctyl ester, acrylic acid 2- second The own ester of base, acrylic acid just and different nonyl ester, acrylic acid just and the carbon atom number of the alkyl such as isodecyl ester, acrylic acid n-dodecane base ester is 2~12 or so alkyl acrylate.As other concrete examples of alkyl acrylate (a1), the carbon to alkyl can also be enumerated The acrylic acid alkyl containing substituent group of substituent group has been imported in the alkyl for the alkyl acrylate that atomicity is 2~12 or so Ester.The substituent group of alkyl acrylate containing substituent group be replace alkyl hydrogen atom group, concrete example include phenyl, Alkoxy, phenoxy group.As the alkyl acrylate containing substituent group, specifically, acrylic acid 2- methoxyl group second can be enumerated Ester, ethioxy methyl esters, phenoxyethyl acrylate, phenoxy group diethylene glycol acrylate etc..Although acrylic acid alkyl The alkyl of ester (a1) also can have ester ring type structure, however the alkyl of preferably straight-chain or branched.
Alkyl acrylate (a1) can both be used only a kind, and also two or more kinds may be used.Wherein, alkyl acrylate (a1) it preferably comprises one kind or two or more in ethyl acrylate, n-butyl acrylate, 2-EHA.From From the viewpoint of adhesive phase 20 possessed by optical film 1 with adhesive phase is to the tracing ability of optical film 10, re-workability, Alkyl acrylate (a1) preferably comprises n-butyl acrylate.
Alkyl acrylate (a2) is the alkyl acrylate other than alkyl acrylate (a1).Alkyl acrylate (a2) Concrete example include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate base ester, the tertiary fourth of acrylic acid Ester etc..
Alkyl acrylate (a2) can both be used only a kind, and also two or more kinds may be used.Wherein, from resistance to metal protection And from the viewpoint of durability, alkyl acrylate (a2) preferably comprises the different ice of methyl acrylate, cyclohexyl acrylate, acrylic acid Piece ester etc., further preferably methyl acrylate.
For the content of the Component units from alkyl acrylate (a2) in (methyl) acrylic resin (A), From the optical film 1 with adhesive phase and the resistance to metal protection and durability of optical laminate comprising the optical film 1 Viewpoint considers, in 100 parts by weight of whole Component units of composition (methyl) acrylic resin (A), preferably 10 parts by weight More than, more than more preferably 15 parts by weight, more than further preferably 20 parts by weight, more than particularly preferably 25 parts by weight.Separately Outside from the viewpoint of the tracing ability and re-workability from adhesive phase 20 to optical film 10, from alkyl acrylate (a2) The content of Component units be preferably 70 parts by weight hereinafter, more preferably 60 parts by weight hereinafter, further preferably 50 parts by weight with Under.
(methyl) acrylic resin (A) can contain other lists other than alkyl acrylate (a1) and (a2) The Component units of body.(methyl) acrylic resin (A) both can only containing a kind of Component units from the other monomers, Two or more can also be contained.The concrete example of other monomers is expressed as follows.
1) with the monomer of polar functional group.
As the monomer with polar functional group, can enumerate with hydroxyl, carboxyl, amino substituted or unsubstituted, epoxy (methyl) acrylate of the substituent groups such as the heterocycles such as base.Specifically, can enumerate (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- (2- '-hydroxyethoxy Base) ethyl ester, (methyl) acrylic acid 2- chlorine-2-hydroxyl propyl ester, (methyl) acrylic acid 3- chlorine-2-hydroxyl propyl ester, diethyl two Alcohol list (methyl) acrylate etc. has the monomer of hydroxyl；Acryloyl morpholine, caprolactam, N- vinyl -2- Pyrrolidones, vinylpyridine, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification tetrahydrofurfuryl acrylate, 3,4- epoxy group Cyclohexyl methyl (methyl) acrylate, (methyl) glycidyl acrylate, 2,5-dihydrofuran etc. have the list of heterocycle Body；(methyl) acrylate, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid dimethylamino Base propyl ester etc. has the monomer of amino substituted or unsubstituted；(methyl) acrylic acid, (methyl) carboxyethyl acrylates etc. have carboxylic The monomer of base.Wherein, preferably with the monomer of hydroxyl, from the reactive side of (methyl) acrylic resin (A) and crosslinking agent Face considers, more preferably with (methyl) acrylate of hydroxyl.
Can also be combined with (methyl) acrylate with hydroxyl has polar functional group comprising above-mentioned others Monomer, from the viewpoint of excessively increasing from the peeling force of the diaphragm for the outer surface for preventing to be laminated in adhesive phase 20, preferably Contain substantially no the monomer with amino.In addition, from the viewpoint of improving the corrosion resistance for ITO, preferably substantially Without containing the monomer with carboxyl.It is described herein to contain substantially no, refer in composition (methyl) acrylic resin (A) For below 0.1 parts by weight in whole 100 parts by weight of Component units.
2) acrylamide monomer
For example, N hydroxymethyl acrylamide, N- (2- hydroxyethyl) acrylamide, N- (3- hydroxypropyl) propylene Amide, N- (4- hydroxybutyl) acrylamide, N- (5- Hydroxy pentyl) acrylamide, N- (6- hydroxyl hexyl) acryloyl Amine, N,N-DMAA, N, N- acrylamide, n-isopropyl acrylamide, N- (3- dimethylamino Base propyl) acrylamide, N- (1,1- dimethyl -3- oxo butyl) acrylamide, N- (2- (2- oxo -1- miaow Oxazolidinyl) ethyl) acrylamide, 2- Acryloyl amino-2- methyl-1-propane sulfonic acid, N- (methoxy) third Acrylamide, N- (ethoxyl methyl) acrylamide, N- (propoxy methyl) acrylamide, N- (1- methylethoxy ylmethyl) Acrylamide, N- (1- methyl propoxy methyl) acrylamide, N- (2- methyl propoxy methyl) acrylamide (alias: N- (isobutoxymethyl) acrylamide), N- (butoxymethyl) acrylamide, N- (1,1- dimethylethoxy ylmethyl) Acrylamide, N- (2- methoxy ethyl) acrylamide, N- (2- ethoxyethyl group) acrylamide, N- (2- propoxyl group Ethyl) acrylamide, N- (2- (1- methyl ethoxy) ethyl) acrylamide, N- (2- (1- methyl propoxyl group) ethyl) Acrylamide, N- (2- (2- methyl propoxyl group) ethyl) acrylamide (alias: N- (2- isobutoxyethy) acryloyl Amine), N- (2- butoxyethyl group) acrylamide, N- (2- (1,1- dimethylethyloxy) ethyl) acrylamide etc..Its In, it is preferable to use N- (methoxy) acrylamide, N- (ethoxyl methyl) acrylamide, N- (propoxy methyl) third Acrylamide, N- (butoxymethyl) acrylamide, N- (2- methyl propoxy methyl) acrylamide.
3) methacrylate (i.e. metacrylate)
For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, The straight-chain alkyl ester of the methacrylic acids such as n octyl methacrylate, lauryl methacrylate；Isobutyl methacrylate, The branched-chain alkyl ester of the methacrylic acids such as 2-Ethylhexyl Methacrylate, isooctyl methacrylate；Methacrylic acid is different Norbornene ester, cyclohexyl methacrylate, methacrylic acid Bicvclopentyl ester, methacrylic acid cyclododecane base ester, metering system Acid methyl cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, methacrylic acid cyclohexyl benzene The ester ring type Arrcostab of the methacrylic acids such as ester；The first such as methacrylic acid 2- methoxy acrylate, methacrylic acid ethyoxyl methyl esters The alkoxy alkyl of base acrylic acid；The methacrylic acids aralkyl ester such as benzyl methacrylate；Methacrylic acid 2- hydroxyl second Ester, methacrylic acid 3- hydroxy propyl ester, methacrylic acid 4- hydroxybutyl, methacrylic acid 2- (2- hydroxyl-oxethyl) second Ester, methacrylic acid 2- chlorine-2-hydroxyl propyl ester, methacrylic acid 3- chlorine-2-hydroxyl propyl ester, diethylene glycol monomethyl third Olefin(e) acid ester etc. has the Arrcostab of the methacrylic acid of hydroxyl；Aminoethyl methacrylate, methacrylic acid N, N- dimethyl Amino ethyl ester, dimethylamine propyl ester etc. have the Arrcostab of the methacrylic acid of amino substituted or unsubstituted； Methacrylic acid 2- phenoxy ethyl, methacrylic acid 2- (2- phenoxy group) ethyl ester, (methyl) acrylic acid epoxy Oxide-modified nonyl benzene phenolic ester, methacrylic acid 2- (adjacent phenylphenoxy) ethyl ester etc. have the metering system of Phenoxyethyl The ester etc. of acid.
4) methacryl amine system monomer
Methacryl amine system monomer for example, corresponding with the acrylamide monomer of above-mentioned 1) middle record.
5) styrenic monomers
For example, styrene；Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethylbenzene The alkane such as ethylene, triethylbenzene ethylene, propylstyrene, butylstyrene, hexyl styrene, heptyl styrene, octyl styrene Base styrene；The halogenated styrenes such as fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethylene；Nitrobenzene second Alkene；Acetylbenzene ethylene；Methoxy styrene；Divinylbenzene etc..
6) vinyl monomer
For example, vinyl acetate, vinyl propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate Equal fatty acid ethylenes base ester；The vinyl halides such as vinyl chloride, vinyl bromide；The vinylidene halides such as vinylidene chloride；Vinylpyridine, second The nitrogenous aromatic vinyl monomer such as vinyl pyrrolidone, vinyl carbazole；Butadiene, isoprene, chlorobutadiene equiconjugate Diene monomers；Unsaturated nitriles such as acrylonitrile, methacrylonitrile etc..
7) in the molecule with the monomer of multiple (methyl) acryloyl groups
For example, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonyl Glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol Two (methyl) acrylate, tripropylene glycol two (methyl) acrylate etc. are in the molecule with the list of 2 (methyl) acryloyl groups Body；Trimethylolpropane tris (methyl) acrylate etc. is in the molecule with the monomer etc. of 3 (methyl) acryloyl groups.
As described above, (methyl) acrylic resin (A) is from the optical film 1 with adhesive phase and includes the optics From the viewpoint of the durability of the optical laminate of film 1 and resistance to metal protection, preferably in addition to from (methyl) alkyl acrylate Other than the Component units of base ester, also containing the Component units from the monomer with polar functional group.With polar functional group Monomer be preferably that there is (methyl) acrylate monomer of polar functional group, more preferably with the monomer of hydroxyl.It comes from List is constituted in the whole of composition (methyl) acrylic resin (A) in the content of the Component units of the monomer with polar functional group In first 100 parts by weight, preferably 0.1~10 parts by weight, more preferably 0.25~5 parts by weight, further preferably 0.5~5 weight Measure part.
In addition, from the viewpoint of the re-workability of the optical film 1 with adhesive phase, (methyl) acrylic resin (A) the structure from methacrylic monomers such as methacrylate (metacrylate), methacryl amine system monomers It is the smaller the better at the content of unit, specifically, the content of this composition unit is in the complete of composition (methyl) acrylic resin (A) In 100 parts by weight of portion's Component units, preferably 10 parts by weight hereinafter, more preferably 5 parts by weight hereinafter, further preferably substantially Without containing this composition unit (below 0.1 parts by weight).
Weight average molecular weight of (methyl) acrylic resin (A) on the elution curve of gel permeation chromatography (GPC) There is single peak in the range of Mw1000~2,500,000.Peak number in the range is 1, containing from alkyl acrylate (a1) and (methyl) acrylic resin (A) of the Component units of (a2) as the adhesive phase 20 of basic polymer is improving band There is the aspect of the optical film 1 of adhesive phase and the durability of the optical laminate comprising the optical film 1 advantageous.In above-mentioned Mw Range in peak number be 2 or more in the case where, sufficient durability can not be obtained.
When seeking the peak number of the GPC elution curve in the range for calculating Mw1000~2,500,000, according to one Xiang Zhongji of embodiment The GPC determination condition of load obtains elution curve.So-called in the above range of resulting elution curve " having single peak " is Refer to that only there is 1 maximum in the range of Mw1000~2,500,000.In this specification, in GPC elution curve, by S/N ratio Curve definitions for 30 or more are peak.
The Mw of the standard polystyren conversion based on GPC of (methyl) acrylic resin (A) is preferably in 500,000~250 Ten thousand range is more preferably in 600,000~2,000,000 range.If Mw is 500,000 or more, be conducive to adhesive phase The raising of the resistance to metal protection and durability of optical film 1 and the optical laminate comprising the optical film 1 has adhesive The trend that the re-workability of the optical film 1 of layer is also improved.In addition, if Mw be 2,500,000 hereinafter, if adhesive phase 20 for light The tracing ability for learning the change in size of film 10 becomes good.It is indicated with the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn Molecular weight distribution is usually 2~10.The Mw and Mn of (methyl) acrylic resin (A) are according to recording in embodiment one GPC determination condition is found out.
When making (methyl) acrylic resin (A) be dissolved in ethyl acetate and the solution of 20 weight % of concentration is made, 25 DEG C of viscosity is preferably 20Pas hereinafter, more preferably 0.1~7Pas.The viscosity of the range is conducive to adhesive The raising of the durability of the optical film 1 and optical laminate comprising the optical film 1 of layer, the optical film 1 with adhesive phase Re-workability.Above-mentioned viscosity can use the measurement of Brookfield viscosimeter.
The glass transition temperature Tg using differential scanning calorimeter (DSC) measurement of (methyl) acrylic resin (A) Preferably -60~-10 DEG C, more preferably -55~-15 DEG C.The Tg of the range is conducive to the optical film with adhesive phase 1 and the optical laminate comprising the optical film 1 resistance to metal protection and durability raising.
Adhesive composition can also contain (methyl) propylene of more than two kinds for belonging to (methyl) acrylic resin (A) Acid system resin.In addition, adhesive composition can also contain the others (methyl) different from (methyl) acrylic resin (A) Acrylic resin.Wherein, from the optical film 1 with adhesive phase and the resistance to gold of the optical laminate comprising the optical film 1 From the viewpoint of belonging to corrosivity and durability, the content of (methyl) acrylic resin (A) is in whole (methyl) acrylic acid series Resin it is total in, preferably 70 weight % or more, more preferably 80 weight % or more, further preferably 90 weight % with On, adhesive composition only contains (methyl) acrylic resin (A) particularly preferable as base polymer.
(methyl) acrylic resin (A) or others (methyl) acrylic resin that can according to need are for example It can use the manufacture of method well known to solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization etc..At (methyl) Usually using polymerization initiator in the manufacture of acrylic resin.Relative to the used in manufacture of (methyl) acrylic resin Total 100 parts by weight of whole monomers, use the polymerization initiator of 0.001~5 parts by weight or so.In addition, (methyl) acrylic acid It is that resin also can use and for example manufacture the method that carries out of polymerization with ultraviolet light isoreactivity energy-ray.
As polymerization initiator, thermal polymerization, Photoepolymerizationinitiater initiater etc. are used.As Photoepolymerizationinitiater initiater, such as 4- (2- hydroxyl-oxethyl) phenyl (2- hydroxyl -2- propyl) ketone etc. can be enumerated.As thermal polymerization, such as can To enumerate 2,2 '-azodiisobutyronitriles, 2,2 '-azos two (2- methylbutyronitrile), 1,1 '-azo, two (hexamethylene -1- first Nitrile), 2,2 '-azos two (2,4- methyl pentane nitrile), 2,2 '-azos two (2,4- dimethyl -4- methoxyl-valeronitrile), two The azo system of 2,2 '-azo of methyl-bis- (2 Methylpropionic acid esters), 2,2 '-azos two (2- hydroxymethyl propionitrile) etc Close object；Lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydroperoxidation are withered Alkene, di-isopropyl peroxydicarbonate, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, peroxidating neopentanoic acid uncle The organic peroxide of butyl ester, peroxidating (3,5,5- trimethyl acetyl) etc；Potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide it The inorganic peroxide etc. of class.Alternatively, it is also possible to by and redox series initiators for having used peroxide and reducing agent etc. make For polymerization initiator use.
As the manufacturing method of (methyl) acrylic resin, preferred solution polymerization process in method indicated above.It is molten An example of liquid polymerization is to mix monomer used and organic solvent, in a nitrogen atmosphere, thermal polymerization is added, 40 ~90 DEG C or so, preferably 50~80 DEG C or so stir 3~15 hours or so.In order to control reaction, can also connect in polymerization Continuous ground intermittently adds monomer or thermal polymerization or adds monomer or thermal polymerization with the state being dissolved in organic solvent Initiator.As organic solvent, the aromatic hydrocarbon of toluene, dimethylbenzene etc can be used for example；Ethyl acetate, butyl acetate Etc. esters；The aliphatic alcohols such as propyl alcohol, isopropanol；Ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc..
(2-2) isocyanates system crosslinking agent (B)
Adhesive composition contains isocyanates system crosslinking agent (B).It is crosslinked by the way that isocyanates system crosslinking agent (B) to be used as Agent uses, so that it may improve the resistance to metal of the optical film 1 with adhesive phase and the optical laminate comprising the optical film 1 Corrosivity and durability.Isocyanates system crosslinking agent (B) may be used alone or in combination of two or more kinds.
Isocyanates system crosslinking agent (B) is compound in the molecule at least two isocyanate group (- NCO), tool For body, toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone diisocyanate, dimethylbenzene two can be enumerated Isocyanates, hydrogenated xylene diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, Naphthalene diisocyanate, triphenylmethane triisocyanate etc..In addition isocyanates system crosslinking agent (B) is also possible to these isocyanic acids The polyol compound adduct (such as adduct of glycerine or trimethylolpropane) of ester compounds, isocyanuric acid esterification Object, biuret form compound and with polyether polyol or polyester polyol, acrylic polyol, polybutadiene polyol, It is derivative that isocyanate compound of carbamate prepolymer type obtained by addition reaction etc. occurs for polyisoprene polyol etc. Object.In above-mentioned, particularly preferred toluene di-isocyanate(TDI), hexamethylene diisocyanate, xylene diisocyanate or this The polyol compound adduct of a little isocyanate compounds, from the optical film 1 with adhesive phase and includes the optical film From the viewpoint of the durability of 1 optical laminate, more preferable xylene diisocyanate or its polyol compound adduct.
The content of isocyanates system crosslinking agent (B) relative to 100 parts by weight of (methyl) acrylic resin (A) be 0.08~ 2.5 parts by weight, preferably 0.1~2 parts by weight (such as below 1 parts by weight).If at the content of isocyanates system crosslinking agent (B) In the range, then in the resistance to gold for taking into account the optical film 1 with adhesive phase and the optical laminate comprising the optical film 1 The aspect for belonging to corrosivity and durability is advantageous.
Adhesive composition can be with isocyanates system crosslinking agent (B) together, and with the crosslinking agent other than it, such as epoxy Compound, aziridine cpd, meal chelate compounds, peroxide etc., however from adhesive phase optical film 1, And from the viewpoint of the resistance to metal protection and durability of the optical laminate comprising the optical film 1, adhesive composition is excellent It is elected to be and only contains isocyanates system crosslinking agent (B) for crosslinking agent, particularly preferably contain substantially no peroxide.It is described herein It contains substantially no, refers to that the content relative to 100 parts by weight of (methyl) acrylic resin (A) is 0.01 parts by weight or less.
(2-3) silane compound (C)
Adhesive composition contains silane compound (C).It is possible thereby to improve adhesive phase 20 and metal layer or glass base The adaptation of plate etc..Also silane compound of more than two kinds (C) can be used.
As silane compound (C), for example, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl three (2- methoxy ethoxy) silane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group Triethoxysilane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl group ethyoxyl dimethyl Silane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- chlorine third Base trimethoxy silane, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane etc..
Silane compound (C) may include the compound of silicone oligomers type.If by the concrete example of silicone oligomers with Combined form between monomer is stated, then as follows.
3-mercaptopropyi trimethoxy silane-tetramethoxy-silicane oligomer,
3-mercaptopropyi trimethoxy silane-tetraethoxysilane oligomer,
3- Mercaptopropyltriethoxysilane-tetramethoxy-silicane oligomer,
The oligomer containing mercaptopropyi such as 3- Mercaptopropyltriethoxysilane-tetraethoxysilane oligomer；
Mercapto methyl trimethoxy silane-tetramethoxy-silicane oligomer,
Mercapto methyl trimethoxy silane-tetraethoxysilane oligomer,
Mercapto methyl triethoxysilane-tetramethoxy-silicane oligomer,
The oligomer containing mercapto methyl such as mercapto methyl triethoxysilane-tetraethoxysilane oligomer；
3- glycidoxypropyltrime,hoxysilane-tetramethoxy-silicane alkyl copolymer,
3- glycidoxypropyltrime,hoxysilane-tetraethoxy-silicane alkyl copolymer,
3- epoxy propoxy propyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,
3- epoxy propoxy propyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,
3- epoxy propoxy propyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3- epoxy propoxy propyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3- glycidoxypropyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
3- glycidoxypropyl diethoxy silane-tetraethoxy-silicane alkyl copolymer etc. contains 3- epoxy third The copolymer of oxygroup propyl；
3- methacryloxypropyl trimethoxy silane-tetramethoxy-silicane oligomer,
3- methacryloxypropyl trimethoxy silane-tetraethoxysilane oligomer,
3- methacryloxypropyl-tetramethoxy-silicane oligomer,
3- methacryloxypropyl-tetraethoxysilane oligomer,
3- methacryloxypropylmethyl dimethoxysilane-tetramethoxy-silicane oligomer,
3- methacryloxypropylmethyl dimethoxysilane-tetraethoxysilane oligomer,
3- methacryloxypropyl methyl diethoxysilane-tetramethoxy-silicane oligomer,
3- methacryloxypropyl methyl diethoxysilane-tetraethoxysilane oligomer etc. contains methyl-prop The oligomer of alkene acryloxypropylethoxysilane；
3- acryloyloxypropyltrimethoxysilane-tetramethoxy-silicane oligomer,
3- acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer,
3- acryloxypropyl triethoxysilane-tetramethoxy-silicane oligomer,
3- acryloxypropyl triethoxysilane-tetraethoxysilane oligomer,
3- acryloxypropyl dimethoxysilane-tetramethoxy-silicane oligomer,
3- acryloxypropyl dimethoxysilane-tetraethoxysilane oligomer,
3- acryloyloxy propyl methyl diethoxysilane-tetramethoxy-silicane oligomer,
3- acryloyloxy propyl methyl diethoxysilane-tetraethoxysilane oligomer etc. contains acryloxy The oligomer of propyl；
Vinyltrimethoxysilane-tetramethoxy-silicane oligomer,
Vinyltrimethoxysilane-tetraethoxysilane oligomer,
Vinyltriethoxysilane-tetramethoxy-silicane oligomer,
Vinyltriethoxysilane-tetraethoxysilane oligomer,
Vinyl methyl dimethoxysilane-tetramethoxy-silicane oligomer,
Vinyl methyl dimethoxysilane-tetraethoxysilane oligomer,
Vinyl methyl diethoxy silane-tetramethoxy-silicane oligomer,
The oligomer containing vinyl such as vinyl methyl diethoxy silane-tetraethoxysilane oligomer；
3- TSL 8330-tetramethoxy-silicane alkyl copolymer,
3- TSL 8330-tetraethoxy-silicane alkyl copolymer,
3-aminopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-aminopropyltriethoxysilane-tetraethoxy-silicane alkyl copolymer,
3- aminopropylmethyldimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3- aminopropylmethyldimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-amino propyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The copolymer etc. containing amino such as 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer.
The content of silane compound (C) in adhesive composition is relative to 100 weight of (methyl) acrylic resin (A) Part, usually 0.01~10 parts by weight, preferably 0.03~5 parts by weight, more preferably 0.05~2 parts by weight, further preferably For 0.1~1 parts by weight.If the content of silane compound (C) be 0.01 parts by weight more than, be easy to get adhesive phase 20 with The adaptation improvement effect of metal layer 30 or glass substrate etc..In addition if content be 10 parts by weight hereinafter, if can inhibit silicon Hydride compounds (C) are from the exudation in adhesive phase 20.
(2-4) ionic compound (D)
Adhesive composition contains ionic compound (D).Ionic compound (D) be indicated with following formula (I) from Sub- property compound:
[changing 6]
By using ionic compound (D), anti-static electricity interference performance can be not only assigned to adhesive phase 20, but also Excellent resistance to metal protection and optical durability can be assigned.Adhesive composition can contain one kind or two or more ion Property compound (D).
In above-mentioned formula (I), R1~R8Hydrogen atom, the alkyl that can have substituent group are each independently represented, can have and take The alkenyl of Dai Ji, the alkynyl that can have substituent group, the aryl that can have substituent group or the heterocycle that can have substituent group Base, R5~R8Ring can also be formed between adjacent substituent group.So-called the case where ring is formed between adjacent substituent group, packet It includes: 1) R5~R8In adjacent 2 substituent group and N atom the case where being formed together ring structure, 2) R5~R8In 3 substitution Base and N atom are formed together unsaturated ring structure (including the aromatic ring structure of the unsaturated bond participated in comprising N atom.) feelings Condition.In addition, R1~R4Ring can also be formed between adjacent substituent group.The so-called feelings that ring is formed between adjacent substituent group Condition refers to R1~R4In adjacent 2 substituent group and B atom be formed together ring structure.
As the alkyl that can have substituent group, the preferably alkyl of carbon atom number 1~30, concrete example is for example including first Base, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth Base, 1- ethylpentyl, cyclopenta, cyclohexyl, trifluoromethyl, 2- ethylhexyl, phenacyl, 1- naphthoyl methyl, 2- Naphthoyl methyl, 4- methylsulfany phenacyl, 4- phenylsulfartyl phenacyl, 4- dimethylaminobenzoyl methyl, 4- cyanophenacyl, 4- methylphenacyl group, 2- methylphenacyl group, 3- fluorobenzoyl methyl, 3- trifluoro Methylphenacyl group, 3- nitrophenacyl.
As the alkenyl that can have substituent group, the preferably alkenyl of carbon atom number 2~10, concrete example is for example including ethylene Base, allyl, styryl.As the alkynyl that can have substituent group, the preferably alkynyl of carbon atom number 2~10, concrete example For example including acetenyl, propinyl, propargyl.
As the aryl that can have substituent group, the preferably aryl of carbon atom number 6~30, concrete example is for example including benzene Base, xenyl, 1- naphthalene, 2- naphthalene, 9- anthryl, 9- phenanthryl, 1- pyrenyl, 5- aphthacene base, 1- indenyl, 2- Azulene It is base, 9- fluorenyl, terphenyl, tetrad phenyl, o-, m- and p-methylphenyl, xylyl, o-, m- and to isopropylbenzene Base,Base, pentalene base, binaphthyl, three binaphthyls, four binaphthyls and cycloheptatriene base (heptalenyl) stretch biphenyl Base, bicyclopentadiene and phenyl (indacenyl), fluoranthene base, acenaphthenyl, ethylene conjunction anthryl (ア セ ア Application ト リ レ ニ Le base), Fu Base (phenalenyl), fluorenyl, anthryl, dianthranide base, three dianthranide bases, tetrad anthryl, anthraquinoline base, phenanthryl, benzo phenanthryl, pyrene Base,Base, aphthacene base, seven days of the week alkenyl (pleiadenyl), Pi base, base, five phenyl, thick five phenyl, connection tetraphenyl, six benzene Base, thick hexaphenyl, Ru Ji (Le ビ セ ニ Le base), coronene base (U ロ ネ ニ Le base), connection stretch three naphthalenes (trinaphthylenyl), seven phenyl, thick seven phenyl, pyrene anthryl (ピ ラ Application ト レ ニ Le base), ovalene base (cowherb Base) (ovalenyl).
As the heterocycle that can have substituent group, the fragrance of nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms is preferably comprised Race or aliphatic heterocycle, concrete example is for example including thienyl, benzo [b] thienyl, naphtho- [2,3-b] thienyl, thianthrene Base, furyl, pyranose, isobenzofuran-base, chromene base, xanthyl, phenoxazine base, 2H- pyrrole radicals, pyrrole radicals, imidazoles Base, pyrazolyl, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, indolizine base, isoindolyl, 3H- indyl, indyl, 1H- Indazolyl, purine radicals, 4H- quinazinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridines base, quinoxaline base, quinazolyl, cinnolines Base, pteridine radicals, 4aH- carbazyl, carbazyl, B-carboline base, phenanthridinyl, acridinyl, pah piperidinyl, phenanthroline, phenazinyl, Phenarsazine base (phenarsazinyl), isothiazolyl, phenothiazinyl, isoxazolyl, furan a word used for translation base, phenoxazine base, different Chromanyl, Chromanyl, pyrroles's piperidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, Yin Diindyl quinoline base, isoindoline base, quinoline are given repeated exhortations ring group, morpholinyl, thioxanthryl.
The above-mentioned alkyl that can have substituent group can be replaced, the alkenyl that can have substituent group, can have substituent group Alkynyl, the hydrogen atom that can have the aryl of substituent group and can have the heterocycle of substituent group substituent group it is specific Example is for example including halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atoms；The alcoxyls such as methoxyl group, ethyoxyl, tert-butoxy Base；Phenoxy group, to the aryloxy group such as toloxyl, methoxycarbonyl, butoxy carbonyl, phenyloxycarbonyl, vinyl Epoxide carbonyl, The alkoxy carbonyls such as aryloxycarbonyl；The acyloxy such as acetoxyl group, propionyloxy, benzoyloxy；Acetyl group, benzoyl, The acyl groups such as isobutyryl, acryloyl group, methylacryloyl, methoxalyl base；The alkylthio groups such as methyl mercapto, tertiary butylthio；Thiophenyl, To arylthios such as Tolylsulfanvls；The alkyl aminos such as methylamino, Cyclohexylamino；Dimethylamino, diethylamino, morpholine The dialkyl amidos such as base, piperidyl；The arylaminos such as phenyl amino, p-methylphenyl amino；Methyl, ethyl, tert-butyl, dodecane The alkyl such as base；The aryl such as phenyl, p-methylphenyl, xylyl, cumenyl, naphthalene, anthryl, phenanthryl；Hydroxyl, carboxyl, sulphonyl Amido, formoxyl, sulfydryl, sulfo group, mesyl, p-toluenesulfonyl, amino, nitro, nitroso, cyano, trifluoromethyl, three Chloromethyl, trimethyl silyl, phosphinico (phosphinico), phosphonic acid base, alkyl sulphonyl, aryl sulfonyl, three alkane Base ammonium, dimethyl sulfonium base, triphenyl phenacyl Phosphonium base.
In above-mentioned substituent group, preferred substituent group is electron-withdrawing substituent group.By with electron-withdrawing substitution Base replaces, it is however generally that ionic compound is easy for dissociating, and anti-static electricity interference ability can be improved.Electron-withdrawing substituent group Concrete example include halogen atom, cyano, carboxyl, nitro, nitroso, acyl group, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphur Acyl group, aryl sulfonyl, trialkyl ammonium, amide groups, perfluoroalkyl, perfluor alkylthio group, perfluoroalkylcarbonyl, sulfoamido, 4- cyano-phenyl.
R1~R4It is respectively independent, it preferably can have the alkyl of substituent group, can have the aryl of substituent group.R5~R8 It is respectively independent, it preferably can have the alkyl of substituent group, can have the aryl of substituent group.Alternatively, it is preferred that R5~R8In 3 A substituent group and N atom are formed together unsaturated ring structure (including the aromatic ring structure comprising unsaturated bond.).
Wherein, R1~R4It preferably can have the aryl of substituent group, the anion of ionic compound (D) is more preferably The borate anion indicated with following formula (II):
[changing 7]
In above-mentioned formula (II), R9~R13It each independently represents hydrogen atom, the alkyl that can have substituent group, can have The alkenyl of substituent group, the alkynyl that can have substituent group, the aryl that can have substituent group, the heterocycle that can have substituent group Base or halogen atom can also form ring between adjacent substituent group.
The above-mentioned alkyl that can have substituent group can be replaced, the alkenyl that can have substituent group, can have substituent group Alkynyl, the hydrogen atom that can have the aryl of substituent group and can have the heterocycle of substituent group substituent group it is specific Example can be with the R for above-mentioned formula (I)1~R8Concrete example it is identical.From the anti-static electricity interference performance of ionic compound (D), resistance to From the viewpoint of metal protection and optical durability, R9~R13It is more preferably all fluorine atom it is preferred that being all halogen atom. In this case, the anion indicated with above-mentioned formula (II) is four (pentafluorophenyl group) borate anion.
Ionic compound (D) cation from the viewpoint of anti-static electricity interference performance, preferably pyridylium, Glyoxaline cation, tetrahydropyrimidine cation, dihydro-pyrimidin cation, pyrazoles cation, pyrazoles cation moiety etc. Cation with the heterocycle structure containing nitrogen-atoms comprising unsaturated bond, wherein pyridylium is more preferably following State the pyridylium of formula (III) expression:
[changing 8]
In above-mentioned formula (III), R14~R19It each independently represents hydrogen atom, the alkyl that can have substituent group, can have The alkenyl of substituted base, the alkynyl that can have substituent group, the aryl that can have substituent group, the heterocycle that can have substituent group Base, hydroxyl, ether, carboxyl, carbonyl or halogen atom can also form ring between adjacent substituent group.
It is preferably N- substituted pyridines cation with the pyridylium that above-mentioned formula (III) indicates.In this case, R14 It preferably can have the alkyl of substituent group, the more preferably straight-chain of carbon atom number 1~20, branched or cricoid alkyl. Carbon atom number is preferably 1~16.R15~R19It is respectively independent, preferably hydrogen atom, the straight-chain of carbon atom number 1~20, branch or The alkyl of the straight-chain of cricoid alkyl, hydroxyl or halogen atom, more preferably hydrogen atom or carbon atom number 1~20.
Ionic compound (D) is from anti-static electricity interference performance and the optical film with adhesive phase 1 and includes the optics From the viewpoint of the resistance to metal protection of the optical laminate of film 1, preferred anionic is the borate indicated with above-mentioned formula (II) Anion, cation are the cation with the heterocycle structure containing nitrogen-atoms comprising unsaturated bond, and more preferable anion is Four (pentafluorophenyl group) borate anions, cation for the heterocycle structure containing nitrogen-atoms comprising unsaturated bond sun from Son, further preferred anion are four (pentafluorophenyl group) borate anions, and cation is the pyridine indicated with above-mentioned formula (III) Cation, particularly preferred anion are four (pentafluorophenyl group) borate anions, and cation is R14For carbon atom number 1~20 The pyridylium of straight-chain or branched or cricoid alkyl indicated with above-mentioned formula (III).
The content of ionic compound (D) in adhesive composition is relative to 100 weight of (methyl) acrylic resin (A) Part is measured, preferably 0.1~10 parts by weight, more preferably 0.2~8 parts by weight, further preferably 0.3~5 parts by weight are especially excellent It is selected as 0.5~3 parts by weight.If the content of ionic compound (D) is 0.1 parts by weight or more, be conducive to anti-static electricity interference The raising of performance, if it is 10 parts by weight hereinafter, being then conducive to have the optical film 1 of adhesive phase and comprising the optical film 1 Optical laminate resistance to metal protection and durability.
Adhesive composition can be also used in combination with the ionic compound (D) of the anion indicated with above-mentioned formula (I) together Anti-static electricity interference agent other than it, the optical laminate from the optical film 1 for having adhesive phase and comprising the optical film 1 The viewpoints such as resistance to metal protection consider that adhesive composition, which only contains above state formula (I) preferably as anti-static electricity interference agent, to be indicated Ionic compound (D).
(2-5) other compositions
Adhesive composition can be containing one kind or two or more solvent, crosslinking catalyst, ultraviolet absorbing agent, weather-proof steady Determine the additives such as agent, tackifier, plasticizer, softening agent, dyestuff, pigment, inorganic filler, light scattering particle.In addition to this, to Cooperate ultra-violet solidified compound in adhesive composition, irradiates ultraviolet light after forming adhesive phase and be allowed to solidify, shape It is also useful way at harder adhesive phase.As crosslinking catalyst, for example, hexamethylene diamine, second two Amine, polyethylene imine, hexa, diethylenetriamines, trien, isophorone diamine, trimethylene The amine compounds such as diamines, poly- amino resins and melamine resin.
Adhesive composition can be containing the optical film 1 that can be improved with adhesive phase and comprising the optical film 1 The antirust agent of the resistance to metal protection of optical laminate.As antirust agent, benzotriazole based compound, others three can be enumerated Three azole compounds such as azole compounds；The thiazole compounds such as benzothiazole based compound, other thiazole compounds；Benzyl The imidazole compounds such as base imidazole compound, other imidazole compounds；Imidazoline based compound；Quinoline based compound； Pyridine based compound；Pyrimidine compound；Indoles based compound；Amine compound；Urea based compound；Sodium benzoate；Benzyl mercapto Base system compound；Di-sec-butyl thioether；And diphenyl sulfoxide.
However, according to the present invention, sufficient resistance to metal protection, therefore antirust can also be obtained even if without containing antirust agent The content of agent is the smaller the better.In particular, adhesive composition preferably contains substantially no three azole compounds as antirust agent, More preferably contain substantially no the antirust agent in above-mentioned compound group.It is described herein to contain substantially no, refer to phase Content for 100 parts by weight of (methyl) acrylic resin (A) is 0.01 parts by weight or less.
(3) composition and manufacturing method of the optical film with adhesive phase
Optical film 1 with adhesive phase includes optical film 10 and the (figure of adhesive phase 20 for being laminated in its at least one face 1).It can also be in the two sides laminate adhesive oxidant layer 20 of optical film 10.In general, adhesive phase 20 is directly laminated in optical film 10 Surface.When adhesive phase 20 to be set to the surface of optical film 10, the preferably binding face to optical film 10 and/or adhesive phase 20 Binding face implement prime coat formation or surface activation processing, such as corona treatment, sided corona treatment, more preferably Implement sided corona treatment.
In the case where optical film 10 is that single side as shown in Figure 2 protects polarization plates, adhesive phase 20 is generally preferably straight Connect unilateral, the i.e. face with 3 opposite side of the first resin film of polarizing film 2 that is laminated in polarization.It is as shown in Figure 3 in optical film 10 In the case where two-sided protection polarization plates, adhesive phase 20 can both be laminated in the outer of the either side of the first, second resin film 3,4 Surface can also be laminated in the outer surface of two sides.
Although anti-static electricity interference layer can also in addition be arranged between optical film 10 and adhesive phase 20, due to this hair Bright adhesive phase 20 can use individual adhesive phase and assign excellent anti-static electricity interference, therefore from optical laminate Filming, laminated body production process simplification from the aspect of, do not have preferably between optical film 10 and adhesive phase 20 anti- Electrostatic interference layer.
Optical film 1 with adhesive phase also may include the diaphragm (removing for being laminated in the outer surface of adhesive phase 20 Film).The diaphragm is usually stripped removing in the use of adhesive phase 20 (such as when being laminated on metal layer 30).Diaphragm is for example It can be to by the various resins such as polyethylene terephthalate, polybutylene terephthalate (PBT), polycarbonate, polyarylate The film that the formation of the film of composition has the face of adhesive phase 20 to implement the demouldings such as silicone-treated processing.
Optical film 1 with adhesive phase can obtain as follows, that is, each ingredient for constituting above-mentioned adhesive composition is molten It solves or is scattered in solvent and the adhesive composition containing solvent is made, then, be coated on the surface of optical film 10 simultaneously It dries and forms adhesive phase 20.In addition, the optical film 1 with adhesive phase can also obtain as follows, that is, in the demoulding of diaphragm Process face landform composite adhesives layer 20 same as above, by the adhesive phase 20 stacking (transfer) in the surface of optical film 10.
< optical laminate >
Fig. 4 and Fig. 5 is the constructed profile for the example for indicating that the layer of optical laminate of the invention is constituted.Implement at 1 Optical laminate of the invention is as shown in Figures 4 and 5 in mode, glues comprising the optical film 1 with adhesive phase with it is laminated in The metal layer 30 of 20 side of mixture layer.Optical laminate 5 shown in Fig. 4 is using polarization plates 10a shown in Fig. 2 as optical film 10 examples used, optical laminate 6 shown in Fig. 5 is used using polarization plates 10b shown in Fig. 3 as optical film 10 Example.In the optical laminate 5,6 shown in Fig. 4 and Fig. 5, the optical film 1 with adhesive phase is by so that its adhesive phase 20 are laminated on metal layer 30 with the mode that metal layer 30 directly contacts.According to the present invention, make like this adhesive phase 20 with In the optical laminate for the composition that metal layer 30 directly contacts, the corrosion of metal layer 30 can also be effectively inhibited.
Fig. 6 is another constructed profile for indicating the layer of optical laminate of the invention and constituting.In another implementation In mode the optical laminate of the invention optical laminate 7 as shown in Fig. 6, the optical film 1 with adhesive phase Adhesive phase 20 is pressed from both sides to be laminated across resin layer 50 and metal layer 30.Adhesive phase 20 is directly contacted with resin layer 50.In the light It learns in laminated body 7, the corrosion of metal layer 30 can also be effectively inhibited.The tree being configured between adhesive phase 20 and metal layer 30 Rouge layer 50 is for example also possible to the solidified material layer of curable resin.It can make as the curable resin for being capable of forming resin layer 50 With well known curable resin, for example, the curable resin recorded in Japanese Unexamined Patent Publication 2009-217037 bulletin.
Fig. 7 is another constructed profile for indicating the layer of optical laminate of the invention and constituting.In another implementation Optical laminate of the invention can also not have metal layer 30 as optical laminate 8 shown in fig. 7 in mode.It should In the case of, the adhesive phase 20 of the optical film 1 with adhesive phase is for example laminated with substrate 40.Substrate 40 is as described later, example For example glass substrate.
Metal layer 30 for example can be containing selected from aluminium, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead and containing choosing From the layer of one or more of the alloy of metal of more than two kinds in them, from the viewpoint of electric conductivity, preferably containing choosing From the layer of the metallic element in aluminium, copper, silver and gold, from the viewpoint of electric conductivity and cost, more preferably containing aluminium element Layer, further preferably contains the layer of aluminium element as principal component.It is so-called to contain as principal component, refer to and constitutes metal layer 30 Metal component is the 30 weight % or more of whole metal components, is further 50 weight % or more.
The metal oxide layer such as being also possible to ITO of metal layer 30, however due to of the invention with adhesive phase Optical film 1 is good particularly with the corrosion resistance of metal simple-substance or alloy, therefore metal layer 30 is preferably comprised by above-mentioned metal The metal simple-substance that element is constituted and/or the alloy of more than two kinds containing above-mentioned metallic element.However, optical laminate can also Together, also there is the transparent electrode layer being made of metal oxides such as ITO with such metal layer 30.
Form (such as thickness etc.), the preparation method of metal layer 30 are not particularly limited, other than it can be metal foil, It can also be the metal layer formed using vacuum vapour deposition, sputtering method, ion plating method, ink jet printing method, gravure printing method, preferably For the metal layer formed using sputtering method, ink jet printing method, gravure printing method, the metal layer more preferably formed using sputtering. In the metal layer and metal foil formed using sputtering, the former side has the tendency that poor corrosion resistance, however according to the present invention Optical laminate, for using sputtering formed metal layer also there is good resistance to metal protection.The thickness of metal layer 30 Usually 3 μm hereinafter, preferably 1 μm hereinafter, more preferably 0.8 μm or less.In addition the thickness of metal layer 30 is usually 0.01 μm More than.In addition, the line width of metal line possessed by metal wiring layer is logical in the case where metal layer 30 is metal wiring layer Often for 10 μm hereinafter, preferably 5 μm hereinafter, further preferably 3 μm or less.In addition, the line width of metal line is usually 0.01 μ M or more, preferably 0.1 μm or more, further preferably 0.5 μm or more.For by the metal layer 30 of the film or the gold of filament Belong to the metal layer 30 that wiring is constituted, optical laminate of the invention also shows that good resistance to metal protection.Especially in gold Belong to wiring for example with a thickness of 3 μm or less and when line width is 10 μm or less, or with a thickness of 3 μm or less and line width for 10 μm with Under, when being formed using sputtering method, its corrosion can also be inhibited, can especially inhibit spot corrosion.
Metal layer 30 for example can be the hardware cloth of touch input element possessed by touch input formula liquid crystal display device Line layer (i.e. electrode layer).In this case, metal layer 30 is usually by with defined shape pattern.It is metal line by metal layer 30 An example of the case where layer is shown in Fig. 8.Also it can be omitted resin layer 50 in optical laminate shown in fig. 8.By pattern In the case where adhesive phase 20 is laminated on the metal layer 30 of change, adhesive 20 also can have the portion not contacted with metal layer 30 Point.Metal layer 30 is also possible to the continuous film containing above-mentioned metal or alloy.
In addition, metal layer 30 is either single layer structure, is also possible to 2 layers or 3 layers or more of multilayered structure.As multilayer The metal layer of structure, for example, the metalliferous layer (metal mesh etc.) of the 3-tier architecture indicated with molybdenum/aluminium/molybdenum.
The metal layer 30 of for example, metal wiring layer can also be formed on substrate 40 as shown in Fig. 4 and Fig. 5 etc., it should In the case of, optical laminate of the invention may include the substrate 40.The formation of metal layer 30 on the substrate 40 for example can be with It is carried out using sputtering.Substrate 40 can be the transparent substrate for constituting liquid crystal cells contained in touch input element.Substrate 40 is excellent It is selected as glass substrate.As the material of glass substrate, for example, soda-lime glass, glass with lower alkali content, alkali-free glass etc..Metal Layer 30 can both be formed in the comprehensive of substrate 40, can also be formed in part of it.The gold being patterned is formed on the substrate 40 When belonging to layer 30, when a part on the surface of substrate 40 forms metal layer 30, a part of adhesive phase 20 can be with example The substrate 40 that is such as made of glass directly contacts, however close due to the adhesive phase of optical laminate of the invention 20 and glass Conjunction property is also excellent, therefore optical laminate and has the liquid crystal display device of the optical laminate in this case resistance to Long property is also excellent.
By the way that the optical film 1 with adhesive phase is pressed from both sides across its adhesive phase on metal layer 30 (or above-mentioned resin layer) 20 fittings, so that it may obtain optical laminate 5,6.It is bonded and makes with metal layer 30 in the optical film 1 that will have adhesive phase Out after optical laminate, in the case where there is any not good situation, it is necessary to by the optical film 1 with adhesive phase from metal layer It is removed in 30, other optical films 1 with adhesive phase is fitted on metal layer 30 again, that is, need so-called reprocessing Operation.Optical film 1 with adhesive phase of the invention is difficult to produce on the surface of the metal layer 30 after removing in metal layer 30 Raw fuzzy, residue glue etc., re-workability is excellent.Optical film 1 according to the present invention with adhesive phase, even if in fitting adhesive When the surface of layer 20 is not metal layer 30 but glass substrate or ITO layer, good re-workability can also be shown.
< liquid crystal display device >
Liquid crystal display device of the invention includes the optical film 1 with adhesive phase of aforementioned present invention, more typical In the case of include above-mentioned optical laminate.Liquid crystal display device of the invention can inhibit the corrosion of metal layer 30, in addition, display Good durability out.
Liquid crystal display device of the invention is preferably the touch input formula liquid crystal display device with touch panel function.Touching It touches input type liquid crystal display device and has touch input element and backlight comprising liquid crystal cells.The composition of touch panel can By be Out-cell type, On-cell type, In-cell type etc. it is known it is any in a manner of, the other manner of execution of touch panel It can be known any modes such as resistive film mode, capacitive way (surface type capacitive way, porjection type capacitive way). Optical film 1 with adhesive phase of the invention can both be configured at the visible side of touch input element (liquid crystal cells), can also To be configured at backlight side, two side sides can also be configured at.The driving method of liquid crystal cells can be TN mode, VA mode, IPS Known any mode such as mode, multidomain mode, OCB mode.In liquid crystal display device of the invention, optical laminate institute The substrate 40 having can be substrate included in above-mentioned liquid crystal cells (typically glass substrate).
[embodiment]
Hereinafter, provide Examples and Comparative Examples and more specific description is carried out to the present invention, however the present invention is not by this A little examples limit.Hereinafter, indicating that usage amount, part of content and % are exactly weight basis as long as no particularly pointing out.
< Production Example 1: the adhesive phase manufacture > of (methyl) acrylic resin (A-1)
Into the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and blender, addition will be shown in table 1 (numerical value of table 1 is parts by weight to composition.) monomer and 81.8 parts of solution being obtained by mixing of ethyl acetate.By the sky in reaction vessel After gas is replaced with nitrogen, making interior temperature is 60 DEG C.Thereafter, addition is dissolved with 0.12 part of azodiisobutyronitrile in 10 parts of ethyl acetate Solution.After mutually synthermal kept for 1 hour, while interior temperature is remained 54~56 DEG C, with 17.3 parts/Hr of adding speed Ethyl acetate is added continuously in reaction vessel, so that the concentration of polymer substantially 35%.In adding from ethyl acetate The beginning is increased until ethyl acetate being added and is adjusted to the concentration of polymer after interior temperature being remained 54~56 DEG C by 12 hours 20%, obtain the ethyl acetate solution of (methyl) acrylic resin (A-1).The weight of (methyl) acrylic resin (A-1) Average molecular weight Mw is 1,390,000, and the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn are 5.32.In gel permeation chromatography (GPC) in elution curve, the ingredient of Mw139 ten thousand shows single peak, does not see in the range of Mw1000~2,500,000 Other peaks.
< Production Example 2: the adhesive phase manufacture > of (methyl) acrylic resin (A-2)
Into the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and blender, it is added group shown in table 1 At monomer and 81.8 parts of solution being obtained by mixing of ethyl acetate.After air in reaction vessel is replaced with nitrogen, make interior temperature It is 60 DEG C.Thereafter, addition is dissolved with 0.03 part of azodiisobutyronitrile of solution in 10 parts of ethyl acetate.In mutually synthermal holding It after 1 hour, while interior temperature is remained 54~56 DEG C, is allowed to react 4~5 hours, until conversion ratio is 75%, obtains weight The mixed solution of copolymer and monomer that average molecular weight Mw is 1,000,000.Then, 200 parts of toluene, azodiisobutyronitrile 0.2 is added Part, then be allowed to react 6 hours, until conversion ratio is 100%, obtain (methyl) propylene that glass transition temperature Tg is -7 DEG C The solution of acid system resin (A-2).(methyl) acrylic resin (A-2) includes the polymerization for being lower than 150,000 without containing molecular weight The high molecular weight components (A-2-1) that object and Mw are 1,000,000, and the polymer without containing 150,000 or more molecular weight and Mw be 2.5 ten thousand low molecular weight compositions (A-2-2).High molecular weight components (A-2-1) and low molecular weight compositions (A-2-2) exist 2 peaks independent are shown in the elution curve of GPC, the area ratio of the two is (A-2-1)/(A-2-2)=75/ 25.It can't see other peaks other than them in the range of Mw1000~2,500,000.
< Production Example 3: the adhesive phase manufacture > of (methyl) acrylic resin (A-3)
Other than being set as the composition of monomer as shown in table 1, (methyl) acrylic acid series tree is obtained identically as Production Example 1 Ethyl acetate solution (the resin concentration: 20%) of rouge (A-3).The weight average molecular weight Mw of (methyl) acrylic resin (A-3) For 1,410,000, Mw/Mn 4.71.In the elution curve of GPC, the ingredient of Mw141 ten thousand shows single peak, Mw1000~ It can't see other peaks in 2500000 range.
In Production Example above, weight average molecular weight Mw and number-average molecular weight Mn are measured as follows, and color is used as in GPC device Compose " the TSKgel XL " of 4 Tosoh (strain) systems of column arranged in series and " the Shodex GPC of 1 Showa electrician (strain) system KF-802 " is 5 total, tetrahydrofuran is used as eluent, in sample solution concentration 5mg/mL, 100 μ L of sample import volume, temperature Under conditions of 40 DEG C, flow velocity 1mL/ minutes, it is measured using standard polystyren conversion.When the elution curve of acquisition GPC Condition is also set as same.
Glass transition temperature Tg is the differential scanning calorimeter using SII Nano Technology Co. Ltd. system (DSC) " EXSTAR DSC6000 ", in a nitrogen atmosphere, in -80~50 DEG C of measuring temperature range, 10 DEG C/min of heating rate Under conditions of be measured.
By the composition of the monomer in each Production Example, (numerical value of table 1 is parts by weight.) and the elution curve of GPC on Peak number (" GPC peak number " is expressed as in table 1) concentration in the range of Mw1000~2,500,000 is shown in table 1.
[table 1]
Abbreviation in " monomer composition " column of table 1 refers to following monomer.
BA: butyl acrylate (glass transition temperature of homopolymer: -54 DEG C),
MA: methyl acrylate (glass transition temperature of homopolymer: 10 DEG C),
HEA: acrylic acid 2- hydroxy methacrylate.
< Examples 1 to 2,1~7 > of comparative example
(1) preparation of adhesive composition
To the ethyl acetate solution (resin concentration: 20%) of (methyl) acrylic resin obtained in above-mentioned Production Example In, relative to 100 parts of solid component of the solution, isocyanide shown in the table 2 of (parts by weight) is measured shown in mixture table 2 respectively Acid esters system crosslinking agent (B), silane compound (C) and ionic compound (D), then so that solid component concentration is 14% Mode adds ethyl acetate and obtains adhesive composition.For the use level of each gradation composition shown in table 2, used Commodity whens containing solvent etc., be the parts by weight as effective component contained therein.
[table 2]
Each gradation composition indicated in table 2 with abbreviation notes at foot.
(isocyanates system crosslinking agent)
B-1: the ethyl acetate solution (solid component concentration of the trimethylolpropane adduct of xylene diisocyanate 75%), the trade name " TAKENATE D-110N " obtained from Mitsui Chemicals (strain).
(silane compound)
C-1:3- glycidoxypropyltrime,hoxysilane, the trade name obtained from SHIN-ETSU HANTOTAI's chemical industry (strain) “KBM403”。
(ionic compound)
D-1:N- picoline four (pentafluorophenyl group) borate,
D-2:N- decyl pyridine four (pentafluorophenyl group) borate,
D-3:N- octyl -4- picoline hexafluorophosphate,
Bis- (fluorosulfonyl) imide salts of D-4:N- picoline.
(2) production of adhesive phase
Each adhesive composition prepared in above-mentioned (1) is used into adhesive applicator so that after dry with a thickness of 20 μm of side Formula is coated on the diaphragm being made of the polyethylene terephthalate film for implementing demoulding processing and (obtains from LINTEC (strain) Trade name " PLR-382051 ") demoulding process face, 100 DEG C dry 1 minute and produce adhesive phase (adhesive Piece).
(3) production of the optical film (P-1) with adhesive phase
By average degree of polymerization about 2400,99.9 moles of % of saponification degree, 60 μm of thickness of polyvinyl alcohol film ((strain) Kuraray The trade name " Kuraray Vinylon VF-PE#6000 " of system) be impregnated in 37 DEG C of pure water after, be impregnated at 30 DEG C containing In iodine and the aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) of potassium iodide.Thereafter, it is impregnated at 56.5 DEG C In aqueous solution (potassium iodide/boric acid/water (weight ratio)=12/3.6/100) containing potassium iodide and boric acid.Film is pure with 10 DEG C After water cleaning, in 85 DEG C of dryings, about 23 μm of thickness of the polarizing film for having adsorbed iodine on polyvinyl alcohol and being orientated is obtained.Stretch master It to be carried out in the process that iodine staining and boric acid are handled, total stretching ratio is 5.3 times.
In the one side of resulting polarizing film, press from both sides thick across the adhesive fitting being made of the aqueous solution of polyvinyl alcohol resin 25 μm of the transparent protective film (trade name of Konica Minolta Opt (strain) system being made of tri acetyl cellulose membrane "KC2UA"〕.Then it in the face with tri acetyl cellulose membrane opposite side of above-mentioned polarizing film, presss from both sides across by polyethenol series tree Thick 23 μm of zero phase difference film (the Japanese Zeon being made of cyclic polyolefin hydrocarbon system resin of adhesive fitting that the aqueous solution of rouge is constituted The trade name " ZEONOR " of (strain) system), produce polarization plates.Then, to the opposite with the contact face of polarizing film of zero phase difference film After implementing the Corona discharge Treatment for improving adaptation, the bonding made in above-mentioned (2) is bonded using laminating machine for the face of side Behind the face (adhesive level) with diaphragm opposite side of oxidant layer, 7 are cured under conditions of 23 DEG C of temperature, relative humidity 65% It, obtains the optical film (P-1) with adhesive phase.
(4) production of the optical film (P-2) with adhesive phase
By average degree of polymerization about 2400,99.9 moles of % of saponification degree, 30 μm of thickness of polyvinyl alcohol film ((strain) Kuraray The trade name " Kuraray Vinylon VF-PE#3000 " of system) be impregnated in 37 DEG C of pure water after, be impregnated at 30 DEG C containing In iodine and the aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) of potassium iodide.Thereafter, it is impregnated at 56.5 DEG C In aqueous solution (potassium iodide/boric acid/water (weight ratio)=12/3.6/100) containing potassium iodide and boric acid.Film is pure with 10 DEG C After water cleaning, in 85 DEG C of dryings, about 12 μm of thickness of the polarizing film for having adsorbed iodine on polyvinyl alcohol and being orientated is obtained.It stretches It is mainly carried out in the process that iodine staining and boric acid are handled, total stretching ratio is 5.3 times.
In the one side of resulting polarizing film, press from both sides thick across the adhesive fitting being made of the aqueous solution of polyvinyl alcohol resin 25 μm of the transparent protective film (trade name of Konica Minolta Opt (strain) system being made of tri acetyl cellulose membrane " KC2UA "), produce polarization plates.Then in the face with the face opposite side for being fitted with protective film of polarizing film, laminating machine is utilized After being bonded the face (adhesive level) with diaphragm opposite side of the adhesive phase made in above-mentioned (2), in 23 DEG C of temperature, relatively It is cured 7 days under conditions of humidity 65%, obtains the optical film (P-2) with adhesive phase.
(5) the resistance to metal protection evaluation of the optical film with adhesive phase
The optical film (P-1) with adhesive phase made in above-mentioned (3) is cut to the examination of the size for 20mm × 50mm Piece is tested, folder is fitted in the metal layer side of the glass substrate with metal layer across adhesive phase.As the glass for having metal layer Substrate has used the glass substrate that the metallic aluminum of thickness about 500nm has been laminated using sputtering on alkali-free glass surface (Geomatec corporation).By resulting optical laminate temperature 60 C, relative humidity 90% baking oven in take care of 500 hours Afterwards, it has been bonded from the back side illuminaton light of glass substrate is from polarization plate surface through magnifying glass (Lupe) with adhesive phase The state of the metal layer of the part of optical film, for spot corrosion (diameter be 0.1mm or more and can through light hole generation), It is evaluated using benchmark below.It the results are shown in Table 3.
4: layer on surface of metal generate spot corrosion number be 2 or less,
3: layer on surface of metal generate spot corrosion number be 3~5,
2: layer on surface of metal generate spot corrosion number be 6 or more,
1: in the multiple spot corrosion of generation comprehensively of layer on surface of metal, and also creating gonorrhoea.
(6) durability evaluation of the optical film with adhesive phase
By the optical film (P-1) with adhesive phase made in above-mentioned (3) so that the stretching axis direction of polarization plates is length The mode on side removes diaphragm after cutting the size for 200mm × 150mm, and the adhesive phase face of exposing is fitted in glass substrate On.By the resulting test film (optical film with adhesive phase for being pasted with glass substrate) for being pasted with glass substrate in high pressure In kettle, with temperature 50 C, pressure 5kg/cm2(490.3kPa) pressurizes 20 minutes.As glass substrate, use Corning public Take charge of the alkali-free glass of system, trade name " Eagle XG ".To resulting optical laminate, following 3 kinds of durabilities examination is implemented It tests.
(durability test)
Kept under 85 DEG C of temperature of drying condition 750 hours heat resistant test,
Kept in the environment of temperature 60 C, relative humidity 90% 750 hours hot resistance test,
It is kept for 30 minutes under 85 DEG C of temperature of drying condition, then keeps 30 under -40 DEG C of temperature of drying condition Minute, which is set as 1 circulation, the heat shock resistance (HS) which is repeated 400 circulations is tested.
Optical laminate after visually observing each test visually observes whether there is or not the tilting of adhesive phase, falls off, sends out The cosmetic variations such as bubble, have rated durability according to following evaluation criteria.It the results are shown in Table 3.
4: can't see tilting completely, fall off, foam etc. cosmetic variations,
3: be hardly visible tilting, fall off, foam etc. cosmetic variations,
2: tilt, fall off, foaming etc. cosmetic variations it is slightly obvious,
1: the cosmetic variations such as being clearly seen that tilting, fall off, foam.
(7) the re-workability evaluation of the optical film with adhesive phase
The optical film (P-1) with adhesive phase made in above-mentioned (3) is cut into the size for 25mm × 150mm Test film.Diaphragm is removed from test film, its adhesive face is pasted on the glass substrate.Glass substrate is pasted with by resulting Test film (optical film with adhesive phase for being pasted with glass substrate) in autoclave, with temperature 50 C, pressure 5kg/ cm2(490.3kPa) pressurizes 20 minutes.Then, it is taken care of 48 hours in 50 DEG C of baking oven, then in 23 DEG C of temperature, relative humidity In 50% atmosphere, optical film is shelled with 300mm/ minutes speed along 180 ° of directions together with adhesive phase from test film From.The state of glass baseplate surface after observation removing, is evaluated using benchmark below.It the results are shown in Table 3.
4: the surface of glass substrate can't see completely it is fuzzy equal,
3: the surface of glass substrate be hardly visible it is fuzzy equal,
2: the surface of glass substrate can see it is fuzzy equal,
1: can see the residual of adhesive phase on the surface of glass substrate.
(8) the decolourising property evaluation of the optical film with adhesive phase
It is shelled after the optical film (P-2) with adhesive phase made in above-mentioned (4) is cut the size for 30mm × 30mm From diaphragm, the adhesive phase face paste of exposing is closed on the glass substrate.As glass substrate, Corning corporation has been used Alkali-free glass, trade name " Eagle XG ".To resulting optical laminate, the spectrophotometer (day for having integrating sphere is used The product name " V7100 " of this light splitting (strain) system) MD transmissivity and TD transmissivity in the range of 380~780nm of wavelength are determined, Monomer transmissivity under each wavelength, degree of polarization are calculated, the JIS Z 8701:1999 " representation method-XYZ table color of color is recycled System and X10Y10Z102 degree of visuals field (illuminant-C) of color specification system " carry out visibility amendment, and the visibility before finding out endurance test is corrected single Body transmissivity (Ty) and visibility amendment degree of polarization (Py).Moreover, by optical laminate so that the triacetyl cellulose of polarization plates Film side is placed in the spectrophotometer with integrating sphere for detector side, from the mode of glass substrate side incident light.
Monomer transmissivity and degree of polarization are defined by the formula respectively:
Monomer transmissivity (λ)=0.5 × (Tp (λ)+Tc (λ))
Degree of polarization (λ)=100 × (Tp (λ)-Tc (λ))/(Tp (λ)+Tc (λ))
Tp (λ) is the light measured using the rectilinearly polarized light of incident wavelength X (nm) and the relationship of parallel-nicol prism The transmissivity (%) of laminated body is learned, Tc (λ) is the rectilinearly polarized light and Nicol crossed using incident wavelength X (nm) The transmissivity (%) of the optical laminate of relationship measurement.
Then, by the optical laminate 80 DEG C of temperature, relative humidity 90% hygrothermal environment under place 24 hours, then It is durable using being found out with method identical before endurance test after being placed 24 hours in the environment of 23 DEG C of temperature, relative humidity 60% Ty and Py after test.Thereafter, the Py before test is individually subtracted in the Py and Ty after test and Ty and before calculating endurance test Variable quantity afterwards finds out degree of polarization variable quantity (Δ Py) and monomer transmissivity variable quantity (Δ Ty).Δ Py is shown in table 3.
[table 3]
< Production Example 4: the adhesive phase manufacture > of (methyl) acrylic resin (A-1)
Into the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and blender, addition will be shown in table 4 (numerical value of table 4 is parts by weight to composition.) monomer and 81.8 parts of solution being obtained by mixing of ethyl acetate.By the sky in reaction vessel After gas is replaced with nitrogen, making interior temperature is 60 DEG C.Thereafter, addition is dissolved with 0.12 part of azodiisobutyronitrile in 10 parts of ethyl acetate Solution.After mutually synthermal kept for 1 hour, while interior temperature is remained 54~56 DEG C, with 17.3 parts/Hr of adding speed Ethyl acetate is added continuously in reaction vessel, so that the concentration of polymer substantially 35%.In adding from ethyl acetate The beginning is increased until ethyl acetate being added and is adjusted to the concentration of polymer after interior temperature being remained 54~56 DEG C by 12 hours 20%, obtain the ethyl acetate solution of (methyl) acrylic resin (A-1).The weight of (methyl) acrylic resin (A-1) Average molecular weight Mw is 1,390,000, and the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn are 5.32.In gel permeation chromatography (GPC) in elution curve, the ingredient of Mw139 ten thousand shows single peak, does not see in the range of Mw1000~2,500,000 Other peaks.
In Production Example above, weight average molecular weight Mw and number-average molecular weight Mn are measured as follows, and color is used as in GPC device Compose " the TSKgel XL " of 4 Tosoh (strain) systems of column arranged in series and " the Shodex GPC of 1 Showa electrician (strain) system KF-802 " is 5 total, tetrahydrofuran is used as eluent, in sample solution concentration 5mg/mL, 100 μ L of sample import volume, temperature Under conditions of 40 DEG C, flow velocity 1mL/ minutes, it is measured using standard polystyren conversion.When the elution curve of acquisition GPC Condition is also set as same.
Glass transition temperature Tg is the differential scanning calorimeter using SII Nano Technology Co. Ltd. system (DSC) " EXSTAR DSC6000 ", in a nitrogen atmosphere, in -80~50 DEG C of measuring temperature range, 10 DEG C/min of heating rate Under conditions of be measured.
By the composition of the monomer in Production Example 4, (numerical value of table 4 is parts by weight.) and the elution curve of GPC on Peak number (" GPC peak number " is expressed as in table 4) concentration in the range of Mw1000~2,500,000 is shown in table 4.
[table 4]
Abbreviation in " monomer composition " column of table 4 refers to following monomer.
BA: butyl acrylate (glass transition temperature of homopolymer: -54 DEG C),
MA: methyl acrylate (glass transition temperature of homopolymer: 10 DEG C),
HEA: acrylic acid 2- hydroxy methacrylate.
< embodiment 3~4,8~9 > of comparative example
(1) preparation of adhesive composition
To (methyl) acrylic resin obtained in Production Example 4 ethyl acetate solution (resin concentration: in 20%), phase For 100 parts of solid component of the solution, isocyanates shown in the table 5 of (parts by weight) is measured shown in mixture table 5 respectively It is crosslinking agent (B), silane compound (C) and ionic compound (D), then in a manner of making solid component concentration 14% It adds ethyl acetate and obtains adhesive composition.For the use level of each gradation composition shown in table 5, in used quotient It is the parts by weight as effective component contained therein whens product contain solvent etc..
[table 5]
Each gradation composition indicated in table 5 with abbreviation notes at foot.
(isocyanates system crosslinking agent)
B-1: the ethyl acetate solution (solid component concentration of the trimethylolpropane adduct of xylene diisocyanate 75%), the trade name " TAKENATE D-110N " obtained from Mitsui Chemicals (strain).
(silane compound)
C-1:3- glycidoxypropyltrime,hoxysilane, the trade name obtained from SHIN-ETSU HANTOTAI's chemical industry (strain) “KBM403”。
(ionic compound)
D-2:N- decyl pyridine four (pentafluorophenyl group) borate,
D-3:N- octyl -4- picoline hexafluorophosphate,
Bis- (fluorosulfonyl) imide salts of D-4:N- picoline.
(2) production of adhesive phase
Each adhesive composition prepared in above-mentioned (1) is used into adhesive applicator so that after dry with a thickness of 20 μm of side Formula is coated on the diaphragm being made of the polyethylene terephthalate film for implementing demoulding processing and (obtains from LINTEC (strain) Trade name " PLR-382051 ") demoulding process face, 100 DEG C dry 1 minute and produce adhesive phase (adhesive Piece).
(3) production of the optical film (P-1) with adhesive phase
By average degree of polymerization about 2400,99.9 moles of % of saponification degree, 60 μm of thickness of polyvinyl alcohol film ((strain) Kuraray The trade name " Kuraray Vinylon VF-PE#6000 " of system) be impregnated in 37 DEG C of pure water after, be impregnated at 30 DEG C containing In iodine and the aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) of potassium iodide.Thereafter, it is impregnated at 56.5 DEG C In aqueous solution (potassium iodide/boric acid/water (weight ratio)=12/3.6/100) containing potassium iodide and boric acid.Film is pure with 10 DEG C After water cleaning, in 85 DEG C of dryings, about 23 μm of thickness of the polarizing film for having adsorbed iodine on polyvinyl alcohol and being orientated is obtained.Stretch master It to be carried out in the process that iodine staining and boric acid are handled, total stretching ratio is 5.3 times.
In the one side of resulting polarizing film, press from both sides thick across the adhesive fitting being made of the aqueous solution of polyvinyl alcohol resin 25 μm of the transparent protective film (trade name of Konica Minolta Opt (strain) system being made of tri acetyl cellulose membrane "KC2UA"〕.Then it in the face with tri acetyl cellulose membrane opposite side of above-mentioned polarizing film, presss from both sides across by polyethenol series tree Thick 23 μm of zero phase difference film (the Japanese Zeon being made of cyclic polyolefin hydrocarbon system resin of adhesive fitting that the aqueous solution of rouge is constituted The trade name " ZEONOR " of (strain) system), produce polarization plates.Then, to the opposite with the contact face of polarizing film of zero phase difference film After implementing the Corona discharge Treatment for improving adaptation, the bonding made in above-mentioned (2) is bonded using laminating machine for the face of side Behind the face (adhesive level) with diaphragm opposite side of oxidant layer, 7 are cured under conditions of 23 DEG C of temperature, relative humidity 65% It, obtains the optical film (P-1) with adhesive phase.
(4) the resistance to metal protection evaluation of the optical film with adhesive phase
The case where (4-1) embodiment 3, comparative example 8
The optical film (P-1) with adhesive phase made in above-mentioned (3) is cut to the examination of the size for 20mm × 50mm Piece is tested, folder is fitted in the metal layer side of the glass substrate with metal layer across adhesive phase.As the glass for having metal layer Substrate has used the glass substrate that the metal copper layer of thickness about 500nm has been laminated using sputtering on alkali-free glass surface (Geomatec corporation).By resulting optical laminate temperature 60 C, relative humidity 90% baking oven in take care of 120 hours Afterwards, the optics with adhesive phase has been bonded from polarization plate surface by amplifying sem observation from the rear projection light of glass substrate The state of the metal layer of the part of film utilizes spot corrosion (diameter is 0.1mm or more and can be through the generation in the hole of light) Benchmark below is evaluated.It the results are shown in Table 6.
The case where (4-2) embodiment 4, comparative example 9
The optical film (P-1) with adhesive phase made in above-mentioned (3) is cut to the examination of the size for 20mm × 50mm Piece is tested, folder is fitted in the metal layer side of the glass substrate with metal layer across adhesive phase.As the glass for having metal layer Substrate, used be laminated on alkali-free glass surface using sputtering thickness about 500nm silver alloy (using silver as principal component and Alloy, APC containing palladium and copper) layer glass substrate (Geomatec corporation).By resulting optical laminate in temperature 60 DEG C, take care of 500 hours in the baking oven of relative humidity 90% after, penetrated from the rear projection light of glass substrate from polarization plate surface Amplification sem observation has been bonded the state of the metal layer of the part of the optical film with adhesive phase, and for spot corrosion, (diameter is 0.1mm or more and can through light hole generation), evaluated using benchmark below.It the results are shown in Table 6.
4: layer on surface of metal generate spot corrosion number be 2 or less,
3: layer on surface of metal generate spot corrosion number be 3~5,
2: layer on surface of metal generate hole number be 6 or more,
1: in the multiple spot corrosion of generation comprehensively of layer on surface of metal, and also creating gonorrhoea.
[table 6]
The explanation of symbol
1 has the optical film of adhesive phase, 2 polarizing films, 3 first resin films, 4 second resin films, the stacking of 5,6,7,8 optics Body, 10 optical films, 10a, 10b polarization plates, 20 adhesive phases, 30 metal layers, 40 substrates, 50 resin layers.

Claims (15)

1. a kind of optical film with adhesive phase,
It includes optical film and the adhesive phase being laminated on its at least one face,
Described adhesive layer is by containing (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), silane compound (C) And the adhesive composition of ionic compound (D) is constituted,
(methyl) acrylic resin (A) is contained from the Component units of alkyl acrylate (a1) and from third The Component units of olefin(e) acid Arrcostab (a2), and the weight average molecular weight 1000~250 on the elution curve of gel permeation chromatography There is single peak in ten thousand range,
The glass transition temperature of the homopolymer of the alkyl acrylate (a1) is lower than 0 DEG C, the alkyl acrylate (a2) Homopolymer glass transition temperature be 0 DEG C or more,
The content of isocyanates system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A) 0.08 parts by weight~2.5 parts by weight,
The ionic compound (D) is the ionic compound indicated with following formula (I):
In formula, R1~R8Each independently represent hydrogen atom, the alkyl with or without substituent group, with or without substitution The alkenyl of base, the alkynyl with or without substituent group, the aryl with or without substituent group or with or without taking The heterocycle of Dai Ji, R1~R4Ring, R are optionally formed between adjacent substituent group5~R8Optionally adjacent substituent group it Between form ring,
The content of the ionic compound (D) is 0.1 weight relative to 100 parts by weight of (methyl) acrylic resin (A) Measure part~10 parts by weight.
2. the optical film according to claim 1 with adhesive phase, wherein
The anion of the ionic compound (D) is the borate anion indicated with following formula (II):
In formula, R9~R13Each independently represent hydrogen atom, the alkyl with or without substituent group, with or without substitution The alkenyl of base, the alkynyl with or without substituent group, the aryl with or without substituent group, with or without substituent group Heterocycle or halogen atom, optionally form ring between adjacent substituent group.
3. the optical film according to claim 1 with adhesive phase, wherein
The anion of the ionic compound (D) is four (pentafluorophenyl group) borate anions.
4. the optical film according to claim 1 with adhesive phase, wherein
The anion of the ionic compound (D) be four (pentafluorophenyl group) borate anions, and cation have comprising The heterocycle structure containing nitrogen-atoms of unsaturated bond.
5. the optical film according to claim 1 with adhesive phase, wherein
The anion of the ionic compound (D) is four (pentafluorophenyl group) borate anions, and cation is with following The pyridylium that formula (III) indicates:
In formula, R14~R19Each independently represent hydrogen atom, the alkyl with or without substituent group, with or without substitution The alkenyl of base, the alkynyl with or without substituent group, the aryl with or without substituent group, with or without substituent group Heterocycle, hydroxyl, ether, carboxyl, carbonyl or halogen atom, optionally form ring between adjacent substituent group.
6. the optical film according to claim 1 with adhesive phase, wherein
(methyl) acrylic resin (A) contains the Component units from the monomer with hydroxyl.
7. the optical film according to claim 1 with adhesive phase, wherein
The weight average molecular weight of (methyl) acrylic resin (A) is 500,000~2,500,000.
8. the optical film according to claim 1 with adhesive phase, wherein
Described adhesive composition contains substantially no peroxide.
9. the optical film according to claim 1 with adhesive phase, wherein
Described adhesive composition contains substantially no three azole compounds.
10. the optical film according to claim 1 with adhesive phase, wherein
(methyl) acrylic resin (A) contains substantially no the Component units from methacrylate ester monomer.
11. the optical film according to claim 1 with adhesive phase, wherein
The optical film contains comprising by the polarizing film of the polyvinyl alcohol resin of iodine staining,
Described adhesive layer is directly laminated on the polarizing film.
12. a kind of liquid crystal display device, it includes the optics with adhesive phase described in any one of claim 1~11 Film.
13. a kind of adhesive composition,
It contains (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), silane compound (C) and ionicization It closes object (D),
(methyl) acrylic resin (A) is contained from the Component units of alkyl acrylate (a1) and from third The Component units of olefin(e) acid Arrcostab (a2), and the weight average molecular weight 1000~250 on the elution curve of gel permeation chromatography There is single peak in ten thousand range,
The glass transition temperature of the homopolymer of the alkyl acrylate (a1) is lower than 0 DEG C, the alkyl acrylate (a2) Homopolymer glass transition temperature be 0 DEG C or more,
The content of isocyanates system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A) 0.08 parts by weight~2.5 parts by weight,
The ionic compound (D) is the ionic compound indicated with following formula (I):
In formula, R1~R8Each independently represent hydrogen atom, the alkyl with or without substituent group, with or without substitution The alkenyl of base, the alkynyl with or without substituent group, the aryl with or without substituent group or with or without taking The heterocycle of Dai Ji, R1~R4Ring, R are optionally formed between adjacent substituent group5~R8Optionally adjacent substituent group it Between form ring；
The content of the ionic compound (D) is 0.1 weight relative to 100 parts by weight of (methyl) acrylic resin (A) Part~10 parts by weight are measured,
Described adhesive composition is used to form the adhesive phase of stacking on the metal layer.
14. a kind of optical film with adhesive phase it includes optical film and is laminated at least one face of the optical film Adhesive phase, and the optical film with adhesive phase using when folder fit on metal layer across described adhesive layer,
Described adhesive layer is formed by following adhesive composition:
Contain (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), silane compound (C) and ionic chemical combination Object (D),
(methyl) acrylic resin (A) is contained from the Component units of alkyl acrylate (a1) and from third The Component units of olefin(e) acid Arrcostab (a2), and the weight average molecular weight 1000~250 on the elution curve of gel permeation chromatography There is single peak in ten thousand range,
The glass transition temperature of the homopolymer of the alkyl acrylate (a1) is lower than 0 DEG C, the alkyl acrylate (a2) Homopolymer glass transition temperature be 0 DEG C or more,
The content of isocyanates system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A) 0.08 parts by weight~2.5 parts by weight,
The ionic compound (D) is the ionic compound indicated with following formula (I):
In formula, R1~R8Each independently represent hydrogen atom, the alkyl with or without substituent group, with or without substitution The alkenyl of base, the alkynyl with or without substituent group, the aryl with or without substituent group or with or without taking The heterocycle of Dai Ji, R1~R4Ring, R are optionally formed between adjacent substituent group5~R8Optionally adjacent substituent group it Between form ring,
The content of the ionic compound (D) is 0.1 weight relative to 100 parts by weight of (methyl) acrylic resin (A) Measure part~10 parts by weight.
15. a kind of optical laminate, it includes:
Optical film according to any one of claims 1 to 10 with adhesive phase, and
It is layered in the metal layer of the adhesive phase side of the optical film with adhesive phase.
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