CN110308509A - Optical laminate and liquid crystal display device - Google Patents

Optical laminate and liquid crystal display device Download PDF

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Publication number
CN110308509A
CN110308509A CN201910645400.0A CN201910645400A CN110308509A CN 110308509 A CN110308509 A CN 110308509A CN 201910645400 A CN201910645400 A CN 201910645400A CN 110308509 A CN110308509 A CN 110308509A
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methyl
film
parts
optical laminate
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CN110308509B (en
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阪上智惠
藤田政大
柳智熙
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • 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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • 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
    • 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

Abstract

The present invention relates to optical laminate and liquid crystal display devices, a kind of optical laminate is provided, it successively includes optical film, adhesive phase and metal layer, metal layer is metal wiring layer, and adhesive phase is by containing (methyl) acrylic resin (A), isocyanates system crosslinking agent (B), silane compound (C) and with formula: M+X(M+Indicate inorganic cation, XIndicate the anion containing fluorine atom.) indicate ionic compound (D) adhesive composition constitute, adhesive composition is relative to 100 parts by weight of (methyl) acrylic resin (A), containing isocyanates system crosslinking agent (B) 0.01~2.5 parts by weight, 0.2~8 parts by weight of 0.01~10 parts by weight of silane compound (C) and ionic compound (D), and provide the liquid crystal display device comprising the optical laminate.Optical laminate and liquid crystal display device of the invention can inhibit the corrosion of metal layer.

Description

Optical laminate and liquid crystal display device
The application be applicant submit application No. is 201610184576.7, entitled " optical laminate and liquid The divisional application of the application of crystal device ".Parent application day is on 03 29th, 2016, and priority date is 03 month 2015 31 Day.
Technical field
The present invention relates to the optical laminate for constituting the image display devices such as liquid crystal display device and include the optical layer The liquid crystal display device of stack.
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 static electricity resistance, it is also known that have within the adhesive layer containing ionic The optical film of 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, will include that the metal layer of metal material is combined with the adhesive phase containing ionic compound Composition in, under hot and humid environment having metal layer, there is a situation where corrode.In corrosion, since spot corrosion is in metal In the case that the thickness of layer is thin or when metal layer is metal line in the case where its line width, metal layer can be run through, therefore especially As problem.
It the object of the present invention is to provide a kind of optical laminate, is laminated on the metal layer of metal wiring layer etc The optical laminate of optical film with adhesive phase can inhibit the corrosion of metal layer, and provide and be laminated comprising the optics The liquid crystal display device of body.
The present invention provide optical laminate as shown below and liquid crystal display device comprising the optical laminate, with And adhesive composition.
[1] a kind of optical laminate, successively includes optical film, adhesive phase and metal 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 the ionic compound (D) indicated with following formula (I) is constituted:
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate the anion containing fluorine atom.
Described adhesive composition contains the isocyanide relative to 100 parts by weight of (methyl) acrylic resin (A) Acid esters system crosslinking agent (B) 0.01~2.5 parts by weight, 0.01~10 parts by weight of the silane compound (C) and described ionic 0.2~8 parts by weight of compound (D).
[2] according to the optical laminate recorded in [1], wherein the inorganic cation is alkali metal cation or alkaline earth Metal cation.
[3] according to the optical laminate recorded in [1] or [2], wherein the alkali metal cation is lithium cation (Li+), potassium cationic (K+) or sodium cation (Na+〕。
[4] according to the optical laminate recorded in [1] or [2], wherein the alkali metal cation is potassium cationic (K+〕。
[5] optical laminate recorded according to any one of [1]~[4], wherein the anion containing fluorine atom is The anion containing fluorine atom indicated with following formula (II):
[Y(SO2CmF2m+1)n]? (II)
In formula (II), Y indicates carbon atom or nitrogen-atoms, and when Y is carbon atom, n is 3, and when Y is nitrogen-atoms, n is 2, m table Show 0~10 integer.
[6] optical laminate recorded according to any one of [1]~[5], wherein the anion containing fluorine atom is Bis- (fluorine sulfo group) imide anion ((FSO2)2N-) or bis- (fluoroform sulfo group) imide anion ((CF3SO2)2N-〕。
[7] optical laminate recorded according to any one of [1]~[5], wherein the anion containing fluorine atom is Bis- (fluorine sulfo group) imide anion ((FSO2)2N-〕。
[8] optical laminate recorded according to any one of [1]~[7], wherein (methyl) acrylic resin (A) it is lower than the Component units of 0 DEG C of alkyl acrylate (a1) containing the glass transition temperature from homopolymer and comes From the Component units for the alkyl acrylate (a2) that the glass transition temperature in homopolymer is 0 DEG C or more.
[9] according to the optical laminate recorded in [8], wherein (methyl) acrylic resin (A) from institute State whole Component units of the content in composition (methyl) acrylic resin (A) of the Component units of alkyl acrylate (a2) To be more than 10 parts by weight in 100 parts by weight.
[10] according to the optical laminate recorded in [8] or [9], wherein the alkyl acrylate (a2) contains propylene Sour methyl esters.
[11] optical laminate recorded according to any one of [1]~[10], wherein (methyl) acrylic resin (A) containing the Component units from the monomer with hydroxyl.
[12] optical laminate recorded according to any one of [1]~[11], wherein (methyl) acrylic resin (A) Component units from the monomer with carboxyl are contained substantially no.
[13] optical laminate recorded according to any one of [1]~[12], wherein described adhesive composition is substantial Without containing selected from three azole compounds, thiazole compound, imidazole compound, imidazoline based compound, quinoline based compound, Pyridine based compound, pyrimidine compound, indoles based compound, amine compound, urea based compound, sodium benzoate, benzyl mercapto Antirust agent in base system compound, di-sec-butyl thioether and diphenyl sulfoxide.
[14] optical laminate recorded according to any one of [1]~[13], wherein the metal layer contain selected from aluminium, 1 kind in copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead and alloy containing the metal of more than two kinds in them with On.
[15] optical laminate recorded according to any one of [1]~[14], wherein the metal layer contains aluminium element.
[16] optical laminate recorded according to any one of [1]~[15], wherein the metal layer is to utilize sputtering shape At layer.
[17] optical laminate recorded according to any one of [1]~[16], wherein the metal layer with a thickness of 3 μm Below.
[18] a kind of liquid crystal display device, it includes the optical laminates that any one of [1]~[17] are recorded.
[19] a kind of adhesive composition contains isocyanide relative to 100 parts by weight of (methyl) acrylic resin (A) Acid esters system crosslinking agent (B) 0.01~2.5 parts by weight, 0.01~10 parts by weight of silane compound (C) and with following formula (I) table 0.2~8 parts by weight of ionic compound (D) shown:
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate the anion containing fluorine atom, described adhesive composition quilt It is used to form the adhesive phase of stacking on the metal layer.
According to the present invention it is possible to provide the optical laminate for the corrosion for being able to suppress metal layer and comprising the optical layer The liquid crystal display device of stack.
Detailed description of the invention
Fig. 1 is the constructed profile for indicating an example of optical laminate 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.
Specific embodiment
< optical laminate >
Fig. 1 is the constructed profile for indicating an example of optical laminate of the invention.As shown in Figure 1, optics of the invention Laminated body successively includes optical film 10, adhesive phase 20 and metal layer 30, can also also include substrate 40.The optical laminate It can be following optical laminate, that is, on the metal layer 30 being formed on substrate 40, comprising optical film 10 and will be laminated in The folder of optical film 1 with adhesive phase of adhesive phase 20 on its at least one face is bonded across its adhesive phase 20.
Adhesive phase 20 is usually directly laminated in the surface of optical film 10.In addition the optical film of adhesive phase is usually had 1 is laminated on metal layer 30 in a manner of contacting its adhesive phase 20 directly with metal layer 30.According to the present invention, in the light It learns in laminated body, the corrosion of metal layer 30 can be effectively inhibited.Hereinafter, will can also inhibit the property of the corrosion of metal layer 30 Referred to as " resistance to metal protection ".
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 series " refer to selected from least one of acrylic acid series and metha crylic.For " (methyl) acrylate " or " (methyl) acryloyl group " etc. is also identical.
(1) optical film
The optical film 10 that optical laminate of the invention has is the optics structure for constituting the optical film 1 with adhesive phase Part can be the various optical films (film with optical characteristics) that can be packed into the image display devices such as liquid crystal display device.Light Learn film 10 either single layer structure optical film, be also possible to the optical film of multilayered structure.The tool of the optical film of single layer structure Body example further includes phase difference film, brightness raising film, antiglare film, antireflection film, diffusion barrier, condensing film etc. other than polarizing film Optical functional film.The concrete example of the optical film of multilayered structure includes polarization plates, phase plate.So-called polarization plates in this specification Refer to that at least one surface layer in polarizing film is laminated with the component of resin film or resin layer.So-called phase plate, refers in phase difference At least one surface layer of film is laminated with the component of resin film or resin layer.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.
The layer of optical laminate when by as optical film 10 using polarization plates 10a, 10b shown in Fig. 2 and Fig. 3 is constituted Example respectively indicate in Fig. 4 and Fig. 5.Optical laminate 5 shown in Fig. 4 be using polarization plates 10a shown in Fig. 2 as The example that optical film 10 uses, optical laminate 6 shown in Fig. 5 is using polarization plates 10b shown in Fig. 3 as optical film 10 The example used.
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.
Film obtained by usually polyvinyl alcohol resin is film-made is used as the raw material film of polarizing film 2.Polyethenol series Resin can use well known method film.The thickness of raw material film is usually 1~150 μm, if also considering being easy for stretching Degree 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 is each independently comprising thermoplastic with translucency, preferably optically transparent Property resin, such as including 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 polymers of cyclic olefin, cyclic olefin and second The copolymer of the chain olefin of alkene, propylene etc or the aromatic compound with vinyl and by them with unsaturated carboxylic The modification (co) polymer etc. that acid or derivatives thereof has been modified.Wherein, it is preferable to use having used norbornene as cyclic olefin Or the norbornene resin of the orbornene-baseds monomer such as 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 for example including ultraviolet absorbing agent, infrared absorbent, organic based dye, pigment, inorganic system's pigment, antioxidant, prevent it is quiet Electric 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 (surface with 2 opposite side of polarizing film) can also have outside it The surface-treated layers (coat) such as standby hard conating, antiglare layer, anti-reflection layer, light diffusion layer, antistatic backing, stain-proofing layer, conductive layer.
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 optical film 1 and optical laminate with adhesive phase, and then is conducive to the light with adhesive phase Learn the filming of film 1 or the liquid crystal display device comprising optical laminate.
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 optical laminate.The durability of so-called optical film 1 and optical laminate with adhesive phase refers 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, adhesive phase can be inhibited 20 and optical component adjacent thereto interface in tilting or fall off, the not good situations such as the foaming of adhesive phase 20.
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 optical layer with adhesive phase of good optical durability (property that the deterioration of optical characteristics can be inhibited) Stack.
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 maintenance process that~45 DEG C or so of temperature is conserved.
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 base system monomer, photocuring can be enumerated Photopolymerization monomers such as property (methyl) acrylic monomer, photo-curable carbamate system monomer or from optical polymerism The oligomer of monomer.As Photoepolymerizationinitiater initiater, generated due to can enumerating containing the irradiation because of active energy beam in free love Base, radical anion, radical cation isoreactivity kind substance Photoepolymerizationinitiater initiater.As containing polymerizable compound And it is preferable to use contain photo-curable epoxy base system monomer for the active energy ray-curable adhesive of Photoepolymerizationinitiater initiater And the solidification compound, poly- containing photo-curable (methyl) acrylic monomer and optical free radical of light cationic polymerization initiator Close the solidification compound of initiator or the mixture of 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 at least any one binding face to them 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.Resin film is bonded on the two sides of polarizing film 2 In the case where for the adhesive that is bonded these resin films either adhesive of the same race, is also possible to gluing not of the same race Agent.
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 With for the phase difference film in the first, second resin film 3,4, in addition to be illustrated above to the resin film comprising thermoplastic resin into Other than stretched film obtained by row stretches, such as it can also be to comprising polyvinyl alcohol resin, polyarylate system resin, polyimides It is resin, polyether sulfone system resin, polyvinylidene fluoride/polymethyl methacrylate system resin, liquid crystal polyester system resin, ethylene- Stretching obtained by the resin film of the saponified, polyvinyl chloride resin of vinyl acetate copolymer etc. is stretched as 1.01~6 times or so Film.Wherein, preferably to polycarbonate-based resin film or annular ethylene series resin film, (methyl) acrylic resin film or fiber Stretched film obtained by prime system resin film is stretched uniaxially or biaxially.In addition, in the present specification, zero-lag film also includes In phase difference film (but can also be used as protective film use.).In addition to this, uniaxiality phase difference will can also be referred to as The film of film, wide viewing angle phase difference film, low modulus of photoelasticity phase difference film etc. 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 orientation of liquid crystal compounds, utilizing inorganic layer The coating of shape compound can also be used as phase difference film use to embody optically anisotropic film.As such phase difference Film has 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 sold with the trade name of " WV film " by film obtained by rod shaped liquid crystal tilted alignment, by Fujiphoto (strain) It is taken by film obtained by disc-like liquid crystal tilted alignment, by Sumitomo Chemical (strain) with the complete twin shaft that the trade name of " VAC film " is sold To the film of type, equally by Sumitomo Chemical (strain) with the film of biaxially oriented version of trade name sale 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
Be configured at adhesive phase 20 between optical film 10 and metal layer 30 by containing (methyl) acrylic resin (A), The adhesive composition of isocyanates system crosslinking agent (B), silane compound (C) and ionic compound (D) is constituted.This is viscous Mixture composite ionic compound (D) is the ionic compound indicated with following formula (I):
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate the anion containing fluorine atom.
Above-mentioned adhesive composition contains isocyanates system relative to 100 parts by weight of (methyl) acrylic resin (A) 0.01~2.5 parts by weight of crosslinking agent (B), 0.01~10 parts by weight of silane compound (C) and ionic compound (D) 0.2~ 8 parts by weight.
According to the adhesive phase 20 being made of above-mentioned adhesive composition, comprising adhesive phase 20 and metal layer 30 Can inhibit the corrosion of metal layer 30 in the optical laminate of composition, furthermore it is possible to improve optical film 1 with adhesive phase and The durability of optical laminate.In addition, having adhesive phase according to the adhesive phase 20 being made of above-mentioned adhesive composition Even optical film 1 and optical laminate composition made of adhesive phase 20 is directly fitted on polarizing film 2, can also show Good optical durability out.
The thickness of adhesive phase 20 is usually 2~40 μm, from the resistance to of the optical film 1 and optical laminate for having adhesive phase The viewpoints such as long property, the re-workability of optical film 1 with adhesive phase consider, preferably 5~30 μm, more preferably 10~25 μ m.In addition, if adhesive phase 20 with a thickness of 10 μm or more, adhesive phase 20 is followed to the change in size of optical film 10 Property become good, if it is 25 μm hereinafter, then re-workability becomes good.
Adhesive phase 20 is preferably the store elastic modulus that 0.1~5MPa is shown in 23~80 DEG C of temperature range Layer.The durability of optical film 1 and optical laminate with adhesive phase can be more efficiently improved as a result,.So-called " The store elastic modulus of 0.1~5MPa is shown in 23~80 DEG C of temperature range ", refer to the arbitrary temperature in the range Under, store elastic modulus is all the value in above range.Since store elastic modulus is usually gradually reduced as temperature increases, So if 23 DEG C and 80 DEG C of store elastic modulus both falls within above range, then can be considered as the range at a temperature of show Store elastic modulus in above range out.Commercially available determination of viscoelasticity dress can be used in the store elastic modulus of adhesive phase 20 It sets, the determination of viscoelasticity device of such as REOMETRIC corporation " DYNAMIC ANALYZER RDA II " measurement.
(2-1) (methyl) acrylic resin (A)
(methyl) acrylic resin (A) is using the Component units from (methyl) acrylic monomer as principal component (preferably comprising 50 weight % or more) polymer or copolymer.(methyl) acrylic monomer is for example containing with (methyl) The monomer of acryloyl group preferably comprises (methyl) alkyl acrylate.The carbon of alkyl possessed by (methyl) alkyl acrylate Atomicity is preferably 1~14, and more preferably 1~12, further preferably 1~8, it can be straight-chain, branched or ring-type.Make For (methyl) alkyl acrylate, the aftermentioned acrylic acid containing substituent group that substituent group has been imported into alkyl also can be used (methyl) alkyl acrylate containing substituent group of Arrcostab etc.(methyl) alkyl acrylate can both be used only a kind, Also two or more kinds may be used.
The concrete example of (methyl) alkyl acrylate includes (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) acrylic acid just and isopropyl ester, (methyl) acrylic acid just, the different and tert-butyl ester, acrylic acid just and isopentyl ester, (methyl) acrylic acid just And dissident's ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid just and isocyanate, (methyl) acrylic acid just and different monooctyl ester, (first Base) 2-EHA, (methyl) acrylic acid just and different nonyl ester, (methyl) acrylic acid just and isodecyl ester, (methyl) propylene Sour isobornyl thiocyanoacetate, (methyl) acrylic acid are just and Permethyl 99A base ester, (methyl) stearyl acrylate base ester etc..
(methyl) acrylic resin (A) preferably comprises the glass transition temperature Tg from homopolymer lower than 0 DEG C The Component units of alkyl acrylate (a1) and the alkyl acrylate (a2) for being 0 DEG C or more from the Tg of homopolymer Component units.The resistance to metal protection and durability for improving optical film 1 and optical laminate with adhesive phase is arranged in this Aspect it is advantageous.The Tg of the homopolymer of alkyl acrylate can for example use POLYMER HANDBOOK (Wiley- ) etc. Interscience literature value.
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 viewpoint of the resistance to metal protection and durability of optical film 1 and optical laminate with adhesive phase, in composition (first Base) acrylic resin (A) 100 parts by weight of whole Component units in, it is more than preferably 10 parts by weight, more preferably 15 weight Part or more, more than further preferably 20 parts by weight, more than particularly preferably 25 parts by weight.In addition from adhesive phase 20 to optics From the viewpoint of the tracing ability and re-workability of film 10, the content from the Component units of alkyl acrylate (a2) is preferably 70 parts by weight hereinafter, more preferably 60 parts by weight hereinafter, below further preferably 50 parts by weight.
(methyl) acrylic resin (A) can contain other lists other than alkyl acrylate (a1) and (a2) The Component units of body.The Component units that (methyl) acrylic resin (A) can be both somebody's turn to do containing a kind from other monomers, Two or more can 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 outside for preventing to be laminated in adhesive phase 20, preferably in fact Without containing the monomer with amino in matter.In addition, from the viewpoint of improving the corrosion resistance for ITO, preferably substantially not Contain the monomer with carboxyl.It is described herein to contain substantially no, refer in the complete of composition (methyl) acrylic resin (A) For below 0.1 parts by weight in 100 parts by weight of portion's 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) propylene Amide, N- (ethoxyl methyl) acrylamide, N- (propoxy methyl) acrylamide, N- (1- methylethoxy ylmethyl) third 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) third Acrylamide, N- (2- methoxy ethyl) acrylamide, N- (2- ethoxyethyl group) acrylamide, N- (2- propoxyl group second Base) acrylamide, N- (2- (1- methyl ethoxy) ethyl) acrylamide, N- (2- (1- methyl propoxyl group) ethyl) third 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 ethylene 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) from adhesive phase optical film 1 and optical laminate it is resistance to From the viewpoint of long property and resistance to metal protection, preferably other than the Component units from (methyl) alkyl acrylate, Also containing the Component units from the monomer with polar functional group.Monomer with polar functional group preferably has polarity (methyl) acrylate monomer of functional group, more preferably with the monomer of hydroxyl.From the list with polar functional group The content of the Component units of body is in 100 parts by weight of whole Component units of composition (methyl) acrylic resin (A), preferably 0.1~10 parts by weight, more preferably 0.25~5 parts by weight, further preferably 0.5~5 parts by weight.
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 of (methyl) acrylic resin (A) preferably on the elution curve of gel permeation chromatography (GPC) Measuring has single peak in the range of Mw1000~2,500,000, have more preferably in the range of Mw1000~2,500,000 single Peak and containing from alkyl acrylate (a1) and (a2) Component units.With (methyl) acrylic resin (A) work For basic polymer adhesive phase 20 improve with adhesive phase optical film 1 and optical laminate durability in terms of Favorably.In the case that peak number in the range of above-mentioned Mw is 2 or more, have the tendency that 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 optical laminate, the reprocessing of the optical film 1 with adhesive phase The trend that property is also improved.In addition, if Mw be 2,500,000 hereinafter, if adhesive phase 20 for optical film 10 change in size Tracing ability becomes good.With the molecular weight distribution that the ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn is indicated be usually 2~ 10.The Mw and Mn of (methyl) acrylic resin (A) are found out according to the GPC determination condition recorded in embodiment one.
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 of layer, optical film 1 with adhesive phase re-workability.It is above-mentioned viscous Degree 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 1 with adhesive phase And the raising of the resistance to metal protection and durability of optical laminate.
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 resistance to metal protection and durability of optical film 1 and optical laminate with adhesive phase Viewpoint considers, the content of (methyl) acrylic resin (A) whole (methyl) acrylic resins it is total in, preferably 70 weight % or more, more preferably 80 weight % or more, further preferably 90 weight % or more, adhesive composition is especially excellent It is elected to be and only contains (methyl) acrylic resin (A) for basic polymer.
(methyl) acrylic resin (A), 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 protection and durability of optical film 1 and optical laminate with adhesive phase.Isocyanide Acid esters 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), specifically For, it is different that toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone diisocyanate, dimethylbenzene two can be enumerated Cyanate, 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 isocyanates The polyol compound adduct (such as adduct of glycerine or trimethylolpropane) of compound, isocyanuric acid carboxylate, Biuret form compound and with polyether polyol or polyester polyol, acrylic polyol, polybutadiene polyol, poly- The derivatives such as the isocyanate compound of carbamate prepolymer type obtained by addition reaction occur for isoprene polyalcohol etc.. In above-mentioned, particularly preferred toluene di-isocyanate(TDI), hexamethylene diisocyanate, xylene diisocyanate or these are different The polyol compound adduct of cyanate esters, from the durability of optical film 1 and optical laminate with adhesive phase From the viewpoint of, more preferable xylene diisocyanate or its polyol compound adduct.
The content of isocyanates system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A), preferably 0.01~2.5 parts by weight, more preferably 0.1~2 parts by weight (such as below 1 parts by weight).If isocyanates system crosslinking agent (B) Content be in the range, then take into account with adhesive phase optical film 1 and optical laminate resistance to metal protection and The aspect of 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 optical laminate, adhesive composition only contains different preferably as crosslinking agent Cyanate system crosslinking agent (B), particularly preferably contains substantially no peroxide.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.
(2-3) silane compound (C)
Adhesive composition contains silane compound (C).It is possible thereby to improve adhesive phase 20 and metal layer 30, 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:
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate the anion containing fluorine atom.By using ionic chemical combination Object (D) can not only assign good antistatic performance to adhesive phase 20, but also can assign excellent resistance to metal protection And optical durability.Adhesive composition can contain one kind or two or more ionic compound (D).
In above-mentioned formula (I), M+Indicate inorganic cation.The concrete example of inorganic cation includes lithium cation (Li+), sodium sun Ion (Na+), potassium cationic (K+), caesium cation (Cs+) etc. alkali metal ions；Beryllium cation (Be2+), magnesium cation (Mg2+〕、 Calcium cation (Ca2+) etc. alkaline-earth metal ions etc..Wherein, from the resistance to gold of optical film 1 and optical laminate with adhesive phase , it is preferable to use lithium cation (Li from the viewpoint of category corrosivity+), potassium cationic (K+) or sodium cation (Na+), from viscous From the viewpoint of the optical film 1 of mixture layer and the durability of optical laminate, potassium cationic (K is more preferably used+〕。
In above-mentioned formula (I), X?Indicate the anion containing fluorine atom.It is quiet that anion containing fluorine atom has easy offer to prevent The trend of the ionic compound (D) of excellent electrical property.Inorganic anion and organic can be used in anion containing fluorine atom Any one of anion.The concrete example that the inorganic anion of ionic compound (D) can be constituted includes tetrafluoroborate yin Ion (BF4 -), hexafluoro-phosphate radical anion (PF6 -), hexafluoroarsenate root anion (AsF6 -), hexafluoroantimonic anion anion 〔SbF6 -), hexafluoro niobium acid radical anion (NbF6 -), hexafluoro tantalum acid radical anion (TaF6 -), bis- (fluorine sulfo group) imide anions 〔(FSO2)2N-), fluorine (poly- (hydrogen fluoride)) anion (F (HF)n -) (n is 1~3 or so) etc..
The concrete example that the organic anion of ionic compound (D) can be constituted includes trifluoroacetic acid root anion 〔CF3COO-), trifluoromethanesulfonic acid root anion (CF3SO3 -), bis- (fluoroform sulfo group) imide anion ((CF3SO2)2N-), three (trifyl) methanides anion ((CF3SO2)3C-), perfluoro butane sulfonate anion (C4F9SO3 -), bis- (five fluorine second Sulfo group) imide anion ((C2F5SO2)2N-), perfluorobutyric acid root anion (C3F7COO-), (trifyl) (fluoroform Alkyl carbonyl) imide anion ((CF3SO2)(CF3CO)N-), perfluoropropane -1,3- disulfonic acid root anion (-O3S(CF2)3SO3 -), four aryl boric acid root anion (such as four (pentafluorophenyl group) borate anions etc.), dicyanamide anion (dca) ((CN)2N-) and the imide anion etc. that is indicated with following formula (III):
[changing 1]
Antistatic performance, resistance to of the anion containing fluorine atom from optical film 1 and optical laminate with adhesive phase From the viewpoint of metal protection and optical durability, the anion containing fluorine atom that is preferably indicated with following formula (II):
[Y(SO2CmF2m+1)n]? (II)
In formula (II), Y indicates carbon atom or nitrogen-atoms, and when Y is carbon atom, n is 3, and when Y is nitrogen-atoms, n is 2, m table Show 0~10 integer.The concrete example of the anion containing fluorine atom indicated with formula (II) includes bis- (fluorine sulfo group) acid imide yin Ion, bis- (fluoroform sulfo group) imide anions, three (trifyl) methanides anion, bis- (five fluorine second sulfo groups) Imide anion etc..Wherein, if used as bis- (fluorine sulfo group) imide anion (FSI?) or it is bis- (fluoroform sulfo group) Imide anion (TFSI?) ionic compound (D), then be particularly conducive to optical film 1 and optics with adhesive phase The raising of the antistatic performance of laminated body, resistance to metal protection and optical durability.Y is preferably nitrogen-atoms, and m is preferably 0~4 Integer, more preferably 0~1 integer, particularly preferably 0.
If enumerating the preferred example of the ionic compound (D) indicated with above-mentioned formula (I), as follows.
Bis- (fluorine sulfo group) imide lis,
Bis- (fluoroform sulfo group) imide lis,
Bis- (five fluorine second sulfo groups) imide lis,
Three (fluoroform sulfo group) acyl methanation lithiums,
Bis- (fluorine sulfo group) acid imide sodium,
Bis- (fluoroform sulfo group) acid imide sodium,
Bis- (five fluorine second sulfo groups) acid imide sodium,
Three (fluoroform sulfo group) acyl methanation sodium,
Bis- (fluorine sulfo group) acid imide potassium,
Bis- (fluoroform sulfo group) acid imide potassium
Bis- (five fluorine second sulfo groups) acid imide potassium,
Three (fluoroform sulfo group) acyl methanation potassium.
The content of ionic compound (D) in adhesive composition is relative to 100 weight of (methyl) acrylic resin (A) Amount part is 0.2~8 parts by weight, preferably 0.2~7 parts by weight, more preferably 0.3~5 parts by weight, particularly preferably 0.5~3 weight Measure part.If the content of ionic compound (D) is 0.2 parts by weight or more, be conducive to the raising of antistatic performance, if it is 8 parts by weight are hereinafter, be then conducive to the resistance to metal protection and durability of optical film 1 and optical laminate with adhesive phase.
Adhesive composition can be with the ionic compound (D) that is indicated with above-mentioned formula (I) together, and with anti-other than it Electrostatic agent, however consider from viewpoints such as the resistance to metal protections of optical film 1 and optical laminate for having adhesive phase, adhesive Composition only contains the above ionic compound (D) for stating formula (I) expression preferably as antistatic agent.
(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 contain the resistance to metal that can be improved optical film 1 and optical laminate with adhesive phase Corrosive antirust agent.As antirust agent, the triazoles systems such as benzotriazole based compound, other three azole compounds can be enumerated Compound；The thiazole compounds such as benzothiazole based compound, other thiazole compounds；Benzyl imidazole based compound, its The imidazole compounds such as his imidazole compound；Imidazoline based compound；Quinoline based compound；Pyridine based compound；Pyrimidine Based compound；Indoles based compound；Amine compound；Urea based compound；Sodium benzoate；Benzylmercapto based compound；Di-secondary fourth Base 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) metal layer and 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, alloy, therefore metal layer 30 is preferably comprised comprising above-mentioned metal The metal simple-substance of element and/or alloy of more than two kinds containing above-mentioned metallic element.However, optical laminate can also be with Such metal layer 30 together, also has the transparent electrode layer comprising metal oxides such as ITO.
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 the had metal line of metal wiring layer is usual in the case where metal layer 30 is metal wiring layer For 10 μm hereinafter, preferably 5 μm hereinafter, further preferably 3 μm or less.In addition the line width of metal line be usually 0.01 μm with On, preferably 0.1 μm or more, further preferably 0.5 μm or more.For the metal of the metal layer 30 comprising the film, filament It is routed the metal layer 30 constituted, optical laminate of the invention also shows that good resistance to metal protection.Especially in metal Wiring for example with a thickness of 3 μm or less, line width be 10 μm or less when, or with a thickness of 3 μm or less, line width be 10 μm or less, using splashing When penetrating method formation, 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.In the metal layer 30 being patterned In the case where upper stacking adhesive phase 20, adhesive 20 also can have the part not contacted with metal layer 30.Metal layer 30 It can be 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.
As shown in Figure 1, the metal layer 30 of for example, metal wiring layer is generally formed on substrate 40, in this case, this hair Bright optical laminate includes the substrate 40.The formation of metal layer 30 on the substrate 40 for example can use sputtering and carry out.Base Plate 40 can be the transparent substrate for constituting liquid crystal cells contained in touch input element.Substrate 40 is preferably glass substrate.Make For 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 entire surface of substrate 40, part of it can also be formed in.Situations such as forming metal layer 30 being patterned on the substrate 40 Under, when a part on the surface of substrate 40 forms metal layer 30, a part of adhesive phase 20 can with for example comprising glass Substrate 40 directly contacts, however since the adhesive phase of optical laminate of the invention 20 and the adaptation of glass are also excellent, because This optical laminate and to have the durability of the liquid crystal display device of the optical laminate in this case also excellent.
(4) composition and manufacturing method of optical laminate
Optical laminate of the invention is as shown in Figures 4 and 5 in 1 embodiment, the light comprising having adhesive phase The metal layer 30 learned film 1 and be laminated in its 20 side of adhesive phase.In the optical laminate 5,6 shown in Fig. 4 and Fig. 5, have The optical film 1 of adhesive phase is laminated on metal layer 30 in a manner of contacting its adhesive phase 20 directly with metal layer 30. It according to the present invention, can also be in the optical laminate for the composition for contacting adhesive phase 20 and metal layer 30 directly Effectively inhibit the corrosion of metal layer 30.
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.
Metal layer 30 as described above is also possible to metal wiring layer.By metal layer 30 be metal wiring layer the case where an example It is shown in Fig. 7.Also it can be omitted resin layer 50 in optical laminate shown in fig. 7.
Optical laminate for example can be by that on the metal layer 30 being formed on substrate 40, will include optical film 10 and layer Be laminated on the adhesive phase 20 on its at least one face with adhesive phase optical film 1 folder across its adhesive phase 20 fitting and Production.
As described above, the optical film 1 with adhesive phase includes optical film 10 and the bonding for being laminated in its at least one face Oxidant layer 20 (Fig. 1).It can also be in the two sides laminate adhesive oxidant layer 20 of optical film 10.In general, adhesive phase 20 be directly laminated in The surface of optical film 10.By adhesive phase 20 be set to optical film 10 surface when, preferably the binding face to optical film 10 and/or The binding face of adhesive phase 20 implements the formation or surface activation processing, such as corona treatment, sided corona treatment of prime coat Deng, more preferably implementation 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 any one of the first, second resin film 3,4 Face can also be laminated in two outsides.
Although antistatic backing can also in addition be arranged between optical film 10 and adhesive phase 20, due to of the invention Adhesive phase 20 can use individual adhesive phase and assign excellent static electricity resistance, thus from the filming of optical laminate, From the aspect of the simplification of laminated body production process, do not have antistatic backing preferably between optical film 10 and adhesive phase 20.
Optical film 1 with adhesive phase also may include the diaphragm (stripping film) for being laminated in the outside of adhesive phase 20. The diaphragm is usually stripped removing in the use of adhesive phase 20 (such as when being laminated on metal layer 30).Diaphragm for example can be with It is to comprising the various resins such as polyethylene terephthalate, polybutylene terephthalate (PBT), polycarbonate, polyarylate The film that the formation of film 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 forms adhesive phase 20 in the same manner as described above, by the adhesive phase 20 stacking (transfer) in the surface of optical film 10.
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.Light is produced the optical film 1 for having adhesive phase to be bonded with metal layer 30 After learning laminated body, in the case where there is what not good situation, it is necessary to will the optical film 1 with adhesive phase from metal layer 30 Other optical films 1 with adhesive phase are fitted on metal layer 30 again, that is, so-called reprocessing are needed to grasp by removing Make.Optical laminate of the invention is difficult the metal layer in the optical film 1 that will have adhesive phase after removing in metal layer 30 30 surface generates fuzzy, residue glue etc., and re-workability is excellent.Optical laminate according to the present invention, 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 laminate of aforementioned present invention.Liquid crystal display device of the invention can To inhibit the corrosion of metal layer 30, in addition, showing good durability.
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 function mode 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 laminate of the invention can both be configured at the observation side of touch input element (liquid crystal cells), can also be configured at backlight Lamp side can also be configured at two sides.The driving method of liquid crystal cells can be TN mode, VA mode, IPS mode, multidomain mode, Known any mode such as OCB mode.In liquid crystal display device of the invention, substrate 40 can possessed by optical laminate To 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)
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-2).The weight average molecular weight Mw of (methyl) acrylic resin (A-2) For 1,410,000, Mw/Mn 4.71.In the elution curve of GPC, the ingredient of Mw141 ten thousand shows single peak, Mw1000~ Other peaks are not seen 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 3,1 > 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: bis- (fluorine sulfo group) acid imide potassium,
D-2: bis- (fluoroform sulfo group) imide lis,
D-3:N- octyl -4- picoline hexafluorophosphate.
(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, the diaphragm for being coated on the polyethylene terephthalate film comprising implementing demoulding processing (are obtained from LINTEC (strain) Trade name " PLR-382051 ") demoulding process face, 100 DEG C dry 1 minute and produce adhesive phase (adhesive sheet).
(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, the adhesive fitting thickness 25 across the aqueous solution comprising polyvinyl alcohol resin is pressed from both sides μm the transparent protective film trade name " KC2UA " of system (Konica Minolta Opt (strain)) comprising tri acetyl cellulose membrane. Then in the face with tri acetyl cellulose membrane opposite side of above-mentioned polarizing film, folder is across including the water-soluble of polyvinyl alcohol resin Zero phase difference film (the trade name of Japanese Zeon (strain) system comprising cyclic polyolefin hydrocarbon system resin of thick 23 μm of adhesive fitting of liquid " ZEONOR "), produce polarization plates.Then, to the face for the face opposite side of zero phase difference film contacted with polarizing film, implement After Corona discharge Treatment for improving adaptation, using laminating machine be bonded above-mentioned (2) in make adhesive phase and diaphragm It behind the face (adhesive level) of opposite side, conserves 7 days, is obtained with viscous under conditions of 23 DEG C of temperature, relative humidity 65% The optical film (P-1) of mixture layer.
(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, the adhesive fitting thickness 25 across the aqueous solution comprising polyvinyl alcohol resin is pressed from both sides μm the transparent protective film trade name " KC2UA " of system (Konica Minolta Opt (strain)) comprising tri acetyl cellulose membrane, Produce polarization plates.Then it in the face with the face opposite side for being fitted with protective film of polarizing film, is bonded using laminating machine above-mentioned (2) behind the face (adhesive level) with diaphragm opposite side of the adhesive phase made in, in 23 DEG C of temperature, relative humidity 65% Under conditions of conserve 7 days, obtain 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 penetrating magnifying glass (Lupe) from polarization plate surface from the rear projection light of glass substrate with adhesive phase Optical film part metal layer state, about spot corrosion (diameter be 0.1mm or more and can through light hole production It is raw), 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: generating multiple spot corrosion in the entire surface of layer on surface of metal, and also create 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 visual sensitivity amendment, the visual acuity before finding out endurance test Degree amendment monomer transmissivity (Ty) and visual sensitivity amendment degree of polarization (Py).Moreover, by optical laminate so that polarization plates Tri acetyl cellulose membrane side is placed in the spectrophotometric with integrating sphere for detector side, from the mode of glass substrate side incident light In meter.
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 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 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 each Production Example, (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 4~5,2~3 > 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 5 of (parts by weight) is measured shown in mixture table 5 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 5, used Commodity whens containing solvent etc., be the parts by weight as effective component contained therein.
[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-1: bis- (fluorine sulfo group) acid imide potassium,
D-2: bis- (fluoroform sulfo group) imide lis,
D-3:N- octyl -4- picoline hexafluorophosphate.
D-4: lithium iodide.
(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, the diaphragm for being coated on the polyethylene terephthalate film comprising implementing demoulding processing (are obtained from LINTEC (strain) Trade name " PLR-382051 ") demoulding process face, 100 DEG C dry 1 minute and produce adhesive phase (adhesive sheet).
(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, the adhesive fitting thickness 25 across the aqueous solution comprising polyvinyl alcohol resin is pressed from both sides μm the transparent protective film trade name " KC2UA " of system (Konica Minolta Opt (strain)) comprising tri acetyl cellulose membrane. Then in the face with tri acetyl cellulose membrane opposite side of above-mentioned polarizing film, folder is across including the water-soluble of polyvinyl alcohol resin Zero phase difference film (the trade name of Japanese Zeon (strain) system comprising cyclic polyolefin hydrocarbon system resin of thick 23 μm of adhesive fitting of liquid " ZEONOR "), produce polarization plates.Then, to the face for the face opposite side of zero phase difference film contacted with polarizing film, implement After Corona discharge Treatment for improving adaptation, using laminating machine be bonded above-mentioned (2) in make adhesive phase and diaphragm It behind the face (adhesive level) of opposite side, conserves 7 days, is obtained with viscous under conditions of 23 DEG C of temperature, relative humidity 65% The optical film (P-1) of mixture layer.
(5) the resistance to metal protection evaluation of the optical film with adhesive phase
2 > of < comparative example
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, the optics with adhesive phase has been bonded from polarization plate surface through amplification sem observation from the rear projection light of glass substrate The state of the metal layer of the part of film is utilized about 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.
< embodiment 4~5,3 > of comparative example
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 about 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 spot corrosion number be 6 or more,
1: generating multiple spot corrosion in the entire surface of layer on surface of metal, and also create 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 optics Body, 10 optical films, 10a, 10b polarization plates, 20 adhesive phases, 30 metal layers, 40 substrates, 50 resin layers.

Claims (21)

1. a kind of optical laminate,
Successively include optical film, adhesive phase and metal layer,
The metal layer is metal wiring layer,
Described adhesive layer is by containing (methyl) acrylic resin (A), crosslinking agent, silane compound (C) and with following formula (I) adhesive composition of the ionic compound (D) indicated is constituted:
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate the anion containing fluorine atom；
The metal layer is the layer being made of the film for leading electric metal.
2. optical laminate according to claim 1, wherein
Described adhesive composition contains the crosslinking agent relative to 100 parts by weight of (methyl) acrylic resin (A) 0.01 parts by weight~2.5 parts by weight, 0.01 parts by weight of the silane compound (C)~10 parts by weight and the ionic chemical combination 0.2 parts by weight of object (D)~8 parts by weight.
3. optical laminate according to claim 1 or 2, wherein
The line width of the metal wiring layer is 10 μm or less.
4. optical laminate described in any one of claim 1 to 3, wherein
The inorganic cation is alkali metal ion or alkaline-earth metal ions.
5. optical laminate according to claim 4, wherein
The alkali metal ion is lithium cation, potassium cationic or sodium cation.
6. optical laminate according to claim 4, wherein
The alkali metal ion is potassium cationic.
7. optical laminate described according to claim 1~any one of 6, wherein
The anion containing fluorine atom is the anion containing fluorine atom indicated with following formula (II):
[Y(SO2CmF2m+1)n]? (II)
In formula (II), Y indicates carbon atom or nitrogen-atoms, and when Y is carbon atom, n is 3, when Y is nitrogen-atoms n be 2, m indicate 0~ 10 integer.
8. optical laminate according to any one of claims 1 to 7, wherein
The anion containing fluorine atom be bis- (fluorine sulfo group) imide anions or bis- (fluoroform sulfo group) acid imide yin from Son.
9. optical laminate described according to claim 1~any one of 8, wherein
The anion containing fluorine atom is bis- (fluorine sulfo group) imide anions.
10. optical laminate described according to claim 1~any one of 9, wherein
(methyl) acrylic resin (A) is contained from the Component units of alkyl acrylate (a1) and from third The glass transition temperature of the Component units of olefin(e) acid Arrcostab (a2), the homopolymer of the alkyl acrylate (a1) is lower than 0 DEG C, The glass transition temperature of the homopolymer of the alkyl acrylate (a2) is 0 DEG C or more.
11. optical laminate according to claim 10, wherein
The content of the Component units from the alkyl acrylate (a2) of (methyl) acrylic resin (A) is in structure At in 100 parts by weight of whole Component units of (methyl) acrylic resin (A) be 10 parts by weight more than.
12. optical laminate described in 0 or 11 according to claim 1, wherein
The alkyl acrylate (a2) contains methyl acrylate.
13. optical laminate described according to claim 1~any one of 12, wherein
(methyl) acrylic resin (A) contains the Component units from the monomer with hydroxyl.
14. optical laminate described according to claim 1~any one of 13, wherein
(methyl) acrylic resin (A) contains substantially no the Component units from the monomer with carboxyl.
15. optical laminate described according to claim 1~any one of 14, wherein
Described adhesive composition is contained substantially no selected from three azole compounds, thiazole compound, imidazole compound, miaow Oxazoline based compound, quinoline based compound, pyridine based compound, pyrimidine compound, indoles based compound, amine compound, Antirust agent in urea based compound, sodium benzoate, Benzylmercapto based compound, di-sec-butyl thioether and diphenyl sulfoxide.
16. optical laminate described according to claim 1~any one of 15, wherein
The metal layer contain selected from by copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead and containing 2 kinds in them with On metal alloy composed by group one or more of.
17. optical laminate described according to claim 1~any one of 16, wherein
The metal layer is the layer formed using sputtering.
18. optical laminate described according to claim 1~any one of 17, wherein
The metal layer with a thickness of 3 μm or less.
19. a kind of liquid crystal display device, it includes the optical laminates described in any one of claim 1~18.
20. a kind of adhesive composition,
It contains 0.01 parts by weight of crosslinking agent~2.5 parts by weight, silicon relative to 100 parts by weight of (methyl) acrylic resin (A) 0.01 parts by weight of hydride compounds (C)~10 parts by weight and 0.2 parts by weight of ionic compound (D) indicated with following formula (I) ~8 parts by weight:
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate that the anion containing fluorine atom, described adhesive composition are used for shape At the adhesive phase being layered on metal layer, the metal layer is metal wiring layer, and to be made of the film for leading electric metal Layer.
21. 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 across described adhesive layer metal layer is fitted in for pressing from both sides,
The metal layer is metal wiring layer, and is the layer being made of the film for leading electric metal,
Described adhesive layer by relative to 100 parts by weight of (methyl) acrylic resin (A) contain 0.01 parts by weight of crosslinking agent~ 2.5 parts by weight, 0.01 parts by weight of silane compound (C)~10 parts by weight and the ionic compound indicated with following formula (I) (D) 0.2 parts by weight~8 parts by weight adhesive composition is formed:
M+X? (I)
In formula (I), M+Indicate inorganic cation, X?Indicate the anion containing fluorine atom.
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