CN109790430A - Adhesive composition - Google Patents

Adhesive composition Download PDF

Info

Publication number
CN109790430A
CN109790430A CN201780058353.9A CN201780058353A CN109790430A CN 109790430 A CN109790430 A CN 109790430A CN 201780058353 A CN201780058353 A CN 201780058353A CN 109790430 A CN109790430 A CN 109790430A
Authority
CN
China
Prior art keywords
methyl
film
acrylic resin
component units
adhesive composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780058353.9A
Other languages
Chinese (zh)
Other versions
CN109790430B (en
Inventor
浅津悠司
小桥亚依
薛明轩
竹田俊之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Kasei Corp
Original Assignee
Nippon Synthetic Chemical Industry Co Ltd
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Synthetic Chemical Industry Co Ltd, Sumitomo Chemical Co Ltd filed Critical Nippon Synthetic Chemical Industry Co Ltd
Publication of CN109790430A publication Critical patent/CN109790430A/en
Application granted granted Critical
Publication of CN109790430B publication Critical patent/CN109790430B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides a kind of adhesive composition; it is the adhesive composition comprising (methyl) acrylic resin (A), crosslinking agent (B) and silane compound (C); (methyl) acrylic resin (A) includes the Component units in source (methyl) acrylate (a1) containing acetoacetyl and the Component units in source (methyl) acrylate (a2) containing hydroxyl, and mass ratio (a2)/(a1) of the Component units is 0.5~5.

Description

Adhesive composition
Technical field
Present patent application is to Japanese patent application the 2016-186152nd (applying date: on September 23rd, 2016) opinion bar Priority on Li Gongyue, by herein with reference to and entire contents are included in this specification.
The present invention relates to as adhesive composition useful for the optical component utilized in liquid crystal display device etc., The adhesive phase that is formed by the adhesive composition, the optical film with adhesive phase comprising the adhesive phase and optics stacking Body and adhesive composition (methyl) acrylic resin.
Background technique
Polarization plates made of fitting transparent resin film are laminated as the optical film quilt of representative in the one or both sides of polarizing film It is widely used as the optical component for constituting the image display devices such as liquid crystal display device, organic EL display device.Polarization plates Etc optical film press from both sides mostly fit in other components (such as liquid crystal cells of liquid crystal display device etc.) across adhesive phase and It uses (referring to patent document 1).Therefore, as optical film, it is known to be previously provided with having for adhesive phase on one side at it and bond The optical film of oxidant layer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-229321 bulletin
Summary of the invention
Problem to be solved by the invention
In recent years, the image display devices such as liquid crystal display device, organic EL display device are extended to smart phone, put down Template terminal is the mobile device purposes of representative, the vehicle-mounted equipment purposes by representative of navigation system.This on the way, have It is likely to be exposed in the environment more harsh than previous indoor TV purposes, therefore the durability for improving device becomes project.
Durability is similarly required in the optical film with adhesive phase for constituting image display device etc..That is, dress Enter the adhesive phase in image display device etc. to be placed in sometimes under high temperature or hot and humid environment, or is placed in high temperature repeatedly and low Temperature environment under, for have adhesive phase optical film, it is desirable that even if can also inhibit under these circumstances adhesive phase with The not good situations such as the tilting or removing, the foaming of adhesive phase that are bonded in the interface of the optical component of the adhesive phase, in addition, Optical characteristics is also required not deteriorate.Especially in the case where optical film is polarization plates, due to the strong contraction under hot environment Stress, therefore endurance quality more higher than general optical film is required for adhesive phase.Since above-mentioned raising image is shown The requirement of the durability of device is surging, and recently, the durability required adhesive phase becomes very strict.
Thus, the object of the present invention is to provide be capable of forming to also show that even if under the conditions of this harsh durable The adhesive composition of the adhesive phase of excellent durability, the adhesive phase formed by the adhesive composition are glued comprising this The optical film and optical laminate with adhesive phase of mixture layer.
Other purpose of the invention is, provides to be capable of forming and also shows that even if under the conditions of above-mentioned harsh durable Adhesive composition (methyl) acrylic resin of the adhesive phase of excellent durability.
The method for solving problem
The present inventor has made intensive studies to solve the above-mentioned problems, as a result completes the present invention.
That is, including content below in the present invention.
[1] a kind of adhesive composition is comprising (methyl) acrylic resin (A), crosslinking agent (B) and silane compound (C) adhesive composition, (methyl) acrylic resin (A) include (methyl) acrylate containing acetoacetyl (a1) Component units of the Component units in source and source (methyl) acrylate (a2) containing hydroxyl, the Component units Mass ratio (a2)/(a1) is 0.5~5.
[2] according to the adhesive composition recorded in [1], wherein the weight average molecular weight of (methyl) acrylic resin (A) 1,000,000 or more are scaled with polystyrene.
[3] according to the adhesive composition recorded in [1] or [2], wherein (methyl) acrylic resin (A) also includes The Component units in the source alkyl acrylate (a3) of the glass transition temperature of homopolymer lower than 0 DEG C and the glass of homopolymer Change the Component units in source alkyl acrylate (a4) that transition temperature is 0 DEG C or more.
[4] adhesive composition recorded according to any one of [1]~[3], wherein the glass transition temperature of homopolymer The Component units in source alkyl acrylate (a3) lower than 0 DEG C and the glass transition temperature of homopolymer are the third of 0 DEG C or more Mass ratio (a3)/(a4) of the Component units in the source olefin(e) acid Arrcostab (a4) is 0.1~4.
[5] adhesive composition recorded according to any one of [1]~[4], wherein (methyl) acrylic resin (A) Contained in (methyl) the acrylate source containing carboxyl Component units ratio relative to composition (methyl) acrylic acid series 100 mass parts of whole Component units of resin (A) are 1.0 below the mass.
[6] adhesive composition recorded according to any one of [1]~[5], wherein (methyl) acrylic resin (A) It also include the Component units of (methyl) acrylamide monomer source.
[7] adhesive composition recorded according to any one of [1]~[6], wherein crosslinking agent (B) is isocyanates system Compound.
[8] adhesive composition recorded according to any one of [1]~[7], wherein the ratio of crosslinking agent (B) relative to 100 mass parts of (methyl) acrylic resin (A) are 0.01~10 mass parts.
[9] adhesive composition recorded according to any one of [1]~[8], wherein silane compound (C) is with following The silane compound that formula (c1) indicates:
[changing 1]
(in formula, B indicates the alicyclic type hydrocarbon of the alkane diyl of carbon atom number 3~20 or the divalent of carbon atom number 3~20, structure At-the CH of the alkane diyl and the alicyclic type hydrocarbon2Optionally it is substituted by-O- or-CO-, R1Indicate carbon atom number 1 ~5 alkyl, R2、R3、R4、R5And R6Each independently represent the alkyl of carbon atom number 1~5 or the alcoxyl of carbon atom number 1~5 Base.)
[10] adhesive composition recorded according to any one of [1]~[9], wherein the ratio phase of silane compound (C) It is 0.01~10 mass parts for 100 mass parts of (methyl) acrylic resin (A).
[11] adhesive composition recorded according to any one of [1]~[10], wherein contain substantially no photopolymerization and draw Send out agent and its decomposition product.
[12] adhesive composition recorded according to any one of [1]~[11], wherein also include ionic compound (D)。
[13] according to the adhesive composition recorded in [12], wherein the ratio of ionic compound (D) is relative to (first Base) acrylic resin (A) 100 mass parts be 0.01~10 mass parts.
[14] according to the adhesive composition recorded in [12] or [13], wherein constitute the yin of ionic compound (D) from Son is selected from bis- (trifluoro methylsulfonyl) imines anion, bis- (fluorine sulphonyl) imines anion and four (pentafluorophenyl group) borate At least one of anion.
[15] a kind of adhesive phase is formed by the adhesive composition that any one of [1]~[14] are recorded.
[16] according to the adhesive phase recorded in [15], wherein the percent gel of described adhesive layer is 70~90%.
[17] a kind of optical film with adhesive phase is comprising optical film and at least one side for being laminated in the optical film The optical film with adhesive phase of adhesive phase, the adhesive phase are the adhesive phase recorded in [15] or [16].
[18] a kind of optical laminate it includes the optical film recorded in [17] with adhesive phase and is laminated in this The substrate of the adhesive phase side of optical film with adhesive phase.
[19] a kind of adhesive composition uses (methyl) acrylic resin (A), and it includes (the first containing acetoacetyl Base) Component units in the source acrylate (a1) and the Component units in source (methyl) acrylate (a2) containing hydroxyl, institute Mass ratio (a2)/(a1) for stating Component units is 0.5~5, and weight average molecular weight is scaled 1,000,000 or more with polystyrene.
[20] (methyl) acrylic resin (A) is used according to the adhesive composition recorded in [19], wherein (methyl) third The composition in olefin(e) acid system resin (A) the also source alkyl acrylate (a3) of the glass transition temperature comprising homopolymer lower than 0 DEG C The Component units in source alkyl acrylate (a4) that the glass transition temperature of unit and homopolymer is 0 DEG C or more.
[21] (methyl) acrylic resin (A) is used according to the adhesive composition recorded in [19] or [20], wherein The vitrifying of the Component units and homopolymer in the source alkyl acrylate (a3) of the glass transition temperature of polymers lower than 0 DEG C turns Mass ratio (a3)/(a4) of the Component units in source alkyl acrylate (a4) that temperature is 0 DEG C or more is 0.1~4.
[22] (methyl) acrylic resin (A) is used according to the adhesive composition that any one of [19]~[21] are recorded, Wherein, the ratio of the Component units in (methyl) the acrylate source contained in (methyl) acrylic resin (A) containing carboxyl Example is 1.0 below the mass relative to 100 mass parts of whole Component units of composition (methyl) acrylic resin (A).
[23] (methyl) acrylic resin (A) is used according to the adhesive composition that any one of [19]~[22] are recorded, Wherein, (methyl) acrylic resin (A) also includes the Component units of (methyl) acrylamide monomer source.
Invention effect
Adhesive composition according to the present invention can be formed under the conditions of harsh durable with excellent resistance to The adhesive phase of long property, the optical film and optical laminate that adhesive phase should be had.In addition, according to adhesive of the invention is included The adhesive composition of composition (methyl) acrylic resin, can be formed has under the conditions of harsh durable The adhesive phase of excellent durability.
Detailed description of the invention
Fig. 1 is the schematic sectional view for indicating an example of the optical film with adhesive phase of the invention.
Fig. 2 is the schematic sectional view of an example for indicating that the layer of polarization plates is constituted.
Fig. 3 is another schematic sectional view for indicating the layer of polarization plates and constituting.
Fig. 4 is the schematic sectional view for indicating an example of optical laminate of the invention.
Fig. 5 is another schematic sectional view for indicating optical laminate of the invention.
Fig. 6 is yet another schematic sectional view for indicating optical laminate of the invention.
Fig. 7 is another schematic sectional view for indicating optical laminate of the invention.
Fig. 8 is yet another schematic sectional view for indicating optical laminate of the invention.
Specific embodiment
[1] adhesive composition
Adhesive composition of the invention includes (methyl) acrylic resin (A), crosslinking agent (B) and silane compound (C)。
[1-1] (methyl) acrylic resin (A)
(methyl) acrylic resin (A) is whole Component units relative to composition (methyl) acrylic resin (A) 100 mass % preferably comprise 50 mass % or more, more preferably comprising 70 mass % or more, further preferably comprising 90 mass % with On (methyl) acrylic monomer source Component units polymer or copolymer, include (the first containing acetoacetyl Base) Component units in the source acrylate (a1) and the Component units in source (methyl) acrylate (a2) containing hydroxyl, institute Mass ratio (a2)/(a1) for stating Component units is 0.5~5.Adhesive composition of the invention is due to (methyl) acrylic acid series tree Rouge (A) includes the Component units (a1) and (a2) of specific mass ratio, therefore even in a high temperature environment, can also be formed has The adhesive phase of excellent durability.
It should be noted that in this specification, it is so-called " (methyl) acrylic compounds ", refer to acrylic compounds or methacrylic acid Class, it is also identical for " (methyl) acrylate ", " (methyl) acryloyl group " etc., refer respectively to acrylate or methacrylic acid Ester, acryloyl group or methylacryloyl.In addition, in this specification, so-called durability, refer to for example under high temperature environment, it is high It can inhibit adhesive phase and optical component adjacent therewith whens under warm high humidity environment, repeatedly in the environment of high temperature and low temperature etc. The bad shape such as the characteristic (sometimes referred to as peel resistance) of tilting, removing in interface and the foaming that adhesive phase can be inhibited The characteristic (sometimes referred to as resistance to foaminess) of condition.In addition, so-called resistance to cohesion is destructive, and referring to can inhibit to bond in this specification The cohesion of oxidant layer destroys the characteristic of (or rupture).
(methyl) acrylate (a1) containing acetoacetyl can containing the substituent group other than acetoacetyl, as Substituent group is for example, cyano etc..As the concrete example of (methyl) acrylate (a1) containing acetoacetyl, such as (methyl) acrylic acid acetoacetoxy groups Arrcostab, such as (methyl) acrylic acid acetoacetoxyethyl, (first can be enumerated Base) (methyl) the acrylic acid acetoacetyl such as acrylic acid acetoacetoxy groups propyl ester, (methyl) acrylic acid acetoacetoxy groups butyl ester Oxygroup C2-10Arrcostab；(methyl) acrylate containing acetoacetyl with substituent group, such as (methyl) acrylic acid 2- Cyano-acetamide acetoxyethyl etc. (methyl) acrylic acid cyano-acetamide acetoxyl group C2-10Arrcostab etc..In them, from viscous The durability of mixture layer, from the viewpoint of obtaining easiness, preferably (methyl) acrylic acid acetoacetoxyethyl, (methyl) third Olefin(e) acid acetoacetoxy groups propyl ester, (methyl) acrylic acid acetoacetoxy groups butyl ester, particularly preferred (methyl) propylene in them Sour 2- acetoacetoxyethyl.These contain acetoacetyl (methyl) acrylate (a1) can individually or combination It uses two or morely.
As the concrete example of (methyl) acrylate (a2) containing hydroxyl, for example, (methyl) acrylic acid 1- Hydroxy methyl, (methyl) acrylic acid 1- hydroxy methacrylate, (methyl) acrylic acid 1- hydroxybutyl, (methyl) acrylic acid 1- hydroxyl (methyl) acrylic acid 1- hydroxyl C such as pentyl ester, (methyl) acrylic acid 1- hydroxyl heptyl ester1-8Arrcostab；(methyl) acrylic acid 2- hydroxyl Base ethyl ester, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 2- hydroxyl penta (methyl) acrylic acid 2- hydroxyl C such as ester, the own ester of (methyl) acrylic acid 2- hydroxyl2-9Arrcostab；(methyl) acrylic acid 3- hydroxyl Propyl ester, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 3- hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 3- hydroxyl, (methyl) acrylic acid 3- hydroxyl such as (methyl) acrylic acid 3- hydroxyl heptyl ester C3-10Arrcostab；(methyl) acrylic acid 4- hydroxyl fourth Ester, (methyl) acrylic acid 4- hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 4- hydroxyl, (methyl) acrylic acid 4- hydroxyl heptyl ester, (methyl) acrylic acid 4- hydroxyl such as (methyl) acrylic acid 4- hydroxyl monooctyl ester C4-11Arrcostab；The chloro- 2- of (methyl) acrylic acid 2- Hydroxy propyl ester, (methyl) acrylic acid 3- chlorine-2-hydroxyl propyl ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyl, (methyl) acrylic acid 5- hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 5- hydroxyl, (methyl) acrylic acid 5- hydroxyl heptyl ester, (first Base) (methyl) acrylic acid 5- hydroxyl C such as acrylic acid 5- hydroxyl monooctyl ester, (methyl) acrylic acid 5- hydroxyl nonyl ester5-12Arrcostab； The own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 6- hydroxyl heptyl ester, (methyl) acrylic acid 6- hydroxyl monooctyl ester, (first Base) (methyl) acrylic acid 6- hydroxyl C such as acrylic acid 6- hydroxyl nonyl ester, (methyl) acrylic acid 6- hydroxyl last of the ten Heavenly stems ester6-13Arrcostab； (methyl) acrylic acid 7- hydroxyl heptyl ester, (methyl) acrylic acid 7- hydroxyl monooctyl ester, (methyl) acrylic acid 7- hydroxyl nonyl ester, (first Base) (methyl) acrylic acid 7- hydroxyl C such as acrylic acid 7- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 7- hydroxyundecyl ester7-14Alkane Base ester；(methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 8- hydroxyl nonyl ester, (methyl) acrylic acid 8- hydroxyl last of the ten Heavenly stems ester, (methyl) the acrylic acid 8- such as (methyl) acrylic acid 8- hydroxyundecyl ester, (methyl) acrylic acid 8- hydroxy dodecyl acrylate Hydroxyl C8-15Arrcostab；(methyl) acrylic acid 9- hydroxyl nonyl ester, (methyl) acrylic acid 9- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 9- hydroxyundecyl ester, (methyl) acrylic acid 9- hydroxy dodecyl acrylate, (methyl) acrylic acid 9- hydroxy tridecyl base ester Deng (methyl) acrylic acid 9- hydroxyl C9-16Arrcostab；(methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 10- hydroxyl Hendecane base ester, (methyl) acrylic acid 10- hydroxy dodecyl acrylate, (methyl) acrylic acid 10- hydroxy tridecyl base ester, (first Base) (methyl) acrylic acid 10- hydroxyl C such as acrylic acid 10- hydroxy-tetradecyl base ester10-17Arrcostab；(methyl) acrylic acid 11- Hydroxyundecyl ester, (methyl) acrylic acid 11- hydroxy dodecyl acrylate, (methyl) acrylic acid 11- hydroxy tridecyl base ester, (methyl) acrylic acid such as (methyl) acrylic acid 11- hydroxy-tetradecyl base ester, (methyl) acrylic acid 11- hydroxypentadecanoic base ester 10- hydroxyl C11-18Arrcostab；(methyl) acrylic acid 12- hydroxy dodecyl acrylate, (methyl) acrylic acid 12- hydroxy tridecyl (methyl) acrylic acid 12- hydroxyl C such as base ester, (methyl) acrylic acid 12- hydroxy-tetradecyl base ester12-19Arrcostab；(methyl) third Olefin(e) acid 13- hydroxypentadecanoic base ester, (methyl) acrylic acid 13- hydroxy-tetradecyl base ester, (methyl) acrylic acid 13- hydroxyl ten Five Arrcostabs etc. (methyl) acrylic acid 13- hydroxyl C13-20Arrcostab；(methyl) acrylic acid 14- hydroxy-tetradecyl base ester, (first Base) (methyl) acrylic acid 14- hydroxyl C such as acrylic acid 14- hydroxypentadecanoic base ester14-21Arrcostab；(methyl) acrylic acid 15- (methyl) acrylic acid 15- hydroxyl C such as hydroxypentadecanoic base ester, (methyl) acrylic acid 15- hydroxyl heptadecane base ester15-22Alkyl Ester etc..
In them, from the viewpoint of the durability of adhesive phase, acquisition easiness, preferably (methyl) acrylic acid 2- (methyl) acrylic acid 2- hydroxyls such as hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl C2-7Arrcostab；(methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 3- hydroxyl Pentyl ester etc. (methyl) acrylic acid 3- hydroxyl C3-8Arrcostab；(methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 4- hydroxyl (methyl) acrylic acid 4- hydroxyl C such as base pentyl ester, the own ester of (methyl) acrylic acid 4- hydroxyl4-9Arrcostab；(methyl) acrylic acid 5- Hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 5- hydroxyl, (methyl) acrylic acid 5- hydroxyl heptyl ester, (methyl) acrylic acid 5- hydroxyl (methyl) acrylic acid 5- hydroxyl C such as monooctyl ester, (methyl) acrylic acid 5- hydroxyl nonyl ester5-9Arrcostab etc., they are particularly preferred in the middle (methyl) acrylic acid 2- hydroxy methacrylate.These contain hydroxyl (methyl) acrylate (a2) can individually or combination two kinds It is used with Shangdi.
The ratio of the Component units in source (methyl) acrylate (a1) containing acetoacetyl is relative to composition (first Base) acrylic resin 100 mass parts of whole Component units, preferably 0.01~10 mass parts, more preferably 0.1~5 matter Measure part, further preferably 0.5~3 mass parts.In addition, the Component units in source (methyl) acrylate (a2) containing hydroxyl Whole Component units 100 mass parts of the ratio relative to composition (methyl) acrylic resin, preferably 0.01~20 mass Part, more preferably 1~10 mass parts, further preferably 1.5~5 mass parts.If the ratio of these Component units is above-mentioned model It encloses, then can be further improved the durability of adhesive phase.
The Component units and (methyl) third containing hydroxyl in source (methyl) acrylate (a1) containing acetoacetyl Mass ratio (a2)/(a1) of the Component units in the source olefin(e) acid ester (a2) be 0.5~5, preferably 0.7~4.5, more preferably 1~ 4, further preferably 1.2~3.7, particularly preferably 1.5~3.5.If these mass ratioes are above range, can be further Improve the durability of adhesive phase.
(methyl) acrylic resin (A) can also include that the glass transition temperature of homopolymer is lower than 0 DEG C of acrylic acid The alkyl acrylate (a4) that the Component units in the source Arrcostab (a3) and the glass transition temperature of homopolymer are 0 DEG C or more The Component units in source.
It is lower than 0 DEG C of alkyl acrylate (a3) as the glass transition temperature (Tg) of homopolymer, for example, Ethyl acrylate, acrylic acid just and isopropyl ester, acrylic acid just and isobutyl ester, acrylic acid n-pentyl ester, acrylic acid just and dissident's ester, third The positive heptyl ester of olefin(e) acid, acrylic acid just and different monooctyl ester, 2-EHA, acrylic acid just and different nonyl ester, acrylic acid just and isodecyl The straight-chain or branched-chain alkyl acrylate that the carbon atom number of the alkyl such as ester, acrylic acid n-dodecane base ester is 2~12 or so Deng.Alkyl acrylate (a3) can be the alkyl acrylate (acrylate base ester) with ester ring type structure, however from To the viewpoints such as the tracing ability of optical film, flexibility or adhesiveness consider, preferably carbon atom number be 2~10 alkyl acrylate, The alkyl acrylate that more preferable carbon atom number is 3~8, the alkyl acrylate that further preferred carbon atom number is 4~6 are special Not preferred n-butyl acrylate.If using n-butyl acrylate, tracing ability can be improved, such as be conducive to peel resistance etc.. These alkyl acrylates (a3) can use individually or in combination of two or more.
The alkyl acrylate (a4) that Tg as homopolymer is 0 DEG C or more, can enumerate methyl acrylate, acrylic acid ring Arrcostab (such as cyclohexyl acrylate, isobornyl acrylate etc.), stearyl acrylate base ester, tert-butyl acrylate etc., especially It is preferred that methyl acrylate.If using methyl acrylate, can be improved high temperature it is durable when adhesive phase intensity, such as can be with It is destructive to improve resistance to cohesion.These alkyl acrylates (a4) can use individually or in combination of two or more.
It should be noted that the Tg of the homopolymer of alkyl acrylate is for example referred to polymer handbook (Wiley- ) etc. Interscience literature value.
For the Component units (a3) in alkyl acrylate source and total ratio of (a4), relative to composition (methyl) third 100 mass parts of whole Component units of olefin(e) acid system resin (A), from the viewpoint of the durability and re-workability of adhesive phase, Such as it can be to be more than 40 mass parts.The lower limit value of total ratio of the Component units (a3) and (a4) is preferably 50 mass Part, more preferably 60 mass parts, further preferably 70 mass parts, particularly preferably 75 mass parts.In addition, the Component units (a3) and the upper limit value of total ratio of (a4) is preferably 98 mass parts, more preferably 95 mass parts, further preferably 90 matter Measure part.Total ratio of Component units (a3) and (a4) can be any combination of lower limit value and upper limit value, such as can be 50 ~98 mass parts, preferably 70~95 mass parts, more preferably 75~95 mass parts.
If the acrylic acid that the Tg of alkyl acrylate (a3) and homopolymer by the Tg of homopolymer lower than 0 DEG C is 0 DEG C or more Arrcostab (a4) is used in combination, then can take into account that resistance to cohesion is destructive and tracing ability (peel resistance), and optical film can be improved (such as partially Vibration plate) for the durability of change in size.
The Component units in the source alkyl acrylate (a3) of the glass transition temperature of homopolymer lower than 0 DEG C and vitrifying Mass ratio (a3)/(a4) of the Component units in source alkyl acrylate (a4) that transition temperature is 0 DEG C or more be preferably 0.1~ 4, more preferably 0.15~3.5, further preferably 0.2~2.5.If these mass ratioes are above range, can be further Improve the durability of adhesive phase.The Component units in the source alkyl acrylate (a3) of glass transition temperature lower than 0 DEG C Ratio is bigger, then tracing ability improves, the composition in source alkyl acrylate (a4) that glass transition temperature is 0 DEG C or more The ratio of unit is bigger, then resistance to cohesion is destructive improves.In addition, if being lower than with the glass transition temperature more than homopolymer The ratio of 0 DEG C of alkyl acrylate (a3) contains the alkyl acrylate that the glass transition temperature of homopolymer is 0 DEG C or more (a4), then it can be further improved durability, even if also showing that excellent durability under the conditions of more harsh durable.
(methyl) acrylic resin (A) can also include the composition list in the alkyl acrylate source containing substituent group Member.
As the alkyl acrylate containing substituent group, for example, to the alkyl acrylate (a3) and (a4) Alkyl imported substituent group (in other words, the hydrogen atom of alkyl by substituent group instead of) alkyl acrylate.The substitution Base for example can be aryl (such as phenyl etc.), aryloxy group (such as phenoxy group etc.), alkoxy (such as methoxyl group, ethyoxyl etc.) Deng.As the alkyl acrylate containing substituent group, for example, acrylic acid alkyl aryl (such as benzyl acrylate, Phenylethyl etc.), alkoxyalkyl acrylate (such as acrylic acid 2- methoxy acrylate, ethioxy methyl esters Deng), acrylic acid aryloxy group alkyl base ester (such as phenoxyethyl acrylate etc.), aryloxy group polyalkylene glycol mono acrylate, Polyalkylene glycol mono acrylate etc..Aryloxy group polyalkylene glycol mono acrylate and polyalkylene glycol mono acrylate Alkylidene can be for example the C such as methylene, ethylidene, propylidene1-6Alkylidene, preferably ethylidene etc. can be selected suitably Select the repetitive unit of oxyalkylene.The repetitive unit of alkylidene is, for example, 1~7, and preferably 1~5, particularly preferably 1 or 2 It is a.These alkyl acrylates can use individually or in combination of two or more.By the inclusion of containing the virtues such as aryl, aryloxy group The alkyl acrylate of fragrant ring, polarization plates when can improve endurance test show money or valuables one carries unintentionally.In addition, by the inclusion of containing alkoxy, Anti-static electricity interference performance can be improved in the alkyl acrylate of the ether structures such as polyalkylene glycol structure.From showing money or valuables one carries unintentionally property, antistatic From the viewpoint of interference, the balance of durability, it is expected that including aryloxy alkyl acrylate, aryloxy group polyalkylene glycol third Olefin(e) acid ester.Specifically, phenoxyethyl acrylate, phenoxy group diethylene glycol acrylate, three second two of phenoxy group can be enumerated Alcohol acrylate, phenoxy group tetraethylene glycol acrylate etc..Particularly preferably use phenoxyethyl acrylate, phenoxy group diethyl two Alcohol acrylate.
The ratio of the Component units in the alkyl acrylate source containing substituent group is relative to composition (methyl) acrylic acid series 100 mass parts of whole Component units of resin (A) are, for example, 0~40 mass parts, preferably 3~30 mass parts, further preferably For 5~25 mass parts, particularly preferably 7~21 mass parts.If the ratio is above range, can be further improved above-mentioned The characteristics such as showing money or valuables one carries unintentionally property, anti-static electricity interference, durability.
(methyl) acrylic resin (A) can also include the composition in the other monomers source other than above-mentioned Component units Unit.Other monomers can use individually or in combination of two or more.As other monomers, can enumerate with other than hydroxyl Polar functional group monomer, (methyl) acrylamide monomer, styrenic monomers, vinyl monomer, have in the molecule There is the monomer etc. of multiple (methyl) acryloyl groups.
As the monomer with the polar functional group other than hydroxyl, can enumerate with the heterocycles such as epoxy group, replace or (methyl) acrylate of the substituent groups such as unsubstituted amino, carboxyl.Specifically, acryloyl morpholine, vinyl can be enumerated Caprolactam, n-vinyl-2-pyrrolidone, vinylpyridine, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification third Olefin(e) acid tetrahydrochysene chaff ester, 3,4- epoxycyclohexyl-methyl (methyl) acrylate, (methyl) glycidyl acrylate, 2,5- bis- Hydrogen furans etc. has the monomer of heterocycle；(methyl) acrylate, (methyl) acrylic acid N, N- dimethylaminoethyl Ester, (methyl) acrylate propyl diester etc. have the monomer of amino substituted or unsubstituted；(methyl) acrylic acid, Malaysia Acid, maleic anhydride, fumaric acid, crotonic acid, (methyl) acrylic acid carboxyalkyl ester (such as (methyl) carboxyethyl acrylates, (first Base) acrylic acid carboxyl pentyl ester) etc. with carboxyl monomer.These monomers can use individually or in combination of two or more.It needs It is noted that from the viewpoint of the reduction of the fissility for the spacer for preventing to be laminated in adhesive phase, preferably substantially Component units not comprising the monomer source with amino.It should be noted that so-called do not include substantially, refer to relative to structure At 100 mass parts of whole Component units of (methyl) acrylic resin (A) less than 1.0 mass parts.
In the present invention, even if the composition list without containing the monomer source with carboxyl for being considered increasing ITO corrosivity First (the sometimes referred to as Component units in (methyl) the acrylate source containing carboxyl), also show that high-durability, therefore can be with Take into account durability and resistance to ITO corrosivity.
On the other hand, if Component units [(methyl) acrylate containing carboxyl containing the monomer source with carboxyl The Component units in source], then it can be further improved durability.In the present invention, even if due to (methyl) propylene containing carboxyl The ratio of the Component units in acid esters source is few can also to effectively improve durability, therefore on a small quantity includes (methyl) containing carboxyl The Component units in acrylate source, thus, it is possible to further increase durability while inhibiting ITO corrosion.
The ratio of the Component units in (methyl) the acrylate source containing carboxyl is relative to composition (methyl) acrylic acid series 100 mass parts of whole Component units of resin are 1.0 below the mass.The composition in (methyl) the acrylate source containing carboxyl The upper limit value of the ratio of unit is preferably 0.8 mass parts, more preferably 0.5 mass parts, further preferably 0.3 mass parts, special It You Xuanwei not 0.2 mass parts, especially preferably 0.15 mass parts.The Component units in (methyl) the acrylate source containing carboxyl The lower limit value of ratio be preferably 0 mass parts, more preferably 0.001 mass parts, further preferably 0.005 mass parts, especially Preferably 0.01 mass parts, especially preferably 0.05 mass parts.The Component units in (methyl) the acrylate source containing carboxyl Ratio can be any combination of these upper limit values and lower limit value, such as can be 0~1 mass parts, preferably 0~0.8 matter Amount part, more preferably 0.001~0.5 mass parts, further preferably 0.005~0.3 mass parts, particularly preferably 0.01~ 0.2 mass parts, especially preferably 0.05~0.15 mass parts.If the Component units in (methyl) the acrylate source containing carboxyl Ratio be upper limit value hereinafter, can then inhibit ITO corrosivity, more than lower limit value, then durability can be improved.
As (methyl) acrylamide monomer, for example, N hydroxymethyl acrylamide, N- (2- hydroxyl second Base) acrylamide, N- (3- hydroxypropyl) acrylamide, N- (4- hydroxybutyl) acrylamide, N- (5- hydroxyl penta Base) acrylamide, N- (6- hydroxyl hexyl) acrylamide, N,N-DMAA, N, N- acrylamide, N-isopropyl acrylamide, N- (3- dimethylaminopropyl) acrylamide, N- (1,1- dimethyl -3- oxo fourth Base) acrylamide, N- (2- (2- oxo -1- imidazolidinyl) ethyl) acrylamide, 2- acrylamido -2- first Base -1- propane sulfonic acid, N- (methoxy) acrylamide, N- (ethoxyl methyl) acrylamide, N- (propoxy methyl) Acrylamide, N- (1- methylethoxy ylmethyl) acrylamide, N- (1- methyl propoxy methyl) acrylamide, N- (2- methyl propoxy methyl) acrylamide (alias: N- (isobutoxymethyl) acrylamide), N- (butoxymethyl) third Acrylamide, N- (1,1- dimethylethoxy ylmethyl) acrylamide, N- (2- methoxy ethyl) acrylamide, N- (2- Ethoxyethyl group) acrylamide, N- (2- Among) acrylamide, N- (2- (1- methyl ethoxy) ethyl) third Acrylamide, N- (2- (1- methyl propoxyl group) ethyl) acrylamide, N- (2- (2- methyl propoxyl group) ethyl) acryloyl Amine (alias: N- (2- isobutoxyethy) acrylamide), N- (2- butoxyethyl group) acrylamide, N- (2- (1, 1- dimethylethyloxy) ethyl) acrylamide etc..
By the inclusion of the structural unit of (methyl) acrylamide monomer source, the resistance to of adhesive phase can be further improved Long property.In them, particularly preferred N- (methoxy) acrylamide, N- (ethoxyl methyl) acrylamide, N- (third Oxygroup methyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2- methyl propoxy methyl) acrylamide etc..
The ratio of the Component units of (methyl) acrylamide monomer source is relative to composition (methyl) acrylic resin 100 mass parts of whole Component units be 5 below the mass.The ratio of the Component units of (methyl) acrylamide monomer source Upper limit value be preferably 3 mass parts, more preferably 2 mass parts, further preferably 1 mass parts.(methyl) acrylamide list The lower limit value of the ratio of the Component units in body source is preferably 0 mass parts, more preferably 0.001 mass parts, further preferably 0.01 mass parts, particularly preferably 0.1 mass parts.The ratio of the Component units of (methyl) acrylamide monomer source can be Any combination of these upper limit values and lower limit value, for example, can be 0~5 mass parts, preferably 0.001~3 mass parts, more preferably For 0.01~2 mass parts, further preferably 0.1~1 mass parts.The Component units of (if methyl) acrylamide monomer source Ratio be above range, then can be further improved the durability of adhesive phase.
As styrenic monomers, for example, styrene；Methyl styrene, dimethyl styrene, trimethylbenzene Ethylene, ethyl styrene, diethyl, triethylbenzene ethylene, propylstyrene, butylstyrene, hexyl styrene, heptan The ring-alkylated styrenes such as base styrene, octyl styrene；Fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene second The halogenated styrenes such as alkene；Nitrostyrolene；Acetylbenzene ethylene；Methoxy styrene；Divinylbenzene etc..
As vinyl monomer, for example, vinyl acetate, vinyl propionate, vinyl butyrate, 2- ethyl The fatty acid vinyl esters such as vinyl caproate, vinyl laurate；The halogen ethylene such as vinyl chloride, vinyl bromide；Vinylidene chloride etc. inclined two Halogen ethylene；The nitrogenous aromatic ethenyl compound such as vinylpyridine, vinyl pyrrolidone, vinyl carbazole；It is butadiene, different Pentadiene, chlorobutadiene equiconjugate diene monomers；Unsaturated nitriles such as acrylonitrile, methacrylonitrile etc..
As the monomer in the molecule with multiple (methyl) acryloyl groups, for example, two (first of 1,4-butanediol Base) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate etc. is in the molecule with the monomer of 2 (methyl) acryloyl groups；Trimethylolpropane tris (methyl) propylene Acid esters etc. is in the molecule with the monomer etc. of 3 (methyl) acryloyl groups.
The standard polystyren conversion obtained using gel permeation chromatography GPC for (methyl) acrylic resin (A) Weight average molecular weight (Mw), in order to further increase the durability of adhesive phase, preferably 1,000,000 or more.The lower limit value of Mw is more Preferably 1,100,000, further preferably 1,200,000, particularly preferably 1,300,000.In addition, the upper limit value for Mw does not limit especially System, however from the viewpoint of coating when adhesive composition to be for example processed as to sheet (being coated on substrate), preferably 2500000, more preferably 2,200,000, further preferably 2,000,000.Mw can be any combination of these upper limit values and lower limit value, example It such as can be 100~2,500,000, more preferably 1,100,000~2,200,000, further preferably 120~2,000,000.In addition, to divide equally again The molecular weight distribution that the ratio (Mw/Mn) of son amount Mw and number-average molecular weight Mn indicates is usually 1~10, and preferably 2~8, further Preferably 3~6.
In addition, the model that Mw of (methyl) acrylic resin (A) preferably on the elution curve of GPC is 1000~2,500,000 There is single peak in enclosing.If (methyl) acrylic resin (A) for the use of the peak number being 1, is conducive to adhesive phase, has The durability of the optical film of adhesive phase and the optical laminate comprising the optical film improves.
It is so-called " to there is single peak " in the above range of resulting elution curve, refer to Mw1000's~2,500,000 Only there is 1 maximum in range.In this specification, in GPC elution curve, it is by the curve definitions that S/N ratio is 30 or more Peak.It should be noted that the Mw and Mn of the peak number of GPC elution curve and (methyl) acrylic resin (A) can use implementation The GPC determination condition recorded in example one is found out.
When the solution of 20 mass % of concentration is made in (methyl) acrylic resin (A) in being dissolved in ethyl acetate, 25 DEG C viscosity be preferably 30,000 mPas hereinafter, more preferably 100~20,000 mPas.If the viscosity of above range, then from general It is advantageous from the viewpoint of coating when adhesive composition is coated on substrate.It should be noted that viscosity can use Bu Shi Viscosimeter measurement.
The glass transition temperature (Tg) of (methyl) acrylic resin (A) for example can be -60~20 DEG C, preferably It is -50~10 DEG C, more preferably -40~0 DEG C.If glass transition temperature is above range, be conducive to adhesive phase The raising of durability.It should be noted that glass transition temperature can use differential scanning calorimetry (DSC) (DSC) measurement.
(methyl) acrylic resin (A) for example can use solution polymerization process, mass polymerization, suspension polymerization, cream Method well known to liquid polymerization etc. manufactures, particularly preferred solution polymerization process.As solution polymerization process, for example, as follows Method, that is, monomer and organic solvent are mixed, in a nitrogen atmosphere, add thermal polymerization, 40~90 DEG C, preferably It is stirred 3~15 hours or so under the conditions of 50~80 DEG C or so of temperature.It, can be continuously in polymerization in order to control reaction Or intermittently add monomer, thermal polymerization.The monomer, thermal initiator are also possible to be added to the state in organic solvent.
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 azos system chemical combination such as 2,2 '-azo two (2 Methylpropionic acid ester) of methyl-, 2,2 '-azos two (2- hydroxymethyl propionitrile) Object；Lauryl 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 peroxides such as butyl ester, (3,5,5- trimethyl acetyl) peroxide；The nothings such as potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide Machine peroxide etc..Alternatively, it is also possible to use and used the redox series initiators etc. of peroxide and reducing agent.
Total amount 100 mass parts of the ratio of polymerization initiator relative to the monomer of composition (methyl) acrylic resin (A) For 0.001~5 mass parts or so.The polymerization of (methyl) acrylic resin (A) can be used using active energy beam, for example The polymerization of ultraviolet light etc..
As organic solvent, for example, toluene, dimethylbenzene etc. are aromatic hydrocarbon；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..
[1-2] crosslinking agent (B)
Adhesive composition of the invention includes crosslinking agent (B).The crosslinking agent (B) as long as can be with (methyl) acrylic acid It is the crosslinking agent of the polar functional group reaction comprising hydroxyl or acetoacetyl in resin (A).In the present invention, it imported into Hydroxyl or acetoacetyl in the side chain of (methyl) acrylic resin (A) are reacted with crosslinking agent (B), are formed with conducive to durable Property (such as the resistance to foaminess of adhesive phase, peel resistance and resistance to cohesion destructiveness etc.) cross-linked structure.
As crosslinking agent (B), usual crosslinking agent, such as isocyanates based compound, epoxide, nitrogen can be enumerated Third acridine compound, meal chelate compounds, peroxide etc., especially from the up time of adhesive composition, crosslinking The viewpoints such as the viewpoint of speed and the durability of optical film, optical laminate with adhesive phase consider, preferably isocyanic acid Ester based compound.
As isocyanates based compound, preferably there is the compound of at least two isocyanate group (- NCO) in the molecule, For example, aliphatic isocyanates based compound (such as hexamethylene diisocyanate etc.), alicyclic isocyanate system Compound (such as isophorone diisocyanate, hydrogenation benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate Ester etc.), aromatic isocyanate based compound (such as toluene di-isocyanate(TDI), benzene dimethylene diisocyanate, diphenylmethyl Alkane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.) etc..In addition, crosslinking agent (B) is also possible to institute The addition product (adduct) using polyol compound for stating isocyanates based compound [such as utilizes glycerol, trihydroxy methyl third The addition product of alkane etc.], isocyanuric acid carboxylate, biuret form compound, with polyether polyol, polyester polyol, acrylic compounds Carbamate prepolymer type is different obtained by the addition reactions such as polyalcohol, polybutadiene polyol, polyisoprene polyol The derivatives such as cyanate esters.Crosslinking agent (B) can use individually or in combination of two or more.It is representative in them Ground can enumerate aromatic isocyanate based compound (such as toluene di-isocyanate(TDI), benzene dimethylene diisocyanate etc.), Aliphatic isocyanates based compound (such as hexamethylene diisocyanate etc.) or they using polyol compound (such as Glycerol, trimethylolpropane etc.) addition product.If crosslinking agent (B) is aromatic isocyanate based compound and/or their benefit With the addition product of polyol compound, then the durability of the optical film with adhesive phase can be improved.Especially if toluene Diisocyanate based compound and/or their addition product using polyol compound, then can be further improved durability.
The ratio of crosslinking agent (B) is preferably 0.01~10 mass relative to 100 mass parts of (methyl) acrylic resin (A) Part, more preferably 0.1~5 mass parts, further preferably 0.15~1 mass parts, particularly preferably 0.2~0.5 mass parts.If The ratio of crosslinking agent (B) is above-mentioned upper limit value hereinafter, being then conducive to the raising of peel resistance, more than above-mentioned lower limit value, then Be conducive to the raising of resistance to foaminess, re-workability.
[1-3] silane compound (C)
Adhesive composition includes silane compound (C).By the inclusion of the silane compound (C), adhesive can be improved The adaptation (or cementability) of layer and substrate (such as metal layer, transparent electrode, glass substrate etc.) etc..As silane compound (C), as long as can be bonded with the reactive group (such as hydroxyl, acetoacetyl) of (methyl) acrylic resin (A) Silane compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, three (2- of vinyl Methoxy ethoxy) silane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group triethoxysilicane Alkane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl group ethyoxyl dimethylsilane, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silicon Bis- (the 3 '-front threes of alkane, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 1,3- Oxygroup propyl) urea etc..
In addition, silane compound (C) can be the compound of silicone oligomers type, if by the silicone oligomers between monomer Combination indicate, then for example, 3- mercaptopropyi two or trimethoxy silane-tetramethoxy-silicane oligomer, 3- Mercapto methyl two or trimethoxy silane-tetraethoxysilane oligomer, 3- mercaptopropyi two or triethoxysilane-four Methoxy silane oligomer, 3- mercapto methyl two or triethoxysilane-tetraethoxysilane oligomer etc. contains sulfydryl alkane The oligomer of base；The mercaptoalkyl of the oligomer for containing mercaptoalkyl is substituted by other substituent groups [such as the third oxygen of 3- epoxy Base propyl, (methyl) acryloxypropyl, vinyl, amino etc.] oligomer etc..
Silane compound (C) can be preferably the silane compound indicated with following formula (c1).If adhesive composition packet It containing the silane compound indicated with following formula (c1), then can be further improved adaptation (or cementability), therefore can be formed The excellent adhesive phase of peel resistance.
Furthermore the re-workability of the adhesive phase is also excellent.Especially under high temperature environment, it is applied to by adhesive phase When (or being laminated in) transparent electrode (such as ito substrate etc.), adaptation (or cementability) can also be maintained, can be shown high resistance to Long property.
[changing 2]
(in formula, B indicates the alicyclic type hydrocarbon of the alkane diyl of carbon atom number 1~20 or the divalent of carbon atom number 3~20, structure At-the CH of the alkane diyl and the alicyclic type hydrocarbon2Optionally it is substituted by-O- or-CO-, R1Indicate carbon atom number 1 ~5 alkyl, R2、R3、R4、R5And R6Each independently represent the alkyl of carbon atom number 1~5 or the alcoxyl of carbon atom number 1~5 Base.)
In formula (c1), B for example indicate methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, heptamethylene, The alkane diyl of the carbon atom numbers such as eight methylene 1~20；Sub- cyclobutyl (such as 1, the Asia 2- cyclobutyl), cyclopentylene (such as 1, 2- cyclopentylene), cyclohexylidene (such as 1,2- cyclohexylidene), the carbon atoms such as cyclooctylene (such as 1,2- cyclooctylene) The alicyclic type hydrocarbon of the divalent of number 3~20；Or constitute the-CH of these alkane diyls and the alicyclic type hydrocarbon2Be substituted by- The group of O- or-CO-.Preferred B is the alkane diyl of carbon atom number 1~10.R1Such as indicate methyl, ethyl, propyl, different The alkyl of the carbon atom numbers such as propyl, butyl, sec-butyl, tert-butyl, amyl 1~5, R2、R3、R4、R5And R6Each independently for example Indicate the R1The alkyl of the carbon atom number 1~5 of middle illustration；Or such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, fourth oxygen The alkoxy of the carbon atom numbers such as base, sec-butoxy, tert-butoxy 1~5.Preferred R2、R3、R4、R5And R6For carbon atom number 1~5 Alkoxy.These silane compounds (C) can use individually or in combination of two or more.
As specific silane compound (c1), for example, (trimethoxysilyl) methane, 1,2- are bis- Bis- (triethoxysilyl) ethane of (trimethoxysilyl) ethane, 1,2-, the bis- (trimethyoxysilanes of 1,3- Base) propane, bis- (triethoxysilyl) propane of 1,3-, bis- (trimethoxysilyl) butane of Isosorbide-5-Nitrae-, Isosorbide-5-Nitrae-be bis- Bis- (trimethoxysilyl) pentanes of (triethoxysilyl) butane, 1,5-, the bis- (triethoxy-silicanes of 1,5- Base) pentane, bis- (trimethoxysilyl) hexanes of 1,6-, bis- (triethoxysilyl) hexanes of 1,6-, 1,6- be bis- Bis- (trimethoxysilyl) octanes of (tripropoxy-silicane base) hexane, 1,8-, the bis- (triethoxy-silicanes of 1,8- Base) bis- (three C such as octane, bis- (tripropoxy-silicane base) octanes of 1,8-1-5Alkoxysilyl) C1-10Alkane；Bis- (two Methoxy silicyl) methane, bis- (dimethoxy-methyl silicyl) ethane of 1,2-, bis- (the dimethoxy second of 1,2- Base silicyl) ethane, bis- (dimethoxy-methyl silicyl) butane of Isosorbide-5-Nitrae-, bis- (the dimethoxy-ethyl monosilanes of Isosorbide-5-Nitrae- Base) butane, bis- (dimethoxy-methyl silicyl) hexanes of 1,6-, bis- (dimethoxy-ethyl silicyl) hexanes of 1,6-, Bis- (two C such as 1,8- bis- (dimethoxy-methyl silicyl) octanes, bis- (dimethoxy-ethyl silicyl) octanes of 1,8-1-5 Alkoxy C1-5AIkylsilyl groups) C1-10Alkane；1,6- bis- (methoxyl group dimetylsilyl) hexanes, the bis- (methoxies of 1,8- Base dimetylsilyl) bis- (single C such as octane1-5- two C of alkoxy1-5AIkylsilyl groups) C1-10Alkane etc..They work as In, due to that can effectively improve peel resistance etc., bis- (trimethoxysilyl) ethane of preferably 1,2-, 1,3- are bis- Bis- (trimethoxysilyl) butane of (trimethoxysilyl) propane, Isosorbide-5-Nitrae-, the bis- (trimethyoxysilanes of 1,5- Base) bis- (three C such as pentane, bis- (trimethoxysilyl) hexanes of 1,6-, bis- (trimethoxysilyl) octanes of 1,8-1-3 Alkoxysilyl) C1-10Alkane, bis- (trimethoxysilyl) hexanes of particularly preferred 1,6-, the bis- (trimethoxies of 1,8- Base silicyl) octane.These silane compounds (c1) can use individually or in combination of two or more.
The ratio of silane compound (C) is preferably 0.01~10 relative to 100 mass parts of (methyl) acrylic resin (A) Mass parts, more preferably 0.05~3 mass parts, further preferably 0.1~1 mass parts, particularly preferably 0.2~0.5 mass Part.If silane compound (C) ratio be above-mentioned upper limit value hereinafter, if be conducive to inhibit silane compound (C) from adhesive phase In exudation be then easy to improve adhesive phase and substrate (such as metal layer, glass substrate etc.) more than above-mentioned lower limit value Adaptation (or cementability), is conducive to the raising of peel resistance etc..
[1-4] anti-static electricity interference agent
Adhesive composition of the invention can also include anti-static electricity interference agent.It, can be with by the inclusion of anti-static electricity interference agent The anti-static electricity interference for improving adhesive phase, can inhibit such as remove mold release film, protective film when the electrostatic that generates caused by Not good situation etc..As anti-static electricity interference agent, usual anti-static electricity interference agent can be enumerated, ionic anti-static electricity interference is suitably for Agent (ionic compound (D)).It, can be with as the cation for constituting ionic anti-static electricity interference agent (ionic compound (D)) Enumerate organic cation, inorganic cation etc..As organic cation, for example, pyridylium, imidazoles are positive Ion, ammonium cation, sulfonium cation, phosphonium cation etc..As inorganic cation, for example, lithium cation, potassium sun from Alkaline earth metal cations such as the alkali metal cations such as son, sodium cation, caesium cation, magnesium cation, calcium cation etc..As structure At the anion of ionic anti-static electricity interference agent (ionic compound (D)), inorganic anion and organic anion can be Any one, however have excellent performance this point from anti-static electricity interference and consider, preferably comprise the anion of fluorine atom.As including fluorine The anion of atom, for example, hexafluoro-phosphate radical anion (PF6 ?), bis- (trifluoro methylsulfonyl) imines anion [(CF3SO2)2N?], bis- (fluorine sulphonyl) imines anion [(FSO2)2N?], four (pentafluorophenyl group) borate anion [(C6F5)4B?] etc..These anti-static electricity interference agent can use individually or in combination of two or more.Particularly preferably it is selected from bis- (fluoroforms Sulphonyl) imines anion [(CF3SO2)2N?], bis- (fluorine sulphonyl) imines anion [(FSO2)2N?] and four (pentafluorophenyl group) boron Acid radical anion [(C6F5)4B?At least one of].It is excellent from the ageing stability of the anti-static electricity interference performance of adhesive composition Different this point considers, is preferably at room temperature the ionic anti-static electricity interference agent (ionic compound (D)) of solid.In addition, ion Property compound (D) be preferably the ionic compound that is formed by the anion comprising fluorine atom and organic cation.
The ratio of ionic anti-static electricity interference agent (ionic compound (D)) is relative to (methyl) acrylic resin (A) 100 mass parts for example can be 0.01~10 mass parts, preferably 0.1~5 mass parts, further preferably 1~3 mass parts.
[1-5] other compositions
Adhesive composition of the invention may include solvent, crosslinking catalyst, ultraviolet absorbing agent, weathering stabilizers, The independent one or two of the additives such as tackifier, plasticizer, softening agent, dyestuff, pigment, inorganic filler, light scattering particle More than.Alternatively, it is also possible to cooperate ultra-violet solidified compound in adhesive composition, irradiated after forming adhesive phase purple Outside line and be allowed to solidify, harder adhesive phase is made.
As crosslinking catalyst, for example, hexamethylene diamine, ethylene diamine, polyethylene imine, six Asias Tetramine, diethylenetriamines, trien, isophorone diamine, trimethylene diamine, poly- amino resins and trimerization Amine compounds such as melamine resin etc..
From the resistance to metal for improving adhesive phase, the optical film with adhesive phase and the optical laminate comprising them From the viewpoint of corrosivity, adhesive composition of the invention may include antirust agent.As antirust agent, for example, benzene And 3 three azole compounds such as azole compounds；The thiazole compounds such as benzothiazole based compound；Benzyl imidazole based compound Equal imidazole compounds；Imidazoline based compound；Quinoline based compound；Pyridine based compound；Pyrimidine compound；Indoles system Close object；Amine compound；Urea based compound；Sodium benzoate；Benzylmercapto based compound；Di-sec-butyl thioether；And diphenyl Sulfoxide etc..
In a preferred manner, adhesive composition of the invention contains substantially no Photoepolymerizationinitiater initiater and its decomposition Object.This is because the Photoepolymerizationinitiater initiater and its decomposition product in adhesive composition are possible to hinder the bonding of excellent in te pins of durability The formation of oxidant layer.Herein, so-called to contain substantially no, refer to relative to 100 mass parts of adhesive composition be 1.0 mass parts with Under, preferably 0.1 below the mass, and more preferably 0.01 below the mass, and further preferably 0.001 below the mass, especially It is most preferably 0 mass parts.
Adhesive composition of the invention is due to as described above comprising specific (methyl) acrylic resin (A), crosslinking Agent (B) and silane compound (C), therefore the durability of the adhesive phase formed by the adhesive composition can be improved, even if Under high temperature environment, the removing (or tilting) and foaming at interface can also be effectively inhibited.Moreover, because even if generating strong shrink Stress, adhesive phase can also effectively alleviate the stress, therefore can prevent the receipts along with optical film (such as deflecting plate) Contracting shows money or valuables one carries unintentionally.Can estimate to this is because of (methyl) acrylic resin (A) contained in adhesive composition of the invention There is reactive different Liang Ge functional group, i.e. hydroxyl and acetoacetyl in the side chain and tool is contained with specific mass ratio There are a Component units of each functional group, therefore adhesive composition can be formed with being most suitable for expressing the friendship of excellent durability It is coupled the adhesive phase of structure, crosslink density.
[2] adhesive phase and optical film and their manufacturing method with adhesive phase
The present invention includes the adhesive phase formed by described adhesive composition.The adhesive phase for example can be by by institute It states and the adhesive composition containing solvent is made after adhesive composition is dissolved or dispersed in solvent, is then coated on light It learns surface and the drying of film or mold release film and is formed.
In addition, the invention also includes the described adhesive layers comprising optical film and at least one side for being laminated in the optical film Optical film with adhesive phase.
It should be formed due to adhesive phase of the invention and with the optical film of adhesive phase by described adhesive composition, because This has excellent durability under harsh durable condition (such as 100 DEG C or more durable condition).
Fig. 1 is the schematic sectional view for indicating an example of the optical film with adhesive phase of the invention.It is shown in FIG. 1 to have The optical film 1 of adhesive phase is optics obtained by the adhesive phase 20 of optical film 10 and the one side positioned at the optical film is laminated Film.The adhesive phase 20 is typically directly laminated in the surface of optical film 10.It should be noted that adhesive phase 20 can also be laminated In the two sides of optical film 10.
When adhesive phase 20 to be laminated in the surface of optical film 10, the preferably binding face in optical film 10 and/or bonding The binding face of oxidant layer 20 forms prime coat, or implements the surface activation process (such as corona treatment, sided corona treatment etc.), Particularly preferably implement sided corona treatment.
In the case where optical film 10 is that single side as shown in Figure 2 protects polarization plates, adhesive phase 20 is usually laminated in (excellent Choosing be directly laminated in) polarize it is unilateral, that is, be laminated in the face with 3 opposite side of the first resin film of polarizing film 2.It is in optical film 10 In the case where two-sided protection polarization plates as shown in Figure 3, adhesive phase 20 can be laminated in appointing for the first, second resin film 3,4 The outer surface of meaning one, can also be laminated in the outer surface of both sides.
Anti-static electricity interference layer can be separately set between optical film 10 and adhesive phase 20.As anti-static electricity interference layer, Inorganic metals based material, polythiophene, the polyphenyl such as the silicon systems such as polysiloxanes material, tin-doped indium oxide can be used, mix tin antimony oxide The organic polymers based material such as vinyl sulfonic acid, polyaniline.
Optical film 1 with adhesive phase may include the spacer film (removing for being laminated in the outer surface of adhesive phase 20 Film).The spacer film is usually stripped in the use of adhesive phase 20 (such as when being laminated to transparent conductive electrode, glass substrate) It removes.Spacer film for example can be to comprising polyethylene terephthalate, polybutylene terephthalate (PBT), poly- carbonic acid The face of the formation adhesive phase 20 of the film of the various resins such as ester, polyarylate implements the film of the demouldings such as silicone-treated processing.
Optical film 1 with adhesive phase can be obtained by operating as follows, that is, will constitute above-mentioned adhesive composition Each ingredient be dissolved or dispersed in solvent, the adhesive composition containing solvent is made, is then coated on optical film 10 Surface and drying, formed adhesive phase 20.In addition, with adhesive phase optical film 1 can also by operate as follows come It arrives, that is, form adhesive phase 20 in the same manner as described above in the demoulding process face of spacer film, which is laminated in The surface of (being needed on) optical film 10.
The thickness of adhesive phase is usually 2~40 μm, from the durability of the optical film with adhesive phase, with adhesive The consideration of the viewpoints such as the re-workability of optical film of layer, preferably 5~30 μm, more preferably 10~25 μm.If the thickness of adhesive phase Degree is upper limit value hereinafter, then re-workability becomes well, and more than lower limit value, then adhesive phase becomes the size of optical film The tracing ability (or followability) of change becomes good.
Adhesive phase is preferably the layer that the storage modulus of 0.1~5MPa is shown in 23~80 DEG C of temperature range.By This, can more efficiently improve the durability of the optical film with adhesive phase.It is so-called " in 23~80 DEG C of temperature range Show the storage modulus of 0.1~5MPa ", refer under the arbitrary temp of the range, storage modulus is in above range Value.Since storage modulus is usually gradually reduced as temperature increases, if 23 DEG C and 80 DEG C of storage modulus is above-mentioned In range, then it can estimate to show the storage modulus in above range in the temperature of the range.The energy storage mould of adhesive phase Determination of viscoelasticity device " the DYNAMIC of commercially available determination of viscoelasticity device, such as REOMETRIC corporation can be used in amount ANALYZER RDA II " measurement.
An index of the percent gel as crosslink density can be used.It is given since adhesive phase of the invention has Crosslink density, thus it is shown that given percent gel.That is, the percent gel of adhesive phase of the invention for example can be with For 70~90 mass %, preferably 75~90 mass %, more preferably 75~85 mass %.If percent gel be lower limit value with On, then be conducive to resistance to foaminess, the re-workability of adhesive phase, if percent gel be upper limit value hereinafter, if be conducive to resistance to stripping From property.It should be noted that percent gel can use the method measurement recorded in embodiment one.
Adhesive phase of the invention has given bonding force.That is, described adhesive layer is fitted in glass substrate, in temperature Under conditions of 23 DEG C of degree, relative humidity 50%, the bonding force of the described adhesive layer after 24 hours is at peeling rate 300mm/ points Zhong Shi, preferably 0.5~25N, more preferably 0.5~20N, further preferably 0.5~15N, particularly preferably 1~10N, especially It is preferably 1.5~10N.If bonding force is lower limit value or more, be conducive to re-workability.It should be noted that bonding force can To be measured using the method recorded in embodiment one.
[2-1] optical film
The optical film 10 for constituting the optical film 1 with adhesive phase can be that can be packed into the images such as liquid crystal display device aobvious The various optical films (film with optical characteristics) of showing device.
The optical film 10 can be single layer structure (such as polarizing film, phase difference film, brightness enhancement film, antiglare film, antireflection film, Optical functionals film such as diffusion barrier, condensing film etc.), it is also possible to multilayered structure (such as polarization plates, phase plate etc.).Optical film 10 be preferably polarization plates, polarizer, phase difference board or phase difference film, particularly preferably polarization plates or polarizing film.It needs to illustrate Be, in this specification, so-called optical film, refer to play a role to perform image display (display picture etc.) film (such as The film to play a role to improve the easy observation degree of image).In addition, so-called polarization plates in this specification, refer in polarizing film At least one side be laminated with the polarization plates of resin film or resin layer, so-called phase plate refers at least one side in phase difference film It is laminated with the phase plate of resin film or resin layer.
[2-2] polarization plates
Fig. 2 and Fig. 3 is the schematic sectional view for the example for indicating that the layer of polarization plates is constituted.Polarization plates 10a shown in Fig. 2 be The one side stacking (or stacking fitting) of polarizing film 2 has the single side protection polarization plates of the first resin film 3, polarization plates 10b shown in Fig. 3 It is that the two-sided protection polarization plates that (or stacking fitting) have the second resin film 4 are also laminated in the another side of polarizing film 2.First, second Resin film 3,4, which can be pressed from both sides, fits in polarizing film 2 across adhesive layer (not shown), adhesive phase.It should be noted that polarization plates 10a, 10b may include other films, layer other than the first, second resin film 3,4.
Polarizing film 2 be the rectilinearly polarized light having Xi Shous with the vibration plane for being parallel to 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 polyvinyl alcohol Film obtained by resin film adsorbs dichroism pigment and is orientated.As dichroism pigment, for example, iodine, dichroism are organic Dyestuff etc..
Polyvinyl alcohol resin can be obtained by by polyvinyl acetate system resin saponification.As polyvinyl acetate Be resin, for example, the polyvinyl acetate of the homopolymer as vinyl acetate, can be with vinyl acetate copolymerization Monomer (such as unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, (methyl) acrylamide with ammonium etc.) with The copolymer etc. of vinyl acetate.
The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of %, preferably 98 moles of % or more.Polyvinyl alcohol Be that resin can be modified, such as can be the polyvinyl formal being modified by aldehydes or polyvinyl acetal etc..It is poly- The average degree of polymerization of vinyl alcohol resin is usually 1000~10000, and preferably 1500~5000.It should be noted that poly- second The average degree of polymerization of enol system resin can be found out according to JIS K 6726.
In general, use polyvinyl alcohol resin is film-made obtained by film as the former material film of polarizing film 2.Polyethenol series tree Rouge can use well known method film.The thickness of former material film is usually 1~150 μm, excellent if considering easness stretched etc. It is selected as 10 μm or more.
Polarizing film 2 can for example manufacture as follows, that is, implement the process being uniaxially stretched to former material film, with dichroism color 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 washing film by element Process is finally dried.The thickness of polarizing film 2 is usually 1~30 μm, from the filming of the optical film 1 with adhesive phase From the viewpoint of, preferably 20 μm hereinafter, more preferably 15 μm hereinafter, particularly preferably 10 μm or less.
Polarizing film 2 made of making polyvinyl alcohol resin film absorption dichroism pigment and being orientated is in addition to can use using poly- The independent film of vinyl alcohol resin film is uniaxially stretched at processing and the dyeing of dichroism pigment as former material film and to film implementation Other than the method (being set as method (1)) of reason obtains, it can also be obtained using following method (being set as method (2)), that is, Xiang Jicai Film is coated with the coating fluid (aqueous solution etc.) containing polyvinyl alcohol resin, is allowed to drying and obtains with polyvinyl alcohol resin layer Base material film after, it is uniaxially stretched together with base material film, to after stretching polyvinyl alcohol resin layer implement dichroism pigment Dyeing processing, then removing remove base material film.As base material film, can be used by with can constitute aftermentioned first, second The film that the identical thermoplastic resin of the thermoplastic resin of resin film 3,4 is formed, preferably by polyethylene terephthalate etc. The cyclic polyolefins such as the cellulose-based resins such as polyester based resin, polycarbonate-based resin, triacetyl cellulose, norbornene resin The film of the formation such as hydrocarbon system resin, polystyrene resin.If being easy to make thin polarizing film 2, example using the above method (2) It is such as also easy to make thick 7 μm of polarizing films 2 below.
First, second resin film 3,4 can be each independently with translucency, preferably by optically transparent thermoplastic Property resin, such as chain polyolefin-based resins (such as polyethylene-based resin, polypropylene-based resin), cyclic polyolefin hydrocarbon system resin Polyolefin-based resins such as (such as norbornene resin etc.)；Cellulose-based resin (such as cellulose esters system resin etc.)；Polyester It is resin (such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT) etc.)；It is poly- Carbonic ester system resin (such as polycarbonate derived from the bis-phenols such as bis- (4- hydroxy phenyl) propane of 2,2- etc.)；(methyl) propylene Acid system resin；Polystyrene resin；Polyether-ether-ketone system resin；Polysulfones system resin；Or the formation such as their mixture, copolymer Film.In them, the first, second resin film 3,4 be preferably respectively by cyclic polyolefin hydrocarbon system resin, polycarbonate-based resin, The film of the compositions such as cellulose-based resin, polyester based resin and (methyl) acrylic resin, particularly preferably for by cellulose-based The film of the compositions such as resin and cyclic polyolefin hydrocarbon system resin.
As chain polyolefin-based resins, for example, polyvinyl resin, acrylic resin etc. are by chain olefin The copolymer etc. that homopolymer, chain olefin of more than two kinds are formed.
Cyclic polyolefin hydrocarbon system resin be comprising with norbornene, tetracyclododecen (alias: dimethano octahydro naphthalene) or they Derivative be typical example cyclic olefin as polymerized unit resin general name.It, can be with as cyclic polyolefin hydrocarbon system resin It enumerates the open loop (co) polymer of cyclic olefin and its adds hydrogen object, the addition polymer of cyclic olefin, cyclic olefin and ethylene, third The copolymer of the chain olefins such as alkene or the aromatic compound with vinyl and by them with unsaturated carboxylic acid or its derivative Modified (co) polymer etc. obtained by object is modified.In them, norbornene, polycyclic drop ice have been used preferably as cyclic olefin The norbornene resin of the orbornene-baseds monomer such as piece alkene 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.In them, preferably 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, generally by polybasic carboxylic acid Or derivatives thereof the resin that is formed with the condensation polymer of polyalcohol.As polyester based resin, for example, poly terephthalic acid Glycol ester, polyethylene naphthalate, polybutylene naphthalate, gathers to benzene two polybutylene terephthalate (PBT) Formic acid propylene glycol ester, polytrimethylene naphthalate, polycyclohexylene's diformazan alcohol ester, poly- naphthalenedicarboxylic acid hexamethylene two Methanol ester etc..
Polycarbonate-based resin is the polyester formed by carbonic acid and glycol or bis-phenol.In them, from heat resistance, weatherability And from the viewpoint of acid resistance, with the aromatic copolycarbonate of diphenyl alkane preferably in strand.As polycarbonate, For example, 2,2- bis- (4- hydroxy phenyl) propane (alias bisphenol-A), 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- Deng polycarbonate as derived from bis-phenol etc..
(methyl) acrylic resin that the first, second resin film 3,4 can be constituted can be to be come with methacrylate (such as this composition unit comprising the 50 mass % or more) polymer of the Component units in source as main body, preferably therewith altogether The copolymer of other copolymer compositions is gathered.
(methyl) acrylic resin may include the Component units in two or more methacrylate sources.As first Base acrylate can enumerate the methacrylic acids such as methyl methacrylate, ethyl methacrylate, butyl methacrylate C1~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.As The concrete example of other copolymer compositions can enumerate the unsaturated acids such as (methyl) acrylic acid；Styrene, halogenated styrenes, α-first The aromatic ethenyl compounds such as base styrene, vinyltoluene；The vinyl cyanide compounds such as (methyl) acrylonitrile；Maleic acid The unsaturated acid anhydrides such as acid anhydride, citraconic anhydride；Unsaturated acyls imines such as phenyl maleimide, N-cyclohexylmaleimide etc. is in molecule Inside there is the compound other than the acrylate of 1 polymerism carbon-to-carbon double bond.Also can be used has 2 or more in the molecule Polymerism carbon-to-carbon double bond compound as copolymer composition.Copolymer composition can make individually or in combination of two or more With.
Consider that (methyl) acrylic resin can have in high polymer main chain from the durability this point that can be improved film Circular structure.The heterocycle structures such as the preferred cyclic acid anhydride structure of ring structure, cyclic imide structure, lactone ring structure.As ring-type The concrete example of acid anhydride structure can enumerate glutaric anhydride structure, succinic anhydride structure etc., as the specific of cyclic imide structure Example, can enumerate glutarimide structure, succimide structure etc., as the concrete example of lactone ring structure, can enumerate fourth Lactone ring structure, valerolactone ring structure etc..
Consider from the viewpoints such as the film formation property of film, the impact resistance of film are made, (methyl) acrylic resin can contain third Olefin(e) acid system rubber particles.So-called acrylic rubber particle is by the elastomeric polymer based on acrylate as required The particle of ingredient can enumerate the rubber particles of the single layer structure substantially only formed by the elastomeric polymer, with flexible polymer Rubber particles of the object as 1 layer of multilayered structure.As the example of elastomeric polymer, can enumerate using alkyl acrylate as Principal component and the crosslinking elastocopolymer for being copolymerized other vinyl monomers and cross-linkable monomer that can be copolymerized therewith.As The alkyl acrylate of principal component as elastomeric polymer, for example, methyl acrylate, ethyl acrylate, acrylic acid The C of the acrylic acid such as butyl ester, 2-EHA1~C8Arrcostab.The carbon atom number of alkyl is preferably 4 or more.
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 preferably 5 mass parts relative to 100 mass parts of (methyl) acrylic resin More than, it is more than more preferably 10 mass parts.If the content of acrylic rubber particle is too many, the surface hardness of film is reduced, separately Outside, the solvent resistance of the organic solvent in surface treating agent may be decreased in the case where film is implemented and is surface-treated.Cause And the content of acrylic rubber particle relative to 100 mass parts of (methyl) acrylic resin be usually 80 below the mass, Preferably 60 below the mass.
First, second resin film 3,4 can contain the common additive in technical field of the invention.As addition Agent, for example, ultraviolet absorbing agent, infrared absorbent, organic based dye, pigment, inorganic system's pigment, antioxidant, anti- Electrostatic interference agent, surfactant, lubricant, dispersing agent, heat stabilizer etc..As ultraviolet absorbing agent, bigcatkin willow can be enumerated Ester compound, benzophenone cpd, benzotriazole cpd, triaizine compounds, cyano (methyl) acrylate compounds, Nickel complex etc..
First, second resin film 3,4 can be times of the film being not stretched or the film Jing Guo uniaxial or biaxial stretching respectively It anticipates one kind.First resin film 3 and/or the second resin film 4 can be the protective film for undertaking the effect of protection polarizing film 2, can also be with It is the protective film that optical function is had both as aftermentioned phase difference film.It should be noted that the first resin film 3 and the second tree Adipose membrane 4 can be identical or different film.
In addition, the first resin film 3 and/or the second resin film 4 can be in its outer surface (tables with 2 opposite side of polarizing film Face) have the surface-treated layers such as hard conating, antiglare layer, anti-reflection layer, light diffusion layer, anti-static electricity interference layer, stain-proofing layer, conductive layer (coating).The thickness of first resin film 3 and the second resin film 4 is usually 1~150 μm respectively, preferably 5~100 μm, more excellent It is selected as 5~60 μm, further preferably 50 μm or less (such as 1~40 μm), particularly preferably 30 μm or less (such as 5~25 μ m)。
Especially in towards the polarization plates of middle-size and small-size equipment as smart phone, panel type terminal, from filming It is required that considering, use 30 μm of thickness thin films below as the first resin film 3 and/or the second resin film 4, this polarization mostly Plate inhibits the power of the convergent force of polarizing film 2 weak, and durability is easy to become inadequate.Even if use this polarization plates as optics In the case where film 10, the optical film 1 with adhesive phase of the invention also has good durability.
First, second resin film 3,4, which can be pressed from both sides, fits in polarizing film 2 across adhesive layer, adhesive phase.It is viscous as being formed Water system bonding agent or active energy ray-curable bonding agent can be used in the bonding agent for connecing oxidant layer.
As water system bonding agent, usual water system bonding agent can be enumerated (such as by polyvinyl alcohol resin aqueous solution shape At bonding agent, water system two-liquid type carbamate system emulsion adhesive, aldehyde compound, epoxide, melamine series Close crosslinking agents such as object, methylol compound, isocyanate compound, amine compounds, multivalent metal salt etc.).It, can be in them Suitably use the water system bonding agent comprising polyvinyl alcohol resin aqueous solution.It should be noted that using water system bonding agent In the case where, it is excellent in order to remove water contained in water system bonding agent after being bonded polarizing film 2 with the first, second resin film 3,4 Choosing is implemented to be allowed to dry process.After drying process, can be set for example cured in 20~45 DEG C or so of temperature it is ripe Chemical industry sequence.
Above-mentioned so-called active energy ray-curable bonding agent refers to by irradiating ultraviolet light, electron beam isoreactivity energy Ray and cured bonding agent, for example, the solidification compound comprising polymerizable compound and Photoepolymerizationinitiater initiater, Solidification compound comprising light reactive resin, the solidification compound comprising binder resin and photoreactivity crosslinking agent Deng preferably ultra-violet solidified bonding agent.
Using active energy ray-curable bonding agent, 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 bonding agent.The light source of active energy beam is not particularly limited, however it is preferred that below wavelength 400nm Ultraviolet light with luminous distribution.
As the method for being bonded polarizing film 2 with the first, second resin film 3,4, can enumerate at least any of them The binding face of one side implements methods of surface activation process such as saponification process, sided corona treatment, corona treatment etc..In polarizing film In the case where 2 two sides fitting resin film, the bonding agent for being bonded these resin films can be bonding agent of the same race, can also To be bonding agent not of the same race.
Polarization plates 10a, 10b can also include other films or layer.Its concrete example is other than aftermentioned phase difference film, also Adhesive phase, coating, protecting film etc. other than brightness enhancement film, antiglare film, antireflection film, diffusion barrier, condensing film, adhesive phase 20. Protecting film is for the film for protecting purpose of the surface of the optical films such as polarization plates 10 from damaging, polluting to use, it is common practice to incited somebody to action Optical film 1 with adhesive phase is stripped removing after fitting on such as metal layer, substrate.
Protecting 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.
[2-3] phase plate
Phase difference film contained in phase plate is as described above, be to show optically anisotropic optical film, in addition to can The phase difference film that can be used in be as the first, second resin film 3,4 other than the thermoplastic resin being illustrated above, such as It can also be by that will include polyvinyl alcohol resin, polyarylate system resin, polyimides system resins, polyether sulfone system resin, gather Vinylidene fluoride/polymethyl methacrylate system resin, liquid crystal polyester system resin, vinyl-vinyl acetate copolymer saponification Stretched film obtained by the resin film of object, polyvinyl chloride resin etc. is stretched to 1.01~6 times or so.In them, will preferably it gather Carbonic ester resin film or annular ethylene series resin film, (methyl) acrylic resin film or cellulose-based resin film are uniaxially stretched Or it is biaxial stretch-formed obtained by stretched film.In addition, in the present specification, zero-lag film is also contained in phase difference film.Wherein, may be used To use zero-lag film as protective film.In addition it is also possible to which uniaxiality phase difference film, big visual angle phase difference film, low will be referred to as The film of modulus of photoelasticity phase difference film etc. is as phase difference film application.
So-called zero-lag film, refers to phase difference value R in faceeAnd thickness direction phase difference value RthIt is -15~15nm's Film.The phase difference film can be suitably employed in the liquid crystal display device of IPS mode.Phase difference value R in faceeAnd thickness direction Phase difference value RthIt is preferably all -10~10nm, is more preferably -5~5nm.Phase difference value R in face described hereineAnd it is thick Spend direction phase 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, nxFor 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, nzFor 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 easily controllable phase difference value, being also easy to obtain, therefore it is preferable to use cellulose-based resins, polyolefin tree Rouge or (methyl) acrylic resin.
Alternatively, it is also possible to embody optically anisotropic film, utilization for coating, the orientation of liquid crystal compounds is utilized The coating of inorganic layered compounds uses to embody optically anisotropic film as phase difference film.As this phase difference Film has film referred to as temperature compensating type phase difference film and by JX days mine days Shi Nengyuan (strain) with the trade name of " NH Film " Sale will be justified by film obtained by rod shaped liquid crystal tilted alignment, by Fujiphoto (strain) with what the trade name of " WV Film " was sold Film obtained by discotic mesogenic tilted alignment, the complete biaxial orientation sold by Sumitomo Chemical (strain) with the trade name of " VAC Film " The film of type, the film of biaxially oriented version similarly sold by Sumitomo Chemical (strain) with the trade name of " new VAC Film " etc..It needs It is noted that the resin film for being laminated in at least one side of phase difference film for example can be above-mentioned protective film.
[3] optical laminate
The present invention includes comprising the optical film with adhesive phase and being laminated in the optical film for having adhesive phase Adhesive phase side substrate optical laminate.Since the adhesive phase of optical laminate of the invention is by described adhesive group It closes object to be formed, therefore with excellent durable under harsh durable condition (such as 100 DEG C or more durable condition) Property.
As substrate, usual substrate can be enumerated, for example, glass substrate, ITO (tin-doped indium oxide) substrate, plastic foil, Organic Conductive Films, metal layer, layer etc. of resinizing outside.
Fig. 4~Fig. 8 is the schematic sectional view for indicating the example of optical laminate of the invention.
Optical laminate 5 shown in Fig. 4 is metal layer 30 (or metal wiring layer 30) stacking that will be laminated on substrate 40 Obtained by the face of the adhesive phase side of the optical film 1a (or polarization plates 1a with adhesive phase) with adhesive phase Optical laminate.The optical film 1a with adhesive phase is the face laminate adhesive in 2 side of polarizing film of the polarization plates 10a Optical film obtained by oxidant layer 20.
Optical laminate 6 shown in fig. 5 is that the metal layer 30 that will be laminated on substrate 40 is laminated in adhesive phase Optical laminate obtained by the face of the adhesive phase side of optical film 1b (or polarization plates 1b with adhesive phase).Described have is glued The optical film 1b of mixture layer is that the surface layer in 4 side of the second resin film of the polarization plates 10b folds optics obtained by adhesive phase 20 Film.
Optical laminate 5,6 can be pressed from both sides by that will have the optical film (1a, 1b) of adhesive phase across the patch of adhesive phase 20 Conjunction is obtained in the metal layer 30 being laminated on substrate 40.
As the method for forming metal layer 30 on the substrate 40, for example, sputtering method etc..Substrate 40 can be touching Touch the transparent substrate that liquid crystal cells are constituted contained in input element, preferably glass substrate.As the material of the glass substrate, Soda-lime glass, glass with lower alkali content, alkali-free glass etc. can be used.Metal layer 30 can be formed in the entire surface of substrate 40, can also be with It is formed in part of it.
Metal layer 30 for example can be comprising selected from aluminium, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead and comprising them At least one of the alloy of metal of more than two kinds metallic element layer.It is excellent from the viewpoint of electric conductivity in them It is selected as comprising the layer selected from least one of aluminium, copper, silver and gold metallic element, from the viewpoint of electric conductivity and cost, more Preferably include the layer of aluminium element, further preferably (constitutes whole metals of metal layer 30 as principal component comprising aluminium element The 50 mass % or more of ingredient) layer.
The transparent electrode layer such as can be ITO of metal layer 30 can also also have together with metal layer 30 and include ITO etc. The transparent electrode layer of metal oxide.It should be noted that the metal wiring layer for being configured with filament on substrate also can be used Metal mesh, the layer that is added to metal nanoparticle, metal nanometer line in binder.
The preparation method of metal layer 30 is not particularly limited, and can be metal foil, is also possible to using vacuum vapour deposition, splashes Penetrate method, ion plating method, ink jet printing method, gravure printing method formed metal layer, preferably using sputtering method, ink jet printing method, The metal layer that gravure printing method is formed, the metal layer more preferably formed using sputtering.The thickness of metal layer 30 does not limit especially It is fixed, usually 3 μm hereinafter, preferably 1 μm hereinafter, more preferably 0.8 μm hereinafter, and usual 0.01 μm or more.In addition, in metal In the case that layer 30 is metal wiring layer (such as metal mesh), the line width of the metal line is usually 10 μm hereinafter, preferably 5 μm Hereinafter, more preferably 3 μm hereinafter, and usually 0.5 μm or more.
Optical laminate 7 shown in fig. 6 is the adhesive of the optical film 1 with adhesive phase of stacking on the substrate 40 Optical laminate obtained by layer 20.
Optical laminate 8 shown in Fig. 7 is will be (opposite with substrate 40 on the face for the metal layer 30 being laminated on substrate 40 On the face of side) resin layer 50 that is further laminated is laminated in 20 side of adhesive phase of the optical film 1 with adhesive phase Face obtained by optical laminate.As formed resin layer 50 resin, for example, the composition first of foregoing illustrative or The resin etc. of second resin film.
Multiple metals are laminated in addition to separating given interval along direction in length and breadth on the substrate 40 in optical laminate 9 shown in Fig. 8 Layer 30, (or gap) and (face with 40 opposite side of substrate on the face of the metal layer 30 between multiple metal layer 30 On) formed other than (or stacking) resin layer 50, it is identical as optical laminate 7.In the form (metal as the optical laminate 9 Layer 30 is by the form of given shape pattern) in the case where, metal layer 30 for example can be touch input formula liquid crystal display dress The metal wiring layer (i.e. electrode layer) of touch input element possessed by setting.
In optical laminate 9, multiple metal layers 30 can be contacted wholly or partly with adhesive phase 20, can also be with It does not contact.In addition, metal layer 30 can be the continuous film comprising above-mentioned metal or alloy.It should be noted that resin layer 50 can To omit.
In the optical film (1,1a, 1b) and substrate 40 (glass substrate, transparent substrate etc.) or metal that will have adhesive phase The fitting of 30 (transparent electrode layer) of layer and after producing optical laminate, in the case where there is what not good situation, need to carry out by Optical film with adhesive phase is removed, from substrate 40 or metal layer 30 again by the other optical film 1 with adhesive phase Fit in the so-called reprocessing operation of substrate 40 or metal layer 30.Optical film 1 with adhesive phase of the invention is difficult to shelling The surface of glass substrate or transparent electrode from after generates fuzzy, residue glue etc., and re-workability is excellent.
[4] image display device
Adhesive phase, the optical film with adhesive phase and optical laminate of the invention can liquid crystal display device, It is used in the image display devices such as organic EL display device, which has excellent durability.
Liquid crystal display device can be the touch input formula liquid crystal display device with touch panel function.Touch input formula Liquid crystal display device has touch input element and backlight comprising liquid crystal cells.The composition of touch panel can be known Mode (such as Out-cell type, On-cell type, In-cell type etc.), in addition the manner of execution of touch panel can be known Mode, such as resistive film mode, electrostatic capacitance method (surface type electrostatic capacitance method, projection type electrostatic capacitance method) etc.. Optical film with adhesive phase of the invention can be configured at the visible side of touch input element (liquid crystal cells), can also match It is placed in backlight side, both sides can also be configured at.The driving method of liquid crystal cells can be TN mode, VA mode, IPS mode, Known any mode such as multidomain mode, OCB mode.It should be noted that in the liquid crystal display device, optical layer Substrate 40 possessed by stack is also possible to substrate included in above-mentioned liquid crystal cells (being glass substrate in typical situation).
In addition, the optical film with adhesive phase of the invention can be configured at the visible side of organic EL display device.
Organic EL display device for example can be to have and be laminated with from substrate-side in each pixel being formed on substrate The display of the composition of lower electrode, the organic EL layer at the position acted due to the substance with optical effect and upper electrode Device, at least across an electrode (conductive film of the translucency) identification in electrode from because flowing through electric current in organic EL layer And the light of luminous organic EL.
[5] adhesive composition uses (methyl) acrylic resin (A)
The present invention includes that adhesive composition uses (methyl) acrylic resin (A).The adhesive composition uses (methyl) Acrylic resin (A) is identical as above-mentioned (methyl) acrylic resin (A), constitutes (methyl) acrylic resin (A) The preferred ratio of preferred Component units and this composition unit etc. is also identical.In addition, the adhesive composition (methyl) third Olefin(e) acid system resin (A) is preferably adhesive composition (methyl) acrylic acid series used in the optical film with adhesive phase Resin.In addition, as the application adhesive composition adhesive composition of (methyl) acrylic resin (A), without special It limits, however it is preferred that enumerates the adhesive composition recorded in above-mentioned [1].
In preferred mode of the invention, adhesive composition (methyl) acrylic resin (A) contains second The Component units in source (methyl) acrylate (a1) of acyl acetyl group and source (methyl) acrylate (a2) containing hydroxyl Component units, mass ratio (a2)/(a1) of the Component units is 0.5~5, and weight average molecular weight (Mw) is with polystyrene It is scaled 1,000,000 or more.This adhesive composition can be formed in hot environment (example with (methyl) acrylic resin (A) Such as 100 DEG C or more of hot environment) under also with the adhesive phase of excellent durability and good re-workability.
[embodiment]
Hereinafter, provide Examples and Comparative Examples and the present invention is further elaborated with, however the present invention is not by these examples Son limits.Hereinafter, indicating that usage amount, part of content and % are quality criteria.
< Production Example 1: the adhesive phase manufacture > of (methyl) acrylic resin (A-1)
Into the reaction vessel for having cooling tube, nitrogen ingress pipe, thermometer and blender, investment will form shown in table 1 The monomer of (numerical value of table 1 is mass parts) is obtained by mixing with 80 parts of ethyl acetate, 40 parts of acetone, 0.012 part of azodiisobutyronitrile Solution.After air in reaction vessel is replaced with nitrogen, interior temperature is increased after reflux temperature reacts 3.5 hours, is added Ethyl acetate and be adjusted in a manner of the concentration 20% for making polymer, obtain (methyl) acrylic resin (A-1) Ethyl acetate/acetone soln.The weight average molecular weight Mw of resulting (methyl) acrylic resin (A-1) is 1,390,000, is divided equally again The ratio (Mw/Mn) of son amount Mw and number-average molecular weight Mn is 3.9.
< Production Example 2-14: the adhesive phase manufacture > of (methyl) acrylic resin (A-2~14)
Other than group in addition to making monomer becomes composition shown in table 1, (methyl) acrylic acid series is obtained identically as Production Example 1 Ethyl acetate/acetone soln (resin concentration: 20%) of resin (A-2~14).Resulting (methyl) acrylic resin (A- 2~14) weight average molecular weight Mw is 1,300,000~1,500,000 range, the range that Mw/Mn is 3~6.
In Production Example above, weight average molecular weight Mw and number-average molecular weight Mn are measured as follows, that is, in high performance liquid chromatography In (Japanese Waters corporation, " Waters 2695 (main body) " and " Waters2414 (detector) "), 3 colors of arranged in series Compose column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 107, separating ranges: 100~2 × 107, theoretical tray Number: 10000 column plates/root, filler material: styrene diethylene benzene copoly mer, filler partial size: 10 μm), use tetrahydro Furans was as eluent, in 1mL/ minutes sample solution concentration 1mg/mL, 100 μ L of sample import volume, 35 DEG C of temperature, flow velocity conditions Under, it is measured using standard polystyren conversion.Keep condition when obtaining the elution curve of GPC also same.
The differential scanning calorimetry (DSC) (DSC) that glass transition temperature Tg uses SII NANOTECHNOLOGY (strain) to make " EXSTAR DSC6000 ", in a nitrogen atmosphere, -80~50 DEG C of measuring temperature range, the condition of 10 DEG C/min of heating rate Lower measurement.
By composition (numerical value of table 1 is mass parts), resulting (methyl) acrylic resin of the monomer in each Production Example Weight average molecular weight and molecular weight distribution (Mw/Mn) be shown in table 1.
[table 1]
Abbreviation in " monomer composition " column of table 1 refers to following monomer.
BA: n-butyl acrylate (glass transition temperature of homopolymer: -54 DEG C)；
MA: methyl acrylate (glass transition temperature of homopolymer: 10 DEG C)；
AAEM: acetoacetoxyethyl methacrylate (a1)；
HEA: acrylic acid 2- hydroxy methacrylate (a2)；
PEA: phenoxyethyl acrylate；
PEA2: phenoxy group diethylene glycol acrylate；
BMAA: butoxy methyl acrylamide；
AA: acrylic acid.
< Examples 1 to 9,1~7 > of comparative example
(1) preparation of adhesive composition
To the ethyl acetate solution (resin concentration: 20%) of (methyl) acrylic resin obtained in above-mentioned Production Example In, relative to 100 parts of solid component of the solution, the crosslinking agent (B) and silane compound of (mass parts) are measured shown in mixture table 2 (C), then ethyl acetate is added in a manner of making solid component concentration 14% and obtain adhesive composition.It is each shown in table 2 The use level of gradation composition is the mass parts as effective component contained therein when used commodity include solvent etc. Number.
[table 2]
Each gradation composition indicated in table 2 with abbreviation notes at foot.
(crosslinking agent)
B-1: the ethyl acetate solution (solid component concentration of the trimethylolpropane adduct of toluene di-isocyanate(TDI) 75%), the trade name " CORONATE L " obtained from Tosoh (strain).
(silane compound)
Bis- (trimethoxysilyl) hexanes of C-1:1,6-.
(2) production of adhesive phase
By each adhesive composition prepared in above-mentioned (1) using gluing machine by make it is dry after with a thickness of 20 μm in a manner of The spacer film formed by the polyethylene terephthalate film for implementing demoulding processing is coated on (to obtain from Lintec (strain) Trade name " PLR-382051 ") demoulding process face, 100 DEG C dry 1 minute and produce adhesive phase (adhesive Piece).
(3) production of the optical film (P-1) with adhesive phase
By average degree of polymerization about 2400,99.9 moles of % of saponification degree, 60 μm of thickness of polyvinyl alcohol film ((strain) Kuraray The trade name " Kuraray Vinylon VF-PE#6000 " of system) be impregnated in 37 DEG C of pure water after, be impregnated at 30 DEG C and include In iodine and the aqueous solution (iodine/potassium iodide/water (mass 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 (mass ratio)=12/3.6/100) comprising 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 being adsorbed with iodine on polyvinyl alcohol and being orientated is obtained.It stretches It is mainly carried out in the process that iodine staining and boric acid are handled, total stretching ratio is 5.3 times.
In the one side of resulting polarizing film, press from both sides thick across the bonding agent fitting formed by the aqueous solution of polyvinyl alcohol resin 25 μm of the transparent protective film (trade name of Konica Minolta Opto (strain) system formed by tri acetyl cellulose membrane "KC2UA"〕.Then it in the face with tri acetyl cellulose membrane opposite side of above-mentioned polarizing film, presss from both sides across by polyethenol series tree Thick 23 μm of zero phase difference film (the Japanese ZEON formed by cyclic polyolefin hydrocarbon system resin of bonding agent fitting that the aqueous solution of rouge is formed The trade name " ZEONOR " of (strain) system), produce polarization plates.Then, to the face phase of zero phase difference film contacted with polarizing film After the Corona discharge Treatment for improving adaptation is implemented in the face of anti-side, the viscous of above-mentioned (2) middle production is bonded using laminating machine The face (adhesive level) with spacer film opposite side of mixture layer, then in 23 DEG C of temperature, the condition of relative humidity 65% Lower curing 7 days, obtains the optical film (P-1) with adhesive phase.
(4) 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 spacer film after cutting the size for 300mm × 220mm, by the adhesive phase face paste of exposing together in glass base Plate.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 With temperature 50 C, pressure 5kg/cm in kettle2(490.3kPa) pressurizes 20 minutes.As glass substrate, Corning company has been used The alkali-free glass of system: trade name " Eagle XG ".
To resulting optical laminate, the resistance to heat examination kept under 105 DEG C of temperature of drying condition 250 hours is implemented It tests.
Optical laminate after visually observing each test, visually observes that whether there is or not the tilting of adhesive phase, removing, foaming Etc. cosmetic variations, have rated durability according to following evaluation criteria.It the results are shown in Table 3.
5: the cosmetic variations such as tilting, removing, foaming are not observed completely,
4: the cosmetic variations such as tilting, removing, foaming are not observed substantially,
3: the cosmetic variations such as tilting, removing, foaming are slightly eye-catching,
2: the cosmetic variations such as tilting, removing, foaming are eye-catching,
1: observing the cosmetic variations such as tilting, removing, foaming significantly.
(5) the bonding force 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.Spacer is removed from test film, its adhesive face is pasted on glass substrate.By the resulting glass substrate of being pasted with Test film (optical film with adhesive phase for being pasted with glass substrate) is in autoclave with temperature 50 C, pressure 5kg/cm2 (490.3kPa) pressurizes 20 minutes.After being taken care of 24 hours in 23 DEG C of temperature, the atmosphere of relative humidity 50%, from test film by light Film is learned to remove with 300mm/ minutes speed along 180 ° of directions together with adhesive phase.Using Average peel force when removing as viscous Resultant force is shown in table 3.In the case where bonding force is 15N situation below, re-workability is excellent, in addition in the situation for 0.5N or more Under, it is difficult to generate removing when being impacted from polarization plates end.
[the ITO erosion analysis of optical laminate]
Band is determined using low-resistivity meter (trade name " Loresta-AX " of Mitsubishi Chemical ANALYTECH (strain) system) There is the sheet resistance (test front surface resistance value) on the surface of the ITO layer of the glass substrate of ITO layer.Then, by system in above-mentioned (3) The test film for the size that the formation of work has the polarization plates of adhesive phase to cut as 20mm × 40mm.From between the removing of resulting test film Spacing body, folder are fitted in the ITO layer side of glass substrate across adhesive phase.By resulting optical laminate in temperature 60 C, opposite After being taken care of 500 hours in the baking oven of humidity 90%, under 23 DEG C of temperature, the atmosphere of relative humidity 50%, in ITO layer and adhesive It is removed between layer.The sheet resistance (test rear surface resistance value) of ITO layer after determining removing.Before calculating test using following formula Resistance change rate afterwards is evaluated according to benchmark below.Resistance change rate is smaller, then ITO corrosivity is lower.By result It is shown in table 3.
Resistance change rate (%)=[(test rear surface resistance value)-(test front surface resistance value)]/[test front surface Resistance value] × 100
The corrosive evaluation criteria > of < ITO
Zero: resistance change rate is less than 50%, the good optical laminate of ITO corrosivity.
×: resistance change rate is 50% or more, and the ITO corrosivity of optical laminate is bad.
(percent gel of adhesive sheet)
Provide the percent gel evaluation method of adhesive sheet of the invention.Percent gel is bigger, then in adhesive into The more cross-linking reaction of row, can be set to the reference value of crosslink density.Percent gel is measured according to (a) below~(d) Value.
(a) will about 8cm × about 8cm area adhesive sheet and about 10cm × about 10cm metal formed by SUS304 Net (its quality is set as Wm) fitting.
(b) it weighs obtained in above-mentioned (1) and is bonded object, its quality is set as Ws, then the side adhesive sheet to be packed in Formula is folded 4 times and is weighed after being fixed with stapler (stapler), its quality is set as Wb.
(c) the fixed net of stapler having been carried out in above-mentioned (2) and being put into glass container, ethyl acetate 60mL is added and impregnates Afterwards, which is taken care of 3 days at room temperature.
(d) net is taken out from glass container, weighs after 24 hours dry at 120 DEG C, its quality is set as Wa, be based on following formula Calculated for gel percentage.
Percent gel (quality %)=({ Wa- (Wb-Ws)-Wm }/(Ws-Wm)) × 100
[table 3]
As shown in table 3, the mass ratio of the AAEM (a1) in the ingredient of (methyl) acrylic resin and HEA (a2) (a2)/(a1) be 0.5~5 in the range of Examples 1 to 9 optical laminate and the mass ratio be 0.5~5 range outside The optical laminate of comparative example 1~7 is compared, and shows excellent durability.In addition, the ingredient of (methyl) acrylic resin is worked as In the embodiment 4 of the AA comprising 0.1 mass parts and the embodiment 5 of the BMAA comprising 0.5 mass parts optical laminate it is aobvious More excellent durability is shown.
< Production Example 15-17: the manufacture > of adhesive phase (methyl) acrylic resin (A-15)~(A-17)
Other than group in addition to making monomer becomes composition shown in table 4, (methyl) acrylic acid series is obtained identically as Production Example 1 Resin (A-15)~(A-17) ethyl acetate/acetone soln (resin concentration: 20%).Resulting (methyl) acrylic acid series tree Rouge (A-15)~(A-17) weight average molecular weight Mw is 1,100,000~1,500,000 range, the range that Mw/Mn is 3~6.Weight is equal Molecular weight Mw and number-average molecular weight Mn is measured using the method recorded in above description.
[table 4]
Abbreviation in " monomer composition " column of table 4 refers to following monomer.
BA: n-butyl acrylate (glass transition temperature of homopolymer: -54 DEG C)；
MA: methyl acrylate (glass transition temperature of homopolymer: 10 DEG C)；
AAEM: acetoacetoxyethyl methacrylate (a1)；
HEA: acrylic acid 2- hydroxy methacrylate (a2)；
PEA: phenoxyethyl acrylate；
PEA2: phenoxy group diethylene glycol acrylate；
BMAA: butoxy methyl acrylamide；
AA: acrylic acid.
< embodiment 10-12 >
(6) preparation of adhesive composition
To (methyl) acrylic resin obtained in above-mentioned Production Example 15-17 ethyl acetate solution (resin concentration: 20%) in, relative to 100 parts of solid component of the solution, the crosslinking agent (B) and silane of (mass parts) are measured shown in mixture table 5 Compound (C), then add ethyl acetate in a manner of making solid component concentration 14% and obtain adhesive composition.5 institute of table The use level of each gradation composition shown is the matter as effective component contained therein when used commodity include solvent etc. Measure number.
[table 5]
Each gradation composition indicated in table 5 with abbreviation notes at foot.
(crosslinking agent)
B-1: the ethyl acetate solution (solid component concentration of the trimethylolpropane adduct of toluene di-isocyanate(TDI) 75%), the trade name " CORONATE L " obtained from Tosoh (strain).
(silane compound)
Bis- (trimethoxysilyl) hexanes of C-1:1,6-.
(7) production of adhesive phase
Other than adhesive composition to be replaced with to each adhesive composition prepared in above-mentioned (6), using with it is above-mentioned " production of (2) adhesive phase " identical method produces adhesive phase (adhesive sheet).
(8) production of the optical film (P-2) with adhesive phase
Other than adhesive phase to be replaced with to the adhesive phase made in above-mentioned (7), using with above-mentioned " (3) are with viscous The identical method of the production of the optical film (P-1) of mixture layer " produces the optical film (P-2) with adhesive phase.
(9) durability evaluation of the optical film with adhesive phase
By the optical film (P-2) with adhesive phase made in above-mentioned (8) so that the stretching axis direction of polarization plates is length The mode on side removes spacer film after cutting the size for 300mm × 220mm, by the adhesive phase face paste of exposing together in glass base Plate.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, the resistance to heat examination kept under 105 DEG C of temperature of drying condition 500 hours is implemented It tests.
Optical laminate after visually observing each test, visually observes that whether there is or not the tilting of adhesive phase, removing, foaming Etc. cosmetic variations, have rated durability according to evaluation criteria.It the results are shown in Table 6.
5: the cosmetic variations such as tilting, removing, foaming are not observed completely,
4: the cosmetic variations such as tilting, removing, foaming are not observed substantially,
3: the cosmetic variations such as tilting, removing, foaming are slightly eye-catching,
2: the cosmetic variations such as tilting, removing, foaming are eye-catching,
1: observing the cosmetic variations such as tilting, removing, foaming significantly.
(10) the bonding force evaluation of the optical film with adhesive phase
In addition to the optical film for having adhesive phase is replaced with the optical film with adhesive phase made in above-mentioned (8) (P-2) other than, band has been carried out using method identical with above-mentioned " bonding force of the optical film of (5) with adhesive phase is evaluated " There is the bonding force of the optical film (P-2) of adhesive phase to evaluate.It the results are shown in Table 6.
[the ITO erosion analysis of optical laminate]
In addition to the optical film for having adhesive phase is replaced with the optical film with adhesive phase made in above-mentioned (8) (P-2) other than, the optical laminate for being laminated with ITO is produced using method identical with the method recorded in above description, into The ITO erosion analysis of the optical laminate obtained using the method recorded in above description is gone.It the results are shown in table 6 In.It should be noted that evaluation criteria is also same as described above.
[percent gel of adhesive sheet]
The percent gel of the adhesive sheet made in above-mentioned (7) is determined using the method recorded in above description.It will As a result it is shown in table 6.
[table 6]
As shown in table 6, the mass ratio of the AAEM (a1) in the ingredient of (methyl) acrylic resin and HEA (a2) (a2)/(a1) be 0.5~5 in the range of embodiment and the mass ratio be 0.5~5 range outside comparative example junior scholar be laminated Body is compared, and shows excellent durability.In addition, in the ingredient of (methyl) acrylic resin, if with more than homopolymer The ratio of alkyl acrylate (a3) of the glass transition temperature lower than 0 DEG C contains the acrylic acid that the Tg of homopolymer is 0 DEG C or more Arrcostab (a4), even then more harsh durability test, also shows that good durability.
< embodiment 13-15,8 > of comparative example
(11) preparation of adhesive composition
To (methyl) acrylic resin obtained in above-mentioned Production Example 2-4,13 ethyl acetate solution (resin concentration: 20%) in, relative to 100 parts of solid component of the solution, crosslinking agent (B), the silanization of (mass parts) are measured shown in mixture table 7 Object (C) and ionic compound (D) are closed, then adds ethyl acetate in a manner of making solid component concentration 14% and is bonded Agent composition.The use level of each gradation composition shown in table 7 is as contained therein when used commodity include solvent etc. Effective component mass fraction.
[table 7]
Each gradation composition indicated in table 7 with abbreviation notes at foot.
(crosslinking agent)
B-1: the ethyl acetate solution (solid component concentration of the trimethylolpropane adduct of toluene di-isocyanate(TDI) 75%), the trade name " CORONATE L " obtained from Tosoh (strain).
(silane compound)
Bis- (trimethoxysilyl) hexanes of C-1:1,6-.
(ionic compound)
Bis- (fluorine sulphonyl) inferior amine salts of D-1:N- decyl pyridine
(12) production of adhesive phase
Other than adhesive composition to be replaced with to each adhesive composition prepared in above-mentioned (11), using with it is above-mentioned " production of (2) adhesive phase " identical method produces adhesive phase.
(13) production of the optical film (P-3) with adhesive phase
By average degree of polymerization 2400,99.9 moles of % of saponification degree, 30 μm of thickness of polyvinyl alcohol film ((strain) Kuraray system Trade name (Kuraray Poval Film VF-PE#3000)) be impregnated in 37 DEG C of pure water after, be impregnated in packet at 30 DEG C In aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) containing iodine and potassium iodide.Thereafter, it is impregnated at 56.5 DEG C In the aqueous solution (potassium iodide/boric acid/water (weight ratio)=12/3.6/100) comprising potassium iodide and boric acid.Then, film is used After 10 DEG C of pure water cleaning, in 85 DEG C of dryings, obtain being adsorbed with iodine on polyvinyl alcohol and be orientated about 12 μm of thickness it is inclined Shake piece A.It stretches and 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 coating A, folder is across the bonding agent formed by the aqueous solution of polyvinyl alcohol resin, fitting Transparent protective film (the commodity of letterpress (strain) system obtained by 7 μm of hard conating are assigned to thick 25 μm of tri acetyl cellulose membrane Name (25KCHCN-TC)).Then, in the face with the face opposite side for being fitted with transparent protective film of polarizing coating A, folder across by Thick 23 μm of the cyclic olefine resin film of bonding agent fitting that the aqueous solution of polyvinyl alcohol resin is formed be (Japanese ZEON (strain) system Trade name (ZF14-023)), obtain polarization plates A.Then, in the face phase contacted with polarizing film to cyclic olefine resin film After the Corona discharge Treatment for improving adaptation is implemented in the face of anti-side, the viscous of above-mentioned (12) middle production is bonded using laminating machine The face (adhesive level) with spacer film opposite side of mixture layer, then in 23 DEG C of temperature, the condition of relative humidity 65% Lower curing 7 days, obtains the optical film (P-3) with adhesive phase.
(14) durability evaluation of the optical film with adhesive phase
In addition to the optical film for having adhesive phase is replaced with the optical film with adhesive phase made in above-mentioned (13) (P-3) other than, band has been carried out using method identical with above-mentioned " durability evaluation of the optical film of (4) with adhesive phase " There is the durability evaluation of the optical film of adhesive phase.It the results are shown in Table 8.It should be noted that evaluation criteria also with it is upper It states identical.
(15) the bonding force evaluation of the optical film with adhesive phase
In addition to the optical film for having adhesive phase is replaced with the optical film with adhesive phase made in above-mentioned (13) (P-3) other than, band has been carried out using method identical with above-mentioned " bonding force of the optical film of (5) with adhesive phase is evaluated " There is the bonding force of the optical film (P-3) of adhesive phase to evaluate.It the results are shown in Table 8.
[the ITO erosion analysis of optical laminate]
In addition to the optical film for having adhesive phase is replaced with the optical film with adhesive phase made in above-mentioned (13) (P-3) other than, it is laminated with the optical laminate of ITO using method identical with the method recorded in above description production, carries out The ITO erosion analysis of the optical laminate obtained using the method recorded in above description.It the results are shown in Table 8. It should be noted that evaluation criteria is also same as described above.
[percent gel of adhesive sheet]
The percent gel of the adhesive sheet made in above-mentioned (12) is determined using the method recorded in above description.It will As a result it is shown in table 8.
It is intrinsic using surface after the spacer for removing the optical film (P-3) with adhesive phase made in above-mentioned (13) Resistance measurement device (" Hiresta-UP MCP-HT450 " (trade name) of Mitsubishi Chemical's (strain) system) determines the table of adhesive Surface resistance.Implement in the case where applying 10 seconds voltage 250V, application time determination conditions.If sheet resistance value is 1.0 × 1012 Ω/ is hereinafter, then available good anti-static electricity interference.
[table 8]
Symbol description
1,1a, 1b have adhesive phase optical film, 2 polarizing films, 3 first resin films, 4 second resin films, 5,6, 7,8,9 optical laminate, 10 optical films, 10a, 10b polarization plates, 20 adhesive phases, 30 metal layers, 40 substrates, 50 trees Rouge layer.

Claims (23)

1. a kind of adhesive composition, it includes (methyl) acrylic resin (A), crosslinking agent (B) and silane compound (C),
(methyl) acrylic resin (A) includes the composition in source (methyl) acrylate (a1) containing acetoacetyl The Component units of unit and source (methyl) acrylate (a2) containing hydroxyl,
Mass ratio (a2)/(a1) of the Component units is 0.5~5.
2. adhesive composition according to claim 1, wherein
The weight average molecular weight of (methyl) acrylic resin (A) is scaled 1,000,000 or more with polystyrene.
3. adhesive composition according to claim 1 or 2, wherein
(methyl) acrylic resin (A) also includes
The glass transition temperature of homopolymer lower than 0 DEG C source alkyl acrylate (a3) Component units and
The Component units in source alkyl acrylate (a4) that the glass transition temperature of homopolymer is 0 DEG C or more.
4. adhesive composition described in any one of claim 1 to 3, wherein
The Component units in the source alkyl acrylate (a3) of the glass transition temperature of homopolymer lower than 0 DEG C and the glass of homopolymer Mass ratio (a3)/(a4) of the Component units in source alkyl acrylate (a4) that glass transition temperature is 0 DEG C or more be 0.1~ 4。
5. adhesive composition according to any one of claims 1 to 4, wherein
The ratio of the Component units in (methyl) the acrylate source contained in (methyl) acrylic resin (A) containing carboxyl 100 mass parts of whole Component units relative to composition (methyl) acrylic resin (A) are 1.0 below the mass.
6. adhesive composition according to any one of claims 1 to 5, wherein
(methyl) acrylic resin (A) also includes the Component units of (methyl) acrylamide monomer source.
7. adhesive composition described according to claim 1~any one of 6, wherein
Crosslinking agent (B) is isocyanates based compound.
8. adhesive composition according to any one of claims 1 to 7, wherein
The ratio of crosslinking agent (B) is 0.01 mass parts~10 mass relative to 100 mass parts of (methyl) acrylic resin (A) Part.
9. adhesive composition described according to claim 1~any one of 8, wherein
Silane compound (C) is the silane compound indicated with following formula (c1):
In formula, B indicates the alicyclic type hydrocarbon of the alkane diyl of carbon atom number 3~20 or the divalent of carbon atom number 3~20, described in composition - the CH of alkane diyl and the alicyclic type hydrocarbon2Optionally it is substituted by-O- or-CO-, R1Indicate carbon atom number 1~5 Alkyl, R2、R3、R4、R5And R6Each independently represent the alkyl of carbon atom number 1~5 or the alkoxy of carbon atom number 1~5.
10. adhesive composition described according to claim 1~any one of 9, wherein
The ratio of silane compound (C) is 0.01 mass parts~10 matter relative to 100 mass parts of (methyl) acrylic resin (A) Measure part.
11. adhesive composition described according to claim 1~any one of 10, contains substantially no Photoepolymerizationinitiater initiater And its decomposition product.
12. adhesive composition described according to claim 1~any one of 11, wherein
Also include ionic compound (D).
13. adhesive composition according to claim 12, wherein
The ratio of ionic compound (D) is 0.01 mass parts~10 relative to 100 mass parts of (methyl) acrylic resin (A) Mass parts.
14. adhesive composition according to claim 12 or 13, wherein
The anion for constituting ionic compound (D) is selected from bis- (trifluoro methylsulfonyl) imines anion, bis- (fluorine sulphonyl) imines At least one of anion and four (pentafluorophenyl group) borate anions.
15. a kind of adhesive phase, the adhesive composition as described in any one of claim 1~14 is formed.
16. adhesive phase according to claim 15, wherein
The percent gel of described adhesive layer is 70%~90%.
17. a kind of optical film with adhesive phase, it includes the bondings of optical film and at least one side for being laminated in the optical film Oxidant layer,
The adhesive phase is adhesive phase described in claim 15 or 16.
18. a kind of optical laminate, it includes the optical film described in claim 17 with adhesive phase and it is laminated in the band There is the substrate of the adhesive phase side of the optical film of adhesive phase.
19. a kind of adhesive composition uses (methyl) acrylic resin (A), it includes (methyl) third containing acetoacetyl The Component units of the Component units in the source olefin(e) acid ester (a1) and source (methyl) acrylate (a2) containing hydroxyl,
Mass ratio (a2)/(a1) of the Component units is 0.5~5, and
The weight average molecular weight of (methyl) acrylic resin (A) is scaled 1,000,000 or more with polystyrene.
20. adhesive composition according to claim 19 uses (methyl) acrylic resin (A), wherein
(methyl) acrylic resin (A) also glass transition temperature comprising homopolymer is lower than 0 DEG C of alkyl acrylate (a3) alkyl acrylate (a4) source that the glass transition temperature of the Component units and homopolymer in source is 0 DEG C or more Component units.
21. adhesive composition described in 9 or 20 uses (methyl) acrylic resin (A) according to claim 1, wherein
The Component units in the source alkyl acrylate (a3) of the glass transition temperature of homopolymer lower than 0 DEG C and the glass of homopolymer Mass ratio (a3)/(a4) of the Component units in source alkyl acrylate (a4) that glass transition temperature is 0 DEG C or more be 0.1~ 4。
22. adhesive composition described in any one of 9~21 uses (methyl) acrylic resin (A) according to claim 1, In,
The ratio of the Component units in (methyl) the acrylate source contained in (methyl) acrylic resin (A) containing carboxyl 100 mass parts of whole Component units relative to composition (methyl) acrylic resin (A) are 1.0 below the mass.
23. adhesive composition described in any one of 9~22 uses (methyl) acrylic resin (A) according to claim 1, In,
(methyl) acrylic resin (A) also includes the Component units of (methyl) acrylamide monomer source.
CN201780058353.9A 2016-09-23 2017-09-21 Adhesive composition Active CN109790430B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016-186152 2016-09-23
JP2016186152 2016-09-23
PCT/JP2017/034139 WO2018056367A1 (en) 2016-09-23 2017-09-21 Adhesive composition

Publications (2)

Publication Number Publication Date
CN109790430A true CN109790430A (en) 2019-05-21
CN109790430B CN109790430B (en) 2021-05-04

Family

ID=61690479

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780058353.9A Active CN109790430B (en) 2016-09-23 2017-09-21 Adhesive composition

Country Status (5)

Country Link
JP (1) JP6991860B2 (en)
KR (1) KR102420444B1 (en)
CN (1) CN109790430B (en)
TW (1) TWI781113B (en)
WO (1) WO2018056367A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214764A (en) * 2020-01-21 2021-08-06 日本电石工业株式会社 Adhesive composition for heat-resistant adhesive sheet and heat-resistant adhesive

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6564995B1 (en) * 2018-06-27 2019-08-28 サイデン化学株式会社 Adhesive sheet
JP7193286B2 (en) * 2018-09-27 2022-12-20 藤森工業株式会社 surface protection film
KR102434825B1 (en) * 2018-09-28 2022-08-22 주식회사 엘지화학 Acryl-based adhesive composition, polarizing plate and display device
JP7286324B2 (en) * 2019-01-17 2023-06-05 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and display
JP2023073161A (en) * 2021-11-15 2023-05-25 日東電工株式会社 Adhesive composition, adhesive sheet, optical laminate, image display panel and image display device
JP7369887B2 (en) * 2021-11-15 2023-10-26 日東電工株式会社 Adhesive compositions, adhesive sheets, optical laminates, image display panels and image display devices

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04171403A (en) * 1990-11-02 1992-06-18 Nippon Synthetic Chem Ind Co Ltd:The Deflecting plate with adhesive layer
JPH11131033A (en) * 1997-08-28 1999-05-18 Lintec Corp Tacky agent composition and tacky sheet using the same
CN1997921A (en) * 2004-07-22 2007-07-11 综研化学株式会社 Adhesive composition for polarizing plate and polarizing plate
WO2016003057A1 (en) * 2014-06-30 2016-01-07 삼성에스디아이 주식회사 Adhesive composition for optical member, optical member comprising same, and optical display device comprising same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5322280B2 (en) 2009-03-27 2013-10-23 サイデン化学株式会社 Optical pressure-sensitive adhesive composition
JP6206070B2 (en) * 2013-10-15 2017-10-04 住友化学株式会社 RESIN FILM WITH ADHESIVE AND OPTICAL LAMINATE USING THE SAME
TWI692514B (en) * 2015-03-31 2020-05-01 日商住友化學股份有限公司 Optical film with adhesive layer and liquid crystal display device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04171403A (en) * 1990-11-02 1992-06-18 Nippon Synthetic Chem Ind Co Ltd:The Deflecting plate with adhesive layer
JPH11131033A (en) * 1997-08-28 1999-05-18 Lintec Corp Tacky agent composition and tacky sheet using the same
CN1997921A (en) * 2004-07-22 2007-07-11 综研化学株式会社 Adhesive composition for polarizing plate and polarizing plate
WO2016003057A1 (en) * 2014-06-30 2016-01-07 삼성에스디아이 주식회사 Adhesive composition for optical member, optical member comprising same, and optical display device comprising same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214764A (en) * 2020-01-21 2021-08-06 日本电石工业株式会社 Adhesive composition for heat-resistant adhesive sheet and heat-resistant adhesive
CN113214764B (en) * 2020-01-21 2024-03-01 日本电石工业株式会社 Adhesive composition for heat-resistant adhesive sheet and heat-resistant adhesive

Also Published As

Publication number Publication date
CN109790430B (en) 2021-05-04
JPWO2018056367A1 (en) 2019-07-04
KR102420444B1 (en) 2022-07-13
TWI781113B (en) 2022-10-21
TW201821574A (en) 2018-06-16
WO2018056367A1 (en) 2018-03-29
KR20190053192A (en) 2019-05-17
JP6991860B2 (en) 2022-01-13

Similar Documents

Publication Publication Date Title
CN109790430A (en) Adhesive composition
CN106019447B (en) Optical laminate and liquid crystal display device
CN105647439B (en) Optical laminate
CN108368403B (en) Adhesive composition
CN110249019B (en) Adhesive composition
CN106010385B (en) Optical film and liquid crystal display device with adhesive phase
CN106010384A (en) Optical film with adhesive layer and liquid crystal display device
CN108368397A (en) The optical film and optical laminate of subsidiary adhesive phase
CN110651017B (en) Adhesive composition
CN108368404B (en) Adhesive composition
CN107177319A (en) Optical component with adhesive phase
CN106010383B (en) Optical laminate and liquid crystal display device
CN108473838B (en) Adhesive composition
TW202323951A (en) Laminate article and display device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20190702

Address after: Tokyo, Japan

Applicant after: Sumitomo Chemical Co., Ltd.

Applicant after: Mitsubishi Kasei Corporation

Address before: Tokyo, Japan

Applicant before: Sumitomo Chemical Co., Ltd.

Applicant before: The Nippon Synthetic Chemical Industry Co., Ltd.

GR01 Patent grant
GR01 Patent grant