CN108473835A - Conductive member bonding sheet, conductive member laminated body and image display device - Google Patents

Conductive member bonding sheet, conductive member laminated body and image display device Download PDF

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Publication number
CN108473835A
CN108473835A CN201680076173.9A CN201680076173A CN108473835A CN 108473835 A CN108473835 A CN 108473835A CN 201680076173 A CN201680076173 A CN 201680076173A CN 108473835 A CN108473835 A CN 108473835A
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China
Prior art keywords
methyl
conductive member
bonding sheet
ester
sheet according
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Granted
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CN201680076173.9A
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CN108473835B (en
Inventor
新美嘉穗儿
山本亮太
稻永诚
吉川秀次郎
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Mitsubishi Kasei Corp
Mitsubishi Plastics Inc
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Mitsubishi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

It provides and does not corrode conductive member, for example, be stale-proof and lose transparency conducting layer and conductive member bonding sheet, conductive member laminated body and image display device with anti-oxidant deterioration and good curing characteristics.Especially it is to provide the conductive member bonding sheet in the image display device that plasma scope (PDP), liquid crystal display (LCD), organic el display (OLED) etc. have used image display panel being suitable for that the conductive members such as transparency conducting layer is made to be bonded.Conductive member bonding sheet has the adhesive phase formed by the adhesive composition for containing (methyl) acrylic copolymer, metal inhibitor and bi-ester of phosphite.

Description

Conductive member bonding sheet, conductive member laminated body and image display device
Technical field
The present invention relates to conductive member bonding sheet and the conductive member laminated bodies etc. for having used the bonding sheet.More particularly to It is aobvious in plasma scope (PDP), liquid crystal display (LCD), organic el display (OLED), inorganic EL display, electrophoresis Show transparent suitable for making in device (EPD), the image display device for interfering the display (IMOD) etc. that modifies tone to use image display panel The conductive member bonding sheet etc. of the conductive members such as conductive layer fitting.
Background technology
In personal computer, mobile terminal (PDA), game machine, television set (TV), onboard navigation system, touch panel, hand It writes the image display device such as plasma scope (PDP) of tablet (pen tablet) etc., liquid crystal display (LCD), have Machine EL display (OLED), inorganic EL display, electrophoretic display device (EPD) (EPD), interference modified tone display (IMOD) etc. planes or In the image display device for having used image display panel with curved surface, in order to ensure it is visual, prevent breakage etc., with bonding Fitting between each construct material is carried out integration without gap is arranged between each member of formation by piece, liquid adhesive.
For example, being formed for having the insertion touch panel between the visible side and surface protection panel of Liquid Crystal Module The image display device of composition configures bonding sheet, liquid adhesive between surface protection panel and the visible side of Liquid Crystal Module, Touch panel is bonded with Liquid Crystal Module, touch panel with surface protection panel with other member of formation such as touch panel to Integration.
Touch panel is generally configured with upper electrode plate and lower electrode plate, and the upper electrode plate and lower electrode plate have By the metal oxides such as tin-doped indium oxide (ITO), indium gallium zinc composite oxide (IGZO), Ga doping zinc-oxides (GZO), The metal materials such as silver, copper, molybdenum formed fine wiring, by the transparency conducting layer of the formation such as nano silver wire, carbon nanotube.In addition, In order to be communicated by collecting the location informations such as the finger detected by transparency conducting layer, felt pen, in transparency conducting layer It is formed with the conductive pattern (wiring pattern) formed by metal material between the control mechanisms such as IC.These are formed by a variety of materials Transparency conducting layer, conductive pattern is usually fixed in such a way that surface contacts with adhesive.The transparency conducting layer, conductive pattern It easily corrodes, under high temperature, hygrothermal environment, due tos the degassing of jointing material (outgas), sour component etc. from dissolved element Corrode, according to circumstances there is the risk that open circuit etc. occurs.
In addition, when determining compositions, the preparation methods such as bonding sheet, liquid adhesive, in order to assign bonding force, cohesive force etc. As the basic physical properties of jointing material, the high polar component such as carboxyl is normally introduced into as copolymer composition or additive.But due to Such highly polar ingredient has oxidation, therefore under the environment such as high temperature and humidity or because taking care of for a long time, bonding sheet meeting sometimes Cause the oxidative degradation etc. of adherend.For the oxidative degradation of such adherend, will be provided with comprising ito film, IGZO films etc. Etc conductive member part conductive member fitting in the case of, it is necessary to give special heed to.
Therefore, in view of this problem, it is proposed that pressed down by the acid ingredients such as carboxyl not being imported adhesive composition The oxidative degradation of adherend processed.For example, disclose a kind of adhesive composition in patent document 1 etc., it includes by alkyl acrylate The matter that oxygroup Arrcostab (ingredient A) and acrylic monomer (ingredient B) with hydroxyl are constituted as necessary monomer component The acrylic polymer of average molecular weight 400,000~1,600,000.
In addition, For example, Patent Document 2 discloses containing as the benzotriazole of metal inhibitor and/or its derivative Metal adhesive sheet for bonding.
In turn, For example, Patent Document 3 discloses a kind of transparent conductive film double-coated pressure sensitive adhesive sheet for fixing, double by making The sour component of the adhesive phase of face bonding sheet contains the nitrogen atom ingredient of specific quantity so that is dropped to the corrosivity of transparent conductive film It is low, take into account the cohesive force of high adhesive phase and the high adhesiveness to transparent conductive film.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-215923 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2006-45315 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2010-144002 bulletins
Invention content
Problems to be solved by the invention
As above-mentioned disclosed in patent document 1, if the acid ingredients such as carboxyl are not imported adhesive composition, spy is bonded Property reduce, albefaction and the optical characteristics such as transparency occur under high temperature and humidity reduce, therefore, it is difficult to maintain containing acidity such as carboxyls The characteristic of the previous adhesive composition of ingredient.
In addition, for the double-sided adhesive sheet containing metal inhibitor of above patent document 2, there are metal inhibitors resistance to The problems such as changing colour in long property experiment, optical characteristics made to reduce.
In turn, for the transparent conductive film double-coated pressure sensitive adhesive sheet for fixing of above patent document 3, there are the resistance value of ITO because Sour component containing carboxyl (methyl) acrylate copolymer and the problem of change.
Therefore, project to be solved by this invention is, provides and does not corrode conductive member and even if adhesive composition Containing acid ingredients such as carboxyls these adherends can be also prevented when fitting in the transparency conducting layer etc. as conductive member The excellent novel conductive component bonding sheet of oxidative degradation, anti-oxidant deterioration.More specifically, it provides and is led even if with transparent It is also corroding them, another that the conductor planes of electric layer, the conductive pattern (wiring pattern) formed by metal material directly fit It is bonded leading for the erosion transparency conducting layer that is also stale-proof with the conductor planes of transparency conducting layer even with insulating protective film (passivating film) outside Electric components bonding sheet.
The solution to the problem
The present invention is mainly characterized in that have by containing (methyl) acrylic copolymer, metal inhibitor and phosphorous The adhesive phase that the adhesive composition of ester compound is formed.
The effect of invention
The conductive member of the present invention has the Corrosion Resistant Reliability to conductive member with bonding sheet, and can also have and make For the resistance to foaming reliability of bonding sheet and good curing characteristics.Therefore, conductive member of the invention uses bonding sheet can be as Suitable for making have transparency conducting layer and/or the conductive member of conductive pattern formed by the metal material comprising copper or silver etc. various The bonding sheet of conductive member fitting uses.The bonding sheet with the device used for image display of touch panel can be especially suitable as It uses.
Description of the drawings
Fig. 1 is the figure of the evaluation test method of the Corrosion Resistant Reliability for illustrating to carry out in aftermentioned embodiment, and (A) is Vertical view or Corrosion Resistant Reliability the evaluation copper glass substrate of the ITO pattern of anti-oxidant deterioration evaluation ito glass substrate Copper pattern vertical view, (B) is to show in the anti-oxidant deterioration evaluation state for being covered with bonding sheet on ito glass substrate Vertical view or in the Corrosion Resistant Reliability evaluation vertical view for the state for being covered with bonding sheet on copper glass substrate, (C) is anti- The sectional view of oxidative degradation sample for evaluation, (D) are the sectional view of Corrosion Resistant Reliability sample for evaluation.
Specific implementation mode
Hereinafter, an example to embodiments of the present invention is described in detail.But the present invention is not limited to following realities Apply mode.
<Conductive member bonding sheet>
The conductive member of an example of embodiments of the present invention (is known as " this bonding sheet " with bonding sheet hereinafter, also omitting.) With by containing (methyl) acrylic compounds (co) polymer, metal inhibitor and the adhesive composition shape of bi-ester of phosphite At adhesive phase.
Described adhesive layer can be single layer, or multilayer, in addition, in the case of multiple layers, it is so-called to can be inserted Other layers as substrate layer.Adhesive phase is the preferred surface of this bonding sheet in the case of being constituted with other layers of multilayer Layer is the adhesive phase formed by aforementioned adhesion agent composition.
In the case that this bonding sheet is multilayer, the thickness of the adhesive phase formed by aforementioned adhesion agent composition does not limit It is fixed, relative to the thickness of this bonding sheet entirety, preferably 10% or more, more preferably 30% or more, be more preferably 50% More than.It, can to the corrosion-resistant of conductive member when the thickness of the adhesive phase formed by aforementioned adhesion agent composition is above range It is good by property, resistance to foaming reliability, curing characteristics, therefore preferably.
It should be noted that in the present invention, " (co) polymer " is the meaning for including homopolymer and copolymer, " (methyl) Acrylate " is the meaning for including acrylate and methacrylate.
[adhesive composition]
The adhesive composition used in this bonding sheet (is known as " this composition " hereinafter, omitting.) contain (methyl) propylene Acids (co) polymer, metal inhibitor and bi-ester of phosphite.
This composition can also contain crosslinking agent, Photoepolymerizationinitiater initiater, antioxidant, other ingredients.
This composition is preferably the composition of photo-curable.
((methyl) acrylic compounds (co) polymer)
As (methyl) acrylic compounds (co) polymer, such as other than the homopolymer of (methyl) alkyl acrylate, Can also enumerate as with copolymer obtained from its polymerizing monomer components with copolymerizable, can more preferably enumerate and include (methyl) alkyl acrylate and selected from can be copolymerized with it carboxyl group-containing monomer, hydroxyl monomer, emulsion stability, contain epoxy group Copolymer of the monomer as structural unit more than any one of monomer, amide-containing monomer and other vinyl monomers.
For (methyl) acrylic compounds (co) polymer, can to it is illustrated below go out monomer etc. as needed using polymerization Initiator is manufactured by conventional method.
(methyl) acrylic compounds (co) polymer is in the case of containing copolymer of the carboxyl group-containing monomer as structural unit, From the viewpoint of obtaining excellent bonding physical property, (methyl) acrylic compounds (co) polymer preferably comprises carboxyl group-containing monomer 1.2 ~15 mass %, wherein further preferably 1.5 mass % or more or 10 mass % or less, wherein further preferably 2.0 mass % or more or 8 mass % or less.
As an example of more specific (methyl) acrylic compounds (co) polymer, can enumerate by the carbon number of side chain be 4~ 18 linear or branched alkyl group (methyl) acrylate (hereinafter also referred to " co-polymerized monomer A ") and can be copolymerized with it selected from Under any one of group more than the copolymer that constitutes of monomer component.
Carboxyl group-containing monomer (hereinafter also referred to " co-polymerized monomer B ".)
Macromonomer (hereinafter also referred to " co-polymerized monomer C ".)
(methyl) acrylate (hereinafter also referred to " co-polymerized monomer D " that the carbon number of side chain is 1~3.)
Hydroxyl monomer (hereinafter also referred to " co-polymerized monomer E ".)
Other vinyl monomers (hereinafter also referred to " co-polymerized monomer F ".)
In addition, an example as (methyl) acrylic compounds (co) polymer, by including (a) co-polymerized monomer A and copolymerizable The copolymer that the monomer component of monomer B and/or co-polymerized monomer C are constituted, by including (b) co-polymerized monomer A, co-polymerized monomer B And/or the copolymer that co-polymerized monomer C and the monomer component of co-polymerized monomer D and/or co-polymerized monomer E are constituted can also be made It is enumerated for particularly suitable illustration.
Linear or branched alkyl group (methyl) acrylate (co-polymerized monomer A) that carbon number as above-mentioned side chain is 4~18, Such as (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) third can be enumerated Enoic acid ter-butyl ester, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) propylene The own ester of acid, (methyl) cyclohexyl acrylate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) propylene Sour n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid T-butyl cyclohexyl methacrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (first Base) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid Cetyl, (methyl) stearyl acrylate, (methyl) isostearyl acrylate, (methyl) behenyl base ester, (first Base) isobornyl acrylate, 3,5,5- trimethyl-cyclohexanes (methyl) acrylate, (methyl) dicyclopentanyl acrylate, (first Base) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) benzyl acrylate etc..These can To use a kind or two or more be applied in combination.
Above-mentioned co-polymerized monomer A preferably comprises 30 mass % or more and 90 mass % in whole monomer components of copolymer Below, wherein further preferably more than 35 mass % or 88 mass % or less, wherein especially more than 40 mass % or 85 Contain in quality % ranges below.
As above-mentioned carboxyl group-containing monomer (co-polymerized monomer B), such as (methyl) acrylic acid, 2- (methyl) propylene can be enumerated Trimethylammonium hexahydrophthalic acid, 2- (methyl) acryloxypropyls hexahydrophthalic acid, 2- (methyl) acryloyl Oxygroup ethyl phthalic acid, 2- (methyl) acryloxypropyls phthalic acid, 2- (methyl) acryloyl-oxyethyl horse Come sour, 2- (methyl) acryloxypropyls maleic acid, 2- (methyl) acryloyl-oxyethyls succinic acid, 2- (methyl) acryloyl Oxygroup propyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid.These can combine one kind or two or more.It needs to illustrate , " (methyl) acrylic acid " is the meaning for including acrylic acid and methacrylic acid.Similarly " (methyl) acryloyl group " is packet Include the meaning of acryloyl group and methylacryloyl.
Above-mentioned co-polymerized monomer B in whole monomer components of copolymer containing 1.2 mass % or more and 15 mass % with Under, wherein from the viewpoint of obtaining excellent bonding physical property, preferably more than 1.5 mass % or 10 mass % or less, wherein Contain particularly preferably more than 2 mass % or in 8 mass % ranges below.
Above-mentioned macromonomer (co-polymerized monomer C) is when forming (methyl) acrylic compounds (co) polymer by polymerization The monomer that the carbon number of side chain is 20 or more.By using co-polymerized monomer C, so as to by (methyl) acrylic compounds (co) polymerization Graft copolymer is made in object.Therefore, can make to connect by the selection of the monomer other than co-polymerized monomer C and its, compounding ratio The main chain of graft copolymer and the characteristic variations of side chain.
As above-mentioned macromonomer (co-polymerized monomer C), preferably framework ingredient is by acrylic polymer or vinyl Based polymer is constituted.As the framework ingredient of macromonomer, such as above-mentioned co-polymerized monomer A, above-mentioned copolymerizable can be enumerated The substance gone out illustrated in monomer B, aftermentioned co-polymerized monomer D, aftermentioned co-polymerized monomer E etc., these can be used alone Or two or more can be applied in combination.
Macromonomer has radically polymerizable group group or hydroxyl, isocyanate group, epoxy group, carboxyl, amino, acyl The functional groups such as amido, mercapto.As macromonomer, preferably there is the radically polymerizable group that can be copolymerized with other monomers Group.One or two or more kinds can be contained in radically polymerizable group group, wherein being particularly preferably one kind.Macromonomer has In the case of functional group, one or two or more kinds of functional groups can be contained, wherein being particularly preferably one kind.In addition, freely Both any one can be contained in base polymerizable group and functional group, can also contain.
The number-average molecular weight of co-polymerized monomer C is preferably 500~20,000, is wherein preferably 800 or more or 8000 or less, it In preferably 1000 or more or 7000 or less.
Macromonomer suitable can use the monomer usually manufactured (for example, Toagosei Co., Ltd's macromolecular list Body etc.).
Above-mentioned co-polymerized monomer C preferably in whole monomer components of copolymer with 5 mass % or more and 30 mass % with Under, wherein 6 mass % or more or 25 mass % or less, be wherein especially 8 mass % or more or 20 mass % ranges below contain Have.
(methyl) acrylate (co-polymerized monomer D) that carbon number as above-mentioned side chain is 1~3, can enumerate (methyl) Methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate etc..These can be with It combines one kind or two or more.
Above-mentioned co-polymerized monomer D preferably comprises 0 mass % or more and 70 mass % in whole monomer components of copolymer Hereinafter, wherein further preferably more than 3 mass % or 65 mass % or less, wherein be especially 5 mass % or more or 60 matter Contain in amount % ranges below.
As above-mentioned hydroxyl monomer (co-polymerized monomer E), (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) can be enumerated (methyl) acrylic acid such as acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls Hydroxy alkyl esters.These can combine one kind or two or more.
Above-mentioned co-polymerized monomer E preferably comprises 0 mass % or more and 30 mass % in whole monomer components of copolymer Below, wherein further preferably more than 0 mass % or 25 mass % or less, wherein be especially 0 mass % or more or 20 matter Contain in amount % ranges below.
As above-mentioned other vinyl monomers (co-polymerized monomer F), can enumerate other than co-polymerized monomer A~E Compound with vinyl in the molecule.As such compound, intramolecular can be exemplified with amide groups, alkoxy alkane The functional monomer's class and (methyl) esters of acrylic acid of polyalkylene glycol two and vinyl acetate, propionic acid of Ji Deng functional groups The vinyl ester monomers such as vinyl acetate and vinyl laurate and styrene, chlorostyrene, 1-chloro-4-methyl-benzene, Alpha-Methyl benzene second The aromatic vinyl monomers such as alkene and other substituted phenylethylenes.These can combine one kind or two or more.
Above-mentioned co-polymerized monomer F preferably comprises 0 mass % or more and 30 mass % in whole monomer components of copolymer Hereinafter, especially further preferably more than 0 mass % or 25 mass % or less, wherein be especially 0 mass % or more or 20 matter Contain in amount % ranges below.
It, as needed can also be suitable for using maleic anhydride, itaconic anhydride etc. containing acid other than substance described in above-mentioned The monomer of anhydride group；(methyl) glycidyl acrylate, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid -3,4- rings Oxygen butyl ester etc. contains epoxy based monomers；(methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester etc. Amino-containing (methyl) acrylate monomer；(methyl) acrylamide, N- tertiary butyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide, diacetone The monomer containing amide groups or imide such as (methyl) acrylamide, maleic acid, maleimide；Ethenyl pyrrolidone The heterocycles such as ketone, vinylpyridine, vinyl carbazole system alkaline monomer etc..
As the most typical example of (methyl) acrylic compounds (co) polymer, such as (methyl) acrylic acid of sening as an envoy to can be enumerated 2- ethylhexyls, (methyl) 2-ethyl hexyl acrylate, (methyl) decyl acrylate, (methyl) isostearyl acrylate, (methyl) propylene The monomer components (a) such as acid butyl ester, (methyl) ethyl acrylate, (methyl) methyl acrylate and (methyl) propylene with carboxyl Acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxypropyls hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxypropyls phthalic acid, 2- (methyl) third Alkene trimethylammonium maleic acid, 2- (methyl) acryloxypropyls maleic acid, 2- (methyl) acryloyl-oxyethyls succinic acid, The monomer components (b) such as 2- (methyl) acryloxypropyls succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid with have (methyl) Hydroxyethyl Acrylate of machine functional group etc., (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) glycerol acrylate, monomethyl maleate, monomethyl itaconate, vinyl acetate, (methyl) glycidyl The monomers such as ester, (methyl) acrylamide, (methyl) acrylonitrile, fluorination (methyl) acrylate, organosilicon (methyl) acrylate (methyl) acrylate copolymer obtained from ingredient (c) copolymerization.
The matter average molecular weight of (methyl) acrylic compounds (co) polymer is preferably 100,000 or more and 1,500,000 or less, wherein excellent It is selected as 150,000 or more or 1,300,000 or less, is wherein particularly preferably 200,000 or more or 1,200,000 or less.
Want in the case of obtaining the high binding compositions of cohesive force, it is more big more the entanglement of strand can be passed through from molecular weight From the perspective of obtaining cohesive force, the matter average molecular weight of (methyl) acrylic compounds (co) polymer is preferably 700,000 or more and 150 Ten thousand or less, particularly 800,000 or more or 1,300,000 or less.On the other hand, it is desirable to obtain the high bonding group of mobility, stress retentivity In the case of closing object, matter average molecular weight is preferably 100,000 or more and 700,000 or less, particularly preferably 150,000 or more or 600,000 or less.
On the other hand, it is big due to being difficult with molecular weight in the case of solvent is not used when by moldings such as bonding sheets Polymer, therefore the matter average molecular weight of (methyl) acrylic compounds (co) polymer is preferably 100,000 or more and 700,000 or less, especially Preferably 150,000 or more or 600,000 or less, 200,000 or more or 500,000 or less are wherein particularly preferably.
(metal inhibitor)
This composition contains metal inhibitor.
As metal inhibitor, benzotriazole based compound, benzimidazole compound, benzothiazole chemical combination can be enumerated Object, other triazole derivatives etc..
As metal inhibitor, it is generally desirable to, it is preferably selected from benzotriazole based compound, 1,2,3-triazoles and 1,2,4- It is more than any one of triazole.Wherein, also excellent from the resistance to foaming reliability other than corrosion inhibition for metal, as bonding sheet Aspect is set out, preferably 1,2,3-triazoles, 1, the triazole derivatives such as 2,4- triazoles, particularly preferred 1,2,3-triazoles.It is because speculating Its reason is that the molecule that copper atom and triazole are formed on the conductive pattern surface formed by the metal material comprising copper carries out chemistry Epithelium is protected made of bonding, so as to prevent from corroding.In addition, with the conductor figure formed by the metal material comprising silver In the conductive member of case, the effect of the protection epithelium brought by triazole equally can be also played.
It should be noted that the solid that it is about 120 DEG C that 1,2,4- triazole, which is fusing point, and the fusing point of 1,2,3-triazoles is about 20 DEG C, substantially liquid condition at room temperature.Therefore, with 1,2,4- triazoles are compared, and 1,2,3-triazoles mixes in adhesive composition When conjunction dispersibility it is excellent, can equably mix, in addition, having the advantages that easy masterbatch etc. is excellent.
In this composition, from the exudation of metal inhibitor, the viewpoints such as effect of corrosion inhibition for metal, metal inhibitor phase For 100 mass parts of (methyl) acrylic compounds (co) polymer preferably with more than 0.01 mass parts and 5 ratios below mass part Contain, wherein still more preferably with more than 0.1 mass parts or more than 1 below mass part, especially 0.2 mass parts or 0.5 mass Part ratio below contains.
It should be noted that metal inhibitor of more than two kinds can also be applied in combination in this composition.Specifically, can 1,2,3- triazoles and 1,2,4- triazoles is applied in combination.Furthermore it is possible to benzotriazole based compound and 1 is applied in combination, 2,3- tri- Azoles and/or 1,2,4- triazoles.
(bi-ester of phosphite)
This composition contains bi-ester of phosphite.
Bi-ester of phosphite not only its own do not have corrosivity, additionally it is possible to make the sour components such as carboxyl stabilize.Therefore, By being compounded bi-ester of phosphite, this combination in this composition comprising defined (methyl) acrylic compounds (co) polymer Even if object can prevent the oxidative degradation of the conductive member as adherend if containing sour component, in this composition without containing acid In the case of ingredient needless to say, the oxidative degradation of the conductive member as adherend can be prevented.
Therefore, when forming bonding sheet by this composition containing bi-ester of phosphite, have (typical to conductive member It is with the transparency conducting layer comprising ITO and/or the conductive member of the conductive pattern by being formed comprising copper, silver-colored metal material) Corrosion Resistant Reliability, and the oxidative degradation of conductive member can be prevented.Therefore, it is possible to function properly as example with touch The bonding sheet of the device used for image display of panel.
The bi-ester of phosphite contained in this composition is not limited.Wherein, preferably sub- shown in following formula (1) Phosphate compound.
Formula (1) P [- OR]3
(R in formula is hydrocarbon, specifically, substituted or non-substituted aromatic series, cycloaliphatic ring and alkyl etc. can be enumerated.Multiple R Can be mutually the same, it can also be different, adjacent multiple R can bond together and form saturated or unsaturated ring structure.)
Furthermore it is possible to for the compound of structural unit shown in the above-mentioned formula (1) comprising 2 or more.
It is compounded in this composition comprising defined (methyl) acrylic compounds (co) polymer and metal inhibitor above-mentioned Various bi-ester of phosphite shown in formula (1) as a result confirm arbitrary bi-ester of phosphite and all show anti-oxidant deterioration Effect especially confirms excellent to the anti-oxidant degradation effects of the transparency conducting layer comprising ITO.
As the bi-ester of phosphite that this composition contains, such as triphenyl phosphite, three nonyl of phosphorous acid can be enumerated Base phenyl ester, tricresyl phosphite, three stearyl ester of phosphorous acid, triethyl phosphite, phosphorous acid three (2- ethylhexyls) ester, phosphorous Sour three last of the ten Heavenly stems esters, trilauryl phosphite, phosphorous acid three (tridecyl) ester, trioleyl phosphite, phosphorous acid diphenyl (2- ethyls Hexyl) ester, phosphorous acid diphenyl list last of the ten Heavenly stems ester, phosphorous acid diphenyl list (tridecyl) ester, tetraphenyl dipropylene dipropylene glycol Diphosphites, four phosphite ester of tetraphenyl four (tridecyl) pentaerythrite, four (C12~C15 alkyl) -4,4- isopropylidenes Diphenyl diphosphites, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous acid three (4- nonyls phenyl) ester, 3,9- are bis- Four oxa- -3,9- of (Nonylphenoxy) -2,4,8,10- two phospha spiral shell [5,5] hendecane, 3,9- bis- (4- Nonylphenoxies) -2, The bis- four oxa- -3,9- two of (decyl oxygroup) -2,4,8,10- of tetra- oxa- -3,9- of 4,8,10- two phospha spiral shell [5,5] hendecane, 3,9- Phospha spiral shell [5,5] hendecane, four oxa- -3,9- of bis- (tridecyl the oxygroup) -2,4,8,10- of 3,9-, two phospha spiral shells [5,5] 11 Four oxa- -3,9- of bis- (stearyl the oxygroup) -2,4,8,10- of alkane, 3,9-, two phospha spiral shell [5,5] hendecanes, bis- (bis- uncles of 2,6- of 3,9- Butyl -4- methylphenoxies) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [5,5] hendecane, bis- (the bis- tertiary fourths of 2,4- of 3,9- Phenoxyl) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [5,5] hendecane, bis- { bis- (the 1- methyl-1s-phenyl of 2,4- of 3,9- Ethyl) phenoxy group four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [5,5] hendecane, 2,2 '-di-2-ethylhexylphosphine oxides (bis- tertiary fourths of 4,6- Base -1- phenyl oxygroup) phosphite ester, 4,4 '-isopropylidene xenol C12-15 alcohol phosphite esters, distearyl pentaerythrite two Phosphite ester, 2,4,8,10- tetra- (1,1- dimethyl ethyls) -6- { (2- ethylhexyls) oxygroup } -12H- dibenzo [d, g] [1, 3,2] dioxy phospha cyclooctane, 2,4,8,10- tetra- (1,1- dimethyl ethyls) -6- (tridecyl oxygroup) -12H- dibenzo [d, G] [1,3,2] dioxy phospha cyclooctane, 1,1 '-biphenyl -4,4 '-diyl bis- [bis- (2,4- di-tert-butyl-phenyls) esters of phosphorous acid], Hydrogenated bisphenol A pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, diethyl phosphite, phosphorous acid Bis- (2- ethylhexyls) esters, phosphorous acid dilauryl, two grease of phosphorous acid, diphenyl phosphite etc..
Wherein, the bi-ester of phosphite contained as this composition, if such as consider with the compatibility of this composition, Preferred aliphat phosphite ester is (for example, phosphorous acid tridecane base ester, the embodiment 3 as bi-ester of phosphite of embodiment 2 Four oxa- -3,9- of bis- (decyl the oxygroup) -2,4,8,10- of 3,9-, two phospha spiral shell [5.5] hendecanes etc.).If in addition, considering water-fast Xie Xing, then optimization aromatic phosphite ester is (for example, (2,4- bis- uncles of phosphorous acid three as bi-ester of phosphite of embodiment 1 Butyl phenyl) ester etc.).In addition, if it is considered that the balance of dissolubility and hydrolytic resistance, then preferred phosphorous acid diphenyl list (13 Alkyl) ester etc. has both the phosphite ester of aliphatic ester group and aromatic series ester group.
In this composition, for the content ratio of bi-ester of phosphite, from can more effectively inhibit the conductive structure such as ITO From the perspective of the oxidative degradation of part is without damaging bond properties, relative to 100 mass of (methyl) acrylic compounds (co) polymer Part, bi-ester of phosphite is preferably with 0.0001 (1 × 10-4) more than mass parts and 2.0 ratios below mass part contain, especially Still more preferably with more than 0.0005 mass parts or more than 0.8 below mass part, especially 0.001 mass parts or 0.7 mass parts Below, particularly more than 0.01 mass parts or 0.6 ratio below mass part contains.
(crosslinking agent)
This composition can include crosslinking agent as needed.
For example, as the crosslinked method of above-mentioned (methyl) acrylic compounds (co) polymer is made, can enumerate addition can with lead Enter to the crosslinking agent of hydroxyl, the bonding of carboxyl isoreactivity group chemical in (methyl) acrylic compounds (co) polymer, by adding The method that heat, curing are reacted；Add multifunctional (methyl) with 2 or more (methyl) acryloyl groups as crosslinking agent The reaction initiators such as acrylate and Photoepolymerizationinitiater initiater carry out crosslinked method by ultraviolet light irradiation etc..Wherein, from can Maintain the high cohesion from polar component, bonding physical property without consuming the carboxyl isopolarity function in this composition because of reaction From the perspective of group, preferably by the cross-linking method of the light such as ultraviolet light irradiation.
As above-mentioned crosslinking agent, for example, can enumerate with selected from (methyl) acryloyl group, epoxy group, isocyanate group, Carboxyl, hydroxyl, carbodiimide, oxazolinyls, '-aziridino, vinyl, amino, imino group, amide groups, N- substitutions (methyl) The crosslinking agent of at least one kind of cross-linking functional group in acrylamido, alkoxysilyl, can use a kind or combine makes Use two or more.It should be noted that the blocking group protection that cross-linking functional group can be deprotected.
Wherein, from the viewpoint of the easiness of the control of cross-linking reaction, preferred multifunctional (methyl) acrylate.
As such multifunctional (methyl) acrylate, it can be cited for example that 1,4-butanediol two (methyl) acrylic acid Ester, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, polyalkylene glycol two (methyl) Acrylate, neopentyl glycol two (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite three (methyl) acrylic acid Ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) propylene The ultraviolet hardenings such as acid esters, trimethylolpropane tris (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters Polyfunctional monomer class in addition to this can also enumerate polyester (methyl) acrylate, epoxy (methyl) acrylate, amino The oligomeric species of multifunctional acrylic compounds, the multifunctional acryloyls such as formic acid esters (methyl) acrylate, polyethers (methyl) acrylate Amine etc..
In addition, as the crosslinking agent with cross-linking functional group of more than two kinds, such as the contracting of (methyl) acrylic acid can be enumerated Water glyceride, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid -3,4- epoxies butyl ester, (methyl) acrylic acid 4- hydroxyls Butyl ester glycidol ether etc. contains epoxy based monomers；(methyl) acrylic acid 2- isocyanato ethyls, 2- (2- (methyl) acryloyl-oxies Base ethyl oxygroup) ethyl isocyanate, (methyl) acrylic acid 2- (O- [1 '-methyl propylidene base amino] carboxyamino) ethyl ester, 2- [(3,5- dimethyl pyrazoles oxazolyl) carbonylamino] ethyl (methyl) acrylate etc. contains isocyanate group or blocked isocyanate The monomer of base；Vinyltrimethoxysilane, vinyltriethoxysilane, 3- glycidoxypropyltrime,hoxysilanes, 3- (methyl) acryloxypropyls diethoxy silane, 3- (methyl) acryloxypropyls triethoxysilane, N- The various silane such as 2- (amino-ethyl) -3- aminopropylmethyldimethoxysilanes, 3- isocyanate propyl triethoxysilanes Coupling agent.
For the crosslinking agent with cross-linking functional group of more than two kinds, may be used makes a kind of functional group and (methyl) third The reaction of olefin(e) acid class (co) polymer is thus structure made of being bonded with (methyl) acrylic compounds (co) polymer.By using in this way Structure, the cross-linking functional group of such as double bonds such as (methyl) acryloyl group, vinyl can be made to be chemically bound in (methyl) Acrylic compounds (co) polymer.In addition, by making crosslinking agent be bonded with (methyl) acrylic compounds (co) polymer, it can to have Inhibit crosslinking agent exudation, can inhibit this bonding sheet unexpected plasticized tendency.In addition, by make crosslinking agent with (methyl) acrylic compounds (co) polymer is bonded, and is promoted to the reaction efficiency of photo-crosslinking, therefore have and can obtain The tendency of the higher solidfied material of cohesive force.
This composition can also contain the monofunctional monomer reacted with the cross-linking functional group of crosslinking agent.As such list Functional monomer, such as (methyl) alkyl acrylate such as can enumerate methyl acrylate；(methyl) Hydroxyethyl Acrylate, (first Base) hydroxyls such as hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, polyalkylene glycol (methyl) acrylate (methyl) acrylate；(methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) propylene Acryloxypropylethoxysilane hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxy Ethyl maleic acid, 2- (methyl) acryloxypropyls maleic acid, 2- (methyl) acryloyl-oxyethyls succinic acid, 2- (methyl) The carboxyl group-containing monomers such as acryloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid；Maleic anhydride, itaconic acid The monomer containing anhydride group such as acid anhydride；The ether-containings such as (methyl) tetrahydrofurfuryl acrylate, methoxy poly (ethylene glycol) (methyl) acrylate Base (methyl) acrylate；(methyl) acrylamide, dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, (first Base) acryloyl morpholine, isopropyl (methyl) acrylamide, dimethylaminopropyl (methyl) acrylamide, phenyl (methyl) (methyl) acryloyls such as acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide Amine system monomer etc..
Wherein, it is preferable to use containing hydroxyl from the viewpoint of improving the adaptation to adherend, inhibiting the effect of damp and hot albefaction (methyl) acrylate, (methyl) acrylamide monomer of base.
For the content of crosslinking agent, from the viewpoint of the flexibility and cohesion dynamic balance that make this composition, relative to preceding 100 mass parts of (methyl) acrylic compounds (co) polymer are stated, are preferably matched with 0.01 or more and 10 ratios below mass part It is mixed, wherein more than particularly preferably 0.05 mass parts or more than 8 below mass part, especially 0.1 mass parts or 5 mass parts with Under.
It should be noted that in the case that this bonding sheet is multilayer, in the layer for constituting bonding sheet, for middle layer, conduct The content of the layer of base material, crosslinking agent can be more than above range.Containing for middle layer, as the crosslinking agent in the layer of base material Amount, it is preferably below mass part with 0.01 or more and 40 relative to aforementioned 100 mass parts of (methyl) acrylic compounds (co) polymer Ratio is compounded, wherein more than particularly preferably 1 mass parts or more than 30 below mass part, especially 2 mass parts or 25 mass Part or less.
(Photoepolymerizationinitiater initiater)
Carry out based on light irradiate it is crosslinked in the case of, preferably comprise Photoepolymerizationinitiater initiater.
Free radical mechanism of production based on Photoepolymerizationinitiater initiater is broadly divided into 2 classes, and having makes the singly-bound of itself crack and decompose α cracking types to generate free radicals and make the hydrogen-abstraction that hydrogen is excited and generated free radicals from the compound in system.These are worked as In it is preferable to use hydrogen-abstraction photo-crosslinking initiators.
Wherein, in the case of using the organic system crosslinking agent with (methyl) acryloyl group as crosslinking agent, particularly preferably Also add Photoepolymerizationinitiater initiater.This is because being generated free radicals by light irradiation, to rising as the polymerisation in system Point.
Photoepolymerizationinitiater initiater suitable can use presently known Photoepolymerizationinitiater initiater.Wherein, from the control of cross-linking reaction Easiness from the perspective of, to wavelength 380nm ultraviolet lights below induction Photoepolymerizationinitiater initiater be preferred.
On the other hand, in terms of obtaining high photoreactivity and the light of induction is accessible to the deep of this bonding sheet The Photoepolymerizationinitiater initiater of aspect, pair photoinduction that wavelength is grown compared with wavelength 380nm is preferred.
Photoepolymerizationinitiater initiater is broadly divided into 2 classes according to free radical mechanism of production, and being roughly divided into makes Photoepolymerizationinitiater initiater certainly The cracking type Photoepolymerizationinitiater initiater so as to generate free radicals is decomposed in the singly-bound cracking of body；With through light activated initiator and body Hydrogen donor in system forms exciplex, can be by the hydrogen-abstraction Photoepolymerizationinitiater initiater of the hydrogen migration of hydrogen donor.
Cracking type Photoepolymerizationinitiater initiater in these becomes anotherization by being decomposed when light irradiation generates free radicals Object is closed, once being excited, then becomes the function of not having as cross-linked evocating agent.Therefore, bonding after cross-linking reaction It will not be remained as reactive species in material, it is impossible to bring unexpected light deterioration etc. to jointing material, therefore preferably.
On the other hand, hydrogen-abstraction Photoepolymerizationinitiater initiater is occurred in the free radical irradiated based on ultraviolet light isoreactivity energy-ray When reaction, decomposition product as cracking type Photoepolymerizationinitiater initiater not will produce, therefore be difficult to become volatilization after the completion of reaction Ingredient is useful in terms of it can reduce to the damage of adherend.
As preceding cleavage type Photoepolymerizationinitiater initiater, in the irritability height to light and after the reaction as decomposition product And the aspect of colour killing, preferably bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, 2,4,6- trimethyl benzoyl diphenyls Base phosphine oxide, (2,4,6- trimethylbenzoyls) ethoxyl phenenyl phosphine oxide, bis- (2,6- Dimethoxybenzoyls) 2,4, The acylphosphine oxides such as 4- trimethylpentylphosphine oxides system Photoepolymerizationinitiater initiater.
As aforementioned hydrogen-abstraction Photoepolymerizationinitiater initiater, such as benzophenone, 4- methyl-benzophenones, 2,4 can be enumerated, 6- tri-methyl benzophenones, 4- phenyl benzophenones, 3,3 '-dimethyl -4- methoxy benzophenones, 4- (methyl) acryloyl-oxy Base benzophenone, 4- [2- ((methyl) acryloxy) ethyoxyl] benzophenone, 4- (methyl) acryloxy -4 '-methoxy Base benzophenone, 2- benzoyls methyl benzoate, methyl benzoylformate, bis- (2- phenyl -2- Oxoacetic Acids) oxygen are double sub- Ethylene, 4- (five oxo tridecyls of 1,3- acryloyl groups -1,4,7,10,13-) benzophenone, thioxanthones, 2-chlorothioxanthone, 3- Methyl thioxanthones, 2,4- dimethyl thioxanthones, anthraquinone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tertiary butyls anthraquinone, 2- amino anthracenes Quinone, camphorquinone, its derivative etc..
In these, preferably benzophenone, 4- methyl-benzophenones, 2,4,6- tri-methyl benzophenones, 4- phenyl hexichol Ketone, 3,3 '-dimethyl -4- methoxy benzophenones, 4- (methyl) acryloxybenzophenone, 4- [2- ((methyl) propylene Acyloxy) ethyoxyl] benzophenone, 4- (methyl) acryloxies -4 '-methoxy benzophenone, 2- benzoyl benzoic acid Methyl esters, methyl benzoylformate.
It should be noted that the Photoepolymerizationinitiater initiater enumerated among the above can use any one or derivatives thereof, also may be used It is used so that these are combined two or more.
In turn, other than Photoepolymerizationinitiater initiater, sensitizer can also be used.It as sensitizer, is not particularly limited, only To be the sensitizer used in Photoepolymerizationinitiater initiater, so that it may which with there is no problem, ground uses.Such as aromatic amine can be enumerated, anthracene spreads out Biology, anthraquinone derivative, coumarin derivative, thioxanthone derivates, phthalocyanine derivates etc., benzophenone, xanthone, thioxanthene The aromatic ketones and their derivative etc. such as ketone, michaelis ketone, 9,10- phenanthrenequione.
It should be noted that Photoepolymerizationinitiater initiater, sensitizer can be to be bonded with (methyl) acrylic compounds (co) polymer State include.It, can as the method for making Photoepolymerizationinitiater initiater, sensitizer are bonded with (methyl) acrylic compounds (co) polymer With using same method of aforementioned the case where making crosslinking agent be bonded with (methyl) acrylic compounds (co) polymer.
The content of Photoepolymerizationinitiater initiater is not particularly limited, it is (total) poly- relative to (methyl) acrylic compounds for typical Close 100 mass parts of object, particularly preferably with it is more than 0.1 or more and 10 below mass part, especially 0.2 mass parts or it is 5 below mass part, More than especially 0.5 mass parts or 3 ratios below mass part are adjusted.But under the balance of other elements, can also More than the range.
(antioxidant)
In addition to the foregoing, this composition can also contain antioxidant as needed.
As antioxidant, such as 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols), hexa-methylene can be enumerated Glycol-bis- (3,5- di-t-butyl -4- hydroxy hydrocinnamates), four (methylene (3,5- di-t-butyl -4- hydroxy group meat Cinnamic acid ester)) methane, the bis- -3- of triethylene glycol-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester, trimethyl -2 1,3,5-, 4,6- tri- (3,5- di-t-butyl -4- Hydroxy-benzvls) benzene, n-octadecane base -3- (4 '-hydroxyls -3 ', 5 '-DI-tert-butylphenol compounds) Propionic ester, 4,4 '-methylene-bis(2,6-di-t-butyl phenol)s, 4,4 '-butanes-bis--(6- tertiary butyl -3- methyl-phenols) Etc. the various antioxidants such as hindered phenolics antioxidant, sulphur system, amine system.
(other ingredients)
In turn, this composition suitable can also contain the well known ingredient being compounded in common adhesive composition.For example, Can suitable for containing Photostabilised dose, ultra-violet absorber, metal deactivator, antirust agent (except metal inhibitor above-mentioned), Antiaging agent, antistatic agent, hygroscopic agent, foaming agent, antifoaming agent, inorganic particle, viscosity modifier, tackifying resin, photosensitizer, The various additives such as fluorescer, catalysts (tertiary amine based compound, quaternary ammonium based compound, tin laurate compound etc.).
(adjustment of adhesive composition)
The adhesive composition (this composition) used in this bonding sheet can be by (total) poly- by (methyl) acrylic compounds It closes object, metal inhibitor and bi-ester of phosphite and other ingredients as needed is mixed respectively with specified amount to obtain .
It as their mixed method, is not particularly limited, the order by merging of each ingredient is also not particularly limited.Separately Outside, heat treatment procedure can be added when this composition manufactures, in this case, it is generally desirable in advance by each ingredient of this composition It is heat-treated after mixing.It can use and various blending constituent is concentrated and carries out masterbatch and winner.
In addition, device when being mixed is it is not also specifically limited, can be used for example omnipotent kneading machine, planet mixing Machine, Banbury mixer, kneader, frame mixing machine (gate mixer), pressure kneader, three-roller, two roller machines.According to need It wants to mix using solvent.In addition, this composition can be used in the form of not solvent-laden solvent-free system.By with The form of solvent-free system uses, and can have that solvent does not remain and heat resistance and light resistance improve such advantage.
In turn, for this composition, be made in advance containing constitute (methyl) acrylic compounds (co) polymer monomer component, The composition of 1,2,3-triazoles, Photoepolymerizationinitiater initiater and other any ingredients, and used with bonding sheet as conductive member When, it can also be come in a manner of carrying out light irradiation and it is made to carry out polymerisation to generate (methyl) acrylic compounds (co) polymer It uses.
<The form of conductive member bonding sheet>
It, can be in addition to this composition to be directly coated to adherend, is formed other than sheet carrys out use for this bonding sheet It is used in the form of being shaped to the bonding sheet with mould release film of sheet of single-layer or multi-layer on mould release film.
As the material of the mould release film, for example, can enumerate polyester film, polyolefin film, polycarbonate film, Polystyrene film, acrylic film, triacetylcellulose film, fluorine resin film etc..In these, particularly preferred polyester Film and polyolefin film.
The thickness of mould release film is not particularly limited.Wherein, from the viewpoint of such as processability and treatability, preferably 25 μm~500 μm, especially further preferably 38 μm or more or 250 μm or less, in particular 50 μm or more or 200 μm or less.
It should be noted that this bonding sheet can also use as described above by this composition direct extrusion molding without Use adherend, the method for mould release film, molding method by injecting in mold.It in turn, can also be by the way that this be combined Object is filled directly into the form that bonding sheet is formed between the components such as conductive member.
<The physical property of conductive member bonding sheet>
(to the anticorrosion ability of the conductive layer of conductive member)
This bonding sheet has to conductive member, especially transparency conducting layer, the conductor figure formed by the metal material comprising copper The anticorrosive property of case.Therefore, it is possible to make change rate [((Ω/Ω of the ITO resistance values measured by the methods of following (1)~(2) 0) -1) × 100] less than 5%, especially less than 3%.In addition, the copper resistance that the method by following (3)~(4) can be made to measure The change rate [((Ω/Ω 0) -1) × 100] of value less than 20%, especially less than 10% and then less than 5%, particularly less than 3%.
(1) make conductive member adhesive composition (this composition) film forming that bonding be made for the sheet of 150 μm of thickness Piece makes aforementioned adhesion piece fit in evaluation ITO made of the ITO wirings comprising indium oxide (ITO) are formed on glass substrate Glass substrate makes the ITO wirings with bonding sheet.
(2) resistance value (Ω 0) of the ITO wirings in the ITO wirings of measured in advance aforementioned strip bonding sheet at room temperature, 65 The ITO that aforementioned strip bonding sheet is taken care of under DEG C 90%RH environment is connected up 500 hours, in the ITO wirings of aforementioned strip bonding sheet Resistance value (Ω) after the aforementioned keeping of ITO wirings is measured.
(3) make conductive member adhesive composition (this composition) film forming that bonding be made for the sheet of 150 μm of thickness Piece makes aforementioned adhesion piece fit in evaluation copper glass substrate made of thin copper film is formed on glass substrate, makes band bonding The thin copper film of piece.
(4) resistance value (Ω 0) of the thin copper film in the thin copper film of measured in advance aforementioned strip bonding sheet at room temperature, 65 The thin copper film of aforementioned strip bonding sheet is taken care of under DEG C 90%RH environment 500 hours, to the copper in the thin copper film of aforementioned strip bonding sheet Resistance value (Ω) after the aforementioned keeping of wiring is measured.
(transparency)
This bonding sheet is preferably optically transparent.That is, preferably transparent pressure-sensitive adhesive sheet.Herein, " optically transparent " refers to total Light transmittance is 80% or more, preferably 85% or more, more preferable 90% or more.
(thickness)
The thickness of this bonding sheet is preferably 10 μm or more and 500 μm or less, be especially more preferably 15 μm or more or 400 μm with Under, wherein especially further preferably 20 μm or more or 350 μm or less.
<The purposes of conductive member bonding sheet>
This bonding sheet is suitble to for example make personal computer, mobile terminal (PDA), game machine, television set (TV), vehicle mounted guidance The image display devices such as system, touch panel, hand-written tablet, such as plasma scope (PDP), liquid crystal display (LCD), Organic el display (OLED), inorganic EL display, electrophoretic display device (EPD) (EPD), interference modified tone display (IMOD) etc. use Each member of formation in the image display device of image display panel, especially conductive member, especially have transparency conducting layer and/or by Include the conductive member fitting for the conductive pattern that the metal material of copper is formed.In addition, being also suitable for making transparent comprising ITO or IGZO Conductive layer and/or conductive member fitting with the transparency conducting layer of conductive pattern formed by the metal material comprising copper, silver.
<Conductive member laminated body>
The conductive member laminated body of the present invention (is known as " this laminated body " hereinafter, also omitting.) can be by making this bonding sheet It is bonded with the conductor planes of conductive member such as transparency conducting layer to obtain.
As long as this laminated body has the conductor planes of at least any one the adhesive level and transparency conducting layer of this bonding sheet It is constituted made of fitting.
In the case that this bonding sheet is double-sided adhesive sheet, this laminated body can be with two adhesive levels of this bonding sheet It is constituted made of being bonded with the conductor planes of transparency conducting layer.
Above-mentioned transparency conducting layer can be formed in a manner of the conductor planes for covering its conductive film to be polymerize based on olefin-based Object, carbamate based polymer, epoxy based polymer, acrylic polymer, silicon-type polymer or unorganic glass etc. Insulating protective film (passivating film).
This laminated body obtained from being bonded with conductor planes can be suitable for touch panel.As touch panel, can arrange Enumerate the touch panel of the modes such as resistive film mode, electrostatic capacity, electromagnetic induction method, preferably electrostatic capacity.
As above-mentioned transparency conducting layer, if at least the surface layer of single side have conductive layer, can enumerate by vapor deposition, The transparency conducting layer made of the surface layer of transparent base setting conductive materials such as sputtering, coating.
The conductive materials used in the conductive layer of transparency conducting layer are not particularly limited.Specifically, in addition to indium oxide, Other than the metal oxides such as indium gallium zinc composite oxide, tin-doped indium oxide (ITO), zinc oxide, gallium oxide, titanium oxide, The metal materials such as silver, copper, molybdenum, aluminium can also be enumerated.Wherein, be suitble to using transparent excellent, tin-doped indium oxide (ITO) and Indium gallium zinc composite oxide (IGZO).In addition, from the viewpoint of excellent electric conductivity, copper, silver can also be suitble to use.
The base material that pattern formation is carried out as conductive materials in the transparent conductive layer, is not particularly limited, can enumerate glass Glass, resin film etc..
At least there is conductive layer on the surface layer of single side for transparency conducting layer typical case.In addition, for typical case, in electrically conducting transparent Layer forms the conductive pattern (wiring pattern) for principal component with copper, silver in a manner of around peripheral portion.Since 1,2,3- triazoles are outstanding It is high to the Corrosion Resistant Reliability of copper, therefore includes that its this bonding sheet can be particularly suitable for having by the metal comprising copper The conductive member for the conductive pattern that material is formed.
As the concrete example of other laminated bodies, such as mould release film/this bonding sheet/touch panel, demoulding can be enumerated Film/this bonding sheet/protection panels, mould release film/this bonding sheet/image display panel, image display panel/this bonding sheet/ Touch panel, image display panel/this bonding sheet/protection panels, image display panel/this bonding sheet/touch panel/this bonding Piece/protection panels, polarizing film/this bonding sheet/touch panel, polarizing film/this bonding sheet/touch panel/this bonding sheet/guarantor The compositions such as protection slab.In addition, can enumerate in above-mentioned composition, this bonding sheet with and its adjacent touch panel, protection Whole compositions of conductive layer above-mentioned are inserted between the components such as panel, image display panel, polarizing film.But it does not limit In these stacking examples.
It should be noted that above-mentioned touch panel also includes to make structure in protection panels in touch panel function, make In the structure of touch panel function in image display panel.
<Image display device>
The image display device of the present invention (is known as " present apparatus " hereinafter, also omitting.) at least have this laminated body, image aobvious Show panel and surface protection panel as member of formation.
More specifically, can enumerate between image display panel and surface protection panel inserted with make this bonding sheet with The image display device of the composition of this laminated body obtained from the conductor planes fitting of transparency conducting layer.At this point, being shown in image Panel side can also use this bonding sheet.
As the material of surface protection panel, other than glass, or acrylic resin, polycarbonate-based tree The ester ring types such as fat, cyclic olefin polymer polyolefin-based resins, phenylethylene resin series, polyvinyl chloride resin, phenolic resin, trimerization The plastics such as cyanamide system resin, epoxy system resin.
Image display panel is by other optical thin films such as polarizing film and phase-contrast film, liquid crystal material and backlight system System constitute (this usual composition or bonding article are optical thin film to the sticky surface of image display panel.), according to liquid crystal material The control mode of material has STN modes, VA modes, IPS modes etc., can be any way.
As this image display device, may be constructed for example liquid crystal display, organic el display, inorganic EL display, The image display devices such as Electronic Paper, plasma scope and MEMS (MEMS) display.
<The explanation of sentence>
In the case of in this specification, being expressed as " X~Y " (X, Y are Any Digit), unless otherwise specified, then wrap Meaning containing " X or more and Y or less " and the also meaning comprising " preferably greater than X " or " preferably smaller than Y ".
In addition, in the case of being expressed as " X or more " (X is Any Digit) or " Y or less " (Y is Any Digit), also include The intention of " preferably greater than X " or " preferably less than Y ".
Usually refer to thin, its thickness very little and flat product compared with length and width in the definition of " piece " in JIS, Usually " film " refers to the thin flat product that thickness is minimum compared with length and width, maximum gauge is arbitrarily limited, and refers to The product (Japanese Industrial Standards JISK6900) being usually supplied in the form of volume.But the boundary of piece and film is indefinite, In the present invention, due to need not differentiate the two on term, in the present invention, referred to as also include in the case of " film " " piece " also includes " film " referred to as in the case of " piece ".
[embodiment]
Hereinafter, being illustrated in more details by Examples and Comparative Examples.But the present invention is not limited to these implementations Example.
[embodiment 1]
Relative to by 4 mass parts shape of 76 mass parts of 2-EHA, 20 mass parts of vinyl acetate and acrylic acid At copolymer (A-1, matter average molecular weight 400,000) 1kg, add pentaerythritol propoxylate polyacrylate as crosslinking agent (villages Xin Zhong chemical industry Co. Ltd. system, trade name " ATM-4PL ") 200g and the 4- methyldiphenyls as Photoepolymerizationinitiater initiater Ketone and 2, mixture (Lamberti corporations, trade name " Esacure TZT ") 10g of 4,6- tri-methyl benzophenones, into Row uniformly mixing, obtains middle layer resin combination.
With release-treated 2 pet films (Mitsubishi Plastics, Inc. system, Trade name " Diafoil MRF ", 75 μm of thickness and Mitsubishi Plastics, Inc. system, trade name " Diafoil 38 μm of MRT ", thickness) clip middle layer resin combination, by the thickness of bonding sheet become 80 μm in the way of figuration as sheet, Middle layer is made with resin sheet (α).
Relative to foregoing acrylates copolymer (A-1) 1kg, add the 1,2,3-triazoles 1.5g as metal inhibitor, Phosphorous acid three (2,4- di-tert-butyl-phenyls) ester (BASF AG's system, trade name " Irgafos as bi-ester of phosphite 168 ") mixture of 5g and 4- methyl benzophenones and 2,4,6- tri-methyl benzophenones as Photoepolymerizationinitiater initiater (Lamberti corporations, trade name " Esacure TZT ") 15g, is uniformly mixed, obtains adhesive phase resin combination Object.
With release-treated 2 pet films (Mitsubishi Plastics, Inc. system, Trade name " Diafoil MRV ", 100 μm of thickness and Mitsubishi Plastics, Inc. system, trade name " Diafoil 38 μm of MRT ", thickness) aforementioned adhesion oxidant layer resin combination is clipped, figuration is in such a way that the thickness of bonding sheet becomes 35 μm Sheet makes adhesive phase with resin sheet (β).
In turn, with release-treated 2 pet films (MitsubishiPlastics, Inc. system, trade name " Diafoil MRQ ", 75 μm of thickness and Mitsubishi Plastics, Inc. system, trade name 38 μm of " Diafoil MRT ", thickness) aforementioned adhesion oxidant layer oil/fat composition is clipped, 35 μ m thicks are become with the thickness of bonding sheet Mode figuration be sheet, make adhesive phase with resin sheet (β ').
Aforementioned middle layer is removed into removal successively with the PET film of the both sides of piece (α), and by adhesive phase resin sheet The PET film of the side of (β) and (β ') is removed, and the adhesive surface of exposing is fitted in two surfaces of middle layer piece (β) successively, is made Make the laminated body being made of (β)/(α)/(β ').
PET film across the surface for remaining on aforementioned (β) and (β '), is become with the accumulated light of wavelength 365nm 2000mJ/cm2Mode high voltage mercury lamp radiation ultraviolet light, make (α), (β) and (β ') carry out ultraviolet-crosslinkable, make bonding sheet Laminated body 1 (150 μm of thickness).Following various evaluations are carried out to the bonding laminate 1.As a result shown in table 1.
[embodiment 2]
It is formed relative to by 81 mass parts of butyl acrylate, 15 mass parts of methyl methacrylate and 4 mass parts of acrylic acid Copolymer (A-2, matter average molecular weight 200,000) 1kg, addition as the 1,2,3-triazoles 3g of metal inhibitor, as phosphite ester Phosphorous acid tridecane base ester (ADEKACorporation systems, trade name " ADK STAB 3010 ") 3g of compound, as crosslinking The pentaerythritol triacrylate and pentaerythritol tetraacrylate (Toagosei Co., Ltd's system, " ARONIX M-306 ") of agent 20g and 1- hydroxy-cyciohexyls phenyl ketone (BASF AG's system, Irgacure184) 10g as Photoepolymerizationinitiater initiater is carried out Uniformly mixing, obtains adhesive phase resin combination.
Then, make aforementioned adhesion oxidant layer resin combination in release-treated polyethylene terephthalate film It is molded in such a way that thickness becomes 150 μm on (Mitsubishi Plastics, Inc. system, Diafoil MRV, 100 μm of thickness) After sheet, covering release-treated polyethylene terephthalate film (Mitsubishi Plastics, Inc. system, Trade name " Diafoil MRQ ", 75 μm of thickness).Across release-treated polyethylene terephthalate film, with wavelength The accumulated light of 365nm becomes 1000mJ/cm2Mode high voltage mercury lamp radiation ultraviolet light, make adhesive phase resin combination Object carries out ultraviolet-crosslinkable, makes bonding laminate 2.Following various evaluations are carried out to the bonding laminate 2.As a result show In table 1.
[embodiment 3]
As bi-ester of phosphite, 3,9- bis- (decyl oxygroups) -2,4,8,10- tetra- oxa- -3,9-, bis- phospha spiral shell are used [5.5] hendecane (north of the city Chemical Co., Ltd. system, trade name " JPE-10 ") 3g is grasped similarly to Example 2 in addition to this Make, makes bonding laminate 3.Following various evaluations are carried out to the bonding laminate 3.As a result shown in table 1.
[comparative example 1]
The 1,2,3- triazoles as metal inhibitor and the (2,4- bis- of phosphorous acid three as bi-ester of phosphite are not added Tert-butyl-phenyl) ester (BASF AG's system, trade name " Irgafos 168 "), it in addition to this, operates similarly with example 1, makes Make bonding laminate 4.Following various evaluations are carried out to the bonding laminate 4.As a result shown in table 1.
[comparative example 2]
The 1,2,3-triazoles as metal inhibitor is not added, in addition to this, is operated similarly with example 1, and is made viscous Close laminate 5.Following various evaluations are carried out to the bonding laminate 5.As a result shown in table 1.
[comparative example 3]
As metal inhibitor, addition benzotriazole (north of the city Chemical Co., Ltd. system, trade name " BT120 ") 1.5g carrys out generation For 1,2,3-triazoles, bi-ester of phosphite is not added, in addition to this, is operated similarly with example 1, bonding sheet stacking is made Body 6.Following various evaluations are carried out to the bonding laminate 6.As a result shown in table 1.
<Various evaluations>
(1) anti-oxidant deterioration
On glass substrate (60mm × 45mm), with thicknessBetween 70 μm of line width, line length 46mm, line 10.5 round-trip modes are carried out every 30 μm, form the round-trip line of indium oxide (ITO), and are formed in two ends of the round-trip line By the square of the ITO 2mm square constituted, ITO pattern (length about 97cm) is formed, anti-oxidant deterioration evaluation ITO is made Glass substrate ((A) referring to Fig.1).
The stripping of the single side of the bonding laminate 1~6 made in above-described embodiment and comparative example (150 μm of thickness) is thin Film stripping pastes PET film (TOYOBO CO., LTD. system, trade name " Cosmoshine in its exposed surface hand pressure roller A4100”、125μm).Then, the bonding sheet of aforementioned strip PET film is cut out as after 52mm × 45mm, by remaining stripping film The bonding sheet in a manner of on the round-trip line for covering ITO, is pasted on anti-oxidant by stripping as shown in (B) of Fig. 1 with hand pressure roller Deterioration evaluation ito glass substrate makes anti-oxidant deterioration sample for evaluation (the ITO wirings with bonding sheet) (referring to Fig.1 (C))。
ITO in the measured in advance anti-oxidant deterioration sample for evaluation (the ITO wirings with bonding sheet) is routed in room temperature Under resistance value (Ω 0).
On the other hand, by the anti-oxidant deterioration sample for evaluation (ITO with bonding sheet is connected up) in 65 DEG C of 90%RH It is taken care of 500 hours under environment, after keeping, the ITO cloth in confrontation oxidative degradation sample for evaluation (the ITO wirings with bonding sheet) The resistance value (Ω) of line is measured.
Then, the change rate (%) [((Ω/Ω 0) -1) × 100] of resistance value between ITO resistance values, that is, line end, table 1 are calculated In shown in the form of " resistance change ".
For anti-oxidant deterioration, by the change rate of resistance value be 5% or more person be determined as " × (poor) ", will be insufficient 5% is determined as " zero (good) ".As a result shown in table 1.
(2) Corrosion Resistant Reliability
On glass substrate (60mm × 45mm), 10.5 are carried out with 70 μm of line width, line length 46mm, 30 μm of line interval Round-trip mode, formation stack gradually thicknessITO, thicknessCopper film made of metal film round-trip line, The square of 2mm square is formed in two ends of the round-trip line, copper pattern (length about 97cm) is formed, makes Corrosion Resistant Reliability Evaluation copper glass substrate ((A) referring to Fig.1).
The stripping of the single side of the bonding laminate 1~6 made in above-described embodiment and comparative example (150 μm of thickness) is thin Film stripping pastes PET film (TOYOBO CO., LTD. system, trade name " Cosmoshine in its exposed surface hand pressure roller A4100”、125μm).Then, the bonding sheet of aforementioned strip PET film is cut out as after 52mm × 45mm, by remaining stripping film Stripping, as shown in Fig. 1 (B), in a manner of on the round-trip line for covering metal film, with hand pressure roller by bonding sheet be pasted on it is corrosion-resistant can By property evaluation copper glass substrate, Corrosion Resistant Reliability sample for evaluation (thin copper film with bonding sheet) is made (referring to Fig.1 (D))。
Thin copper film in the measured in advance Corrosion Resistant Reliability sample for evaluation (thin copper film with bonding sheet) is at room temperature Resistance value (Ω 0).
On the other hand, by the Corrosion Resistant Reliability sample for evaluation (thin copper film with bonding sheet) in 65 DEG C of 90%RH rings It is taken care of 500 hours under border, after keeping, to the thin copper film in Corrosion Resistant Reliability sample for evaluation (thin copper film with bonding sheet) Resistance value (Ω) is measured.
Then the change rate (%) [((Ω/Ω 0) -1) × 100] of resistance value between copper resistance value, that is, line end is calculated, in table 1 It is shown in the form of " resistance change ".
It is that 20% or more person is determined as " × (poor) " by the change rate of resistance value for Corrosion Resistant Reliability, it will be insufficient 20% is determined as " zero (good) ".As a result shown in table 1.
[table 1]
(evaluation result)
The bonding sheet of Examples 1 to 3 contains metal inhibitor and phosphite ester, to ITO wirings, the resistance value of thin copper film Variation it is few, Corrosion Resistant Reliability and anti-oxidant deterioration are excellent.
On the other hand, comparative example 1 is free of bi-ester of phosphite and metal inhibitor, Corrosion Resistant Reliability and antioxygen simultaneously It is poor to change deterioration.
Comparative example 2 is notable due to the corrosion for being free of metal inhibitor, especially thin copper film.
Comparative example 3 is free of bi-ester of phosphite, poor to the anti-oxidant deterioration of ITO wirings.
Industrial availability
It (is with transparency conducting layer for typical that the conductive member bonding sheet of the present invention, which can have to conductive member, And/or the conductive member of conductive pattern formed by the metal material comprising copper or silver) Corrosion Resistant Reliability, and have Anti-oxidant deterioration, therefore can be as being suitble to make the bonding sheet of various conductive members fittings to use.It can especially be suitable as The bonding sheet of device used for image display with touch panel uses.

Claims (13)

1. a kind of conductive member bonding sheet has by containing (methyl) acrylic copolymer, metal inhibitor and phosphorous The adhesive phase that the adhesive composition of ester compound is formed.
2. conductive member bonding sheet according to claim 1, wherein the bi-ester of phosphite includes selected from fat Race's phosphite ester, aromatic series phosphite ester and any one of the phosphite ester with aliphatic ester group and aromatic series ester group More than.
3. conductive member bonding sheet according to claim 1 or 2, which is characterized in that the metal inhibitor contains three Azole compounds.
4. conductive member bonding sheet according to claim 3, wherein three azole compounds include to be selected from benzo three It is more than any one of azole compounds, 1,2,3- triazoles and 1,2,4- triazoles.
5. conductive member bonding sheet according to any one of claims 1 to 4, wherein (methyl) acrylic compounds Copolymer contains carboxyl group-containing monomer as structural unit.
6. conductive member bonding sheet according to claim 5, wherein (methyl) acrylic copolymer contains 1.2~15 mass % of carboxylic monomer.
7. according to conductive member bonding sheet according to any one of claims 1 to 6, wherein described adhesive composition has There is photo-curable.
8. conductive member bonding sheet according to any one of claims 1 to 7, wherein described adhesive composition contains Crosslinking dose.
9. according to conductive member bonding sheet according to any one of claims 1 to 8, wherein the conductive member has saturating Bright conductive layer.
10. conductive member bonding sheet according to claim 9, wherein the conductive member has：Including tin dope oxygen The conductive pattern changed the transparency conducting layer of indium and/or formed by the metal material comprising copper.
11. a kind of conductive member laminated body, having makes conductive member bonding sheet according to any one of claims 1 to 10 It is constituted made of being bonded with conductive member.
12. a kind of image display device, with conductive member laminated body, image display panel and the table described in claim 11 Face protection panels are as member of formation.
13. a kind of conductive member adhesive composition contains (methyl) acrylic copolymer, metal inhibitor and phosphorous Ester compound.
CN201680076173.9A 2015-12-25 2016-12-21 Adhesive sheet for conductive member, conductive member laminate, and image display device Active CN108473835B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102732193A (en) * 2011-04-11 2012-10-17 王子制纸株式会社 Double-faced adhesive sheet, double-faced adhesive sheet with stripping sheet and optical laminated body
WO2012173247A1 (en) * 2011-06-17 2012-12-20 積水化学工業株式会社 Transparent adhesive tape, film laminate with metal thin film, cover panel-touch panel module laminate, cover panel-display panel module laminate, touch panel module-display panel module laminate, and image display device
CN103571362A (en) * 2012-08-07 2014-02-12 日东电工株式会社 Double-sided pressure-sensitive adhesive sheet and portable electronic device
CN103805076A (en) * 2010-09-06 2014-05-21 三菱树脂株式会社 Method for producing laminate for configuring image display device, and image display device using the same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55164262A (en) * 1979-06-07 1980-12-20 Toshiba Chem Corp Electrical insulating varnish for cloth pipe
JP2000239633A (en) * 1999-02-16 2000-09-05 Sanyo Chem Ind Ltd Acrylic pressure-sensitive adhesive composition, pressure- sensitive adhesive tape or sheet coated therewith, and masker therefor
JP2006035914A (en) * 2004-07-22 2006-02-09 Bando Chem Ind Ltd Surface protecting film for automobile wheel
JP5299804B2 (en) 2004-08-03 2013-09-25 綜研化学株式会社 Adhesive sheet for attaching metal
JP4531099B2 (en) 2007-09-06 2010-08-25 日東電工株式会社 Adhesive composition, and adhesive product and display using the same
JP5277937B2 (en) 2008-12-17 2013-08-28 Ｄｉｃ株式会社 Double-sided adhesive sheet for fixing transparent conductive film, transparent conductive film laminate, touch panel device
JP5625625B2 (en) * 2010-08-30 2014-11-19 大日本印刷株式会社 Adhesive sheet for metal sticking
JP6271156B2 (en) * 2013-02-14 2018-01-31 日東電工株式会社 Adhesive composition, adhesive layer, adhesive sheet, optical member, and touch panel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103805076A (en) * 2010-09-06 2014-05-21 三菱树脂株式会社 Method for producing laminate for configuring image display device, and image display device using the same
CN102732193A (en) * 2011-04-11 2012-10-17 王子制纸株式会社 Double-faced adhesive sheet, double-faced adhesive sheet with stripping sheet and optical laminated body
WO2012173247A1 (en) * 2011-06-17 2012-12-20 積水化学工業株式会社 Transparent adhesive tape, film laminate with metal thin film, cover panel-touch panel module laminate, cover panel-display panel module laminate, touch panel module-display panel module laminate, and image display device
CN103571362A (en) * 2012-08-07 2014-02-12 日东电工株式会社 Double-sided pressure-sensitive adhesive sheet and portable electronic device

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