WO2014208696A1 - 粘着剤組成物、透明導電層用粘着剤層、積層体、及び画像表示装置 - Google Patents
粘着剤組成物、透明導電層用粘着剤層、積層体、及び画像表示装置 Download PDFInfo
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- WO2014208696A1 WO2014208696A1 PCT/JP2014/067062 JP2014067062W WO2014208696A1 WO 2014208696 A1 WO2014208696 A1 WO 2014208696A1 JP 2014067062 W JP2014067062 W JP 2014067062W WO 2014208696 A1 WO2014208696 A1 WO 2014208696A1
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- sensitive adhesive
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- transparent conductive
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- conductive layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- 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
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- 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
Definitions
- the present invention relates to a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer, and a pressure-sensitive adhesive for a transparent conductive layer formed from the pressure-sensitive adhesive composition.
- the agent layer Furthermore, this invention relates to the image display apparatus which uses a base film, the said adhesive layer for transparent conductive layers, and the laminated body which contains a transparent conductive layer in this order, and the said laminated body as a touch panel.
- a base material for example, a transparent conductive film
- a transparent conductive layer is formed on a transparent base material made of a glass plate or a transparent resin film.
- a capacitive touch panel A laminate in which a double-sided PSA sheet is laminated on the surface of the transparent conductive layer of the substrate having the transparent conductive layer is formed, and is fixed to another substrate via the PSA layer of the laminate.
- the transparent conductive layer is formed by evaporating a metal having high transparency and conductivity, such as indium tin oxide (ITO).
- ITO indium tin oxide
- the indium tin oxide (ITO) has good etching characteristics in the etching process at the time of patterning of the wiring, and moreover, amorphous (amorphous) indium tin oxide (ITO) is more advantageous, Often used.
- a carboxyl group-containing monomer or the like is used as a pressure-sensitive adhesive component in order to increase the cohesive strength of the pressure-sensitive adhesive component.
- a pressure-sensitive adhesive layer containing an acid component is in direct contact with the transparent conductive layer, the transparent conductive layer is corroded by acid, so that it has been difficult to use in this application.
- a pressure-sensitive adhesive composition in which a specific amount of a nitrogen atom-containing component is added to reduce the acid component content (for example, see Patent Document 1), and an acrylic resin having no acidic group as a main component.
- Proposed pressure-sensitive adhesive compositions for example, see Patent Document 2
- pressure-sensitive adhesives containing a (meth) acrylic polymer substantially free of acidic groups for example, see Patent Document 3
- an adhesive containing a phosphate ester compound for example, an acrylic copolymer having a hydroxyl group and an alkylene oxide chain in the side chain, an ionic compound, a curing agent, and an antistatic acrylic adhesive containing a phosphate ester compound (For example, see Patent Document 4).
- JP 2010-144002 A Special table 2011-225835 gazette JP 2013-018227 A Japanese Patent Laid-Open No. 2007-2111
- the pressure-sensitive adhesive compositions of Patent Documents 1 to 3 have a certain effect on the metal corrosion inhibition effect because the content of the acid component such as a carboxyl group-containing resin is reduced or no acid component is used. Is. However, in the pressure-sensitive adhesive compositions of Patent Documents 1 to 3, since the content of the acid component is small, the cohesive strength of the resin is insufficient, and basic physical properties such as adhesive strength and holding power are insufficient. In particular, it cannot be said that it has sufficient performance as an adhesive for a transparent conductive layer.
- the antistatic acrylic pressure-sensitive adhesive disclosed in Patent Document 4 is used as a pressure-sensitive adhesive for a surface protective pressure-sensitive adhesive film, and is not sufficient in terms of adhesive strength, adhesion reliability, etc. for a transparent conductive layer. There wasn't.
- the present invention is excellent in adhesiveness, and even when laminated on the transparent conductive layer, corrosion of the transparent conductive layer is suppressed, and an increase in the surface resistance value of the transparent conductive layer can be suppressed. It aims at providing the adhesive composition which can form an adhesive layer. Furthermore, the present invention provides a laminate comprising, in this order, a pressure-sensitive adhesive layer for a transparent conductive layer, a base film, the pressure-sensitive adhesive layer for a transparent conductive layer, and a transparent conductive layer formed from the pressure-sensitive adhesive composition, Another object of the present invention is to provide an image display apparatus using the touch panel as a touch panel.
- the present inventors have found that the object can be achieved by using the following pressure-sensitive adhesive composition, and have completed the present invention.
- the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer, A carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of 1,200,000 to 3,000,000, an isocyanate-based crosslinking agent, and the following general formula (1): (Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom) Containing a compound represented by The pressure-sensitive adhesive characterized in that the content of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the agent composition is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer, A carboxyl group-
- the carboxyl group-containing (meth) acrylic acid ester copolymer is obtained by polymerizing a monomer component containing a (meth) acrylic acid ester and a carboxyl group-containing monomer,
- the carboxyl group-containing monomer is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of all monomer components forming the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the pressure-sensitive adhesive composition contains phosphoric acid, and one of R 1 and R 2 in the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom.
- Phosphoric acid monoester which is a hydrocarbon residue of ⁇ 18
- R 1 and R 2 of the general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom It is preferable to contain one or more phosphate esters selected from the group consisting of phosphate diesters.
- the pressure-sensitive adhesive composition contains phosphoric acid and phosphoric acid monoester. Moreover, it is preferable that the total amount of phosphoric acid and phosphoric acid monoester is 80 weight% or more with respect to the whole quantity (100 weight%) of the compound represented by the said General formula (1).
- the hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the isocyanate-based crosslinking agent is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the transparent conductive layer is preferably formed from indium tin oxide.
- the indium tin oxide is preferably amorphous indium tin oxide.
- the present invention also relates to a pressure-sensitive adhesive layer for a transparent conductive layer, which is formed from the pressure-sensitive adhesive composition.
- this invention contains the transparent conductive base material which has a base film, the said adhesive layer for transparent conductive layers, and the transparent conductive layer in this order, and the said adhesive layer for transparent conductive layers is the said transparent conductive substrate. It is related with the laminated body characterized by contacting with the transparent conductive layer of this.
- the base film is preferably an iodine polarizing film having a transparent protective film on at least one side of an iodine polarizer containing iodine and / or iodine ions.
- iodine-based polarizer containing iodine and / or iodine ions means iodine-based polarizer containing iodine, iodine-based polarizer containing iodine ions, iodine containing both iodine and iodine ions It is a system polarizer, and any of them can be suitably used in the present invention.
- this invention relates to the image display apparatus characterized by using the said laminated body as a touchscreen.
- the pressure-sensitive adhesive composition of the present invention includes a carboxyl group-containing (meth) acrylic acid ester copolymer
- the pressure-sensitive adhesive composition has a high cohesive force
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition has a high adhesive force.
- the adhesive composition of this invention contains the carboxyl group-containing (meth) acrylic acid ester copolymer which is an acid component
- the adhesive layer formed from the said adhesive composition is used as a transparent conductive layer. Also when laminated
- the compound represented by the general formula (1) contained in the pressure-sensitive adhesive composition of the present invention is phosphoric acid
- the phosphoric acid is passivated with the metal ions of the transparent conductive layer on the surface of the transparent conductive layer.
- the phosphate ester is selectively adsorbed on the surface of the transparent conductive layer to form a film. Since H + is repelled and kept away, it is considered that corrosion of the transparent conductive layer is hindered and an increase in the surface resistance value can be suppressed.
- the isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition of the present invention may gel due to the catalytic effect of the acid component, but in the pressure-sensitive adhesive composition of the present invention, a specific acidic phosphate ester is specified. Since the amount is included, the gelation can be controlled and the pot life is good.
- the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer in contact with the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer, A carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of 1,200,000 to 3,000,000, an isocyanate-based crosslinking agent, and the following general formula (1): (Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom) And The content of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer.
- phosphoric acid in which both R 1 and R 2 in the general formula (1) are hydrogen atoms can also be suitably used, and a salt of the phosphoric acid (Metal salts such as sodium, potassium, and magnesium, ammonium salts, and the like) can also be suitably used.
- a phosphate ester in which at least one of R 1 and R 2 is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom is also preferably used.
- the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms,- (CH 2 CH 2 O) n R 3 (R 3 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is 0 to And an integer of 15.).
- the alkyl group and alkenyl group may be linear or branched.
- the hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, and has 2 to 6 carbon atoms.
- a linear or branched alkyl group is more preferred.
- examples of the compound represented by the general formula (1) include the following general formula (2): (Wherein R 1 is the same as defined above, R 3 is an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and n is an integer of 0 to 15). Acid esters are preferred.
- R 1 in the general formula (2) is the same as R 1 in the general formula (1), a hydrogen atom, or may contain an oxygen atom, a hydrocarbon residue having 1 to 18 carbon atoms.
- Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include the same ones as described above.
- R 1 in the general formula (2) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
- a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms is more preferable.
- R 3 examples include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms.
- An aryl group having 6 to 18 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 2 to 6 carbon atoms is more preferable.
- N is an integer of 0 to 15, and preferably an integer of 0 to 10.
- does not contain polyethylene oxide structure (CH 2 CH 2 O) (i.e., in formula (2), n 0) it is from the viewpoint of preventing deterioration.
- R 1 is a hydrogen atom
- R 3 is a linear or branched alkyl group having 1 to 18 carbon atoms from the viewpoint of the adsorption effect on the transparent conductive layer.
- the phosphoric acid monoester is preferably a phosphoric acid monoester in which R 1 is a hydrogen atom and R 3 is a linear or branched alkyl group having 1 to 10 carbon atoms, and R 1 is a hydrogen atom
- More preferred are phosphoric acid monoesters in which R 3 is a linear or branched alkyl group having 2 to 6 carbon atoms.
- salts of the compound represented by the general formula (2) metal salts such as sodium, potassium and magnesium, ammonium salts, etc.
- metal salts such as sodium, potassium and magnesium, ammonium salts, etc.
- R 1 an oxygen atom
- diesters monoester Forma (2), 1 carbon atoms
- the mixing ratio of the monoester and the diester of the “mono / di mixture” can be calculated from the measurement result of 31 P-NMR.
- the measuring method is as described in the examples.
- the compound represented by the general formula (1) or the compound represented by the general formula (2) used in the present invention may be used alone or in combination of two or more. From the viewpoint of the adsorption effect on the transparent conductive layer, it is preferably a mixture of two or more selected from the group consisting of phosphoric acid, phosphoric acid monoester, and phosphoric acid diester, containing phosphoric acid, and phosphorous A mixture containing one or more phosphate esters selected from the group consisting of an acid monoester and a phosphate diester is more preferable, and a mixture containing a phosphate monoester and phosphoric acid is particularly preferable.
- one kind selected from the group consisting of phosphoric acid, phosphoric acid monoester, and phosphoric acid diester can be used alone, but when phosphoric acid is used alone, the pot life of the pressure-sensitive adhesive composition May be insufficient.
- Phosphoric acid is a very polar compound, and its compatibility with (meth) acrylic acid ester copolymer is not sufficient, so phosphoric acid bleeds out to the surface of the adhesive layer, resulting in durability. There may be a problem with this point.
- phosphoric acid is not used and only phosphoric acid ester (phosphoric acid monoester and / or phosphoric acid diester) is used, there is a problem in durability under extremely severe conditions (for example, heat cycle test).
- a phosphoric acid-based compound containing phosphoric acid and phosphoric acid monoester from the viewpoint of the balance between the suppression of the corrosion of the transparent conductive layer and the durability under extremely severe conditions.
- the total amount of phosphoric acid and phosphoric acid monoester is not particularly limited, but is preferably 80% by weight or more based on the total amount (100% by weight) of the compound represented by the general formula (1).
- the phosphoric acid monoester is a carbon atom having 1 to 18 carbon atoms in which one of R 1 and R 2 in the general formula (1) is a hydrogen atom and the other may contain an oxygen atom.
- a compound which is a hydrocarbon residue having 1 to 18 carbon atoms which may be contained in the case of the general formula (2), R 1 may contain an oxygen atom and a hydrocarbon residue having 1 to 18 carbon atoms may be contained.
- Compound which is a group
- the adsorption effect on the transparent conductive layer is considered that the transparent conductive layer and the phosphoric acid-based compound are defined by the HSAB rule, that is, it is related to the “law of hard and soft acid base”.
- Combining a soft acid with a soft base has a high adsorption effect, and as a result, it is considered that a high deterioration preventing effect can be obtained. That is, for example, In of ITO corresponds to a hard acid defined by the HSAB rule, and the phosphoric acid compound is changed from a hard base to a soft base in the order of phosphoric acid, phosphoric monoester, and phosphoric diester. It can be adsorbed to ITO effectively in order, and as a result, it is considered that a high deterioration preventing effect can be obtained.
- a mixture containing a large amount of a monoester is preferable.
- it is preferable to include a large amount of monoester since the adsorption effect on the transparent conductive layer is high.
- the amount of phosphoric acid added is phosphoric ester compound 100.
- the amount is preferably 10 to 400 parts by weight, more preferably 10 to 100 parts by weight, and more preferably 10 to 50 parts by weight from the viewpoint of the adsorbing effect on the adherend.
- the amount of phosphoric acid added is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the phosphoric ester compound. More preferably, it is a part.
- the acid value of the phosphoric acid compound used in the present invention is preferably 900 mgKOH / g or less, more preferably 50 to 800 mgKOH / g, and preferably 50 to 700 mgKOH / g. Further, from the viewpoint of handling in production, the acid value of the acidic phosphate is preferably 80 to 400 mgKOH / g, more preferably 80 to 350 mgKOH / g, and 100 to 300 mgKOH / g. More preferred is 100 to 280 mgKOH / g. It is preferable that the acid value of the acidic phosphoric acid ester is within the above range, so that the increase in the surface resistance value of the transparent conductive layer can be suppressed and the durability against heating and humidification can be improved. .
- the acidic phosphate ester may act as a reaction catalyst for the crosslinking reaction of the isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition of the present invention, which may shorten the pot life of the pressure-sensitive adhesive composition. It was. However, it is preferable from the viewpoint of the pot life of the pressure-sensitive adhesive composition, because the acid value of the acidic phosphate ester tends to be able to suppress the action as a reaction catalyst by setting the acid value in the above range. Moreover, it is preferable from the viewpoint that an acidic phosphate ester having an acid value in the above range is added in an addition amount to be described later so that the gelation suppressing effect can be efficiently exhibited.
- a compound represented by the general formula (1) a dimer such as an acidic phosphate ester represented by the general formula (2), and a multimer such as a trimer can also be used. .
- the amount of the compound represented by the general formula (1) is 0.005 to 3 parts by weight with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer described later, Is preferably 2.5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.01 to 2 parts by weight, and 0.02 to 0.4 parts by weight. It is particularly preferred.
- the amount of the compound represented by the general formula (1) is within the above range, an increase in the surface resistance value of the transparent conductive layer can be suppressed, and durability against heating and humidification can be improved. Is preferable.
- two or more compounds represented by the general formula (1) can be used. In that case, the total amount can be added within the above range.
- the surface resistance raise of a transparent conductive layer can be suppressed.
- the compound represented by the general formula (1) contained in the pressure-sensitive adhesive composition of the present invention is phosphoric acid
- the phosphoric acid is passivated with the metal ions of the transparent conductive layer on the surface of the transparent conductive layer.
- the phosphate ester is selectively adsorbed on the surface of the transparent conductive layer to form a film. Since H + is repelled and kept away, it is considered that corrosion of the transparent conductive layer is hindered and an increase in the surface resistance value can be suppressed.
- metal oxides are corroded by a mechanism different from general metal corrosion.
- the corrosion reaction dissolves the metal oxide in the presence of a general acidic substance, and as a result, the resistance of the layer containing the metal oxide (metal oxide layer). This causes problems such as an increase in value. Further, in the case of a substance other than the acidic substance, the substance soaks into the metal oxide layer and decreases the carrier mobility of the metal oxide, so that the resistance value increases.
- the compound represented by the general formula (1) used in the present invention is an acidic substance
- the influence of corrosion by the acidic substance is small, and a pressure-sensitive adhesive layer is formed by forming a film or the like on the surface of a metal or metal oxide.
- the rise in resistance due to acids and other substances that cause deterioration is suppressed.
- the effect of inhibiting corrosion by the compound represented by the general formula (1) is particularly great when it is a metal oxide used for a transparent conductive layer, and even better when it is ITO.
- the carboxyl group-containing (meth) acrylic acid ester copolymer used in the present invention is not particularly limited. For example, it is obtained by polymerizing a monomer component containing a (meth) acrylic acid ester and a carboxyl group-containing monomer. Preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms as a main component and also containing a carboxyl group-containing alkyl (meth) acrylate. More preferably.
- Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
- alkyl group having 4 to 18 carbon atoms various linear or branched ones can be used.
- Specific examples of the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl ( (Meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) Acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth)
- (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable
- n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable
- n-butyl (meth) acrylate is particularly preferable. preferable.
- the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is 50 parts by weight or more with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. Preferably, it is 60 parts by weight or more, more preferably 70 parts by weight or more, still more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.
- carboxyl group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation.
- the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These may be used alone or in combination. Can be used.
- the carboxyl group-containing monomer is preferably 0.05 to 10 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. It is more preferable that Setting the carboxyl group-containing monomer within the above range is preferable because the cohesive force of the carboxyl group-containing (meth) acrylic acid ester copolymer can be improved and sufficient adhesive force and holding power can be obtained.
- the monomer component for forming the carboxyl group-containing (meth) acrylic acid ester copolymer includes, in addition to the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms and the carboxyl group-containing alkyl (meth) acrylate. , Hydroxyl group-containing monomers, aryl group-containing monomers, and other copolymerization monomers can be added.
- hydroxyl group-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation.
- examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( And (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and the like.
- Two or more kinds can be mixed and used.
- 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is more preferable because a crosslinking point with an isocyanate group of the isocyanate-based crosslinking agent can be efficiently secured.
- 4-hydroxybutyl acrylate is more preferable because a crosslinking point with an isocyanate group of the isocyanate-based crosslinking agent can be efficiently secured. preferable.
- the hydroxyl group-containing monomer is preferably 10 parts by weight or less, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. Is more preferable, and 0.1 to 3 parts by weight is even more preferable.
- aryl group-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an aryl group can be used without particular limitation.
- the aryl group-containing monomer include (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.
- the aryl group-containing monomer is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight based on 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer. Part is more preferable.
- the other copolymerization monomer is not particularly limited as long as it has a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- propyl (meth) acrylate or the like Alkyl (meth) acrylates having an alkyl group having 3 or less carbon atoms or 19 or more carbon atoms; (meth) acrylic acid alicyclic hydrocarbons such as cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate Esters; for example, vinyl esters such as vinyl acetate and vinyl propionate; for example, styrenic monomers such as styrene; for example, epoxy group-containing monomers such as glycidyl (meth
- copolymerizable monomers include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; for example, N-methylitaconimide, N-ethylitaconimide, N Itaconimide monomers such as butyl itaconimide, N-octyl itaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl itaconimide, N-lauryl itaconimide; N- (meth) acryloyloxymethylene succinimide, N- Succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide; for example, styrene sulfonic acid Examples include sulfonic acid group
- glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate
- examples include, for example, tetrahydrofurfuryl (meth) acrylate, a heterocyclic ring such as fluorine (meth) acrylate, and an acrylate monomer containing a halogen atom.
- a polyfunctional monomer can be used as the copolymerizable monomer.
- the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group.
- alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Esterified product of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compound such as divinylbenzene; allyl (meth) acrylate, (meth) Examples thereof include compounds having a reactive unsaturated double bond such as vinyl acrylate.
- polyester (meta) having two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as functional groups similar to the monomer component is added to a skeleton such as polyester, epoxy, and urethane.
- a skeleton such as polyester, epoxy, and urethane.
- Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can also be used.
- the proportion of the other copolymerization monomer is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic ester copolymer. Part by weight or less is more preferable, and 15 parts by weight or less is particularly preferable. If the proportion of the copolymerization monomer is too large, adhesive properties such as reduced adhesion to various adherends such as glass and films of the adhesive layer formed from the adhesive composition of the present invention, and transparent conductive layers, etc. May decrease.
- the weight average molecular weight of the carboxyl group-containing (meth) acrylic acid ester copolymer used in the present invention is 1,200,000 to 3,000,000, preferably 1,200,000 to 2,700,000, and more preferably 1,400,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it is not preferable from the viewpoint of heat resistance. Moreover, when the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may impair transparency.
- the pressure-sensitive adhesive layer obtained using a (meth) carboxyl group-containing (meth) acrylic acid ester copolymer having a weight average molecular weight of less than 1,200,000 may have poor solvent resistance and mechanical properties.
- the weight average molecular weight is larger than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost.
- the weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).
- carboxyl group-containing (meth) acrylic acid ester copolymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations, and is not particularly limited. Moreover, any of a random copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as the carboxyl group-containing (meth) acrylic acid ester copolymer obtained.
- solution polymerization for example, ethyl acetate or toluene is used as a polymerization solvent.
- the reaction is carried out under an inert gas stream such as nitrogen and a polymerization initiator is added, usually at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of the carboxyl group-containing (meth) acrylic acid ester copolymer can be controlled by the amount of the polymerization initiator, the amount of chain transfer agent used, and the reaction conditions. Is adjusted.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, -Sec-butylperoxydicarbon
- the polymerization initiator may be used alone, or may be used in combination of two or more, but the total content is the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the amount is preferably about 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer component to be formed.
- chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
- silane coupling agents can be added in order to improve adhesion under high-temperature and high-humidity conditions.
- the silane coupling agent one having any appropriate functional group can be used. Examples of the functional group include vinyl group, epoxy group, amino group, mercapto group, (meth) acryloxy group, acetoacetyl group, isocyanate group, styryl group, polysulfide group and the like.
- vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycol Epoxy group-containing silane coupling agents such as sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine, N
- the silane coupling agent may be used alone or in combination of two or more, but the total content is the same as the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the amount is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.8 part by weight based on 100 parts by weight of the monomer component to be formed. 0.05 to 0.7 parts by weight is particularly preferable.
- the amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the viewpoint of durability.
- the silane coupling agent when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component.
- the ratio is preferably 0.005 to 0.7 parts by weight with respect to 100 parts by weight of the monomer component forming the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the pressure-sensitive adhesive composition of the present invention can impart cohesive force related to the durability of the pressure-sensitive adhesive by including an isocyanate-based crosslinking agent.
- the isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by blocking agents or quantification) in one molecule.
- isocyanate-based crosslinking agent examples include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexa Isocyanurate
- the blending ratio of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition of the present invention is not particularly limited. For example, 0.01 to 10 weights with respect to 100 weight parts of the carboxyl group-containing (meth) acrylic acid ester copolymer. Part is preferable, and 0.01 to 5 parts by weight is more preferable.
- the pressure-sensitive adhesive composition of the present invention it is preferable to use a peroxide-based crosslinking agent together with the isocyanate-based crosslinking agent.
- peroxide-based crosslinking agent examples include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxyneodecanoate.
- di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide which are particularly excellent in crosslinking reaction efficiency, are preferably used.
- the compounding ratio of the peroxide type crosslinking agent in the pressure-sensitive adhesive composition of the present invention is not particularly limited, for example, 10 parts by weight or less with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic acid ester copolymer.
- the amount is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight.
- cross-linking agent other cross-linking agents such as the isocyanate cross-linking agents and peroxide cross-linking agents can be used.
- crosslinking agent examples include organic crosslinking agents and polyfunctional metal chelates other than those described above.
- organic crosslinking agents other than the above include epoxy crosslinking agents, carbodiimide crosslinking agents, imine crosslinking agents, oxazoline crosslinking agents, and aziridine crosslinking agents.
- a polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound.
- polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned.
- Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents can be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition of the present invention includes a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and other inorganic powders as necessary.
- Additives such as fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers and the like are used as appropriate without departing from the scope of the present invention. You can also
- the pressure-sensitive adhesive composition of the present invention contains a carboxyl group-containing (meth) acrylic acid ester copolymer and an isocyanate-based crosslinking agent, and can form a pressure-sensitive adhesive layer by crosslinking the pressure-sensitive adhesive composition. it can. Since the compound represented by the general formula (1) contained in the pressure-sensitive adhesive composition of the present invention has a cross-linking promoting effect of a crosslinking agent such as an isocyanate-based crosslinking agent or a peroxide-based crosslinking agent, the pressure-sensitive adhesive of the present invention. The composition can increase the gel fraction of the pressure-sensitive adhesive layer from the initial production stage. As a result, a pressure-sensitive adhesive layer excellent in processability can be obtained.
- a crosslinking agent such as an isocyanate-based crosslinking agent or a peroxide-based crosslinking agent
- the gel fraction of the pressure-sensitive adhesive layer after 2 hours after heat-crosslinking (155 ° C., 2 minutes) of the pressure-sensitive adhesive composition is 45 to It is preferably 95% by weight, more preferably 55 to 95% by weight, and still more preferably 60 to 85% by weight.
- the gel fraction is less than 45% by weight, since the pressure-sensitive adhesive layer is too soft, processing in this state tends to cause problems such as sticking of the blade during processing.
- dents are generated in the step of winding the pressure-sensitive adhesive layer after crosslinking, resulting in problems in appearance, resulting in poor productivity.
- the measurement of the gel fraction of an adhesive layer can be performed by the method as described in an Example.
- the pressure-sensitive adhesive layer for transparent conductive layer of the present invention is formed from the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive composition the above-mentioned pressure-sensitive adhesive composition of the present invention can be used. Moreover, the formation method of an adhesive layer is mentioned later.
- the laminated body of this invention contains the transparent conductive base material which has a base film, the said adhesive layer for transparent conductive layers, and a transparent conductive layer in this order, and the said adhesive layer for transparent conductive layers is the said transparent conductive layer. It contacts the transparent conductive layer of a conductive substrate.
- a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition of the present invention can be used.
- the method for forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive composition is applied on various substrates, dried by a dryer such as a heat oven, and the pressure-sensitive adhesive layer is formed by evaporating the solvent and the like.
- a method of transferring the pressure-sensitive adhesive layer onto the base film may be used, or the pressure-sensitive adhesive composition may be directly applied onto the base film to form a pressure-sensitive adhesive layer.
- the substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.
- Various methods are used as the coating method on the base film or base material. Specifically, for example, fountain coater, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Daiko Examples of the method include an extrusion coating method using a catalyst.
- the drying conditions are not particularly limited and can be appropriately set depending on the composition, concentration, etc. of the pressure-sensitive adhesive composition, and are, for example, about 80 to 170 ° C., preferably 90 to 200 ° C. 1 to 60 minutes, preferably 2 to 30 minutes.
- the thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and further preferably 12 to 40 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is less than 5 ⁇ m, the adhesion to the adherend becomes poor, and the durability under high temperature and high temperature and humidity tends to be insufficient.
- the thickness of the pressure-sensitive adhesive layer exceeds 100 ⁇ m, the pressure-sensitive adhesive composition is not sufficiently dried during the application and drying of the pressure-sensitive adhesive layer, and bubbles remain or the surface of the pressure-sensitive adhesive layer. There is a tendency that unevenness in thickness occurs and problems in appearance tend to become apparent.
- constituent material of the release film examples include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
- porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- An appropriate thin leaf body can be used, but a resin film is preferably used from the viewpoint of excellent surface smoothness.
- the resin film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
- -Vinyl acetate copolymer film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
- -Vinyl acetate copolymer film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybuty
- the thickness of the release film is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- release agent and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed.
- the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.
- the transparent resin film substrate is not particularly limited, and various resin films having transparency are used.
- the resin film is formed of a single layer film.
- the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
- polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
- the thickness of the transparent resin film substrate is preferably 15 to 200 ⁇ m.
- an anchor layer may be provided between the base film and the pressure-sensitive adhesive layer.
- the material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols.
- the anchor agent forming the anchor layer can contain an antistatic agent.
- the thickness of the anchor layer is not particularly limited, but is preferably about 5 to 300 nm.
- the anchor agent can be blended with various additives for the purpose of suppressing deterioration of the pressure-sensitive adhesive layer and the base film generated when coming into contact with the anchor coat layer, and imparting a function to the anchor coat layer.
- additives can be blended for the purpose. For example, antioxidants, deterioration inhibitors, ultraviolet absorbers, fluorescent brighteners, and the like can be added.
- the base film used in the laminate of the present invention various films such as a resin film and an optical film used for forming an image display device such as a liquid crystal display device can be used, and the type is not particularly limited.
- the resin film include the resin films described in this specification.
- the optical film include a polarizing film.
- the polarizing film one having a transparent protective film on one side or both sides of a polarizer is generally used.
- the polarizer is not particularly limited, and various types can be used.
- polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable, and an iodine polarizer containing iodine and / or iodine ions is more preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
- a thin polarizer having a thickness of 10 ⁇ m or less can also be used.
- the thickness is preferably 1 to 7 ⁇ m.
- Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
- the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, WO2010 / 100917, or a patent.
- the thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned.
- These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
- PVA-based resin polyvinyl alcohol-based resin
- International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing.
- those obtained by a production method including a step of stretching in a boric acid aqueous solution as described in International Publication No. 2010/100917 pamphlet, or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
- Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
- polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic polymers such as polymethyl methacrylate
- styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
- AS resin acrylonitrile / styrene copolymer
- polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include blends of the polymer.
- the transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
- the thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin film properties.
- the polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like.
- the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
- examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
- the electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films.
- the adhesive used in the present invention can contain a metal compound filler.
- the surface of the transparent protective film to which the polarizer is not bonded may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
- an iodine-based polarizing film having a transparent protective film on at least one surface of the iodine-based polarizer containing iodine and / or iodine ions can be used as the substrate film.
- a transparent conductive layer such as ITO
- a trace amount of iodine from the iodine-based polarizing film oozes into the adhesive layer, which is transparent such as ITO. There was also a problem of corroding the conductive layer.
- the compound represented by the general formula (1) contained in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention forms a film on the surface of the transparent conductive layer as described above, it stains from the polarizer. It is also possible to prevent the released iodine from moving to the surface of the transparent conductive layer.
- optical film other than the polarizing film examples include liquid crystal display devices such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation of etc. is mentioned. These can be used alone as an optical film, or can be laminated on the polarizing film in practical use to be used in one layer or in two or more layers.
- the optical film can be activated.
- Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.
- the transparent conductive substrate having a transparent conductive layer is not particularly limited, and a known one can be used. Generally, a transparent conductive layer having a transparent conductive layer on a transparent substrate is used. ing.
- the transparent substrate may be any material as long as it has transparency, and examples thereof include a resin film and a substrate made of glass (for example, a sheet-like, film-like, or plate-like substrate). A film is particularly preferred.
- the thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 ⁇ m, more preferably about 15 to 150 ⁇ m.
- the material of the resin film is not particularly limited, and various plastic materials having transparency can be mentioned.
- the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
- polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
- the transparent base material is subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or undercoating treatment on the surface in advance, and the transparent conductive layer provided thereon You may make it improve the adhesiveness with respect to a transparent base material. Moreover, before providing a transparent conductive layer, you may remove and clean by solvent washing
- the constituent material of the transparent conductive layer is not particularly limited and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten.
- a metal oxide of at least one metal is used.
- the metal oxide may further contain a metal atom shown in the above group, if necessary.
- ITO indium tin oxide
- tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used.
- ITO amorphous indium tin oxide is preferable because the effect of the present invention is remarkably exhibited.
- ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
- the thickness of the transparent conductive layer is not particularly limited, but is preferably 10 nm or more, more preferably 15 to 40 nm, and further preferably 20 to 30 nm.
- the method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.
- the thickness of the substrate having the transparent conductive layer can be 15 to 200 ⁇ m. Further, from the viewpoint of thinning, the thickness is preferably 15 to 150 ⁇ m, and more preferably 15 to 50 ⁇ m.
- a thickness of 100 to 200 ⁇ m can be mentioned.
- a thickness of 15 to 100 ⁇ m is preferable, and in particular, a thickness of 15 to 50 ⁇ m is more preferable due to a recent demand for further thinning, and a thickness of 20 to 50 ⁇ m is more preferable. .
- an undercoat layer, an oligomer prevention layer, and the like can be provided between the transparent conductive layer and the transparent substrate as necessary.
- the pressure-sensitive adhesive layer of the present invention can suppress corrosion of the transparent conductive layer even when the pressure-sensitive adhesive layer is laminated on the transparent conductive layer, and increase the surface resistance of the transparent conductive layer. It can be suppressed. Therefore, the pressure-sensitive adhesive layer of the present invention can be suitably used as long as it is an aspect in contact with the transparent conductive layer of the image display device having the transparent conductive layer.
- the laminate having the pressure-sensitive adhesive layer of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, and the like provided with an input device (touch panel or the like). ),
- a base material (member) constituting a device such as an input device (touch panel, etc.) or a base material (member) used in these devices, but it is particularly suitable for an optical base material for a touch panel. It can use suitably in manufacture of this.
- it can be used irrespective of systems, such as a touch panel, such as a resistive film system and a capacitive system.
- the laminated body of the present invention is subjected to treatments such as cutting, resist printing, etching, silver ink printing, and the like, and the resulting transparent conductive film can be used as a substrate for optical devices (optical member).
- the substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics.
- an image display device liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel)
- Examples include base materials (members) constituting devices such as electronic paper) and input devices (touch panels, etc.) or base materials (members) used in these devices.
- the image display device using the pressure-sensitive adhesive layer of the present invention include, for example, an image display device that uses a transparent conductive layer as an antistatic layer, and an image display device that uses a transparent conductive layer as an electrode for a touch panel. Can be mentioned.
- an image display device using the transparent conductive layer as an antistatic layer for example, as shown in FIG. 1, a polarizing film 1 / adhesive layer 2 / antistatic layer 3 / glass substrate 4 / liquid crystal Examples thereof include an image display device comprising a layer 5 / driving electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 wherein the antistatic layer 3 and the driving electrode 6 are formed of a transparent conductive layer.
- the pressure-sensitive adhesive layer of the present invention can be used as the pressure-sensitive adhesive layer 2 on the upper side (viewing side) of the image display device.
- an image display device using the transparent conductive layer as an electrode for a touch panel for example, polarizing film 1 / adhesive layer 2 / antistatic layer / sensor layer 7 / glass substrate 4 / liquid crystal layer 5 / driving electrode / sensor Layer 8 / glass substrate 4 / adhesive layer 2 / polarizing film 1 configuration (in-cell type touch panel, FIG.
- An image display device 6 is formed of a transparent conductive layer.
- the polarizing film with an adhesive layer of the present invention can be used as the polarizing film with an adhesive layer (1, 2) on the upper side (viewing side) of the image display device.
- a stretched laminate was produced by air-assisted stretching at a stretching temperature of 130 ° C. from a laminate in which a 9 ⁇ m-thick polyvinyl alcohol (PVA) layer was formed on an amorphous polyethylene terephthalate (PET) substrate.
- PVA polyvinyl alcohol
- PET polyethylene terephthalate
- a colored laminate was produced by dyeing the stretched laminate.
- the colored laminate is stretched integrally with an amorphous PET base material in boric acid water at a temperature of 65 ° C. so that the total stretch ratio is 5.94 times, and an optical film laminate including a PVA layer having a thickness of 4 ⁇ m. Generated body.
- the PVA molecules in the PVA layer formed on the amorphous PET base material are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the higher order in one direction as a polyiodine ion complex.
- a high-functional polarizer is applied.
- amorphous PET After applying a saponified 40 ⁇ m thick acrylic resin film (transparent protective film (1)) while applying a polyvinyl alcohol-based adhesive on the surface of the polarizer of the optical film laminate, amorphous PET The base material was peeled off to produce a one-side protective polarizing film using a thin polarizer.
- this is called a base film (1).
- Production Example 2 (Preparation of base film (2)) A PVA film having a thickness of 80 ⁇ m was stretched up to 3 times while being dyed in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the film was stretched so that the total draw ratio was 6 times while immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 ⁇ m.
- a norbornene-based film (transparent protective film (2)) having a thickness of 40 ⁇ m was bonded with a PVA adhesive to prepare a double-sided protective polarizing film.
- this is called a base film (2).
- Production Example 3 (Preparation of a solution containing an acrylate copolymer (A-1))
- a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and 2,2′-azobis as an initiator 1 part of isobutyronitrile (AIBN) was added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylate copolymer (A-1) having a weight average molecular weight of 2 million (solid content concentration: 30% by weight).
- AIBN isobutyronitrile
- Production Example 11 (Preparation of a solution containing an acrylate copolymer (A-9))
- a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 84.9 parts of butyl acrylate, 0.1 part of 4-hydroxybutyl acrylate, 5 parts of acrylic acid, 10 parts of benzyl acrylate, and an initiator
- 1 part of AIBN was added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream.
- ethyl acetate was added to the reaction solution to obtain a solution containing an acrylate copolymer (A-9) having a weight average molecular weight of 2 million (solid content concentration 30% by weight).
- the weight average molecular weight of the acrylate copolymer obtained in Production Examples 3 to 11 was measured by the following measuring method. ⁇ Measurement of weight average molecular weight (Mw) of acrylic ester copolymer> The weight average molecular weight of the prepared acrylate copolymer was measured by GPC (gel permeation chromatography).
- HLC-8220GPC column Sample column: manufactured by Tosoh Corporation, TSK guard column Super HZ-H (1) + TSK gel Super HZM-H (2) Reference column: TSKgel Super H-RC (1), manufactured by Tosoh Corporation Flow rate: 0.6mL / min Injection volume: 10 ⁇ L Column temperature: 40 ° C Eluent: THF Injection sample concentration: 0.2% by weight Detector: differential refractometer The weight average molecular weight was calculated in terms of polystyrene.
- Example 1 Adjustment of acrylic adhesive composition
- a crosslinking agent hexamethylene diisocyanate with trimethylolpropane 0.1 part adduct (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.), 0.3 part dibenzoyl peroxide, acid phosphate ester, phosphanol SM-172 (trade name, acid Value: 219 mg KOH / g, manufactured by Toho Chemical Industry Co., Ltd.) 0.07 parts, and ⁇ -glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent )
- a phenolic antioxidant and pentaerythritol tetrakis [3- (3,5-di-tert
- the acrylic pressure-sensitive adhesive composition is uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes.
- a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m was formed on the surface of the substrate.
- the separator which formed the adhesive layer was transferred to the surface which does not have a protective film of a base film (1), and the base film with an adhesive layer was produced.
- Examples 2-4 A base film with an adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the acidic phosphate ester was changed from 0.07 parts to the number of parts shown in Table 3.
- Example 5 Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.07 parts, Phosphanol RS-410 (trade name, acid value: 105 mg KOH / g, manufactured by Toho Chemical Industry Co., Ltd.) 0
- a base film with an adhesive layer was produced in the same manner as in Example 1 except that the content was changed to 0.07 parts.
- Example 6 Except for changing 0.07 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to 0.05 part of phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.) In the same manner as in Example 1, a base film with an adhesive layer was produced.
- Phosphanol SM-172 trade name, manufactured by Toho Chemical Co., Ltd.
- phosphoric acid special grade reagent
- Example 7-11 The solutions containing the acrylic ester copolymer (A-1) obtained in Production Example 3 were used as the acrylic acid ester copolymers (A-2) to (A-) obtained in Production Examples 4 to 7, respectively. 5), and in Example 8, a base film with an adhesive layer was produced in the same manner as in Example 1 except that dibenzoyl peroxide was not added.
- base film (1) was prepared by using base film (2) obtained in Production Example 2, base film (3) (thickness of 38 ⁇ m). Except for changing to polyethylene terephthalate (PET) film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), base film (4) (100 ⁇ m thick polyethylene terephthalate (PET) film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), In the same manner as in Example 1, a base film with an adhesive layer was produced.
- PET polyethylene terephthalate
- base film (4) 100 ⁇ m thick polyethylene terephthalate (PET) film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.
- Example 15 Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.3 parts was changed to MP-4 (acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.08 parts. Except having done, it carried out similarly to Example 1, and produced the base film with an adhesive layer.
- Example 16 The solution containing the acrylate copolymer (A-1) obtained in Production Example 3 was changed to a solution containing the acrylate copolymer (A-9) obtained in Production Example 11, In addition, the same procedure as in Example 15 was conducted except that the addition amount of MP-4 (acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.08 part to the addition amount shown in Table 3. Thus, a base film with an adhesive layer was produced.
- MP-4 acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.
- Example 18 In Example 17 (Preparation of base film with pressure-sensitive adhesive layer), except that base film (1) was changed to base film (2) obtained in Production Example 2, it was the same as Example 17. Thus, a base film with an adhesive layer was produced.
- Examples 20-22 In the same manner as in Example 1, except that the type of acrylic ester copolymer-containing solution, the type and addition amount of phosphoric acid and / or phosphate ester were changed to the types and addition amounts shown in Table 3, adhesion was performed. A base film with an agent layer was produced.
- Comparative Example 1 A base film with an adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the acidic phosphate ester was changed from 0.07 part to 5 parts.
- Comparative Example 2 A base film with an adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the acidic phosphate ester was changed from 0.07 part to 0.002 part.
- Comparative Examples 3-5 The solutions containing the acrylate copolymer (A-1) obtained in Production Example 3 were used as the acrylate ester copolymers (A-6) to (A-) obtained in Production Examples 8 to 10, respectively. 8), and in Comparative Examples 3 and 5, a base film with an adhesive layer was produced in the same manner as in Example 1 except that the acidic phosphate was not added.
- the phosphate ester used in Examples and Comparative Examples was analyzed as follows. The results are shown in Table 2. (Analysis method) The composition of the phosphate ester used in the examples and comparative examples was calculated based on the measurement results of 31 P-NMR (acetone-d6, room temperature). After calculating mol% from the integrated value of the peak obtained by measurement, the content ratio (% by weight) was calculated from the alkyl chain of the alcohol component of the ester.
- the phosphoric acid monoester has 1 to 18 carbon atoms in which one of R 1 and R 2 in the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. It is a compound that is a hydrocarbon residue (in the case of general formula (2), a compound in which R 1 is a hydrogen atom), and a phosphoric acid diester is a compound in which R 1 and R 2 in general formula (1) are oxygen atoms.
- a compound that is a hydrocarbon residue having 1 to 18 carbon atoms in the case of the general formula (2), R 1 may contain an oxygen atom and a hydrocarbon having 1 to 18 carbon atoms
- Compound that is a residue Compound that is a residue).
- ⁇ Gel fraction> The acrylic pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were subjected to a crosslinking reaction at 155 ° C. for 2 minutes to obtain a pressure-sensitive adhesive layer. After 2 hours from completion of the crosslinking reaction, 0.2 g of the pressure-sensitive adhesive layer was taken. The film was wrapped in a fluororesin film (TEMISH NTF-1122, manufactured by Nitto Denko Corporation) (weight: Wa), the weight of which was measured in advance, and was bound so that the acrylic pressure-sensitive adhesive composition did not leak. This is a measurement sample. The measurement sample was weighed (weight: Wb) and placed in a sample bottle. 40 cc of ethyl acetate was added to the sample bottle and left for 7 days.
- TEMISH NTF-1122 fluororesin film
- transparent conductive substrate (E-1) transparent conductive substrate having an amorphous ITO layer formed on the surface
- the resistance value measured after putting the measurement sample in an environment of temperature 60 ° C. and humidity 90% for 500 hours was defined as “resistance value after wet heat”.
- said resistance value was measured using HL5500PC by Accent Optical Technologies. From the “initial resistance value” and “resistance value after wet heat” measured as described above, the resistance value change rate (%) was calculated by the following equation, and evaluated according to the following evaluation criteria.
- Resistance value change rate is less than 150% (small increase in resistance value due to wet heat (corrosion resistance is good))
- ⁇ Resistance value change rate is 150% or more and less than 300%
- ⁇ Resistance value change rate is 300% or more and less than 400%
- ⁇ Resistance value change rate is 400% or more Corrosive failure
- Transparent conductive substrate (E-2) a film on which a crystalline ITO layer is formed (trade name: V150-G5Y, manufactured by Nitto Denko Corporation)
- Transparent conductive substrate (E-3) Glass on which an amorphous ITO layer is formed
- Transparent conductive substrate (E-4) Glass on which a crystalline ITO layer is formed
- a transparent conductive base material (E-3) and a transparent conductive base material (E-4) is as follows.
- E-1 Transparent conductive substrate
- E-2 Transparent conductive substrate
- E-3 Transparent conductive substrate
- E-4 Transparent conductive substrate
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Abstract
Description
重量平均分子量が120万~300万であるカルボキシル基含有(メタ)アクリル酸エステル共重合体、イソシアネート系架橋剤、及び下記一般式(1):
で表される化合物を含有し、
前記一般式(1)で表される化合物の含有量が、前記カルボキシル基含有(メタ)アクリル酸エステル共重合体100重量部に対して0.005~3重量部であることを特徴とする粘着剤組成物に関する。
前記カルボキシル基含有モノマーは、前記カルボキシル基含有(メタ)アクリル酸エステル共重合体を形成する全モノマー成分100重量部に対して0.05~10重量部であることが好ましい。
本発明の粘着剤組成物は、透明導電層を有する透明導電性基材の前記透明導電層と接触する粘着剤層を形成するための粘着剤組成物であって、
重量平均分子量が120万~300万であるカルボキシル基含有(メタ)アクリル酸エステル共重合体、イソシアネート系架橋剤、及び下記一般式(1):
前記一般式(1)で表される化合物の含有量が、前記カルボキシル基含有(メタ)アクリル酸エステル共重合体100重量部に対して0.005~3重量部であることを特徴とする。
前記一般式(2)で示される酸性リン酸エステルの市販品としては、東邦化学工業(株)製の「フォスファノールSM-172」(一般式(2)のR1=R3=C8H17、n=0、モノ・ジ混合物、酸価:219mgKOH/g)、「フォスファノールGF-185」(一般式(2)のR1=R3=C13H27、n=0、モノ・ジ混合物、酸価:158mgKOH/g)、「フォスファノールBH-650」(一般式(2)のR1=R3=C4H9、n=1、モノ・ジ混合物、酸価:388mgKOH/g)、「フォスファノールRS-410」(一般式(2)のR1=R3=C13H27、n=4、モノ・ジ混合物、酸価:105mgKOH/g)、「フォスファノールRS-610」(一般式(2)のR1=C13H27、R3=C13H27、n=6、モノ・ジ混合物、酸価:82mgKOH/g)、「フォスファノールML-220」(一般式(2)のR1=R3=C12H25、n=2、モノ・ジ混合物)、「フォスファノールML-200」(一般式(2)のR1=R3=C12H25、n=0、モノ・ジ混合物)、「フォスファノールED-200」(一般式(2)のR1=R3=C8H17、n=1、モノ・ジ混合物)、「フォスファノールRL-210」(一般式(2)のR1=R3=C18H37、n=2、モノ・ジ混合物)、「フォスファノールGF-339(一般式(2)のR1=R3=C6H13~C10H21の混合、n=0、モノ・ジ混合物)、「フォスファノールGF-199」(一般式(2)のR1=R3=C12H25、n=0、モノ・ジ混合物)、「フォスファノールRL-310」(一般式(2)のR1=R3=C18H37、n=3、モノ・ジ混合物)、日光ケミカルズ(株)製の「ニッコールDDP-2」(一般式(2)のR1=R3=C12H25~C15H31の混合物、n=2)、「フォスファノールLP-700」(一般式(2)のR1=R3=C6H5、n=6、モノ・ジ混合物)、大八化学工業(株)製の「AP-1」(一般式(2)のR1=R3=CH3、n=0、モノ・ジ混合物、酸価:650mgKOH/g以上)、「AP-4」(一般式(2)のR1=R3=C4H9、n=0、モノ・ジ混合物、酸価:452mgKOH/g)、「DP-4」(一般式(2)のR1=R3=C4H9、n=0、モノ・ジ混合物、酸価:292mgKOH/g)、「MP-4」(一般式(2)のR1=H、R3=C4H9、n=0、モノ・ジ混合物、酸価:670mgKOH/g)、「AP-8」(一般式(2)のR1=R3=C8H17、n=0、モノ・ジ混合物、酸価:306mgKOH/g)、「AP-10」(一般式(2)のR1=R3=C10H21、n=0、モノ・ジ混合物、酸価:263mgKOH/g)、「MP-10」(一般式(2)のR1=H、R3=C10H21、n=0、モノ・ジ混合物、酸価:400mgKOH/g)、城北化学(株)製の「JP-508」(一般式(2)のR1=R3=C8H17、n=0、モノ・ジ混合物、酸価:288mgKOH/g)、「JP-513」(一般式(2)のR1=R3=C13H27、n=0、モノ・ジ混合物)、「JP-524R」(一般式(2)のR1=R3=C24H49、n=0、モノ・ジ混合物)、「DBP」(一般式(2)のR1=R3=C4H9、n=0、モノ・ジ混合物、酸価:266mgKOH/g)、「LB-58」(一般式(2)のR1=R3=C8H17、n=0、ジエステル体、酸価:173mgKOH/g)、SIGMA-ALDRICH製のモノ-N-ブチルホスフェート(O=P(OH)2(OC4H9)、一般式(2)のR1=H、R3=C4H9、n=0、Product Nomber:CDS001281、モノエステル体)等ならびにそれらの塩を挙げることができる。なお、上記「モノ・ジ混合物」とは、モノエステル(一般式(2)のR1=H)とジエステル(一般式(2)のR1=酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基)の混合物であることを示すものであり、例えば、フォスファノールSM-172の場合、モノエステル(一般式(2)のR1=H、R3=C8H17、n=0)と、ジエステル(一般式(2)のR1=R3=C8H17、n=0)の混合物であることを示す。前記「モノ・ジ混合物」のモノエステルとジエステルの混合割合は、31P-NMRの測定結果より算出することができる。測定方法については、実施例に記載の通りである。
本発明の透明導電層用粘着剤層は、前記粘着剤組成物から形成されることを特徴とする。粘着剤組成物としては、前述の本発明の粘着剤組成物を用いることができる。また、粘着剤層の形成方法は、後述する。
本発明の積層体は、基材フィルム、前記透明導電層用粘着剤層、及び透明導電層を有する透明導電性基材をこの順に含み、前記透明導電層用粘着剤層が前記透明導電性基材の透明導電層に接触することを特徴とする。
前述の通り、本発明の粘着剤層は、透明導電層に当該粘着剤層を積層した場合にも、透明導電層の腐食を抑制することができ、透明導電層の表面抵抗上昇を抑制できるものである。従って、本発明の粘着剤層は、透明導電層を有する画像表示装置の当該透明導電層に接する態様であれば、好適に用いることができる。
非晶性ポリエチレンテレフタレート(PET)基材に、9μm厚のポリビニルアルコール(PVA)層が製膜された積層体を、延伸温度130℃の空中補助延伸によって延伸積層体を生成した。次に、延伸積層体を染色によって着色積層体を生成した。さらに、着色積層体を、温度65℃のホウ酸水中において、総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸し、4μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によって、非晶性PET基材に製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向され、高機能偏光子とすることができる。さらに、当該光学フィルム積層体の偏光子の表面にポリビニルアルコール系接着剤を塗布しながら、けん化処理した40μm厚のアクリル樹脂フィルム(透明保護フィルム(1))を貼合せたのち、非晶性PET基材を剥離し、薄型偏光子を用いた片側保護偏光フィルムを作製した。以下、これを基材フィルム(1)という。
厚さ80μmのPVAフィルムを、速度比の異なるロール間において、30℃、0.3%濃度のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。その後、60℃、4%濃度のホウ酸、10%濃度のヨウ化カリウムを含む水溶液中に0.5分間浸漬しながら総延伸倍率が6倍になるように延伸した。次いで、30℃、1.5%濃度のヨウ化カリウムを含む水溶液中に10秒間浸漬することで洗浄した後、50℃で4分間乾燥を行い、厚さ20μmの偏光子を得た。さらに、当該偏光子の一方の表面にPVA系接着剤を塗布しながら、けん化処理した40μm厚のアクリル樹脂フィルム(透明保護フィルム(1))を貼合せたのち、偏光子の他の表面に、厚さ40μmのノルボルネン系フィルム(透明保護フィルム(2))を、PVA系接着剤により貼り合せて、両面保護偏光フィルムを作製した。以下、これを基材フィルム(2)という。
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、ブチルアクリレート95部、4-ヒドロキシブチルアクリレート1部、アクリル酸4部、及び、開始剤として、2,2’-アゾビスイソブチロニトリル(AIBN)をモノマー(固形分)100部に対して1部を酢酸エチルと共に加えて、窒素ガス気流下、60℃で7時間反応させた。その後、その反応液に、酢酸エチルを加えて、重量平均分子量200万のアクリル酸エステル共重合体(A-1)を含有する溶液を得た(固形分濃度30重量%)。
モノマーの組成を表1に示す組成に変更した以外は、製造例3と同様にして、アクリル酸エステル共重合体(A-2)~(A-8)を含有する溶液を得た(それぞれの溶液について、固形分濃度30重量%)。
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、ブチルアクリレート84.9部、4-ヒドロキシブチルアクリレート0.1部、アクリル酸5部、ベンジルアクリレート10部及び、開始剤として、AIBNをモノマー(固形分)100部に対して1部を酢酸エチルと共に加えて窒素ガス気流下、60℃で7時間反応させた。その後、その反応液に、酢酸エチルを加えて、重量平均分子量200万のアクリル酸エステル共重合体(A-9)を含有する溶液を得た(固形分濃度30重量%)。
BA:ブチルアクリレート
BzA:ベンジルアクリレート
AA:アクリル酸
HEA:2-ヒドロキシエチルアクリレート
HBA:4-ヒドロキシブチルアクリレート
<アクリル酸エステル共重合体の重量平均分子量(Mw)の測定>
作製したアクリル酸エステル共重合体の重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィー)により測定した。
装置:東ソー社製、HLC-8220GPC
カラム:
サンプルカラム:東ソー社製、TSKguardcolumn Super HZ-H(1本)+TSKgel Super HZM-H(2本)
リファレンスカラム:東ソー社製、TSKgel Super H-RC(1本)
流量:0.6mL/min
注入量:10μL
カラム温度:40℃
溶離液:THF
注入試料濃度:0.2重量%
検出器:示差屈折計
なお、重量平均分子量はポリスチレン換算により算出した。
(アクリル系粘着剤組成物の調整)
製造例3で得られたアクリル酸エステル共重合体(A-1)を含有する溶液(固形分濃度30重量%)の固形分100部あたり、架橋剤として、ヘキサメチレンジイソシアネートのトリメチロールプロパンとのアダクト体(商品名:タケネートD160N、三井化学(株)製)を0.1部と、ジベンゾイルパーオキサイドを0.3部、酸性リン酸エステルとして、フォスファノールSM-172(商品名、酸価:219mgKOH/g、東邦化学工業(株)製)を0.07部と、シランカップリング剤としてγ-グリシドキシプロピルトリメトキシシラン(商品名:KBM-403、信越化学工業(株)製)を0.075部と、フェノール系酸化防止剤として、ペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート(IRGANAOX 1010、BASFジャパン(株)製)0.3部を配合して、アクリル系粘着剤組成物を得た。
前記アクリル系粘着剤組成物を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(基材)の表面に、ファウンテンコーターで均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、基材の表面に厚さ20μmの粘着剤層を形成した。次いで、基材フィルム(1)の保護フィルムを有さない面に、粘着剤層を形成したセパレータを移着させ、粘着剤層付基材フィルムを作製した。
酸性リン酸エステルの添加量を、0.07部から表3に記載の部数に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
フォスファノールSM-172(商品名、東邦化学工業(株)製)0.07部を、フォスファノールRS-410(商品名、酸価:105mgKOH/g、東邦化学工業(株)製)0.07部に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
フォスファノールSM-172(商品名、東邦化学工業(株)製)0.07部を、リン酸(試薬特級)(和光純薬工業(株)製)0.05部に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
製造例3で得られたアクリル酸エステル共重合体(A-1)を含有する溶液を、それぞれ、製造例4~7で得られたアクリル酸エステル共重合体(A-2)~(A-5)を含有する溶液に変更し、かつ、実施例8では、ジベンゾイルパーオキサイドを添加しなかった以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
実施例1の(粘着剤層付基材フィルムの作製)において、基材フィルム(1)を、製造例2で得られた基材フィルム(2)、基材フィルム(3)(厚さ38μmのポリエチレンテレフタレート(PET)フィルム、三菱化学ポリエステルフィルム(株)製)、基材フィルム(4)(厚さ100μmのポリエチレンテレフタレート(PET)フィルム、三菱化学ポリエステルフィルム(株)製)に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
フォスファノールSM-172(商品名、東邦化学工業(株)製)0.3部を、MP-4(酸価:670mgKOH/g、大八化学工業(株)製)0.08部に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
製造例3で得られたアクリル酸エステル共重合体(A-1)を含有する溶液を、製造例11で得られたアクリル酸エステル共重合体(A-9)を含有する溶液に変更し、かつ、MP-4(酸価:670mgKOH/g、大八化学工業(株)製)の添加量を0.08部から表3に記載の添加量に変更した以外は、実施例15と同様にして、粘着剤層付基材フィルムを作製した。
実施例17の(粘着剤層付基材フィルムの作製)において、基材フィルム(1)を、製造例2で得られた基材フィルム(2)に変更した以外は、実施例17と同様にして、粘着剤層付基材フィルムを作製した。
MP-4(酸価:670mgKOH/g、大八化学工業(株)製)0.05部を、リン酸(試薬特級)(和光純薬工業(株)製)0.08部とMP-4(酸価:671mgKOH/g、大八化学工業(株)製)0.02部(リン酸:MP-4=4:1(重量比))に変更した以外は、実施例16と同様にして、粘着剤層付基材フィルムを作製した。
アクリル酸エステル共重合体含有する溶液の種類、リン酸及び/又はリン酸エステルの種類と添加量を表3に記載の種類と添加量に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
酸性リン酸エステルの添加量を0.07部から、5部に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
酸性リン酸エステルの添加量を0.07部から、0.002部に変更した以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
製造例3で得られたアクリル酸エステル共重合体(A-1)を含有する溶液を、それぞれ、製造例8~10で得られたアクリル酸エステル共重合体(A-6)~(A-8)を含有する溶液に変更し、かつ、比較例3、5では、酸性リン酸エステルを添加しなかった以外は、実施例1と同様にして、粘着剤層付基材フィルムを作製した。
(分析方法)
実施例及び比較例で使用したリン酸エステルの組成を、31P-NMR(Acetone-d6、室温)の測定結果に基づき算出した。測定により得られたピークの積分値より、mol%を算出した後、エステルのアルコール成分のアルキル鎖から含有量比(重量%)を算出した。
(31P-NMR測定条件)
測定装置:Bruker Biospin、AVANCEIII-400
観測周波数:160MHz(31P)
フリップ角:30°
測定溶媒:Acetone-d6(重アセトン)
測定温度:室温
化学シフト標準:P=(OCH3)3 in Acetone-d6(31P;140ppm 外部標準)
実施例及び比較例で得られたアクリル系粘着剤組成物を、155℃、2分で架橋反応させて粘着剤層を得、架橋反応終了後2時間後、当該粘着剤層を0.2gとり、あらかじめ重量を測定したフッ素樹脂フィルム(TEMISH NTF-1122、日東電工(株)製)(重量:Wa)に包み、アクリル系粘着剤組成物が漏れないように縛った。これを、測定サンプルとする。測定サンプルの重量を測定し(重量:Wb)、サンプル瓶にいれた。サンプル瓶に酢酸エチルを40cc加えて、7日間放置した。その後、測定サンプル(フッ素樹脂フィルム+アクリル系粘着剤組成物)を取り出し、当該測定サンプルをアルミカップ上で、130℃、2時間乾燥させた。測定サンプルの重量(Wc)を測定し、次式によりゲル分率を求めた。
表面に非晶性ITO層が形成された導電性フィルム(商品名:エレクリスタ(P400L)、日東電工(株)製、以下「透明導電性基材(E-1)」ということもある)を15mm×15mmに切断し、この導電性フィルム上の中央部に、実施例、及び比較例で得られた粘着剤層付基材フィルムを8mm×8mmに切断して貼り合わせた後、50℃、5atmで15分間オートクレーブにかけたものを耐腐食性の測定用サンプルとした。得られた測定用サンプルの抵抗値を後述の測定装置を用いて測定し、これを「初期抵抗値」とした。
その後、測定用サンプルを、温度60℃、湿度90%の環境に、500時間投入した後に、抵抗値を測定したものを、「湿熱後の抵抗値」とした。なお、上記の抵抗値は、Accent Optical Technologies社製 HL5500PCを用いて測定を行った。上述のように測定した「初期抵抗値」及び「湿熱後の抵抗値」から、次式にて抵抗値変化率(%)を算出し、以下の評価基準により評価した。
◎:抵抗値変化率が、150%未満(湿熱による抵抗値の上昇幅小さい(耐腐食性良好))
○:抵抗値変化率が、150%以上300%未満
△:抵抗値変化率が、300%以上400%未満
×:抵抗値変化率が、400%以上(湿熱による抵抗値の上昇幅大きい(耐腐食性不良))
透明導電性基材(E-2):結晶性ITO層が形成されたフィルム(商品名:V150-G5Y、日東電工(株)製)
透明導電性基材(E-3):非晶性ITO層が形成されたガラス
透明導電性基材(E-4):結晶性ITO層が形成されたガラス
無アルカリガラスの一方の面に、スパッタリング法によりITO膜を形成し、結晶化ITO薄膜を有する透明導電性基材(E-4)、及び非結晶化ITO膜を有する透明導電性基材(E-3)を作製した。それぞれの基材を、実施例及び比較例で得られた粘着剤層付基材フィルムと貼り合せる前に140℃30分間の加熱処理をした。結晶性ITO薄膜のSn比率は、10重量%であった。非結晶性ITO薄膜のSn比率は、3重量%であった。なお、ITO薄膜のSn比率の算出方法は前述の通りである。
実施例、比較例で得られた粘着剤層付基材フィルムのセパレータを剥がし、結晶性ITOが形成されたガラス(透明導電性基材(E-4))のITO面に貼り合わせ、50℃、5atm、15分間のオートクレーブ処理を行った後、80℃及び100℃の加熱オーブン及び60℃/90%RH及び85℃/85%RHの恒温恒湿機に投入した。500時間後の基材フィルムの剥がれ及び発泡を目視で観察し、以下の評価基準で評価した。また、85℃と-40℃の環境を1サイクル1時間で300サイクル施した後(ヒートショック試験(HS試験))の偏光フィルムの剥がれ及び発泡を目視で観察し、以下の評価基準で評価した。
◎:全く剥がれまたは発泡が認められなかった。
○:目視では確認できない程度の剥がれまたは発泡が認められた。
△:目視で確認できる小さな剥がれまたは発泡が認められた。
×:明らかな剥がれまたは発泡が認められた。
(酸性リン酸エステル)
B-1:フォスファノールSM-172、酸価:219mgKOH/g、モノ・ジ混合物、東邦化学工業(株)製
B-2:フォスファノールRS-410、酸価:105mgKOH/g、モノ・ジ混合物、東邦化学工業(株)製
B-3:リン酸(試薬特級)、和光純薬工業(株)製
B-4:MP-4、酸価:670mgKOH/g、モノ・ジ混合物、大八化学工業(株)製
B-5:モノ-N-ブチルホスフェート(O=P(OH)2(OC4H9)、Product Nomber:CDS001281)、SIGMA-ALDRICH製
過酸化物系:ジベンゾイルパーオキサイド
イソシアネート系:トリメチロールプロパンキシリレンジイソシアネート(商品名:タケネートD110N)(三井化学(株)製)
E-1:透明導電性基材(E-1)
E-2:透明導電性基材(E-2)
E-3:透明導電性基材(E-3)
E-4:透明導電性基材(E-4)
2 粘着剤層
3 帯電防止層
4 ガラス基板
5 液晶層
6 駆動電極
7 帯電防止層兼センサー層
8 駆動電極兼センサー層
9 センサー層
Claims (13)
- 前記カルボキシル基含有(メタ)アクリル酸エステル共重合体が、(メタ)アクリル酸エステル及びカルボキシル基含有モノマーを含有するモノマー成分を重合して得られるものであり、前記カルボキシル基含有モノマーは、前記カルボキシル基含有(メタ)アクリル酸エステル共重合体を形成する全モノマー成分100重量部に対して0.05~10重量部であることを特徴とする請求項1に記載の粘着剤組成物。
- 前記粘着剤組成物が、リン酸を含有し、かつ、一般式(1)のR1及びR2のいずれか一方が水素原子であり、他方が、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基であるリン酸モノエステル、及び、一般式(1)のR1及びR2が、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基であるリン酸ジエステルからなる群から選択される1つ以上のリン酸エステルを含有することを特徴とする請求項1又は2に記載の粘着剤組成物。
- 前記粘着剤組成物が、リン酸及びリン酸モノエステルを含有することを特徴とする、請求項3に記載の粘着剤組成物。
- 前記炭素数1~18の炭化水素残基が、炭素数1~10の直鎖又は分岐のアルキル基であることを特徴とする請求項1~4のいずれかに記載の粘着剤組成物。
- 前記イソシアネート系架橋剤が、前記カルボキシル基含有(メタ)アクリル酸エステル共重合体100重量部に対して、0.01~10重量部であることを特徴とする請求項1~5のいずれかに記載の粘着剤組成物。
- さらに、過酸化物系架橋剤を含有することを特徴とする請求項1~6のいずれかに記載の粘着剤組成物。
- 前記透明導電層が、酸化インジウムスズから形成されることを特徴とする請求項1~7のいずれかに記載の粘着剤組成物。
- 前記酸化インジウムスズが、非結晶性の酸化インジウムスズであることを特徴とする請求項8に記載の粘着剤組成物。
- 請求項1~9のいずれかに記載の粘着剤組成物から形成されることを特徴とする、透明導電層用粘着剤層。
- 基材フィルム、請求項10に記載の透明導電層用粘着剤層、及び透明導電層を有する透明導電性基材をこの順に含み、前記透明導電層用粘着剤層が前記透明導電性基材の透明導電層に接触することを特徴とする積層体。
- 前記基材フィルムが、ヨウ素及び/又はヨウ素イオンを含有するヨウ素系偏光子の少なくとも片面に透明保護フィルムを有するヨウ素系偏光フィルムであることを特徴とする請求項11に記載の積層体。
- 請求項11又は12に記載の積層体をタッチパネルとして用いることを特徴とする画像表示装置。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016158513A1 (ja) * | 2015-03-31 | 2016-10-06 | 日東電工株式会社 | 液晶パネル及び画像表示装置 |
JP2017003906A (ja) * | 2015-06-15 | 2017-01-05 | 日東電工株式会社 | 両面粘着剤層付偏光フィルムおよび画像表示装置 |
JP2018060172A (ja) * | 2016-09-29 | 2018-04-12 | 日東電工株式会社 | 粘着剤層付偏光フィルム及び画像表示装置 |
JP2020101814A (ja) * | 2020-02-13 | 2020-07-02 | 日東電工株式会社 | 両面粘着剤層付偏光フィルムおよび画像表示装置 |
CN111936668A (zh) * | 2018-03-14 | 2020-11-13 | 株式会社自动网络技术研究所 | 表面保护剂组合物和具有端子的包覆电线 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104951169B (zh) * | 2015-07-10 | 2019-03-15 | 张家港康得新光电材料有限公司 | 透明导电膜与包含其的电容式触摸屏 |
CN104951168B (zh) * | 2015-07-10 | 2019-03-22 | 张家港康得新光电材料有限公司 | 透明导电膜与包含其的电容式触摸屏 |
CN104951164B (zh) * | 2015-07-10 | 2019-03-22 | 张家港康得新光电材料有限公司 | 透明导电膜与包含其的电容式触摸屏 |
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CN104951167B (zh) * | 2015-07-10 | 2019-03-22 | 张家港康得新光电材料有限公司 | 透明导电膜与包含其的电容式触摸屏 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008189838A (ja) * | 2007-02-06 | 2008-08-21 | Nitto Denko Corp | 光学部材用粘着剤層およびその製造方法、粘着剤付光学部材、ならびに画像表示装置 |
WO2012014814A1 (ja) * | 2010-07-30 | 2012-02-02 | 日東電工株式会社 | 透明導電性フィルム用粘着剤層、粘着剤層付き透明導電性フィルム、透明導電性積層体、およびタッチパネル |
JP2012092184A (ja) * | 2010-10-25 | 2012-05-17 | New Tac Kasei Co Ltd | 錫ドープ酸化インジウム膜用粘着剤および両面粘着シート |
JP2013054516A (ja) * | 2011-09-02 | 2013-03-21 | Nitto Denko Corp | 粘着剤層付き透明導電性フィルム、その製造方法及びタッチパネル |
WO2014103952A1 (ja) * | 2012-12-28 | 2014-07-03 | 日東電工株式会社 | 透明導電層用水分散型粘着剤組成物、透明導電層用粘着剤層、粘着剤層付き光学フィルム、及び、液晶表示装置 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5955579B2 (ja) * | 2011-07-21 | 2016-07-20 | 日東電工株式会社 | ガラスエッチング用保護シート |
-
2014
- 2014-06-26 WO PCT/JP2014/067062 patent/WO2014208696A1/ja active Application Filing
- 2014-06-27 TW TW103122407A patent/TWI695048B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008189838A (ja) * | 2007-02-06 | 2008-08-21 | Nitto Denko Corp | 光学部材用粘着剤層およびその製造方法、粘着剤付光学部材、ならびに画像表示装置 |
WO2012014814A1 (ja) * | 2010-07-30 | 2012-02-02 | 日東電工株式会社 | 透明導電性フィルム用粘着剤層、粘着剤層付き透明導電性フィルム、透明導電性積層体、およびタッチパネル |
JP2012092184A (ja) * | 2010-10-25 | 2012-05-17 | New Tac Kasei Co Ltd | 錫ドープ酸化インジウム膜用粘着剤および両面粘着シート |
JP2013054516A (ja) * | 2011-09-02 | 2013-03-21 | Nitto Denko Corp | 粘着剤層付き透明導電性フィルム、その製造方法及びタッチパネル |
WO2014103952A1 (ja) * | 2012-12-28 | 2014-07-03 | 日東電工株式会社 | 透明導電層用水分散型粘着剤組成物、透明導電層用粘着剤層、粘着剤層付き光学フィルム、及び、液晶表示装置 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016158513A1 (ja) * | 2015-03-31 | 2016-10-06 | 日東電工株式会社 | 液晶パネル及び画像表示装置 |
JP2016191865A (ja) * | 2015-03-31 | 2016-11-10 | 日東電工株式会社 | 液晶パネル及び画像表示装置 |
CN107430300A (zh) * | 2015-03-31 | 2017-12-01 | 日东电工株式会社 | 液晶面板及图像显示装置 |
CN107430300B (zh) * | 2015-03-31 | 2020-10-20 | 日东电工株式会社 | 液晶面板及图像显示装置 |
JP2017003906A (ja) * | 2015-06-15 | 2017-01-05 | 日東電工株式会社 | 両面粘着剤層付偏光フィルムおよび画像表示装置 |
US10310333B2 (en) | 2015-06-15 | 2019-06-04 | Nitto Denko Corporation | Double-sided pressure-sensitive-adhesive-layer-attached polarizing film, and image display device |
JP2018060172A (ja) * | 2016-09-29 | 2018-04-12 | 日東電工株式会社 | 粘着剤層付偏光フィルム及び画像表示装置 |
JP7030436B2 (ja) | 2016-09-29 | 2022-03-07 | 日東電工株式会社 | 粘着剤層付偏光フィルム及び画像表示装置 |
CN111936668A (zh) * | 2018-03-14 | 2020-11-13 | 株式会社自动网络技术研究所 | 表面保护剂组合物和具有端子的包覆电线 |
JP2020101814A (ja) * | 2020-02-13 | 2020-07-02 | 日東電工株式会社 | 両面粘着剤層付偏光フィルムおよび画像表示装置 |
JP2021140160A (ja) * | 2020-02-13 | 2021-09-16 | 日東電工株式会社 | 両面粘着剤層付偏光フィルムおよび画像表示装置 |
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