WO2014208695A1 - 粘着剤層付偏光フィルム、積層体、及び、画像表示装置 - Google Patents
粘着剤層付偏光フィルム、積層体、及び、画像表示装置 Download PDFInfo
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- WO2014208695A1 WO2014208695A1 PCT/JP2014/067059 JP2014067059W WO2014208695A1 WO 2014208695 A1 WO2014208695 A1 WO 2014208695A1 JP 2014067059 W JP2014067059 W JP 2014067059W WO 2014208695 A1 WO2014208695 A1 WO 2014208695A1
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- WIPO (PCT)
- Prior art keywords
- polarizing film
- adhesive layer
- sensitive adhesive
- pressure
- iodine
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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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
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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
- 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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- G—PHYSICS
- G06—COMPUTING OR CALCULATING; COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
Definitions
- the present invention relates to a polarizing film with an adhesive layer.
- the present invention provides a laminate in which the polarizing film with an adhesive layer and a substrate having a transparent conductive layer are bonded together, and an image in which the polarizing film with an adhesive layer and a liquid crystal panel having a transparent conductive layer are bonded.
- the present invention relates to a display device and an image display device using the laminate as a touch panel.
- transparent conductive films such as indium tin oxide (ITO) thin films have been widely used in various applications.
- the transparent conductive film is formed on the opposite side of the liquid crystal display device using an in-plane switching (IPS) type liquid crystal cell from the side in contact with the liquid crystal layer of the transparent substrate constituting the liquid crystal cell. It is known to be a layer.
- the transparent conductive film having the transparent conductive film formed on the transparent resin film is used for an electrode substrate of a touch panel, for example, a liquid crystal display device or an image display device used for a mobile phone, a portable music player, and the like. Input devices using a combination of touch panels have become widespread.
- a transparent conductive film in which a transparent conductive layer is formed on a transparent substrate made of a glass plate or a transparent resin film is used on a liquid crystal display device (visual recognition of a liquid crystal display device)
- the out-cell type provided on the upper side of the side polarizing film has been widely used.
- an on-cell type in which an electrode made of a transparent conductive film is formed on an upper glass substrate of a liquid crystal cell, or an electrode made of a transparent conductive film is used in a liquid crystal cell
- Various configurations are known, such as an in-cell type with internal capture. It is also known to realize a touch panel function by using an ITO layer as an antistatic layer of an image display device as a touch sensor and patterning it.
- a polarizing film with an adhesive layer is usually laminated on a liquid crystal cell having the antistatic layer, and the antistatic layer and the polarizing film are made of a transparent conductive film. Are bonded together via an adhesive layer.
- a transparent conductive film as an electrode application of a touch panel, depending on the configuration of the touch panel, a polarizing film with an adhesive layer is laminated on the transparent conductive film for an electrode, and an antistatic layer and a polarizing film made of a transparent conductive film May be bonded via an adhesive layer.
- the polarizing film is an iodine polarizing film
- the humidified durability test normal durability test
- the resistance value of the transparent conductive layer is There was a case of rising. It has been found that the increase in the resistance value is due to the corrosion of the transparent conductive layer when iodine contained in the polarizer oozes out to the pressure-sensitive adhesive layer and the iodine reaches the transparent conductive layer.
- the present invention provides a polarizing film with a pressure-sensitive adhesive layer that can suppress corrosion of the transparent conductive layer and suppress an increase in surface resistance of the transparent conductive layer even when laminated on the transparent conductive layer.
- the purpose is to provide.
- the present invention provides an image obtained by laminating the polarizing film with the pressure-sensitive adhesive layer, a laminate obtained by laminating a substrate having a transparent conductive layer, and the liquid crystal panel having the polarizing film with a pressure-sensitive adhesive layer and a transparent conductive layer.
- Another object is to provide a display device and an image display device using the laminate as a touch panel.
- the present inventors have used a pressure-sensitive adhesive layer formed from an acrylic pressure-sensitive adhesive composition containing a phosphoric acid compound and a (meth) acrylic polymer. The inventors have found that the object can be achieved, and have completed the present invention.
- the present invention provides at least one surface of an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and / or iodine ions.
- R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.
- iodine-based polarizer containing iodine and / or iodine ions means an iodine-based polarizer containing iodine, an 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.
- the iodine and / or iodine ion content in the iodine polarizer may be 1 to 14% by weight or 3 to 12% by weight.
- the phosphoric acid compound 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
- a mixture containing one or more phosphate esters selected from the group consisting of phosphate diesters is preferred.
- the phosphoric acid compound is a mixture containing 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 in 100 weight% of phosphoric acid compounds.
- the hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the iodine-based polarizing film is a single-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizer, and the surface of the single-sided protective polarizing film that does not have a transparent protective film, and the adhesive It is preferred that the layers are in contact.
- the iodine-based polarizer has a thickness of 10 ⁇ m or less.
- the total thickness of the iodine-based polarizing film is preferably 80 ⁇ m or less.
- the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the base material having the transparent conductive layer are bonded and used.
- the addition amount of the phosphoric acid compound is preferably 0.001 to 4 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
- the (meth) acrylic polymer preferably contains an alkyl (meth) acrylate and a hydroxyl group-containing monomer as monomer units.
- the hydroxyl group-containing monomer is preferably 4-hydroxybutyl acrylate.
- the weight average molecular weight of the (meth) acrylic polymer is preferably 1.2 million to 3 million.
- the acrylic pressure-sensitive adhesive composition preferably further contains a crosslinking agent, and the crosslinking agent is at least one crosslinking agent selected from the group consisting of peroxide-based crosslinking agents and isocyanate-based crosslinking agents. More preferably.
- the acrylic pressure-sensitive adhesive composition further contains an ionic compound.
- this invention makes the adhesive layer of the said polarizing film with an adhesive layer, and the transparent conductive layer of the said member contact the said polarizing film with an adhesive layer, and the transparent conductive member which has a transparent conductive layer. It is related with the laminated body characterized by having bonded together.
- the transparent conductive layer is preferably formed of indium tin oxide, and the indium tin oxide is more preferably amorphous indium tin oxide.
- this invention is the adhesive layer of the said polarizing film with an adhesive layer, and the liquid crystal panel which has a transparent conductive layer,
- the adhesive layer of the said polarizing film with an adhesive layer and the transparent conductive layer of the said liquid crystal panel are The present invention relates to an image display device that is bonded so as to come into contact with each other.
- this invention relates to the image display apparatus characterized by using the said laminated body as a touchscreen.
- the polarizing film with the pressure-sensitive adhesive layer of the present invention uses an iodine-based polarizer, even when a transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer, corrosion of the transparent conductive layer is suppressed.
- the increase in surface resistance of the transparent conductive layer can be suppressed.
- the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer of the present invention contains a phosphoric acid compound.
- the phosphoric acid compound contains phosphoric acid
- a passive film is formed on the surface of the transparent conductive layer with phosphoric acid and metal ions in the transparent conductive layer.
- the phosphoric acid compound contains a phosphoric acid compound (for example, phosphoric acid ester, etc.), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film, and as a result, in the polarizer This is probably because the iodine does not migrate to the surface of the transparent conductive layer, and the corrosion of the transparent conductive layer is hindered.
- a phosphoric acid compound for example, phosphoric acid ester, etc.
- Polarizing film with pressure-sensitive adhesive layer The polarizing film with a pressure-sensitive adhesive layer of the present invention is provided on at least one surface of an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and / or iodine ions.
- R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.
- the iodine polarizing film used in the present invention has a transparent protective film on at least one side of an iodine polarizer containing iodine and / or iodine ions.
- it may be a single-sided protective polarizing film having a transparent protective film on one side of the iodine-based polarizer or a double-sided protective polarizing film having transparent protective films on both sides of the iodine-based polarizer.
- the protective polarizing film is used, the effect of the present invention is remarkable.
- the effect of this invention is remarkable also when the thickness of the transparent protective film in the side which contact
- an adhesive layer can be directly provided on the polarizer surface of the side which does not have the said transparent protective film.
- any iodine-based polarizer can be used as long as it contains iodine and / or iodine ions.
- polyvinyl alcohol (PVA) film partially formalized PVA film
- a polarizer made of a PVA film and iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer obtained by dyeing a PVA-based film with iodine and uniaxially stretching it can be produced, for example, by dyeing PVA in an iodine aqueous 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 PVA film may be immersed in water and washed before dyeing. Washing the PVA film with water can clean the surface of the PVA film and the anti-blocking agent. In addition, swelling the PVA film has the effect of preventing unevenness such as uneven 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 iodine-based polarizer having a thickness of 10 ⁇ m or less can also be suitably used.
- the thickness is preferably 1 to 7 ⁇ m.
- Such a thin iodine-based 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 a PVA-based resin layer and a stretching resin substrate in the state of a laminate and a step of dyeing. 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.
- the thin polarizing film can be stretched at a high magnification and can improve the polarization performance among the production methods including a step of stretching in the state of a laminate and a step of dyeing.
- WO2010 / 100917 Pamphlet In particular, 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.
- the iodine-based polarizer used in the present invention may have an iodine and / or iodine ion content (hereinafter sometimes referred to as iodine content) of 1 to 14% by weight in the polarizer. It may be ⁇ 12% by weight or 4 ⁇ 7.5% by weight.
- the polarizing film with a pressure-sensitive adhesive layer of the present invention suppresses an increase in the surface resistance of the transparent conductive layer laminated on the polarizing film with a pressure-sensitive adhesive layer even if the iodine content in the iodine-based polarizer is as large as the above range. it can.
- the phosphoric acid compound contained in the pressure-sensitive adhesive layer forms a film on the surface of the transparent conductive layer. This is probably because the corrosion of the layer is prevented.
- the phosphoric acid compound contains phosphoric acid
- the phosphoric acid forms a passive film with the metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and the phosphoric acid compound is phosphoric acid.
- the phosphate compound can be selectively adsorbed on the surface of the transparent conductive layer to form a film.
- 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 iodine polarizer and the transparent 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 iodine-based polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
- the total thickness of the iodine-based polarizing film used in the present invention is preferably 80 ⁇ m or less, more preferably 70 ⁇ m or less, and more preferably 60 ⁇ m or less in order to meet the demand for thinning the polarizing film with the pressure-sensitive adhesive layer. More preferably. Although it does not specifically limit as a minimum of the total thickness of a polarizing film, For example, 10 micrometers is mentioned.
- Adhesive layer used for the polarizing film with an adhesive layer of this invention is formed from an acrylic adhesive composition.
- Acrylic adhesive composition The following general formula (1): (In the formula, R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.) And a phosphoric acid compound selected from the group consisting of multimers of the compound represented by the general formula (1), and a (meth) acrylic polymer.
- phosphoric acid compounds examples include phosphoric acid, phosphoric acid esters, salts thereof, dimers, trimers and the like as described later. These will be described in detail below.
- 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.
- 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.
- phosphoric acid H 3 PO 4 in which both R 1 and R 2 in the general formula (1) are hydrogen atoms
- salts of the phosphoric acid metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.
- metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.
- the compound shown by General formula (1) is acidic phosphate ester.
- the acidic phosphoric acid ester is a hydrocarbon residue having 1 to 18 carbon atoms in which both R 1 and R 2 in the general formula (1) may contain an oxygen atom ( A diester form) or one of R 1 and R 2 is a hydrogen atom and the other is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom (monoester form)
- R 1 is as defined above
- 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
- n is (I
- 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 having 1 to 18 carbon atoms from the viewpoint of the adsorption effect on the adherend.
- the phosphoric acid monoester which is a group is preferable, R 1 is a hydrogen atom, R 3 is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and R 1 is a hydrogen atom. More preferably, R 3 is a phosphoric acid monoester in which R 3 is a linear or branched alkyl group having 2 to 6 carbon atoms.
- two or more compounds represented by the general formula (2) may be mixed and used, or a mixture of the compound represented by the general formula (2) and the phosphoric acid may be used. You can do it.
- the phosphoric ester compound represented by the general formula (2) is often obtained as a mixture of a monoester and a diester, and the phosphoric acid is further added to the mixture of the monoester and the diester. Are preferably used.
- 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 phosphoric acid compound used in the present invention is selected from the group represented by the compound represented by the general formula (1) (or the compound represented by the general formula (2)), or a salt or multimer thereof.
- the compounds may be used alone or in admixture of two or more, but adherends (particularly adherends having a layer made of metal or metal oxide or metal or metal oxide) From the viewpoint of the adsorbing effect on the phosphoric acid, it is preferably a mixture of two or more selected from the group consisting of phosphoric acid, phosphoric monoester, and phosphoric diester, and includes phosphoric acid and phosphoric monoester And a mixture containing one or more phosphate esters selected from the group consisting of phosphoric acid diesters, and particularly preferably a mixture containing phosphate monoesters and phosphoric acid.
- 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 is not sufficiently compatible with acrylic polymers, so phosphoric acid bleeds out to the surface of the adhesive layer, resulting in problems with durability. There is a case.
- 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). There is a case.
- 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 in 100% by weight of the phosphoric acid compound.
- 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 adherend is considered to be related to the adherence surface and the phosphate compound, which is defined by the HSAB rule, that is, the “hard and soft acid-base law”.
- the adsorption effect is high, 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.
- 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 10 to 700 mgKOH / g. From the viewpoint of handling in production, the acid value of the phosphoric acid compound is preferably 400 mgKOH / g or less, more preferably 50 to 400 mgKOH / g, and 50 to 350 mgKOH / g. Is more preferable, and 100 to 300 mgKOH / g is particularly preferable.
- the phosphoric acid compound may act as a reaction catalyst for the cross-linking reaction depending on the type of cross-linking agent described below (for example, an isocyanate-based cross-linking agent), and in that case, the pot life as an adhesive is shortened. There was a case.
- the acid value of a phosphoric acid compound into the said range, since it can suppress acting as a reaction catalyst, it is preferable from a viewpoint of the pot life of an adhesive.
- examples of the multimer of the compound represented by the general formula (1) include a dimer and a trimer of the compound represented by the general formula (1).
- the addition amount of the phosphoric acid compound is preferably 0.001 to 4 parts by weight and more preferably 0.001 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer described later.
- the amount is 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight, still more preferably 0.01 to 1 part by weight, and 0.02 to 0. 0 part by weight. 2 parts by weight is particularly preferred.
- the addition amount of the phosphoric acid compound is within the above range because an increase in the surface resistance value of the transparent conductive layer can be suppressed and durability against heating and humidification can be improved.
- phosphoric acid compounds such as phosphoric acid and phosphoric acid ester, can be used together, in that case, it can add so that a total amount may become the said range.
- the pressure-sensitive adhesive layer-attached polarizing film having the pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition containing the phosphoric acid compound on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive layer-attached polarizing film, Even if a transparent conductive layer is laminated, an increase in surface resistance of the transparent conductive layer can be suppressed.
- the phosphoric acid When phosphoric acid is contained in the phosphoric acid compound, the phosphoric acid forms a passive film with the metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and the iodine in the polarizer reaches the surface of the transparent conductive layer.
- the phosphoric acid compound contains a phosphoric acid compound (for example, phosphoric acid ester, etc.), the phosphoric acid compound is selective.
- iodine in the polarizer does not migrate to the surface of the transparent conductive layer, and as a result, corrosion of the transparent conductive layer is hindered.
- the metal oxide is corroded by a mechanism different from the generally known metal corrosion.
- a metal oxide such as ITO
- iodine derived from a polarizer soaks into the metal oxide layer and lowers the carrier mobility of the metal oxide, so that the resistance value increases.
- the (meth) acrylic polymer used in the present invention is not particularly limited.
- the (meth) acrylic polymer is preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate. It is preferably obtained by polymerizing a monomer component containing a (meth) acrylate and a hydroxyl group-containing monomer.
- Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
- alkyl group related to the alkyl (meth) acrylate various linear or branched ones can be used.
- Specific examples of the alkyl (meth) acrylate include, for example, propyl (meth) acrylate, 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)
- alkyl (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are preferable, (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable, n-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate is more preferred, and n-butyl (meth) acrylate is particularly preferred.
- the alkyl (meth) acrylate is preferably 50 parts by weight or more, preferably 60 parts by weight or more, and 70 parts by weight or more with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. Is more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.
- hydroxyl 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 hydroxyl group can be used without particular limitation.
- hydroxyl group-containing monomer examples 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. Among these, 4-hydroxybutyl acrylate is preferable.
- an isocyanate-based crosslinking agent when used as the crosslinking agent described later, the use of 4-hydroxybutyl acrylate as the hydroxyl group-containing monomer can efficiently secure a crosslinking point with the isocyanate group of the isocyanate-based crosslinking agent. This is preferable because it is possible.
- the hydroxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 1 to 3 parts by weight is more preferable.
- the monomer component forming the (meth) acrylic polymer used in the present invention may contain the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, and optionally the hydroxyl group-containing monomer.
- alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms
- hydroxyl group-containing monomer optionally the hydroxyl group-containing monomer.
- carboxyl group-containing monomers, aryl group-containing monomers, and other copolymerization monomers can be used as monomer components.
- 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 10 parts by weight or less, more preferably 8 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer, and in particular, almost influence on the transparent conductive layer. In terms of the amount not added, it is more preferably 6 parts by weight or less, further preferably 2 parts by weight or less, and particularly preferably 0.5 parts by weight or less.
- 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 proportion of the aryl group-containing monomer is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, and further preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 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.
- epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; for example, alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyeth
- 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 20 parts by weight or less, and even more preferably 15 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 10 parts by weight or less is particularly preferable.
- 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 acrylic adhesive composition, transparent conductive layer, etc. May decrease.
- the weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably in the range of 1,200,000 to 3,000,000, more preferably 1,200,000 to 2,700,000, and even more preferably 1,200,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it may not be preferable in terms 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. Moreover, the pressure-sensitive adhesive layer obtained using a (meth) acrylic polymer 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. Moreover, it is preferable from a viewpoint of corrosion resistance and durability because a weight average molecular weight exists in the said range.
- the weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).
- the production of such a (meth) acrylic polymer 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. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
- 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 a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.
- 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 100 weight of monomer component forming the (meth) acrylic polymer.
- the amount is preferably about 0.005 to 1 part by weight with respect to parts.
- 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 100% of all monomer components constituting the (meth) acrylic polymer.
- 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, and more preferably 0.05 to 1 part by weight. Particularly preferred is 0.7 part by weight.
- 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 proportion is preferably 0.005 to 0.7 parts by weight with respect to 100 parts by weight of all monomer components constituting the (meth) acrylic polymer.
- the acrylic pressure-sensitive adhesive composition used in the present invention is preferable because a cohesive force related to the durability of the pressure-sensitive adhesive can be imparted by adding a crosslinking agent.
- a polyfunctional compound is used, and an organic crosslinking agent and a polyfunctional metal chelate are exemplified.
- the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a peroxide crosslinking agent.
- a polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound.
- polyvalent metal atoms examples 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.
- 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. Among these, a peroxide type crosslinking agent and an isocyanate type crosslinking agent are preferable, and it is more preferable to use these in combination.
- 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
- 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 blending ratio of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is usually about 10 parts by weight or less of the crosslinking agent (solid content) with respect to 100 parts by weight of the (meth) acrylic polymer (solid content). Formulated in proportions.
- the blending ratio of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight.
- a peroxide-based crosslinking agent when a peroxide-based crosslinking agent is used, about 0.05 to 1 part by weight is preferable with respect to 100 parts by weight of the (meth) acrylic polymer (solid content), and 0.06 to 0.001. 5 parts by weight is more preferred.
- an ionic compound to the acrylic pressure-sensitive adhesive composition used in the present invention from the viewpoint of preventing the film from being charged during the process operation.
- an alkali metal salt and / or an organic cation-anion salt can be preferably used.
- an organic salt or inorganic salt of an alkali metal can be used.
- organic cation-anion salt refers to an organic salt whose cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. There may be. “Organic cation-anion salt” is also called an ionic liquid or ionic solid.
- alkali metal salt examples include lithium, sodium, and potassium ions. Of these alkali metal ions, lithium ions are preferred.
- the anion part of the alkali metal salt may be composed of an organic material or an inorganic material.
- Examples of the anion part constituting the organic salt include CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , and C 4 F 9 SO 3.
- an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained.
- the anion part constituting the inorganic salt includes Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , AsF 6 ⁇ , SbF. 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN) 2 N ⁇ , and the like are used.
- (perfluoroalkylsulfonyl) imide represented by the general formula (4) such as (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , etc. is preferable, (Trifluoromethanesulfonyl) imide represented by CF 3 SO 2 ) 2 N ⁇ is preferable.
- alkali metal organic salts include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, lithium hexafluorophosphate (LiPF 6 ), LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (C 4 F 9 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C, KO 3 S (CF 2 ) 3 SO 3 K, LiO 3 S (CF 2 ) 3 SO 3 K and the like can be mentioned.
- lithium hexafluorophosphate (LiPF 6 ), LiCF 3 SO 3 , Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) 2 N, Li (CF 3 SO 2) 3 C are preferable Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) fluorine-containing lithium imide salt is more preferred, such as 2 N, lithium hexafluorophosphate ( LiPF 6 ) and lithium bistrifluoromethanesulfonylimide (LiTFSI, Li (CF 3 SO 2 ) 2 N) are particularly preferred.
- examples of the alkali metal inorganic salt include lithium perchlorate and lithium iodide.
- the organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is composed of an organic substance.
- the cation component specifically, pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, Examples include pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, and tetraalkylphosphonium cation.
- anion component examples include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO.
- a compound comprising a combination of the above cation component and anion component is appropriately selected and used.
- CIL-314 manufactured by Nippon Carlit Co., Ltd.
- ILA2-1 manufactured by Guangei Chemical Industry Co., Ltd.
- tetramethylammonium bis (trifluoromethanesulfonyl) imide trimethylethylammonium bis (trifluoromethanesulfonyl) imide, trimethylbutylammonium bis (trifluoromethanesulfonyl) imide, trimethylpentylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptyl Ammonium bis (trifluoromethanesulfonyl) imide, trimethyloctylammonium bis (trifluoromethanesulfonyl) imide, tetraethylammonium bis (trifluoromethanesulfonyl) imide, triethylbutylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium bis (trifluoromethanesulfonyl) Imide, te
- 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethane) Sulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl
- bis (trifluoromethanesulfonyl) imide bis (pentafluorosulfonyl) imide, bis (heptafluoropropanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, trifluoromethanesulfonyl nonafluorobutanesulfonylimide, And compounds using heptafluoropropanesulfonyl trifluoromethanesulfonylimide, pentafluoroethanesulfonylnonafluorobutanesulfonylimide, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide anion, and the like.
- ionic compound examples include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the alkali metal salt and organic cation-anion salt. . These ionic compounds can be used alone or in combination.
- the mixing ratio of the ionic compound in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is preferably about 10 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (solid content). More preferably, it is more preferably 2 parts by weight or less. Moreover, although a lower limit is not specifically limited, 0.01 weight part or more is preferable.
- the acrylic pressure-sensitive adhesive composition used in the present invention includes, as necessary, a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and others.
- a viscosity modifier e.g., a Brookcosity modifier, a stackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and others.
- Various kinds of fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, etc. which do not depart from the object of the present invention.
- These additives can also be used as appropriate.
- These additives can also be blended as an emulsion.
- Polarizing film with pressure-sensitive adhesive layer forms a pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition on at least one surface of the iodine-based polarizing film. It is obtained with.
- the method for forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive layer is formed by applying the acrylic pressure-sensitive adhesive composition on various substrates, drying it with a dryer such as a heat oven, and evaporating the solvent. And forming the pressure-sensitive adhesive layer by directly applying the acrylic pressure-sensitive adhesive composition onto the iodine-based polarizing film. May be.
- 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 a coating method on the substrate or polarizing film. 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 acrylic pressure-sensitive adhesive composition. For example, about 80 to 170 ° C., preferably 90 to 200. C. for 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 10 ⁇ 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 acrylic pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer cannot be fully dried at the time of drying and air bubbles remain, or the pressure-sensitive adhesive layer There is a tendency that unevenness in thickness occurs on the surface of the surface, and problems in appearance tend to become obvious.
- 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 film substrate is preferably 15 to 200 ⁇ m.
- an anchor layer may be provided between the iodine-based polarizing 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. Among these, polymers are particularly preferably used.
- the polymer may be used in any of a solvent-soluble type, a water-dispersed type, and a water-soluble type.
- polymers examples include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, polystyrene resins, and the like.
- polyurethane resins, polyester resins, and acrylic resins are particularly preferable. These resins can be appropriately mixed with a crosslinking agent.
- These other binder components can be used singly or in combination of two or more as appropriate.
- a water dispersion polymer When the anchor layer is formed of a water dispersion material, a water dispersion polymer is used.
- the water-dispersible polymer include those obtained by emulsifying various resins such as polyurethane and polyester using an emulsifier, and introducing a water-dispersible anionic group, cationic group, or nonionic group into the resin. Examples include self-emulsified ones.
- the anchor agent can contain an antistatic agent.
- the antistatic agent is not particularly limited as long as it is a material that can impart conductivity, and examples thereof include ionic surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. Among these, a conductive polymer is preferable, and a water-dispersible conductive polymer is more preferable.
- water-soluble conductive polymer examples include polyaniline sulfonic acid (weight average molecular weight of 150,000 in terms of polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.). TRON series).
- the blending amount of the antistatic agent is, for example, 70 parts by weight or less, preferably 50 parts by weight or less with respect to 100 parts by weight of the polymers used for the anchor agent. From the viewpoint of the antistatic effect, it is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more.
- the anchor agent can be blended with various additives for the purpose of suppressing deterioration of the pressure-sensitive adhesive layer and the polarizer generated when contacting the anchor coat layer, and imparts 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 thickness of the anchor layer is not particularly limited, but is preferably 5 to 300 nm.
- the method for forming the anchor layer is not particularly limited and can be performed by a generally known method.
- the iodine polarizing 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 method for forming the pressure-sensitive adhesive layer on the anchor layer on the iodine-based polarizing film is as described above.
- the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer of the present invention may be protected with a release film (separator) until practical use.
- a release film is used as a base material in the production of the above-mentioned pressure-sensitive adhesive layer
- the release film is bonded to the iodine-type polarizing film by bonding the pressure-sensitive adhesive layer on the release film to the pressure-sensitive adhesive layer. It can be used as a release film for the pressure-sensitive adhesive layer of the attached polarizing film, and the process can be simplified.
- the laminated body of this invention is the transparent conductive layer of the member which has the adhesive layer of the said polarizing film with an adhesive layer, and the member which has the said transparent conductive layer. It is characterized by being bonded so as to be in contact with each other.
- the above-mentioned polarizing film with an adhesive layer can be used.
- the member having a transparent conductive layer is not particularly limited, and a known member can be used. However, a member having a transparent conductive layer on a transparent substrate such as a transparent film, a transparent conductive layer and a liquid crystal can be used. The member which has a cell can be mentioned.
- 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.
- indium oxide (ITO) containing tin oxide and tin oxide containing antimony are preferably used, and ITO is particularly preferably used.
- ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
- examples of the ITO include crystalline ITO and non-crystalline (amorphous) ITO.
- Crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating amorphous ITO. Since the deterioration due to iodine occurs remarkably in non-crystalline ITO, the polarizing film with the pressure-sensitive adhesive layer of the present invention is particularly effective in non-crystalline ITO.
- the thickness of the transparent conductive layer is not particularly limited, but is preferably 7 nm or more, more preferably 10 nm or more, further preferably 12 to 60 nm, further preferably 15 to 45 nm, 18 More preferably, the thickness is set to ⁇ 45 nm, and particularly preferably 20 to 30 nm. If the thickness of the transparent conductive layer is less than 7 nm, the transparent conductive layer is likely to be deteriorated by iodine, and the change in the electric resistance value of the transparent conductive layer tends to increase. On the other hand, when it exceeds 60 nm, the productivity of the transparent conductive layer decreases, the cost also increases, and the optical characteristics tend to decrease.
- 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 substrate of the liquid crystal cell including the configuration of a substrate (for example, a glass substrate) / liquid crystal layer / substrate used in an image display device such as various liquid crystal display devices.
- a transparent conductive layer on the side not in contact with the liquid crystal layer.
- a transparent conductive layer may be provided on the color filter. The method for forming the transparent conductive layer on the substrate of the liquid crystal cell is the same as described above.
- Image display device The laminate of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) provided with an input device (touch panel, etc.), input device
- image display device liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.
- input device touch panel, etc.
- the base material member
- it is especially suitable in manufacture of the optical base material for touch panels.
- it can be used suitably in manufacture of the base material (member) which comprises apparatuses, such as (a touch panel etc.), or the base material (member) used for these apparatuses
- optical base material for touch panels Can be used.
- 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 polarizing film with the pressure-sensitive adhesive layer of the present invention can suppress corrosion of the transparent conductive layer even when the transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer.
- the increase in surface resistance of the transparent conductive layer can be suppressed. Therefore, if it is an image display apparatus which has the structure which the adhesive layer of the polarizing film with an adhesive layer touches a transparent conductive layer, the polarizing film with an adhesive layer of this invention can be used conveniently.
- the liquid crystal panel having the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the present invention is bonded so that the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the liquid crystal panel are in contact with each other, An image display device can be obtained.
- an image display device using the transparent conductive layer as an antistatic layer application and an image display device using the 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 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.
- 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.
- iodine content in polarizer was measured by the following procedure. 1) X-ray fluorescence intensity was measured for a plurality of polarizers containing a predetermined amount of potassium iodide, and a relational expression between iodine content and fluorescence X-ray intensity was derived. 2) Fluorescent X-rays of an iodine polarizer with unknown iodine content were measured, and the iodine amount was calculated from the numerical values using the relational expression.
- a stretched laminate was produced from the laminate in which a 9 ⁇ m-thick polyvinyl alcohol (PVA) layer was formed on an amorphous PET substrate by air-assisted stretching at a stretching temperature of 130 ° C.
- the stretched laminate was immersed in a dyeing solution containing 0.1 parts by weight of iodine and 0.7 parts by weight of potassium iodide with respect to 100 parts by weight of water to produce a colored laminate.
- an optical film laminate including a 4 ⁇ m-thick PVA layer in which the colored laminate is stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 ° C.
- the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 ⁇ m, which constitutes a highly functional polarizing layer.
- a saponified 40 ⁇ m thick acrylic resin film transparent protective film (1)
- a PVA adhesive to the surface of the polarizing layer of the optical film laminate
- an amorphous PET group The material was peeled off to produce a polarizing film having a transparent protective film only on one side using a thin iodine-based polarizer.
- a polarizing film (1) The iodine content of the polarizing film (1) was 5.1% by weight.
- Production Examples 2 and 3 Transparent protection only on one side using a thin iodine-based polarizer, as in Production Example 1, except that the dyeing time was changed from 60 seconds to 120 seconds (Production Example 2) and 180 seconds (Production Example 3).
- a polarizing film having a film was prepared.
- polarizing films (2) and (3) These are referred to as polarizing films (2) and (3).
- the iodine contents of the polarizing films (2) and (3) were 7.2% by weight and 11.1% by weight, respectively.
- Production Example 4 (Production of Polarizing Film (4)) A polyvinyl alcohol film having a thickness of 80 ⁇ m was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Then, the total draw ratio was drawn up to 6 times while being immersed in an aqueous solution containing 60%, 4% concentration boric acid and 10% concentration 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, it was dried at 50 ° C. for 4 minutes, having a thickness of 25 ⁇ m and an iodine content of 2.3% by weight.
- a polarizer was obtained.
- An acrylic resin film (transparent protective film (1)) having a thickness of 40 ⁇ m was bonded to one surface of the polarizer with a polyvinyl alcohol-based adhesive to produce a polarizing film.
- a polarizing film (4) This is referred to as a polarizing film (4).
- the iodine content of the polarizing film (4) was 2.3% by weight.
- Production Example 5 (Production of Polarizing Film (5)) After peeling off the amorphous PET substrate in Production Example 1, a norbornene-based film (transparent protective film (2)) having a thickness of 25 ⁇ m was bonded to the other surface with a polyvinyl alcohol-based adhesive to obtain a polarizing film. Produced. Hereinafter, this is referred to as a thin polarizing film (5).
- the iodine content of the polarizing film (5) was 5.1% by weight.
- Production Example 6 (Production of Polarizing Film (6)) A 40 ⁇ m thick acrylic resin film (transparent protective film (1)) and a 25 ⁇ m thick norbornene film (transparent protective film (transparent protective film (1)) are formed on both sides of a polarizer having an iodine content of 2.3% by weight obtained in Production Example 4. 2)) was bonded with a polyvinyl alcohol adhesive to produce a polarizing film.
- a polarizing film (6) The iodine content of the polarizing film (6) was 2.3% by weight.
- Polarizers of the polarizing films (1) to (6) obtained in Production Examples 1 to 6 transparent protective film thickness, total polarizing film thickness, iodine content (content of iodine and / or iodine ions in the polarizer) are summarized in Table 1 below.
- Production Example 7 (Preparation of solution containing acrylic polymer (A-1))
- a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 2,2′-azobisisobutyronitrile (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. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-1) having a weight average molecular weight of 1.6 million (solid content concentration: 30% by weight).
- Production Example 8 (Preparation of a solution containing an acrylic polymer (A-2))
- a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer 99 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, and AIBN as an initiator for 100 parts of monomer (solid content) 1 part was added with ethyl acetate, and it was made to react at 60 degreeC under nitrogen gas stream for 7 hours. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-2) having a weight average molecular weight of 1.6 million (solid content concentration: 30% by weight).
- Production Example 9 (Production of solution containing acrylic polymer (A-3)) To a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 100 parts of butyl acrylate and, as an initiator, 1 part of AIBN with 100 parts of monomer (solid content) are added together with ethyl acetate. The reaction was carried out 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 acrylic polymer (A-3) having a weight average molecular weight of 1.6 million (solid content concentration 30% by weight).
- Production Example 10 (Preparation of a solution containing an acrylic polymer (A-4))
- a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirring device 98.6 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 0.4 part of acrylic acid, and AIBN as a monomer (Solid content) 1 part with 100 parts of ethyl acetate was added 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 acrylic polymer (A-4) having a weight average molecular weight of 1,600,000 (solid content concentration: 30% by weight).
- Production Example 11 (Production of solution containing acrylic polymer (A-5))
- a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and AIBN as a monomer (solid content)
- ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-5) having a weight average molecular weight of 150,000 (solid content concentration 30% by weight).
- Production Example 12 (Preparation of solution containing acrylic polymer (A-6))
- a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirring device 91 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, 8 parts of acrylic acid, and AIBN as a monomer (solid content)
- 0.75 part was added together with ethyl acetate and reacted at 60 ° C. for 9 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-6) having a weight average molecular weight of 1.9 million (solid content concentration: 30% by weight).
- Production Example 13 (Preparation of solution containing acrylic polymer (A-7))
- a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and AIBN as an initiator for 100 parts of monomer (solid content) 1.5 parts was added 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 acrylic polymer (A-7) having a weight average molecular weight of 900,000 (solid content concentration: 30% by weight).
- Production Example 14 (Production of solution containing acrylic polymer (A-8))
- 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 acrylic polymer (A-8) having a weight average molecular weight of 1,800,000 (solid content concentration: 30% by weight).
- weight average molecular weights of the acrylic polymers obtained in Production Examples 7 to 14 were measured by the following measuring method. ⁇ Measurement of weight average molecular weight (Mw) of acrylic polymer> The weight average molecular weight of the prepared acrylic polymer 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
- Trimethylolpropane xylylene diisocyanate trade name: Takenate D110N
- a crosslinking agent per 100 parts of solid content of the solution containing the acrylic polymer (A-1) obtained in Production Example 7 (solid content concentration: 30% by weight) 0.1 part of Mitsui Chemicals Co., Ltd.), 0.3 part of dibenzoyl peroxide, and 0 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound.
- 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 polarizing film (1), and the polarizing film with an adhesive layer was produced.
- Examples 2-5 A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the phosphoric acid compound was changed from 0.03 part to the number of parts shown in Table 3.
- Example 6 Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.1 part of Phosphanol RS-410 (manufactured by Toho Chemical Industry Co., Ltd.) In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Phosphanol SM-172 trade name, manufactured by Toho Chemical Industry Co., Ltd.
- Phosphanol RS-410 manufactured by Toho Chemical Industry Co., Ltd.
- Example 7 Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.1 part of Phosphanol RS-710 (manufactured by Toho Chemical Industry Co., Ltd.) In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Phosphanol SM-172 trade name, manufactured by Toho Chemical Industry Co., Ltd.
- Phosphanol RS-710 manufactured by Toho Chemical Industry Co., Ltd.
- Example 8 Except for changing 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to 0.05 part of DBP (manufactured by Johoku Chemical Co., Ltd.), the same as in Example 1. A polarizing film with an adhesive layer was prepared.
- Example 9 Except for changing 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to 0.03 part of phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.) In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Phosphanol SM-172 trade name, manufactured by Toho Chemical Industry Co., Ltd.
- phosphoric acid special grade reagent
- Examples 10-14 The solutions containing the acrylic polymer (A-1) obtained in Production Example 7 are the solutions containing the acrylic polymers (A-2) to (A-6) obtained in Production Examples 8 to 12, respectively.
- a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the change was made.
- Examples 15-17 In the same manner as in Example 1 except that the polarizing film (1) is changed to the polarizing films (2), (3), and (4) in (Preparation of polarizing film with pressure-sensitive adhesive layer) in Example 1, A polarizing film with an agent layer was produced.
- Example 18 Adjustment of acrylic adhesive composition
- Trimethylolpropane xylylene diisocyanate trade name: Takenate D110N
- a crosslinking agent per 100 parts of solid content of the solution containing the acrylic polymer (A-1) obtained in Production Example 7 (solid content concentration: 30% by weight) 0.1 part of Mitsui Chemicals Co., Ltd.), 0.3 part of dibenzoyl peroxide, and 0 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound.
- a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition was used.
- Example 19 0.5 part of lithium bistrifluoromethanesulfonylimide (Morita Chemical Co., Ltd.) is added to 0.5 part of 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (Kishida Chemical Co., Ltd.) A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 18 except for changing to.
- Example 20 The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and phosphanol SM- 172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 parts was changed to 0.05 parts of phosphoric acid (special reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.), as in Example 1. Thus, a polarizing film with an adhesive layer was produced.
- phosphoric acid special reagent grade
- Example 21 A polarizing film with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 20, except that the addition amount of phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.) was changed from 0.05 part to 0.1 part. Produced.
- phosphoric acid special grade reagent
- Example 22 Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 part, MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.01 Except having changed into the part, it carried out similarly to Example 1, and produced the polarizing film with an adhesive layer.
- Example 23 Except that the addition amount of MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.01 part to 0.06 part, the same as in Example 22, A polarizing film with an adhesive layer was prepared.
- MP-4 trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.
- Example 24 The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and phosphanol SM- 172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 parts was changed to MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.1 parts Produced a polarizing film with an adhesive layer in the same manner as in Example 1.
- Example 25 and 26 Example 24 except that the addition amount of MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.8 part and 3 parts. In the same manner, a polarizing film with a pressure-sensitive adhesive layer was produced.
- MP-4 trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.
- Example 27 The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and phosphanol SM- 172 (trade name, manufactured by Toho Chemical Co., Ltd.) 0.03 parts, MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.04 parts and phosphoric acid ( A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the mixture was changed to 0.01 parts of a reagent special grade (Wako Pure Chemical Industries, Ltd.).
- Example 28 The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and phosphanol SM- 172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 parts, Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.04 parts and phosphoric acid (special grade reagent) (Japanese A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the mixture was changed to 0.01 part of a mixture of Kojunkaku Kogyo Co., Ltd.
- Examples 29-34 Polarized light with pressure-sensitive adhesive layer in the same manner as in Example 1 except that the type of solution containing the acrylic polymer and the type and amount added of the phosphoric acid compound were changed to the types and parts shown in Table 3. A film was prepared.
- Comparative Example 1 The procedure was carried out except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-2) obtained in Production Example 8, and the phosphate ester was not used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Comparative Example 2 The procedure was carried out except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-3) obtained in Production Example 9 and no phosphate ester was used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Comparative Example 3 The procedure was carried out except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-5) obtained in Production Example 11 and no phosphate ester was used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Comparative Example 4 The procedure was carried out except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-7) obtained in Production Example 13 and no phosphate ester was used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
- Examples 35 and 36 In the same manner as in Example 1 except that the polarizing film (1) was changed to the polarizing films (5) and (6) in (Preparation of polarizing film with pressure-sensitive adhesive layer) in Example 1, polarized light with pressure-sensitive adhesive layer. A film was prepared. The pressure-sensitive adhesive layer was laminated on the protective film (2) side.
- Example 37 A polarizing film with an adhesive layer was prepared in the same manner as in Example 24 except that the polarizing film (1) was changed to the polarizing film (5) in (Preparation of polarizing film with an adhesive layer) in Example 24. .
- the pressure-sensitive adhesive layer was laminated on the protective film (2) side.
- Example 1 Adjustment of acrylic pressure-sensitive adhesive composition
- a phosphoric acid ester was not used, and in (Preparation of polarizing film with pressure-sensitive adhesive layer), the polarizing film (1) was changed to a polarizing film (5).
- a polarizing film with a pressure-sensitive adhesive layer was produced.
- the pressure-sensitive adhesive layer was laminated on the protective film (2) side.
- Example 1 Preparation of acrylic pressure-sensitive adhesive composition
- the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-3) obtained in Production Example 9.
- the polarizing film (1) was changed to the polarizing film (6) in (Preparation of polarizing film with pressure-sensitive adhesive layer) without using a phosphate ester.
- a polarizing film with a layer was produced.
- the pressure-sensitive adhesive layer was laminated on the protective film (2) side.
- the phosphoric acid compounds used in Examples and Comparative Examples were analyzed as follows. The results are shown in Table 2. (Analysis method) The composition of the phosphoric acid compound used in Examples and Comparative Examples was calculated based on the measurement result 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).
- ⁇ Corrosion resistance test> A conductive film (trade name: Electrysta (P400L), manufactured by Nitto Denko Co., Ltd.) with an ITO layer formed on the surface is cut into 15 mm ⁇ 15 mm.
- the sample obtained in the example was cut to 8 mm ⁇ 8 mm and bonded together, and then subjected to autoclaving at 50 ° C. and 5 atm for 15 minutes was used as a corrosion resistance measurement sample.
- the resistance value of the obtained measurement sample was measured using a measuring device described later, and this was set as “initial resistance value”. Thereafter, 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”.
- 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
- B-5 phosphoric acid (reagent special grade), Wako Pure Chemical Industries, Ltd.
- B-6 MP-4, acid value: 670 mg KOH / g, mono- Di mixture, manufactured by Daihachi Chemical Industry Co., Ltd.
- E-1 Lithium bistrifluoromethanesulfonylimide (Morita Chemical Co., Ltd.)
- E-2 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.)
- the iodine content in Tables 3 and 5 is the content (% by weight) of iodine and / or iodine ions in the polarizer.
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Abstract
Description
下記一般式(1):
で表される化合物及び前記一般式(1)で表される化合物の多量体からなる群から選択される1種以上のリン酸系化合物、並びに(メタ)アクリル系ポリマーを含有するアクリル系粘着剤組成物から形成される粘着剤層を有することを特徴とする粘着剤層付偏光フィルムに関する。ここで、「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」とは、ヨウ素を含有するヨウ素系偏光子、ヨウ素イオンを含有するヨウ素系偏光子、ヨウ素及びヨウ素イオンの両方を含有するヨウ素系偏光子のことであり、本発明においてはいずれであっても好適に用いることができる。
本発明の粘着剤層付偏光フィルムは、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の少なくとも一方の面に、
下記一般式(1):
で表される化合物及び前記一般式(1)で表される化合物の多量体からなる群から選択される1種以上のリン酸系化合物、並びに(メタ)アクリル系ポリマーを含有するアクリル系粘着剤組成物から形成される粘着剤層を有することを特徴とする。
本発明において用いるヨウ素系偏光フィルムは、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ものである。本発明においては、ヨウ素系偏光子の片面に透明保護フィルムを有する片面保護偏光フィルムであっても、ヨウ素系偏光子の両面に透明保護フィルムを有する両面保護偏光フィルムであってもよいが、片面保護偏光フィルムを用いる場合に、本発明の効果が顕著である。また、両面保護偏光フィルムであっても、粘着剤層と接する側の透明保護フィルムの厚さが薄い(例えば、25μm以下)の場合にも、本発明の効果が顕著である。なお、偏光フィルムが、片面保護偏光フィルムである場合には、粘着剤層は、前記透明保護フィルムを有さない側の偏光子表面に直接設けることができる。
本発明の粘着剤層付偏光フィルムに用いられる粘着剤層は、アクリル系粘着剤組成物から形成される。アクリル系粘着剤組成物は、
下記一般式(1):
で表される化合物、及び、前記一般式(1)で表される化合物の多量体からなる群より選ばれるリン酸系化合物、及び、(メタ)アクリル系ポリマーを含有する。
で表されるリン酸エステル系化合物を挙げることができる。
アルカリ金属塩のカチオン部を構成するアルカリ金属イオンとしては、リチウム、ナトリウム、カリウムの各イオンが挙げられる。これらアルカリ金属イオンの中でも、リチウムイオンが好ましい。
(4):(CnF2n+1SO2)2N- (但し、nは1~10の整数)、
(5):CF2(CmF2mSO2)2N- (但し、mは1~10の整数)、
(6):-O3S(CF2)lSO3 - (但し、lは1~10の整数)、
(7):(CpF2p+1SO2)N-(CqF2q+1SO2) (但し、p、qは1~10の整数)、
で表わされるものなどが用いられる。特に、フッ素原子を含むアニオン部は、イオン解離性の良いイオン化合物が得られることから好ましく用いられる。無機塩を構成するアニオン部としては、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-、などが用いられる。アニオン部としては、(CF3SO2)2N-、(C2F5SO2)2N-、等の前記一般式(4)で表わされる、(ペルフルオロアルキルスルホニル)イミドが好ましく、特に(CF3SO2)2N-、で表わされる(トリフルオロメタンスルホニル)イミドが好ましい。
本発明で用いられる有機カチオン-アニオン塩は、カチオン成分とアニオン成分とから構成されており、前記カチオン成分は有機物からなるものである。カチオン成分として、具体的には、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、ピロリン骨格を有するカチオン、ピロール骨格を有するカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオンなどが挙げられる。
(4):(CnF2n+1SO2)2N- (但し、nは1~10の整数)、
(5):CF2(CmF2mSO2)2N- (但し、mは1~10の整数)、
(6):-O3S(CF2)lSO3 - (但し、lは1~10の整数)、
(7):(CpF2p+1SO2)N-(CqF2q+1SO2) (但し、p、qは1~10の整数)、
で表わされるものなどが用いられる。これらの中でも、特に、フッ素原子を含むアニオン成分は、イオン解離性の良いイオン化合物が得られることから好ましく用いられる。
本発明の粘着剤層付偏光フィルムは、前記ヨウ素系偏光フィルムの少なくとも一方の面に、前記アクリル系粘着剤組成物から形成される粘着剤層を形成することで得られる。
本発明の積層体は、前記粘着剤層付偏光フィルムと、透明導電層を有する部材とを、前記粘着剤層付偏光フィルムの粘着剤層と前記透明導電層を有する部材の透明導電層とが接触するように貼り合せたことを特徴とする。
本発明の積層体は、入力装置(タッチパネル等)を備えた画像表示装置(液晶表示装置、有機EL(エレクトロルミネッセンス)表示装置、PDP(プラズマディスプレイパネル)、電子ペーパーなど)、入力装置(タッチパネル等)等の機器を構成する基材(部材)又はこれらの機器に用いられる基材(部材)の製造において好適に用いることができるが、特に、タッチパネル用の光学基材の製造において好適に用いることができる。また、抵抗膜方式や静電容量方式といったタッチパネル等の方式に関係なく使用することができる。
偏光子中のヨウ素含有量(ヨウ素及び/又はヨウ素イオンの含有量)は、以下の手順により測定した。
1)複数の、所定量のヨウ化カリウムを含む偏光子について蛍光X線強度を測定し、ヨウ素含有量と蛍光X線強度の関係式を導きだした。
2)ヨウ素含有量が未知のヨウ素系偏光子の蛍光X線を測定し、その数値から前記関係式を用いてヨウ素量を計算した。
非晶性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、水100重量部に対して、ヨウ素0.1重量部、ヨウ化カリウム0.7重量部を含有する染色液に60秒間浸漬して、着色積層体を生成した。さらに、着色積層体を延伸温度65℃のホウ酸水中延伸によって総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸された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た高機能偏光層を構成する、厚さ4μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の偏光層の表面に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、非晶性PET基材を剥離して、薄型のヨウ素系偏光子を用いた片側にのみ透明保護フィルムを有する偏光フィルムを作製した。以下、これを偏光フィルム(1)という。偏光フィルム(1)のヨウ素含有量は5.1重量%であった。
染色時間を、60秒から、120秒(製造例2)、180秒(製造例3)に変更した以外は、製造例1と同様に、薄型のヨウ素系偏光子を用いた片側にのみ透明保護フィルムを有する偏光フィルムを作製した。以下、これらを偏光フィルム(2)、(3)という。偏光フィルム(2)、(3)のヨウ素含有量は、それぞれ、7.2重量%、11.1重量%であった。
厚さ80μmのポリビニルアルコールフィルムを、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、総合延伸倍率が6倍まで延伸した。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分間乾燥し、厚さ25μm、ヨウ素含有量2.3重量%の偏光子を得た。当該偏光子の片面に、厚さ40μmのアクリル樹脂フィルム(透明保護フィルム(1))をポリビニルアルコール系接着剤により貼り合せて、偏光フィルムを作製した。以下、これを偏光フィルム(4)という。偏光フィルム(4)のヨウ素含有量は2.3重量%であった。
製造例1で、非晶性PET基材を剥離した後、他の片面に厚さ25μmのノルボルネン系フィルム(透明保護フィルム(2))を、ポリビニルアルコール系接着剤により貼り合せて、偏光フィルムを作製した。以下、これを薄型偏光フィルム(5)という。偏光フィルム(5)のヨウ素含有量は5.1重量%であった。
製造例4により得られたヨウ素含有量2.3重量%の偏光子の両面に、厚さ40μmのアクリル樹脂フィルム(透明保護フィルム(1))、厚さ25μmのノルボルネン系フィルム(透明保護フィルム(2))をポリビニルアルコール系接着剤により貼り合せて、偏光フィルムを作製した。以下、これを偏光フィルム(6)という。偏光フィルム(6)のヨウ素含有量は2.3重量%であった。
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99部、4-ヒドロキシブチルアクリレート1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160万のアクリル系ポリマー(A-1)を含有する溶液を得た(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99部、2-ヒドロキシエチルアクリレート1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160万のアクリル系ポリマー(A-2)を含有する溶液を得た(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100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160万のアクリル系ポリマー(A-3)を含有する溶液を得た(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98.6部、4-ヒドロキシブチルアクリレート1部、アクリル酸0.4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160万のアクリル系ポリマー(A-4)を含有する溶液を得た(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、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155万のアクリル系ポリマー(A-5)を含有する溶液を得た(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91部、2-ヒドロキシエチルアクリレート1部、アクリル酸8部、及び、開始剤として、AIBNをモノマー(固形分)100部に対して0.75部を酢酸エチルと共に加えて窒素ガス気流下、60℃で9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190万のアクリル系ポリマー(A-6)を含有する溶液を得た(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99部、4-ヒドロキシブチルアクリレート1部、及び、開始剤として、AIBNをモノマー(固形分)100部に対して1.5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90万のアクリル系ポリマー(A-7)を含有する溶液を得た(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180万のアクリル系ポリマー(A-8)を含有する溶液を得た(固形分濃度30重量%)。
<アクリル系ポリマーの重量平均分子量(Mw)の測定>
作製したアクリル系ポリマー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7で得られたアクリル系ポリマー(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、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)を0.1部と、ジベンゾイルパーオキサイドを0.3部、リン酸化合物として、フォスファノールSM-172(商品名、東邦化学工業(株)製)を0.03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、偏光フィルム(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、粘着剤層付偏光フィルムを作製した。
リン酸化合物の添加量を、0.03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、粘着剤層付偏光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)0.03部を、フォスファノールRS-410(東邦化学工業(株)製)0.1部に変更した以外は、実施例1と同様にして、粘着剤層付偏光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)0.03部を、フォスファノールRS-710(東邦化学工業(株)製)0.1部に変更した以外は、実施例1と同様にして、粘着剤層付偏光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)0.03部を、DBP(城北化学(株)製)0.05部に変更した以外は、実施例1と同様にして、粘着剤層付偏光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)0.03部を、リン酸(試薬特級)(和光純薬工業(株)製)0.03部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
製造例7で得られたアクリル系ポリマー(A-1)を含有する溶液を、それぞれ、製造例8~12で得られたアクリル系ポリマー(A-2)~(A-6)を含有する溶液に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(粘着剤層付偏光フィルムの作製)において、偏光フィルム(1)を偏光フィルム(2)、(3)、(4)に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
(アクリル系粘着剤組成物の調整)
製造例7で得られたアクリル系ポリマー(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、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)を0.1部と、ジベンゾイルパーオキサイドを0.3部、リン酸化合物として、フォスファノールSM-172(商品名、東邦化学工業(株)製)を0.03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、イオン性化合物として、リチウムビストリフルオロメタンスルホニルイミド(森田化学工業(株)製)0.5部、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用いた以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
リチウムビストリフルオロメタンスルホニルイミド(森田化学工業(株)製)0.5部を、1-メチル-1-エチルピロリジニウムビス(トリフルオロメタンスルホニル)イミド(キシダ化学(株)製)0.5部に変更した以外は、実施例18と同様にして、粘着剤層付偏光フィルムを作製した。
製造例7で得られたアクリル系ポリマー(A-1)を含有する溶液を、製造例14で得られたアクリル酸エステル共重合体(A-8)に変更し、かつ、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.03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、粘着剤層付偏光フィルムを作製した。
リン酸(試薬特級)(和光純薬工業(株)製)の添加量を0.05部から0.1部に変更した以外は、実施例20と同様にして、粘着剤層付偏光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)0.03部を、MP-4(商品名、酸価:670mgKOH/g、大八化学工業(株)製)0.01部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
MP-4(商品名、酸価:670mgKOH/g、大八化学工業(株)製)の添加量を0.01部から0.06部に変更した以外は、実施例22と同様にして、粘着剤層付偏光フィルムを作製した。
製造例7で得られたアクリル系ポリマー(A-1)を含有する溶液を、製造例14で得られたアクリル酸エステル共重合体(A-8)に変更し、かつ、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.03部を、MP-4(商品名、酸価:670mgKOH/g、大八化学工業(株)製)0.1部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
MP-4(商品名、酸価:670mgKOH/g、大八化学工業(株)製)の添加量を、0.1部から、0.8部、3部に変更した以外は、実施例24と同様にして、粘着剤層付偏光フィルムを作製した。
製造例7で得られたアクリル系ポリマー(A-1)を含有する溶液を、製造例14で得られたアクリル酸エステル共重合体(A-8)に変更し、かつ、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.03部を、MP-4(商品名、酸価:670mgKOH/g、大八化学工業(株)製)0.04部とリン酸(試薬特級)(和光純薬工業(株)製)0.01部の混合物に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
製造例7で得られたアクリル系ポリマー(A-1)を含有する溶液を、製造例14で得られたアクリル酸エステル共重合体(A-8)に変更し、かつ、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.03部を、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.04部とリン酸(試薬特級)(和光純薬工業(株)製)0.01部の混合物に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
得られたアクリル系ポリマーを含有する溶液の種類、リン酸化合物の種類と添加量を、表3に記載の種類と部数に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
アクリル系ポリマー(A-1)を含有する溶液を、製造例8で得られたアクリル系ポリマー(A-2)を含有する溶液に変更し、かつ、リン酸エステルを用いなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
アクリル系ポリマー(A-1)を含有する溶液を、製造例9で得られたアクリル系ポリマー(A-3)を含有する溶液に変更し、かつ、リン酸エステルを用いなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
アクリル系ポリマー(A-1)を含有する溶液を、製造例11で得られたアクリル系ポリマー(A-5)を含有する溶液に変更し、かつ、リン酸エステルを用いなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
アクリル系ポリマー(A-1)を含有する溶液を、製造例13で得られたアクリル系ポリマー(A-7)を含有する溶液に変更し、かつ、リン酸エステルを用いなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(粘着剤層付偏光フィルムの作製)において、偏光フィルム(1)を偏光フィルム(5)、(6)に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。なお、粘着剤層は、保護フィルム(2)側に積層した。
実施例24の(粘着剤層付偏光フィルムの作製)において、偏光フィルム(1)を偏光フィルム(5)に変更した以外は、実施例24と同様にして、粘着剤層付偏光フィルムを作製した。なお、粘着剤層は、保護フィルム(2)側に積層した。
実施例1(アクリル系粘着剤組成物の調整)においてリン酸エステルを用いず、(粘着剤層付偏光フィルムの作製)において、偏光フィルム(1)を偏光フィルム(5)に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。なお、粘着剤層は、保護フィルム(2)側に積層した。
実施例1(アクリル系粘着剤組成物の調整)において、アクリル系ポリマー(A-1)を含有する溶液を、製造例9で得られたアクリル系ポリマー(A-3)を含有する溶液に変更し、かつ、リン酸エステルを用いず、(粘着剤層付偏光フィルムの作製)において、偏光フィルム(1)を偏光フィルム(6)に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。なお、粘着剤層は、保護フィルム(2)側に積層した。
(分析方法)
実施例及び比較例で使用したリン酸系化合物の組成を、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)
表面に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)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サンプルを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))
実施例、比較例で得られた粘着剤層付偏光フィルムサンプルのセパレータフィルムを剥がし、無アルカリガラス及び、下記の非結晶ITOが形成されたガラスのITO面に貼り合わせに貼り合わせ、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。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
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膜を形成して、非結晶化ITO薄膜を有する被着体を作製した。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比率は、Sn原子の重量/(Sn原子の重量+In原子の重量)から算出した。
(リン酸化合物)
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:フォスファノールRS-710、酸価:62mgKOH/g、モノ・ジ混合物、東邦化学工業(株)製
B-4:DBP、酸価:266mgKOH/g、モノ・ジ混合物、城北化学(株)製
B-5:リン酸(試薬特級)、和光純薬工業(株)製
B-6:MP-4、酸価:670mgKOH/g、モノ・ジ混合物、大八化学工業(株)製
B-7: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:リチウムビストリフルオロメタンスルホニルイミド(森田化学工業(株)製)
E-2:1-メチル-1-エチルピロリジニウムビス(トリフルオロメタンスルホニル)イミド(キシダ化学(株)製)
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 (22)
- 前記ヨウ素系偏光子中のヨウ素及び/又はヨウ素イオンの含有量が、1~14重量%であることを特徴とする請求項1に記載の粘着剤層付偏光フィルム。
- 前記ヨウ素系偏光子中のヨウ素及び/又はヨウ素イオンの含有量が、3~12重量%であることを特徴とする請求項2に記載の粘着剤層付偏光フィルム。
- 前記リン酸系化合物が、リン酸を含み、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む混合物であることを特徴とする請求項1~3のいずれかに記載の粘着剤層付偏光フィルム。
- 前記リン酸系化合物が、リン酸及びリン酸モノエステルを含む混合物であることを特徴とする、請求項4に記載の粘着剤層付偏光フィルム。
- 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1~5のいずれかに記載の粘着剤層付偏光フィルム。
- 前記ヨウ素系偏光フィルムが、前記ヨウ素系偏光子の片側にのみ透明保護フィルムを有する片面保護偏光フィルムであり、かつ、前記片面保護偏光フィルムの透明保護フィルムを有していない面と、前記粘着剤層が接触してい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層付偏光フィルム。
- 前記ヨウ素系偏光子の厚みが、10μm以下であ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層付偏光フィルム。
- 前記ヨウ素系偏光フィルムの総厚みが、80μm以下であることを特徴とする請求項1~8のいずれかに記載の粘着剤層付偏光フィルム。
- 請求項1~9のいずれかに記載の粘着剤層付偏光フィルムの粘着剤層と、透明導電層を有する部材の透明導電層とが接触するように貼り合せて用いることを特徴とする、請求項1~9のいずれかに記載の粘着剤層付偏光フィルム。
- 前記リン酸系化合物の添加量が、前記(メタ)アクリル系ポリマー100重量部に対して0.001~4重量部であることを特徴とする請求項1~10のいずれかに記載の粘着剤層付偏光フィルム。
- 前記(メタ)アクリル系ポリマーが、モノマー単位として、アルキル(メタ)アクリレート、及びヒドロキシル基含有モノマーを含有することを特徴とする請求項1~11のいずれかに記載の粘着剤層付偏光フィルム。
- ヒドロキシル基含有モノマーが、4-ヒドロキシブチルアクリレートであることを特徴とする請求項12に記載の粘着剤層付偏光フィルム。
- (メタ)アクリル系ポリマーの重量平均分子量が、120万~300万であることを特徴とする請求項1~13のいずれかに記載の粘着剤層付偏光フィルム。
- 前記アクリル系粘着剤組成物が、さらに、架橋剤を含有することを特徴とする請求項1~14のいずれかに記載の粘着剤層付偏光フィルム。
- 架橋剤は、過酸化物系架橋剤、及びイソシアネート系架橋剤からなる群から選択される1種以上の架橋剤であることを特徴とする請求項15に記載の粘着剤層付偏光フィルム。
- 前記アクリル系粘着剤組成物が、さらに、イオン性化合物を含有することを特徴とする請求項1~16のいずれかに記載の粘着剤層付偏光フィルム。
- 請求項1~17のいずれかに記載の粘着剤層付偏光フィルムと、透明導電層を有する透明導電性部材とを、前記粘着剤層付偏光フィルムの粘着剤層と前記基材の透明導電層とが接触するように貼り合せたことを特徴とする積層体。
- 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18に記載の積層体。
- 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19に記載の積層体。
- 請求項1~17のいずれかに記載の粘着剤層付偏光フィルムの粘着剤層と、透明導電層を有する液晶パネルとを、前記粘着剤層付偏光フィルムの粘着剤層と前記液晶パネルの透明導電層とが接触するように貼り合せたことを特徴とする画像表示装置。
- 請求項18~20のいずれか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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| PCT/JP2014/067059 Ceased WO2014208695A1 (ja) | 2013-06-28 | 2014-06-26 | 粘着剤層付偏光フィルム、積層体、及び、画像表示装置 |
Country Status (2)
| Country | Link |
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| TW (1) | TWI634176B (ja) |
| WO (1) | WO2014208695A1 (ja) |
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