Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

Definitions

• the present invention relates to an optical laminate, an adhesive composition and a protective material, in particular, relates to an optical laminate having high antistatic property when the protective material is peeled, and an adhesive composition and a protective material used for these.
• An adhesive agent having antistatic properties is used as an adhesive layer of a surface protect film, and, for example, is used to prevent flaws or contaminations from adhering on a surface during processing or transporting an optical component or an electronic component such as a Flat Panel Display (FPD).
• FPD Flat Panel Display
• an adhesive agent having antistatic properties like this is used in a surface protect film, adherence of extraneous materials such as dust or dirt to a target object to which the surface protect film was adhered, due to electrification of static electricity generated during peeling, or electric inconvenience to the electronic components or the like due to electrostatic discharging may be prevented.
• antistatic property having higher function may be expected.
• a conductive polymer that is widely used in the present time is a water-dispersive type, it was difficult to add them directly to an adhesive agent of a nonaqueous solvent system.
• Patent Document 1 an adhesive composition that uses a conductive polymer in which a monoanion is doped is known.
• Patent Document 1 an adhesive composition that uses a conductive polymer in which a monoanion is doped.
• the conductive polymer like this was used, it was demanded to lower surface resistivity to further enhance antistatic performance or to more enhance light transmittance of the adhesive layer.
• the present invention intends to provide an optical laminate provided with a protective material having high antistatic property when peeled from an optical member and having high light transmittance, and an adhesive composition and a protective material used for these.
• a first invention of the present invention is an optical laminate provided with an optical member, and a protective material laminated on the optical member, in which the protective material has a substrate, and an adhesive layer provided on the substrate, and the adhesive layer contains a (meth)acrylic adhesive polymer having a glass transition temperature of 0°C or lower, a conductive polymer containing a conjugated polymer and a polyanion, and an amphiphilic compound, and is provided so as to adjacent a surface of the optical member.
• a second invention of the present invention is the optical laminate of the first invention, in which the amphiphilic compound contained in the adhesive layer is an ether or ester of trivalent or more polyvalent alcohol, or a nonionic compound having an oxyalkylene chain.
• a third invention of the present invention is the optical laminate according to any one of the first to the second invention, in which the polyanion contained in the adhesive layer has a hydrogenated or unhydrogenated diene structure.
• a fourth invention of the present invention is the optical laminate according to any one of the first to the third invention, in which the polyanion contained in the adhesive layer has a block structure.
• a fifth invention of the present invention is the optical laminate according to any one of the first to the fourth invention, in which a rate of (meth)acrylic acid ester units having alkyl groups having 4 or more carbon atoms is 50% by mass or larger among repeating units constituting the adhesive polymer of the adhesive layer.
• a sixth invention of the present invention is the optical laminate according to any one of the first to the fifth invention, in which a content of the conductive polymer in the adhesive layer is 0.01 to 20 parts by mass relative to 100 parts by mass of the conductive polymer.
• a seventh invention of the present invention is the optical laminate according to any one of the first to the sixth invention, in which a content of the amphiphilic compound in the adhesive layer is 0.1 to 10 parts by mass relative to 100 parts by mass of the adhesive polymer.
• n eighth invention of the present invention is the optical laminate according to any one of the first to the seventh invention, in which the optical member is a polarizing plate, a retardation plate, an antireflective film or a transparent conductive film.
• a ninth invention of the present invention is an adhesive composition including: (A) an adhesive polymer that is formed by repeating a (meth)acrylic unit structure and has a glass transition temperature of 0°C or lower; (B) a conductive polymer containing a conjugated polymer and polyanion; (C) an amphiphilic compound; and (D) a nonaqueous solvent or dispersion medium.
• a tenth invention of the present invention is the adhesive composition according to the ninth invention, in which the (D) solvent or dispersion medium is one or more kinds selected from ethyl acetate, butyl acetate, toluene, methyl ethyl ketone and anisole.
• An eleventh invention of the present invention is the adhesive composition according to the ninth or tenth invention, in which the amphiphilic composition is an ether or an ester of trivalent or more polyvalent alcohol, or a nonionic compound having an oxyalkylene chain.
• a twelfth invention of the present invention is the adhesive composition according to any one of the ninth to eleventh invention, in which the polyanion has a hydrogenated or unhydrogenated diene structure.
• a thirteenth invention of the present invention is the adhesive composition according to any one of the ninth to twelfth invention, in which the polyanion has a block structure.
• a fourteenth invention of the present invention is the adhesive composition according to any one of the ninth to thirteenth invention, in which a rate of (meth)acrylic acid alkyl ester units having an alkyl group having 4 or more carbon atoms is 50% by mass or higher among repeating units constituting the adhesive polymer.
• a fifteenth invention of the present invention is the adhesive composition according to any one of the ninth to fourteenth invention, in which a content of the conductive polymer is from 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive polymer.
• a sixteenth invention of the present invention is the adhesive composition according to any one of the ninth to fifteenth invention, in which a content of the amphiphilic compound is from 0.1 to 10 parts by mass relative to 100 parts by mass of the adhesive polymer.
• a seventeenth invention of the present invention is the protective material that includes a substrate and an adhesive layer provided on the substrate, in which the adhesive layer includes a (meth)acrylic adhesive polymer having the glass transition temperature of 0°C or lower, a conductive polymer containing a conjugated polymer and polyanion, and an amphiphilic compound.
• An eighteenth invention of the present invention is the protective material according to the seventeenth invention, in which the amphiphilic compound contained in the adhesive layer is an ether or ester of a trivalent or more polyvalent alcohol or a nonionic compound having an oxyalkylene chain.
• a nineteenth invention of the present invention is the protective material according to the seventeenth or eighteenth invention, in which the haze of the adhesive layer is smaller than 5.
• a twentieth invention of the present invention is the protective material according to any one of the seventeenth to nineteenth invention, in which polyanion contained in the adhesive layer has a hydrogenated or unhydrogenated diene structure.
• a twenty first invention of the present invention is the protective material according to any one of the seventeenth or twentieth invention, in which the polyanion contained the adhesive layer has a block structure.
• a twenty second invention of the present invention is the protective material according to any one of the seventeenth to twenty first invention, in which a rate of (meth)acrylic acid alkyl ester units having an alkyl group having 4 or more carbon atoms is 50% by mass or higher among repeating units constituting the adhesive polymer of the adhesive layer.
• a twenty third invention of the present invention is the protective material according to any one of the seventeenth to twenty second invention, in which a content of the conductive polymer in the adhesive layer is from 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive polymer.
• a twenty fourth invention of the present invention is the protective material according to any one of the seventeenth to twenty third invention, in which a content of the amphiphilic compound in the adhesive layer is from 0.1 to 10 parts by mass relative to 100 parts by mass of the adhesive polymer.
• an optical laminate provided with a protective material having high antistatic property when peeled from an optical member and having high light transmittance, and an adhesive composition and a protective material used for these are obtained.
• the optical laminate, the adhesive composition and the protective material of the present invention have high-function antistatic characteristics, adhesion of extraneous materials due to electrification of static electricity generated and electrical inconveniences to electronic components due to static discharge during peeling the protective material may be reduced.
• An optical laminate of the present invention is provided with an optical member and a protective material laminated on the optical member.
• the protective material provided on a surface of the optical member is provided with a substrate and an adhesive layer, and the adhesive layer is laminated on the substrate.
• the respective layers are laminated such that one side of the adhesive layer is adjacent to the substrate, and the other side is adjacent to the optical member.
• optical member members having the form of a plate, a sheet, a film or the like that are used in optical application are cited, and examples thereof include a polarizing plate, a retardation film, an elliptical polarizing plate, an anti-reflection film, a transparent conductive film, a luminance improving film, a light diffusion film, a glass scattering prevention film and a surface protective film.
• the polarizing plate, the retardation film, the anti-reflection film, or the transparent conductive film is preferable, which are frequently adhered to a surface of a liquid crystal element.
• the protective material is provided with a substrate and an adhesive layer provided on the substrate thereof, and is detachably provided on a surface of the optical member.
• the protective layer may be preferably used in an application (for a protective film or the like) to protect the surface of an optical member from scratch or contamination.
• the substrate used in the protective material is selected from materials in the form of a thin plate, a sheet or a film or the like to which the adhesive layer may be adhered.
• plastic materials, metals and metal oxides may be used.
• substrates having high light transmittance for example, substrates made of plastic materials, ITO (indium tin oxide), or glass having high light transmittance are preferably used.
• plastic films having flexibility, plasticity and high light transmittance are preferably used.
• the plastic films like this include films made of polymers such as Oriented PolyPropylene (OPP), polycarbonate, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), or polymers such as polymethylmethacrylates (PMMA), polycarbonates, polysulfones, polyether sulfones (PES), polyimides, polyamides, polyethylenes, polypropylenes or cyclic polyolefin or cyclic olefin copolymers (COC), polyvinyl chloride, polystyrene, hydrogenated styrene polymers, or hydrogenated styrene copolymers.
• OPP Oriented PolyPropylene
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PMMA polymethylmethacrylates
• PES polysulfones
• PES
• a thickness of the substrate is appropriately set in accordance with its application.
• a film thickness is set to preferably 5 ⁇ m or thicker, more preferably 10 ⁇ m or thicker, and more preferably 25 ⁇ m or thicker.
• the upper limit of the thickness of the substrate at this time may be set to preferably 5000 ⁇ m or thinner, more preferably 2500 ⁇ m or thinner, and still more preferably 1000 ⁇ m or thinner.
• a surface of the substrate may be pre-treated prior to forming the adhesive layer, for example by corona treatment, primer treatment, flame treatment, fluorination or plasma treatment, to improve the polarity of the surface, more specifically, the wettability and chemical affinity to the adhesive composition.
• the surface of the substrate is preferably treated with a primer.
• An adhesive layer provided on the substrate is formed of an adhesive composition described below, and has low surface resistivity and high antistatic property. According to the adhesive layer like this, generation of the static electricity is reduced when the protective material is peeled off the optical member. Therefore, contamination of a surface of the optical member due to adhesion of extraneous materials such as dusts or dirt generated when a surface of the optical member to which the protective material is adhered is electrified may be reduced.
• the antistatic property when the protective material is peeled may be evaluated by, for example, peeling electrification voltage or surface resistivity.
• the peeling electrification voltage in the protective material of the present invention is preferably 1.00 kV or smaller, more preferably 0.70 kV or smaller, still more preferably 0.50 kV or smaller, and particularly preferably 0.25 kV or smaller when the protective material is adhered to an adherend made of triacetyl cellulose, followed by peeling at a speed of 30 m/min.
• the surface resistivity of the adhesive layer is preferably smaller than 1 ⁇ 10 13 ⁇ / ⁇ , more preferably smaller than 1 ⁇ 10 12 ⁇ / ⁇ , still more preferably smaller than 1 ⁇ 10 11 ⁇ / ⁇ , and further more preferably smaller than 1 ⁇ 10 10 ⁇ / ⁇ .
• the adhesive layer like this, high antistatic properties may be exhibited. Therefore, contamination due to adhesion of extraneous materials such as dust or dirt due to the electrification of static electricity to an adherend of the adhesive layer may be reduced.
• the adhesive layer is one that can form an adhesive layer having high total light transmittance and low haze.
• the total light transmittance in an adhesive layer when the adhesive layer is formed and dried such that a dry film thickness is 10 ⁇ m is preferably 60% or higher, more preferably 70% or higher, still more preferably 80% or higher, and furthermore preferably 90% or higher.
• the haze in the adhesive layer at this time is preferably smaller than 5.0%, more preferably smaller 3.0%, and still more preferably smaller than 1.5%.
• the haze (haze degree) in the adhesive layer is obtained from (Td/Tt) ⁇ 100 when the total light transmittance is assumed as Tt and the diffusion transmittance is assumed as Td.
• a film thickness of the adhesive layer is set according to the kind of adhesive polymer, and has, for example, a film thickness of 0.1 ⁇ m or thicker, more preferably 1 ⁇ m or thicker, and still more preferably 5 ⁇ m or thicker.
• this adhesive layer has a film thickness of, for example, 100 ⁇ m or thinner, more preferably 50 ⁇ m or thinner, and still more preferably 30 ⁇ m or thinner.
• An adhesive composition capable of forming an adhesive layer like this contains (A) a (meth)acrylic adhesive polymer, (B) a conductive polymer containing a conjugated polymer and polyanion, and (C) an amphiphilic compound and these are dissolved or dispersed in (D) a nonaqueous solvent or a nonaqueous dispersion medium.
• a “solution” in the present specification is a concept including also a dispersion liquid, and indicates a state of being dissolved or dispersed in a solvent or a dispersion medium.
• An adhesive polymer used in the adhesive composition of the present invention is a polymer having adhesiveness at least at a use temperature and preferably having adhesiveness at room temperature.
• the adhesive polymer is formed by repeating a (meth)acryl-based unit structure and may be a copolymer.
• the adhesive physical properties of the adhesive composition may be suitably adjusted.
• the (meth)acryl in the present specification means acryl or methacryl.
• the (meth)acryl-based polymers those which are formed by polymerizing a monomer having a polymerizable unsaturated bond having a (meth)acrylic acid ester as a main component may be used. That is, a repeating unit ((meth)acrylic acid ester component unit) derived from (meth)acrylic acid ester is contained by 50% by mass or more, preferably by 70% by mass or more, and more preferably by 90% by mass or more in terms of monomers.
• copolymers of n-butyl acrylate/2-ethylhexyl acrylate/2-hydroxyethyl acrylate copolymers of n-butyl acrylate/2-ethylhexyl acrylate/2-hydroxyethyl acrylate/acrylic acid, copolymers of 2-ethylhexyl acrylate/2-hydroxyethyl acrylate, copolymers of 2-ethylhexyl acrylate/2-hydroxyethyl acrylate/acrylic acid, copolymers of 2-methoxyethyl acrylate/2-hydroxyethyl acrylate/acrylic acid, and copolymers of 2-methoxyethyl acrylate/2-hydroxyethyl acrylate/acryl amide are exemplified.
• esters between alcohols having an alkyl group having 1 to 20 carbon atoms and (meth)acrylic acid esters between alicyclic alcohols having 3 to 14 carbon atoms and (meth)acrylic acid, or esters between aromatic alcohols having 6 to 14 carbon atoms and (meth)acrylic acid may be used.
• esters between alcohols having an alkyl group having 1 to 20 carbon atoms and (meth)acrylic acid include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate.
• An alkyl group having 3 or more carbon atoms may have a linear structure or a branched structure.
• esters between alcohol having an alkyl group having 4 or more carbon atoms and (meth)acrylic acid. Furthermore, among repeating units that constitute the adhesive polymer, a rate of (meth)acrylic acid alkyl ester units having an alkyl group having 4 or more carbon atoms is set preferably to 50% by mass or higher, more preferably to 65% by mass or higher, and further preferably to 80% by mass or higher.
• esters between alicyclic alcohols having 3 to 14 carbon atoms and (meth)acrylic acid cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are exemplified
• esters between aromatic alcohols having 6 to 14 carbon atoms and (meth)acrylic acid (meth)acrylic acid aryl esters such as phenyl (meth)acrylate, benzyl (meth)acrylate and phenoxyethyl (meth)acrylate are exemplified.
• (Meth)acrylic acid esters like this may be used alone or in a combination thereof.
• the (meth)acryl-based polymer may have repeating units derived from monomers copolymerizable with (meth)acrylic acid esters, other than the above (meth)acrylic acid ester component units.
• the monomers like this include alkoxyalkyl (meth)acrylates such as (meth)acrylic acid, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and ethoxypropyl (meth)acrylate; salts such as alkali metal (meth)acrylate; di(meth)acrylic acid esters of (poly)alkylene glycol such as di(meth)acrylic acid ester of ethylene glycol, di(meth)acrylic acid ester of diethylene glycol, di(meth)acrylic acid ester of triethylene glycol, di(meth)acrylic acid ester of polyethylene glycol
• a weight-average molecular weight of the (meth)acryl-based polymer is preferably 50,000 or larger and 2,000,000 or smaller, and more preferably 100,000 or larger and 1,500,000 or smaller from the viewpoint of providing adhesiveness under room temperature.
• the weight-average molecular weight is smaller than 50,000, the heat resistance of the obtained adhesive layer may be drastically degraded, and, when the weight-average molecular weight exceeds 2,000,000, a uniform casting operation may be difficult.
• the weight-average molecular weight of the adhesive polymers including (meth)acryl-based polymers may be obtained by, for example, gel permeation chromatography (GPC).
• the glass transition temperature (Tg) of the (meth)acryl-based polymer is preferably 0°C or lower, more preferably -20°C or lower, still more preferably -40°C or lower, and most preferably -50°C or lower, from the viewpoint of imparting the adhesiveness under room temperature in the same manner.
• the lower limit of the glass transition temperature (Tg) of the (meth)acryl-based polymer is not particularly limited but may be set to -85°C.
• Tg 1 to Tg m glass transition temperatures (Tg 1 to Tg m ) of homopolymers made of respective polymers in the Fox's equation, values described in Polymer Handbook Fourth Edition (Wiley-Interscience Company, 2003) may be used, for example.
• a hydroxyl value of the relevant polymer is 150 mgKOH/g or smaller, preferably 75 mgKOH/g or smaller, and more preferably 40 mgKOH/g or smaller.
• the hydroxyl value of the polymer may be measured according to, for example, a neutral titration method defined by JIS K 0070-1992.
• the adhesive polymers may be used alone or in a combination of two or more kinds.
• the adhesive polymer may be used for preparation of the adhesive composition in a state dissolved or dispersed in (D) a solvent or a dispersion medium described below for making it easy to prepare the adhesive composition.
• the (B) conductive polymer contained in the adhesive composition of the present invention contains (B1) a conjugated polymer and (B2) a polyanion. More specifically, by oxidatively polymerizing monomers under the presence of the (B2) polyanion to form a conjugated polymer, the (B) conductive polymer may be obtained.
• a concentration of the (B) conductive polymer in the adhesive composition of the present invention is preferably 0.01 parts by mass or higher, more preferably 0.05 parts by mass or higher, still more preferably 0.1 parts by mass or higher relative to 100 parts by mass of the (A) adhesive polymer.
• concentration of the conductive polymer is preferably 20.0 parts by mass or lower, more preferably 10.0 parts by mass or lower, still more preferably 5.0 parts by mass or lower relative to 100 parts by mass of the (A) adhesive polymer.
• the mixing stability of the adhesive composition may be improved and aggregated precipitates in the adhesive composition may be reduced, and, the light transmittance in the adhesive layer may be increased and the haze may be reduced.
• conjugated polymer contained in the conductive polymer a ⁇ electron conjugated system polymer is preferable, and it is more preferable to contain polythiophene present as an electrically conductive polymer.
• the polythiophene preferably includes a repeated unit of a general formula (I) (in the formula, R 4 and R 5 , independently from each other, respectively represent H, an optionally substituted C 1 -C 18 alkyl radical or an optionally substituted C 1 -C 18 alkoxy radical, and R 4 and R 5 together represent an optionally substituted C 1 -C 8 alkylene radical (in the optionally substituted C 1 -C 8 alkylene radical, one or more C atoms may be substituted by one or more identical or different heteroatoms selected from O or S, preferably a C 1 -C 8 dioxyalkylene radical), an optionally substituted C 1 -C 8 oxythialkylene radical or an optionally substituted C 1 -C 8 dithialkylene radical, or an optionally substituted C 1 -C 8 alkylidene radical (in the optionally substituted C 1 -C 8 alkylidene radical, at least one C atom may be optionally substituted by a heteroatom selected from
• the polythiophene includes repeating units of the general formula (I-a) and/or (I-b).
• A represents an optionally substituted C 1 -C 5 alkylene radical, preferably an optionally substituted C 2 -C 3 alkylene radical
• Y represents O or S
• R 6 represents a linear or branched, optionally substituted C 1 -C 18 alkyl radical, preferably a linear or branched, optionally substituted C 1 -C 14 alkyl radical, an optionally substituted C 5 -C 12 cycloalkyl radical, an optionally substituted C 6 -C 14 aryl radical, an optionally substituted C 7 -C 18 aralkyl radical, an optionally substituted C 7 -C 18 alkaryl radical, an optionally substituted C 1 -C 4 hydroxyalkyl radical or a hydroxyl radical
• y represents an integer of from 0 to 8, preferably 0, 1 or 2, particularly preferably 0 or 1, in which, when
• the polythiophene including repeating units of the general formula (I) is a polythiophene including repeating units of the general formula (I-aa) and/or of the general formula (I-ab) (In the formula, R 6 and y have the meaning given above.)
• the polythiophene including repeating units of the general formula (I) is a polythiophene including a polythiophene of the general formula (I-aaa) and/or the general formula (I-aba).
• poly is understood to mean that a plurality of identical or different repeating units are included in the polythiophene.
• the polythiophene includes in total n repeating units of the general formula (I), wherein n may be an integer of from 2 to 2000, preferably 2 to 100.
• the repeating units of the general formula (I) within a polythiophene may be in each case identical with each other or different from each other. Polythiophene including identical repeating units of the general formula (I) is preferred in each case.
• each conjugated polymer has H at the end groups.
• poly(3,4-ethylenedioxythiophene), poly(3,4-ethyleneoxythiathiophene) or poly(thieno[3,4-b]thiophene), that is, a homopolythiophene having repeating units of the general formula (I-aaa), (I-aba) or (I-b) where Y S is particularly preferred, and homopolymer (poly(3,4-ethylene-dioxythiophene)) including repeating units of the formula (I-aaa) is most preferred.
• the conjugated polymers are cationic, wherein the "cationic" relates only to the charges located on the polythiophene main chain.
• the polythiophene may bear positive and negative charges in the structural unit, and in this case, the positive charges may be located on the polythiophene main chain and the negative charges may be optionally located on the radicals R substituted with sulphonate or carboxylate groups.
• the positive charges of the polythiophene main chain may be partially or completely saturated by the optionally present anionic groups on the radicals R.
• the polythiophenes in these cases may be cationic, neutral or even anionic.
• n is the total number of all repeating units (identical or different) within the polythiophene).
• thiophene monomer that becomes a base of a conjugated polymer optionally substituted 3,4-alkylenedioxythiophenes may be used, and, as an example, can be represented by the general formula (II) (in the formula, A, R 6 and y have the meaning described in connection with formula (I-a), and when a plurality of radicals R are bonded to A, these may be identical or different).
• 4-ethylenedioxythiophenes may be used, most preferably, unsubstituted 3, 4-ethylenedioxythiophene may be used.
• (B2) Polyanion As the polyanion contained as a dopant in the conductive polymer, one having a structure of a homopolymer, a random polymer, or a block copolymer structure may be used, among these, one having a block copolymer structure is preferred. Furthermore, as the polyanion, one having a plurality of anions in one molecule may be used, for example, at least partially sulfonated polymers such as homopolymers of (meth)acrylic acid ester having styrenesulfonic acid, vinylsulfonic acid or sulfonic acid in a molecule, and these copolymers may be used.
• sulfonated synthetic rubbers may be used.
• the sulfonated synthetic rubber is a block copolymer having a styrene unit that is at least partially sulfonated and a diene unit.
• the conductive polymer becomes easily dissolved or dispersed in an organic solvent. Therefore, while maintaining the transparency of the adhesive layer, the surface resistivity of the adhesive layer formed of the adhesive composition may be reduced, and static electricity when peeling the adhesive layer may be suppressed to a low level.
• sulphonated is preferably understood to mean that in the styrene units and/or diene units concerned, preferably in the optionally hydrogenated butadiene or isoprene units, an -SO 3 X group is bonded to at least one C atom of these units via a sulphur atom (X is preferably selected from the group consisting of H + , NH 4 + , Na + , K + and Li + .) It is particularly preferable when the -SO 3 X groups are almost exclusively bonded to the styrene units and accordingly sulphonated styrene units are present.
• hydrophilid, optionally partially alkyl-substituted styrene-diene block copolymers or “hydrogenated, styrene-isoprene block copolymers” are understood respectively to refer to block copolymers, in which the double bond of the diene unit has been hydrogenated but the aromatic ring system of the styrene unit is not hydrogenated.
• styrene-diene block copolymers is further understood to refer to a polymer which includes at least styrene and diene monomer units, and accordingly the presence of further co-monomers is not excluded.
• alkyl-substituted styrene-diene block copolymers is understood as referring to block copolymers in which the styrene unit is alkyl-substituted, whereby in particular a methyl group, an ethyl group, an isopropyl group or a tert-butyl group is considered as an alkyl substituent.
• a "sulphonated styrene unit” in this context is preferably understood to mean the unit (III), and on the other hand, a “sulphonated butadiene unit” is preferably understood to mean, for example, the unit (IV).
• the sulphonate group may also be bonded in the form of a salt, for example in the form of an ammonium salt or an alkali salt, in particular in the form of an Na + , K + or Li + salt.
• the hydrogenated or unhydrogenated, optionally partially alkyl-substituted styrene-diene copolymers contained as the sulfonated synthetic rubber in the conductive polymer are preferably obtainable by sulphonating a styrene-diene copolymer (this may optionally be hydrogenated).
• the hydrogenated or unhydrogenated, optionally partially alkyl-substituted styrene-diene copolymer may in principle be a styrene-diene block copolymer.
• a "block” in this context is understood to be a polymer unit consisting of at least 2, preferably at least 4, still more preferably at least 6, still more preferably at least 8 and most preferably at least 10 identical monomer units continuous with each other.
• the hydrogenated or unhydrogenated block copolymers may be copolymers in which only the styrene units are present in blocks, copolymers in which only the diene units (or the hydrogenated forms of the diene units) are present in blocks, or copolymers in which both the diene units (or the hydrogenated forms of the diene units) and the styrene units are present in blocks.
• the sulphonated synthetic rubber includes hydrogenated or unhydrogenated, preferably hydrogenated styrene-isoprene block copolymers having a structure A-B-A, in which the block A corresponds to a sulphonated polystyrene block and the block B corresponds to a hydrogenated or unhydrogenated, preferably however hydrogenated polyisoprene block (a fully hydrogenated polyisoprene block corresponds chemically to a block of alternating copolymerized ethylene-propylene units).
• the lengths of the blocks A and B are preferably at least 5 monomer units, particularly preferably at least 10 units and most preferably at least 20 units.
• the sulphonated synthetic rubber includes a hydrogenated or unhydrogenated, preferably, a hydrogenated styrene-isoprene block copolymer having a structure of A-B-C-B-A in which the block A corresponds to a polystyrene block which is at least partially substituted with tert-butyl groups, the block B corresponds to a hydrogenated or unhydrogenated, preferably however hydrogenated polyisoprene block (a fully hydrogenated polyisoprene block corresponds chemically to a block of alternating copolymerized ethylene-propylene units), and the block C corresponds to a sulphonated polystyrene block.
• a hydrogenated or unhydrogenated preferably, a hydrogenated styrene-isoprene block copolymer having a structure of A-B-C-B-A in which the block A corresponds to a polystyrene block which is at least partially substituted with tert
• the lengths of the blocks A, B and C are preferably at least 5 monomer units, particularly preferably at least 10 units, and most preferably at least 20 units.
• Such copolymers are obtainable, for example, from the company Kraton Polymers, Houston, USA, under the product name NEXAR (R) .
• the block copolymer may be based on 5 to 95% by mass, particularly preferably 15 to 80% by mass and most preferably 25 to 65% by mass of polymerized styrene and 95 to 5% by mass, preferably 80 to 15% by mass and most preferably 65 to 25% by mass of polymerized, optionally hydrogenated diene, whereby the total amount of optionally hydrogenated diene and styrene is preferably 100% by mass.
• the total amount does not need to be 100% by mass when further monomer units are present in the block copolymer in addition to the styrene units and the optionally hydrogenated diene units.
• this sulphonated synthetic rubber is furthermore preferable to have a weight-average molecular weight (Mw) in the range of from 1000 to 10,000,000 g/mol, particularly preferably in the range of from 10,000 to 1,000,000 g/mol and most preferably in the range of from 100,000 to 1,000,000 g/mol.
• Mw weight-average molecular weight
• the molecular weight is determined by gel permeation chromatography using polymers having definite molecular weights, in particular using polystyrene in the case of water-immiscible solvents or dispersion media, or using polystyrene sulphonic acid in the case of water-miscible solvents or dispersion media.
• a mass ratio of the (B1) conjugated polymer to the (B2) polyanion (conjugated polymer : polyanion) in the conductive polymer is preferably in the range of from 1 : 0.1 to 1 : 100, more preferably in the range of from 1 : 0.2 to 1 : 20 and further preferably in the range of from 1 : 0.5 to 1 : 10.
• An oxidant or its reactant may be contained in the conductive polymer. This is because a polymerization reaction of a thiophene monomer under the presence of the sulfonated synthetic rubber is oxidatively performed by using an oxidant.
• iron (III) salts such as Fe 2 (SO 4 ) 3 , FeCl 3 , Fe(ClO 4 ) 3 and the iron(III) salts of organic acids and the iron (III) salts of inorganic acids including organic radicals may be used.
• the iron (III) salts of sulphuric acid hemiesters of C 1 -C 20 alkanols, for example the Fe (III) salt of lauryl sulphate, are cited by way of example of iron (III) salts of inorganic acids including organic radicals.
• iron(III) salts of organic acids the Fe(III) salts of C 1 -C 20 alkyl sulphonic acids, such as methane sulphonic acid and dodecane sulphonic acid; Fe (III) salts of aliphatic C 1 -C 20 carboxylic acids such as 2-ethylhexyl carboxylic acid; Fe (III) salts of aliphatic perfluorocarboxylic acids, such as trifluoroacetic acid and perfluorooctanoic acid; Fe (III) salts of aliphatic dicarboxylic acids such as oxalic acid; and, above all, Fe (III) salts of aromatic sulphonic acids optionally substituted with C 1 -C 20 alkyl groups, such as benzenesulphonic acid, p-toluenesulphonic acid and dodecylbenzenesulphonic acid.
• C 1 -C 20 alkyl sulphonic acids such as methane sulph
• the iron (III) salts of organic acids have the big applicational advantage that they are partially or completely soluble in organic solvents and in particular in water-immiscible organic solvents.
• organic peroxides such as tert-butyl peroxide, benzoyl peroxide, diisobutyryl peroxide, di-n-propyl peroxydicarbonate, didecanoyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-amyl peroxide may also be used as oxidants.
• organic azo compounds such as 2,2'-azodiisobutyronitrile and inorganic oxidants such as ammonium persulfate may also be used.
• the adhesive composition in the present invention includes an amphiphilic compound.
• the amphiphilic compound like this is contained, lower surface resistivity may be stably provided to the adhesive layer, and, haze of the adhesive layer may be reduced to enhance light transmittance.
• amphiphilic compound compounds having high affinity to both aqueous solvents (solvents or dispersion media) and nonaqueous solvents may be used, and nonionic compounds having a hydrophilic group and a hydrophobic group in a molecule are preferable.
• nonionic amphiphilic compounds nonionic compounds having an ether or ester of trivalent or more polyvalent alcohol, or an oxyalkylene chain as a hydrophilic group are preferred.
• esters of trivalent or more polyvalent alcohols are preferred, and compounds that are aliphatic acid esters of trivalent or more polyvalent alcohols and do not have a polyoxyalkylene structure are more preferred.
• an influence on the surface resistivity and antistatic property due to the kind of the substrate may be reduced.
• ethers and esters of trivalent or more polyvalent alcohols are compounds having three or more in total of hydroxyl groups, ether bonds or ester bonds in a molecule.
• compounds having an oxyalkylene chain compounds having oxyethylene or oxypropylene as a repeating structural unit may be used, and the number of repeating units in the oxyalkylene chain is preferably 2 or larger and more preferably 5 or larger.
• the hydrophilicity is exhibited in the hydroxyl group, ether bond and ester bond.
• nonionic amphiphilic compounds include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; polyoxyalkylene derivatives such as polyoxyethylene alkylene alkyl ether; polyoxyethylene alkenyl ether and polyoxyethylene alkyl phenyl ether; sorbitan aliphatic acid esters such as sorbitan octadecanoic acid ester, sorbitan lauric acid ester, sorbitan oleic acid ester, sorbitan stearic acid ester and sorbitan palmitic acid ester; sucrose fatty acid esters such as sucrose oleic acid ester; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monooleate; polyoxyethylene sorbitol fatty acid ester; glycerin fatty acid ester;
• a content of the (C) amphiphilic compound is adjusted to, preferably, for example, 0.1 part by mass or higher, more preferably 0.5 parts by mass or higher, and further preferably 1.0 parts by mass or higher relative to 100 parts by mass of the (A) adhesive polymer. Furthermore, the content of the (C) amphiphilic compound is adjusted to, preferably, for example, 10.0 part by mass or lower, more preferably 8.0 parts by mass or lower, and further preferably 5.0 parts by mass or lower relative to 100 parts by mass of the (A) adhesive polymer.
• the adhesive composition includes a nonaqueous solvent or dispersion medium. More specifically, the adhesive composition contains a solvent or a dispersion medium in which a concentration of water in the solvent or dispersion medium is preferably smaller than 1% by mass, more preferably smaller than 0.5% by mass, still more preferably smaller than 0.1% by mass, and furthermore preferably smaller than 0.01% by mass.
• a concentration of water in the solvent or dispersion medium is preferably smaller than 1% by mass, more preferably smaller than 0.5% by mass, still more preferably smaller than 0.1% by mass, and furthermore preferably smaller than 0.01% by mass.
• linear, branched or cyclic aliphatic hydrocarbons such as pentane, hexane, heptane, octane, petroleum ether, cyclohexane, methyl cyclohexane or cycloheptane; aromatic hydrocarbons such as benzene, toluene or xylene; mono- or bivalent alcohols such as methanol, ethanol, iso-propanol, butanediol, diethylene glycol, or triethylene glycol; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether or anisole; halogenated hydrocarbons such as dichloromethane, chloroform, tetrachloromethane, trichloroethane and trichloroethene; halogenated aromatic hydrocarbons such as chlorobenzene; aliphatic nitrile
• the solvent or dispersion medium one or more kinds selected from ethyl acetate, butyl acetate, toluene, methyl ethyl ketone, propylene glycol, and anisole are preferably used.
• a content of the (D) solvent or dispersion medium to, for example, 10 parts by mass or higher, more preferably 25 parts by mass or higher, still more preferably 100 parts by mass or higher relative to 100 parts by mass of the (A) adhesive polymer. Furthermore, it is preferable to adjust the content of the (D) solvent or dispersion medium to, for example, 50,000 parts by mass or lower, more preferably to 10,000 parts by mass or lower, and furthermore preferably to 1,000 parts by mass relative to 100 parts by mass of the (A) adhesive polymer.
• an antioxidant In the adhesive composition, an antioxidant, a light stabilizer, a metal corrosion inhibitor, an adhesion imparting agent, a plasticizer, an antistatic agent, a crosslinking accelerator, and a rework agent may be further blended in the range that does not damage an effect of the present invention. Furthermore, various components such as a high conductivity enhancing agent and so on may be contained to improve the electric conductivity of the conductive polymer.
• water content in the adhesive composition is preferable to be slight. More specifically, a concentration of water in the adhesive composition is preferably lower than 0.5% by mass, more preferably lower than 0.1% by mass, and still more preferably lower than 0.01% by mass. When water content in the adhesive composition is reduced, formation of aggregated precipitates in the adhesive composition may be reduced, furthermore, the surface resistivity of the adhesive layer may be reduced.
• a protective material provided with an adhesive layer may be obtained.
• known methods for example, wire-bar coating, spin coating, dipping (immersing), pouring, dropping on, injecting, spraying, doctor blade coating, coating or printing may be used.
• means for printing inkjet printing, screen printing, relief printing, offset printing or pad printing may be used.
• a film thickness before drying of the adhesive composition provided to the substrate is set in accordance with a concentration of a non-volatile component in the adhesive composition or a thickness of the adhesive layer after drying.
• the adhesive composition may be applied to the substrate at a thickness of preferably 0.1 ⁇ m or thicker, more preferably 0.5 ⁇ m or thicker, and may be applied to the substrate at a thickness of preferably 250 ⁇ m or thinner, and more preferably 150 ⁇ m or thinner.
• an adhesive layer may be obtained.
• the organic solvent may be partially removed by drying at a temperature of from 20°C to 200°C.
• the polymer may be cured.
• the adhesive polymer solution contains an acryl polymer that contains 2-ethylhexyl acrylate/2-hydroxyethyl acrylate/acrylic acid at a monomer weight ratio of 96.5/3/0.5 and a mixed solvent that has a solvent composition of ethyl acetate/toluene at 50/50.
• a weight-average molecular weight (Mw) of the obtained adhesive polymer solution was measured according to the following measurement conditions of gel permeation chromatography (GPC). Also, a heating residue (nV) at 105°C was measured under the following condition and it was confirmed that the solid content is 30%. Furthermore, regarding the viscosity of the adhesive polymer solution, initial viscosity at 25°C was measured using a viscometer (B II Type, manufactured by Toki Sangyo Co., Ltd.) and found to be 2.5 Pa ⁇ s.
• Measurement Device HLC-8120GPC (manufactured by TOSOH Corporation)
• GPC Column Configuration The following 5 Consecutive Column Configuration (all manufactured by TOSOH Corporation) (1)TSK-GEL HXL-H (Guard Column) (2)TSK-GEL G7000HXL (3)TSK-GEL GMHXL (4)TSK-GEL GMHXL (5)TSK-GEL G2500HXL Sample concentration: Diluted with tetrahydrofuran so as to be 1.0 mg/cm 3
• Mobile phase solvent Tetrahydrofuran Flow rate: 1 ml/min Column temperature: 40°C
• Example A-2 As the adhesive polymer, a copolymer of n-butyl acrylate and 2-hydroxyethyl acrylate (weight-average molecular weight: 500,000, glass transition temperature: -48°C, hydroxyl value: 5 mgKOH/g) was prepared according to the following procedure. In the same flask as in Experimental Example A-1, n-butyl acrylate (289.5 g), 2-hydroxyethyl acrylate (9.0 g), acrylic acid (1.5 g) and ethyl acetate (580 g) were charged, followed by heating the content of flask at 66°C while introducing nitrogen gas into the flask.
• the adhesive polymer solution contains an acryl polymer that contains n-butyl acrylate/2-hydroxyethyl acrylate/acrylic acid at a monomer weight ratio of 96.5/3/0.5 and an ethyl acetate as the solvent.
• a weight-average molecular weight (Mw) of the obtained adhesive polymer solution was measured according to the above measurement conditions of gel permeation chromatography (GPC), in the same manner as in Experimental Example A-1. Also, a heating residue (nV) at 105°C was measured under the above condition and it was confirmed that the solid content is 30%. Furthermore, regarding the viscosity of the adhesive polymer solution, initial viscosity at 25°C was measured using a viscometer (B II Type, manufactured by Toki Sangyo Co., Ltd.) and found to be 4.1 Pa ⁇ s.
• Example B-2 In the present Experimental Example, by using an aqueous dispersion of poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT/PSS), an operation of substituting the dispersion medium with an organic solvent was performed.
• PEDOT/PSS poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate
• EDOT 3,4-ethylenedioxythiophene
• AOT Di-2-ethylhexyl Sodium Sulfosuccinate
• the obtained PEDOT/AOT powder (0.12 g) was added to methyl ethyl ketone (MEK) (10.0 g) that is a solvent or a dispersion medium and subjected to ultrasonic dispersion, and thus a dispersion liquid of the PEDOT/AOT was prepared, and this was taken as a conductive polymer dispersion (B-3).
• MEK methyl ethyl ketone
• B-3 conductive polymer dispersion
• Amphiphilic compound (C) As an amphiphilic compound (C), the following materials were prepared.
• Amphiphilic compound (C-1) octyl phenol ethoxylate (manufactured by Dow Chemical, product name: Triton X 100)
• Amphiphilic compound (C-2) polyethylene glycol-polypropylene oxyglycol block copolymer (manufactured by Sigma-aldrich, product name: Pluronic (R) F-68).
• Amphiphilic compound (C-3) Sorbitan mono-octadecanoate (manufactured by Croda, product name: Span 60)
• Amphiphilic compound (C-4) polyoxyethylene sorbitan monostearate (manufactured by Croda, product name: Tween 60).
• Amphiphilic compound (C-5) Sucrose oleic acid ester (manufactured by Mitsubishi Chemical Foods Corporation, product name: Ryoto Sugar Ester O-1570)
• each of the adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 4 was laminated on a substrate made of a PET film (manufactured by DuPont, product name: Melinex OD) having a thickness of 175 ⁇ m with a primer layer on a surface thereof (hereinafter referred to as “substrate A”) and on a substrate made of a PET film (manufactured by DuPont, product name: Melinex 5066) having a thickness of 175 ⁇ m without a primer layer on a surface thereof (hereinafter referred to as “substrate B”) such that each dry film thickness may be 10 ⁇ m by a wire-bar coat, followed by drying at a temperature of 90°C for 5 minutes to form an adhesive layer, thus a protective material was obtained. Surface resistivity and haze of the obtained protective material were measured and the presence or absence of aggregated matter was evaluated.
• the surface resistivity was measured according to JIS-K-6911 at an input voltage of 1000 V under atmosphere of a temperature of 23°C and humidity of 50% RH, by using a resistivity meter (Hi-Rester UX MCP-HT800, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Then, a ratio ( ⁇ / ⁇ ) of the surface resistivity ( ⁇ ) of a protective material formed on the substrate A and the surface resistivity ( ⁇ ) of a protective material formed on the substrate B was obtained as a substrate-dependent factor, and, from a magnitude of the numerical value, an influence due to the kind of the substrate on the antistatic property was evaluated.
• a laminate was formed by adhering an acryl plate (70 mm ⁇ 150 mm ⁇ 1 mm) and a polarizing plate made of triacetyl cellulose (AG polarizing plate, plane polarizing plate) such that an AG surface or a plane surface of the polarizing plate is located on an outer side, followed by neutralizing by a static eliminator (SJ-F300, manufactured by KEYENCE Corp.).
• Adhesive sheets (samples prepared with a PET with primer (substrate A)) obtained in Examples and Comparative Examples were cut into 40 mm ⁇ 150 mm, followed by pressure molding with a 2 Kg rubber roller on an AG surface and a plane surface of a laminated body that was neutralized in advance. After leaving for 1 day under a condition of air temperature of 25°C and humidity of 65%, followed by neutralizing again, further followed by measuring a surface potential of the laminate when peeled at a peeling speed of 30 m/min and a peeling angle of 180° by a potential measurement device (SK-200, manufactured by KEYENCE Corp.).
• SK-200 potential measurement device
• Example 1 where a conductive polymer dispersion (B-1) having a diene structure in a molecule was used, the surface resistivity of the protective material formed on the substrate A was 8 ⁇ 10 10 ⁇ / ⁇ . This value was a value lower than 7 ⁇ 10 11 ⁇ / ⁇ that is the surface resistivity of Example 3 in which the conductive polymer dispersion (B-2) that does not have a diene structure was used.
• Example 1 where the conductive polymer dispersion (B-1) was used, the peeling electrification voltage of the protective material formed on the substrate A was 0.07 kV, and became a value lower than 0.23 kV that is the surface resistivity of Example 3 in which a conductive polymer dispersion (B-2) was used. From these, it is assumed that by using the conductive polymer having a diene structure in a molecule, the antistatic properties of the adhesive layer may be further enhanced.
• the surface resistivities of the protective materials formed on the substrate B were also lower than 1 ⁇ 10 14 ⁇ / ⁇ , more specifically 6 ⁇ 10 13 ⁇ / ⁇ , and the substrate dependent factor became 67 or smaller.
• the surface resistivities of the protective materials formed on the substrate B were 1 ⁇ 10 14 ⁇ / ⁇ or higher, and the substrate dependent factor exceeded also 100. From these, it is assumed that by using the ester of, in particular, trivalent or more polyvalent alcohol as the amphiphilic compound, influences on the surface resistivity or antistatic property due to the kind of the substrate may be reduced.
• evaluation results about the presence or absence of aggregated material, and evaluation results of the haze were the same irrespective of the presence or absence of primer coating on the PET substrate.

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