WO2012132115A1 - Feuille adhésive transparente double face et dispositif d'affichage d'image avec panneau tactile - Google Patents

Feuille adhésive transparente double face et dispositif d'affichage d'image avec panneau tactile Download PDF

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Publication number
WO2012132115A1
WO2012132115A1 PCT/JP2011/077627 JP2011077627W WO2012132115A1 WO 2012132115 A1 WO2012132115 A1 WO 2012132115A1 JP 2011077627 W JP2011077627 W JP 2011077627W WO 2012132115 A1 WO2012132115 A1 WO 2012132115A1
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Prior art keywords
sensitive adhesive
adhesive sheet
adhesive layer
acrylic
transparent double
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PCT/JP2011/077627
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English (en)
Japanese (ja)
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加那予 中田
森下　義弘
晋弥 大下
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株式会社クラレ
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Priority to JP2013507055A priority Critical patent/JP5840200B2/ja
Publication of WO2012132115A1 publication Critical patent/WO2012132115A1/fr

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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
    • 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
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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]
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2453/00—Presence of block copolymer
    • 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
    • C09J2453/00—Presence of block copolymer
    • C09J2453/006—Presence of block copolymer in the substrate

Definitions

  • the present invention relates to a transparent double-sided pressure-sensitive adhesive sheet that can be suitably used when adhering and fixing a touch panel and an image display panel or a touch panel and a surface protection panel, and an image display device with a touch panel provided with the transparent double-sided pressure-sensitive adhesive sheet.
  • Patent Document 1 proposes an adhesive sheet in which a plurality of adhesive layers having different viscoelastic behaviors are stacked and integrated.
  • an adhesive sheet consists only of an adhesive layer, it has poor portability and punchability, and there is room for improvement.
  • the adherend is a plastic resin such as an acrylic resin or a polycarbonate resin, there is a problem that foaming occurs due to outgas generated from the plastic resin.
  • Patent Document 2 discloses a double-sided PSA sheet in which PSA layers are formed on both sides of a transparent substrate such as a polyethylene terephthalate (PET) film in the Examples.
  • a double-sided PSA sheet has a problem in that since the refractive index of the PSA layer is different from that of the transparent substrate, reflection occurs at the interface and image visibility and brightness are lowered.
  • the transparent base material is a hard plastic material, there is a problem that the requirements for step absorbency and impact resistance cannot be satisfied.
  • Patent Document 3 proposes a double-sided pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is made of a (meth) acrylate block copolymer.
  • an object of the present invention is to provide a transparent double-sided pressure-sensitive adhesive sheet excellent in impact resistance and corrosion resistance. Moreover, the other object of this invention is to provide the image display apparatus with a touch panel excellent in visibility provided with the said transparent double-sided adhesive sheet.
  • the above object is [1] A polymer block (A) having a glass transition temperature of 50 ° C. or higher obtained by polymerizing at least one monomer selected from a methacrylic acid ester and an acrylic acid ester, and a methacrylic acid ester and an acrylic layer.
  • the adhesive layer has the following general formula (II): A3-B2-A4 (II) (In the formula, A3 and A4 each independently represent a methacrylic acid ester polymer block having a glass transition temperature of 100 ° C. or higher, and B2 represents an acrylate polymer block having a glass transition temperature of ⁇ 20 ° C.
  • the weight average molecular weight (Mw) is 50,000 to 300,000, the content of the polymer block B2 is 77 to 95% by mass, and the molecular weight distribution (Mw / Mn) is 1.0 to 1.
  • the transparent double-sided PSA sheet of [1] to [3], which is 05 or less; [5] The transparent layer according to [4], wherein the adhesive layer (a) and the adhesive layer (b) both have a refractive index of 1.45 to 1.65 and the base layer has a refractive index of 1.46 to 1.65. Double-sided adhesive sheet.
  • the base material layer has the following general formula (I); A1-B1-A2 (I) (In the formula, A1 and A2 each independently represent a methacrylic ester polymer block having a glass transition temperature of 100 ° C. or higher, and B1 represents an acrylate polymer block having a glass transition temperature of ⁇ 20 ° C.
  • the weight average molecular weight (Mw) is 50,000 to 300,000, the content of the polymer block B1 is 49 to 5% by mass, and the molecular weight distribution (Mw / Mn) is 1.0 to 1.
  • Mw weight average molecular weight
  • Mn molecular weight distribution
  • Adhesive sheet [10] The transparent double-sided pressure-sensitive adhesive sheet of [1] to [9], having a thickness of 210 ⁇ m or more and 1000 ⁇ m or less; [11] The transparent double-sided pressure-sensitive adhesive sheet of [1] to [10] for sticking and fixing the touch panel and the image display panel or the touch panel and the surface protection panel; [12] A member provided with a touch panel on one main surface of the transparent double-sided pressure-sensitive adhesive sheet of [1] to [11] and an image display panel or a surface protection panel on the other main surface; [13] A touch panel member comprising the transparent double-sided pressure-sensitive adhesive sheet of [1] to [11], which is either an out-cell type, an in-cell type, an on-cell type, a cover glass integrated type, or a cover sheet integrated type; [14] A touch panel member comprising the member of [12]; and [15] An image display device comprising the touch panel member according to [13] or [14]; Is achieved by providing
  • a transparent double-sided pressure-sensitive adhesive sheet that is useful as a transparent double-sided pressure-sensitive adhesive sheet for touch panels and is excellent in impact resistance and corrosion resistance.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention comprises a polymer block (A) having a glass transition temperature of 50 ° C. or higher, wherein the pressure-sensitive adhesive layer is obtained by polymerizing at least one monomer selected from methacrylic acid esters and acrylic acid esters. Containing an acrylic block copolymer (0) containing a polymer block (B) having a glass transition temperature of 20 ° C. or lower obtained by polymerizing at least one monomer selected from methacrylic acid esters and acrylic acid esters To do.
  • Examples of the monomer used for the polymer block (A) include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, Methacrylic acid esters such as isobornyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate; methyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, etc. Examples include acrylic acid esters.
  • the polymer block (A) may be composed of one of these methacrylic acid esters and acrylic acid esters, or may be composed of two or more.
  • the acrylic block copolymer (0) preferably contains two or more polymer blocks (A) from the viewpoint of enhancing durability. In that case, these polymer blocks (A) may be the same or different.
  • Examples of the monomer used for the polymer block (B) include n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, and methacrylic acid.
  • Methacrylic acid esters such as 2-ethylhexyl, pentadecyl methacrylate, dodecyl methacrylate, phenoxyethyl methacrylate, 2-methoxyethyl methacrylate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate -Butyl, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, Benzyl acrylic acid, phenoxyethyl acrylate and acrylic acid esters such as 2-methoxyethyl acrylate.
  • the polymer block (B) may be composed of one of these methacrylic acid esters and acrylic acid esters, or may be composed of two or more kinds. Moreover, when two or more polymer blocks (B) are contained in the acrylic block copolymer (0), the polymer blocks (B) may be the same or different.
  • the monomer used for the polymer block (A) and the polymer block (B) further has methacrylic acid having a reactive group.
  • Esters and acrylic esters may be used.
  • the methacrylic acid ester and acrylic acid ester having a reactive group include glycidyl methacrylate, allyl methacrylate, glycidyl acrylate, and allyl acrylate.
  • these monomers are usually used in a small amount, but the amount is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total mass of the monomers used for each polymer block. Used in.
  • the monomer used for the polymer blocks (A) and (B) may be other monomers as necessary. May be used in combination.
  • Examples of such other monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, vinyl acetate, anhydrous Maleic acid, vinyl chloride, vinylidene chloride and the like can be mentioned.
  • these monomers are usually used in a small amount, but the amount is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total mass of the monomers used for each polymer block. Used in.
  • the acrylic block copolymer (0) used in the present invention may have other polymer blocks as necessary in addition to the polymer block (A) and the polymer block (B).
  • examples of such other polymer blocks include styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, vinyl acetate, anhydrous
  • examples thereof include a polymer block or copolymer block composed of maleic acid, vinyl chloride, vinylidene chloride and the like; a polymer block composed of polyethylene terephthalate, polylactic acid, polyurethane, polydimethylsiloxane, and the like.
  • the polymer block also includes a hydrogenated polymer block containing a conjugated diene compound such as butadiene or isoprene.
  • the glass transition temperatures of the polymer block (A) and the polymer block (B) in the present invention are observed in a curve obtained by measuring the acrylic block copolymer (0) with a differential scanning calorimeter (DSC). It is the extrapolation start temperature (Tgi) of the transition region of the polymer block (A) and the polymer block (B). As a specific measuring method, the method described in detail in Examples described later is adopted. As the glass transition temperature, literature values described in “Synthesis / design of acrylic resin and development of new applications” (published by Chubu Business Development Center, published in 1985) may be used.
  • the plurality of glass transition temperatures derived from the polymer block (A) and the polymer block (B) are respectively Since the glass transition temperature of the polymer having the same chemical structure (monomer composition, stereoregularity, etc.) as that of the polymer block is the same as or close to that, these multiple glass transition temperatures originate from which polymer block It can be easily determined whether or not to do.
  • the polymer having the same chemical structure as the polymer block (A) and the polymer block (B) is obtained by analyzing the acrylic block copolymer (0) by 1 H-NMR, 13 C-NMR, etc.
  • the chemical structure such as the monomer composition and stereoregularity of the polymer block (A) and the polymer block (B) can be obtained and polymerized appropriately so that the chemical structure is reproduced.
  • the structure of the acrylic block copolymer (0) includes, for example, the formula (AB) a , the formula (AB) b -A, the formula (BA) c -B, and the formula (AB).
  • m- Z and formula (BA) m- Z [wherein A represents a polymer block (A), B represents a polymer block (B), and a, b and c are the same or different.
  • A represents a polymer block (A)
  • B represents a polymer block (B)
  • a, b and c are the same or different.
  • m represents an integer of 3 to 30
  • Z represents a coupling site (a coupling site after a coupling agent reacts with a polymer terminal to form a chemical bond). And the like.
  • acrylic block copolymer (0) examples include an AB diblock copolymer, an ABA triblock copolymer, and an ABAB tetrablock copolymer. , ABABABA or BABABAB pentablock copolymer, (AB) m -Z star block copolymer, and the like. Especially, it is preferable from a viewpoint of the heat resistance of the transparent double-sided adhesive sheet of this invention, mechanical strength, surface sticking, etc. to have the structure which the polymer block (A) couple
  • the acrylic block copolymer (0) used for the pressure-sensitive adhesive layer in the transparent double-sided pressure-sensitive adhesive sheet of the present invention includes functional groups having active hydrogen such as amino groups, thiol groups, and carboxyl groups, and sodium salts thereof. It is preferable not to have a metal salt; a functional group containing nitrogen such as a dimethylamino group or a diethylamino group; a functional group containing sulfur such as a thioether. Since the transparent double-sided pressure-sensitive adhesive sheet containing such an acrylic block copolymer (0) in the pressure-sensitive adhesive layer does not corrode ITO (indium tin oxide) forming the conductive film in the touch panel, the transparent double-sided pressure-sensitive adhesive sheet was used. The touch panel is excellent in durability.
  • A3-B2-A4 (II) As the acrylic block copolymer (0) contained in the adhesive layer, the following general formula (II): A3-B2-A4 (II) (In the formula, A3 and A4 each independently represent a methacrylic acid ester polymer block having a glass transition temperature of 100 ° C. or higher, and B2 represents an acrylate polymer block having a glass transition temperature of ⁇ 20 ° C. or lower.) It is particularly preferable to use an acrylic block copolymer (II) represented by
  • the total content of the polymer block A3 and the polymer block A4 is 5 to 23% by mass, preferably 5 to 18% by mass, and more preferably 10 to 18% by mass. preferable.
  • the content of the polymer block B2 is 77 to 95% by mass, preferably 82 to 95% by mass, and preferably 82 to 90% by mass. More preferred. If it is in the said range, it will be excellent by the level
  • the total content of the polymer block A3 and the polymer block A4 is smaller than the above range, the shape-retaining property of the transparent double-sided PSA sheet may be deteriorated and the durability may be inferior.
  • the flexibility of the acrylic block copolymer (II) is insufficient, and the adhesive physical properties tend to be inferior.
  • the weight average molecular weight of the acrylic block copolymer (II) is 50,000 to 300,000 in terms of polystyrene calculated by gel permeation chromatography (GPC) from the viewpoint of adhesive properties. It is preferably 50,000 to 200,000.
  • GPC gel permeation chromatography
  • the molecular weight distribution (weight average molecular weight / number average molecular weight) of the acrylic block copolymer (II) is 1.0 to 1.5 from the viewpoint of surface stickiness and transparency, and is 1.0 to 1.4. Preferably, it is 1.0 to 1.3, more preferably 1.0 to 1.2.
  • the molecular weight distribution is in the above range, the transparency, flexibility and durability are excellent.
  • the molecular weight distribution is within this range, the content of (meth) acrylic acid derived from the monomer (generated by hydrolysis of the remaining monomer) is so small that it can be ignored, so that it is resistant to ITO (indium tin oxide) corrosion. Is also preferable.
  • the content of the acrylic block copolymer (II) with respect to the total mass of the pressure-sensitive adhesive layer is 20% by mass or more. It is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, and further preferably 50% by mass to 100% by mass.
  • the pressure-sensitive adhesive layer may further contain an acrylic diblock copolymer having an AB structure.
  • an acrylic diblock copolymer having an AB structure.
  • the acrylic diblock copolymer is preferably 70% by mass or less, more preferably 10% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass with respect to the total mass of the adhesive layer. % Is more preferable.
  • the acrylic diblock copolymer is included within the above range, the pressure-sensitive adhesive layer becomes highly viscous and has excellent tack and step absorbability.
  • the content of the polymer block (A) is preferably 3 to 70% by mass, more preferably 5 to 55% by mass.
  • the content of the polymer block B is preferably 30 to 97% by mass, and more preferably 45 to 95% by mass.
  • the durability tends to be inferior.
  • the content of the polymer block (A) is larger than the above range, the step absorbability, the adhesive properties, and the compatibility with the acrylic triblock copolymer tend to be inferior.
  • the polystyrene equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement is preferably 50,000 to 300,000, more preferably 50,000 to 200,000. Is more preferably 50,000, more preferably 50,000 to 100,000, and particularly preferably 50,000 to 75,000.
  • GPC gel permeation chromatography
  • the pressure-sensitive adhesive layer constituting the transparent double-sided pressure-sensitive adhesive sheet of the present invention is a polymer, softener, curing agent, lubricant, plasticizer, pressure-sensitive adhesive, tackifying resin, and heat stabilizer as long as the effects of the present invention are not impaired. Further, additives such as an antioxidant, a light stabilizer, an antistatic agent, a flame retardant, a foaming agent, a coloring agent, a dyeing agent, a refractive index adjusting agent and a filler may be contained. These other polymers and additives may be included in one kind or in two or more kinds.
  • Examples of the other polymer include acrylic resins such as polymethyl methacrylate and methacrylate ester copolymer; polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly-4-methylpentene- 1.
  • Olefin resin such as polynorbornene; ethylene ionomer; styrene resin such as polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin Resin; Methyl methacrylate-styrene copolymer; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate and polylactic acid; Polyamide such as nylon 6, nylon 66 and polyamide elastomer; Polycarbonate; Polyvinyl chloride Polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl alcohol copolymer; Polyacetal; Polyvinylidene fluoride; Polyurethane; Modified polyphenylene ether; Polyphenylene sulfide; Silicone rubber modified resin; Acrylic rubber; Silicone rubber; SEPS, SEBS, SIS, etc.
  • Styrenic thermoplastic elastomers such as IR, EPR and EPDM.
  • acrylic resin, ethylene-vinyl acetate copolymer, AS resin, polylactic acid, polyfluoride, Vinylidene chloride is preferred.
  • the softening agent examples include mineral oils such as paraffinic process oil and naphthenic process oil.
  • the filler examples include inorganic fibers such as glass fibers and carbon fibers, and organic fibers; inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. .
  • inorganic fiber and organic fiber are contained, a reinforcing effect is imparted to the resulting adhesive layer.
  • heat resistance and weather resistance are imparted to the obtained adhesive layer.
  • the heat stabilizer or antioxidant is contained in the adhesive layer, the heat resistance and weather resistance are further improved, so that it is practically included in the adhesive layer used in the transparent double-sided pressure-sensitive adhesive sheet. preferable.
  • curing agent examples include photocuring agents such as UV curing agents, thermosetting agents, and the like, and examples include benzoins, benzoin ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diacetyls. .
  • curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a monomer may be added.
  • these monomers include acrylic acid, methacrylic acid, ⁇ -cyanoacrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, and acrylic acid esters, methacrylic acid, Esters such as acid esters, crotonic acid esters, maleic acid esters; acrylamides; methacrylamides; acrylamide derivatives such as N-methylolacrylamide, N-hydroxyethylacrylamide, N, N- (dihydroxyethyl) acrylamide; N-methylolmethacrylamide, Methacrylamide derivatives such as N-hydroxyethyl methacrylamide and N, N- (dihydroxyethyl) methacrylamide; vinyl esters; vinyl ethers; mono-N-vinyl derivatives; styrene derivatives; The oligomer etc.
  • esters such as acrylic acid esters, methacrylic acid esters, crotonic acid esters, maleic acid esters; vinyl ethers; styrene derivatives; And the oligomer which contains the said monomer as a structural component is preferable.
  • a cross-linking agent composed of a bifunctional or higher functional monomer or oligomer may be added.
  • the refractive index of the pressure-sensitive adhesive layer constituting the transparent double-sided pressure-sensitive adhesive sheet of the present invention is preferably 1.45 to 1.65 from the viewpoint of transparency.
  • the method described in detail in Examples described later is employed as a specific method for measuring the refractive index of the pressure-sensitive adhesive layer.
  • the adhesive layer requires an elastic modulus and flexibility that can maintain its form. Therefore, the adhesive layer of the transparent double-sided PSA sheet preferably has a storage shear modulus at 20 ° C. of 5.0 ⁇ 10 3 Pa or more and 2.0 ⁇ 10 6 Pa or less, and 2.0 ⁇ 10 4 Pa. or more preferably 5.0 at ⁇ 10 5 Pa or less, still more preferably not more than 6.0 ⁇ 10 4 Pa or more 5.0 ⁇ 10 5 Pa.
  • the storage shear modulus at 20 ° C. of the adhesive layer is larger than the above range, the adhesive property tends to be inferior due to insufficient flexibility. Conversely, when it is smaller than the above range, the durability tends to be inferior.
  • the method described in detail in Examples described later is employed as a specific method for measuring the storage shear modulus at 20 ° C.
  • the method for forming the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive sheet of the present invention is not particularly limited, and examples thereof include a hot melt molding method and a solution casting method described later. Among these, the solution casting method is preferable from the viewpoint of high thickness accuracy.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention may be composed of one pressure-sensitive adhesive layer, or may be composed of two or more layers having a base material layer and a pressure-sensitive adhesive layer. It is preferable that the acrylic block copolymer (0) is contained in all layers regardless of whether it is composed of one adhesive layer or two or more layers.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention comprises two or more layers, the base layer is provided with an adhesive layer (a) on one main surface and the other main surface is provided with an adhesive layer (b). Is preferred. With such a configuration, a transparent double-sided pressure-sensitive adhesive sheet having excellent durability such as portability and foam resistance is obtained.
  • the base material layer is 20 ° C.
  • the storage tensile elastic modulus is preferably 6.0 ⁇ 10 6 Pa or more and 3.3 ⁇ 10 9 Pa or less, more preferably 2.0 ⁇ 10 7 Pa or more and 3.3 ⁇ 10 9 Pa or less. It is more preferable that it is 0 ⁇ 10 7 Pa or more and 1.0 ⁇ 10 9 Pa or less.
  • the storage tensile elastic modulus at 20 ° C. of the base material layer is larger than the above range, the flexibility is insufficient and the step absorbability is inferior. Conversely, when it is smaller than the above range, the portability and foam resistance are poor.
  • the method described in detail in Examples described later is employed as a specific method for measuring the storage tensile elastic modulus at 20 ° C.
  • a base material layer having the above storage tensile modulus there are a method of adding a plasticizer to the base material layer, a method of changing a copolymerization ratio of a copolymer used for the base material layer, and the like.
  • the material constituting the base layer of the transparent double-sided pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it satisfies the above-described range of the storage tensile modulus at 20 ° C.
  • an acrylic random copolymer such as copolymers and acrylic multilayered structure polymers (see Patent Documents 4 and 5); olefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; Ethylene ionomer; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and other styrene resins; SIS, SBS, SEBS, SEPS, etc.
  • Styrene thermoplastic elastomers methyl methacrylate-styrene copolymer Body: Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid; polyamide resin such as nylon 6, nylon 66, polyamide elastomer; polyurethane resin; ester polyurethane elastomer, ether polyurethane elastomer, non-yellowing ester polyurethane elastomer, Polyurethane thermoplastic elastomers such as non-yellowing carbonate polyurethane elastomer; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, modified polyphenylene ether, polyphenylene sulfide, silicone Rubber-modified resins, core-shell rubber, acrylic rubber, etc. and compositions containing these It is. 1 type may be sufficient as
  • the material constituting the base layer of the transparent double-sided pressure-sensitive adhesive sheet of the present invention is an acrylic block copolymer among the acrylic resin and the composition containing the acrylic resin.
  • a composition containing a polymer and an acrylic block copolymer is preferred.
  • a polymer block (B) having a glass transition temperature of 20 ° C. or lower obtained by polymerizing at least one monomer selected from an ester and an acrylate ester In particular, a substrate excellent in flexibility, light resistance and transparency can be obtained.
  • A1-B1-A2 (In the formula, A1 and A2 each independently represent a methacrylic ester polymer block having a glass transition temperature of 100 ° C. or higher, and B1 represents an acrylate polymer block having a glass transition temperature of ⁇ 20 ° C. or lower.) It is particularly preferable to use an acrylic block copolymer (I) represented by
  • the total content of the polymer block A1 and the polymer block A2 is 51 to 95% by mass, and preferably 51 to 80% by mass.
  • the content of the polymer block B1 is 49 to 5% by mass, preferably 49 to 20% by mass. If it is in the said range, it is easy to make the storage tensile elasticity modulus of a base material layer into the range of this invention.
  • the total content of the polymer block A1 and the polymer block A2 is less than the above range, the shape retainability of the base material layer is lowered, and the shape retainability, portability and durability of the transparent double-sided pressure-sensitive adhesive sheet are lowered. To do.
  • the flexibility of the acrylic block copolymer is inferior.
  • the acrylic block copolymer (I) has a weight average molecular weight of 50,000 to 300,000 in terms of polystyrene calculated by gel permeation chromatography (GPC) measurement from the viewpoint of moldability. 50,000 to 200,000 is preferable.
  • GPC gel permeation chromatography
  • the molecular weight distribution (value of weight average molecular weight / number average molecular weight) of the acrylic block copolymer (I) is 1.0 to 1.5 from the viewpoint of surface stickiness and transparency. 4, more preferably 1.0 to 1.3, and even more preferably 1.0 to 1.2. When the molecular weight distribution is in the above range, transparency and durability are excellent.
  • the base material layer containing the acrylic block copolymer (I) has a microphase separation structure.
  • a microphase-separated structure usually varies depending on the mass ratio, volume ratio, degree of polymerization, etc. of each polymer block, but a spherical structure in which a spherical phase exists in the matrix phase, and a rod-like phase in the matrix phase.
  • the co-continuous structure refers to a structure other than a spherical structure, a cylinder structure, and a lamella structure, and typically includes a gyroidal structure, a porous lamella structure, and the like.
  • TEM transmission electron microscope
  • AFM atomic force microscope
  • SAXS X-ray small angle scattering
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention has a microphase separation structure in which the polymer block A1 and the polymer block A2 constituting the acrylic block copolymer (I) used for the base material layer are continuous phases. It is preferable.
  • the polymer block (A) of the acrylic block copolymer (I), that is, the total of the polymer block A1 and the polymer block A2, and the polymer block (B), That is, the composition ratio (polymer block (A) / polymer block (B)) to the polymer block B1 is preferably 51/49 to 95/5 as a mass ratio.
  • the polymer block B1 may be a dispersed phase or a continuous phase, but both the polymer blocks A1 and A2 and the polymer block B1 are continuous phases. It is preferable.
  • Typical examples of the structure include a cylinder structure, a co-continuous structure, and a lamella structure. From the viewpoint of flexibility and durability, a lamella structure is more preferable.
  • the content of the acrylic block copolymer (I) with respect to the total mass of the base material layer is 20% by mass or more. It is preferably 20% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass.
  • the base material layer may be composed of only the acrylic block copolymer (I). It may consist of a composition containing the system block copolymer (I).
  • the substrate layer is composed of a composition containing the acrylic block copolymer (I), an acrylic block copolymer or an acrylic random copolymer different from the acrylic block copolymer (I).
  • Other acrylic resins may be contained.
  • acrylic resins acrylic resins mainly composed of methacrylic acid esters such as “Parapet GF” manufactured by Kuraray Co., Ltd. are preferable.
  • the content contains the above acrylic block copolymer (I)
  • the content of the composition is preferably 0.1 to 50% by mass.
  • “mainly” means, for example, containing 50 to 100% by mass of a methacrylic ester unit in an acrylic resin.
  • the base material layer used for the transparent double-sided pressure-sensitive adhesive sheet of the present invention is composed of a composition containing the acrylic block copolymer (I), as the resin that may be contained, in addition to the acrylic resin.
  • the acrylic block copolymer (I) examples thereof include resins selected from ⁇ -methylstyrene, polyvinyl acetal resins, polyvinyl butyral resins and copolymers thereof, block copolymers containing acrylic polymer blocks and conjugated diene polymer blocks, and the like.
  • a polyvinyl acetal resin, a polyvinyl butyral resin and a copolymer thereof, and a block copolymer containing an acrylic polymer block and a conjugated diene polymer block are particularly preferable.
  • the base material layer used for the transparent double-sided pressure-sensitive adhesive sheet of the present invention is within the range that does not impair the effects of the present invention, other polymers, softeners, plasticizers, tackifier resins, heat stabilizers, light stabilizers, antistatic agents. Additives such as flame retardants, foaming agents, coloring agents, dyeing agents, refractive index adjusting agents, fillers and the like may be included. These other polymers and additives may be included in one kind or in two or more kinds.
  • Examples of the other polymer include acrylic rubbers; silicone rubbers; styrene thermoplastic elastomers such as SEPS, SEBS, and SIS; and olefin rubbers such as IR, EPR, and EPDM.
  • the softening agent examples include mineral oils such as paraffinic process oil and naphthenic process oil.
  • the filler examples include inorganic fibers such as glass fibers and carbon fibers, and organic fibers; inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. .
  • inorganic fibers and organic fibers are contained, a reinforcing effect is imparted to the obtained base material layer.
  • heat resistance and weather resistance are imparted to the obtained base material layer.
  • the heat stabilizer or the antioxidant is contained in the base material layer, the heat resistance and weather resistance are further improved, so that it is practically preferred to be contained in the base material layer.
  • the refractive index difference between the pressure-sensitive adhesive layer and the base material layer in the transparent double-sided pressure-sensitive adhesive sheet can be reduced by adding the refractive index adjusting agent to the base material layer used in the transparent double-sided pressure-sensitive adhesive sheet of the present invention.
  • the visibility of the touch panel using the transparent double-sided pressure-sensitive adhesive sheet can be improved.
  • the refractive index adjusting agent include aromatic organic phosphorus compounds, silica-containing composite oxide spherical fine particles, and the like (see Patent Documents 6 and 7). Of these, aromatic organophosphorus compounds are preferred from the viewpoint of transparency.
  • Other methods for adjusting the refractive index include a method for selecting an appropriate monomer (see Patent Document 8).
  • a base material layer what was shape
  • a base material layer you may use a commercially available thing, for example, brand name "Acryprene” (Mitsubishi Rayon Co., Ltd., storage tensile elasticity modulus 1.2 * 10 ⁇ 9 > Pa, refractive index 1.49) etc. Can be used.
  • the refractive index of the base material layer is preferably 1.46 to 1.65. Within this range, the range of the refractive index difference defined in the present invention is likely to be satisfied, and reflection at the interface of the adhesive layer / base material layer is reduced, so that the visibility tends to be excellent. In addition, as a specific method for measuring the refractive index of the base material layer, the method described in detail in Examples described later is employed.
  • the thickness of the base material layer is preferably 20 ⁇ m or more and 950 ⁇ m or less, and more preferably 50 ⁇ m or more and 900 ⁇ m or less. When the thickness of the base material layer is within the above range, the step absorbability, impact resistance, punchability, portability, and foam resistance are excellent.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention includes the pressure-sensitive adhesive layer (a) on one main surface of the base material layer and the pressure-sensitive adhesive layer (b) on the other main surface, the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer Either or both of (b) contain an acrylic block copolymer (0).
  • one of the above-mentioned adhesive layer (a) and adhesive layer (b) contains an acrylic block copolymer (0), the other does not have an acrylic block copolymer (0). May be.
  • adhesives include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, polyurethane adhesives, and the like. Among these, an acrylic pressure-sensitive adhesive is preferable from the viewpoint of transparency.
  • acrylic pressure-sensitive adhesive examples include an emulsion type, a solution type, a UV curing type, and a hot melt type.
  • the polymers used for the above-mentioned types of acrylic pressure-sensitive adhesives include acrylic random copolymers, crosslinked acrylic random copolymers, and acrylic block copolymers other than acrylic block copolymers (0).
  • examples thereof include an acrylic polymer and an acrylic multilayer structure polymer. These may be used individually by 1 type, and may mix and use 2 or more types.
  • an acrylic adhesive used for an adhesion layer you may use a commercially available thing, for example, the "SK Dyne" series by Soken Chemical Co., Ltd. etc. are mentioned.
  • a commercially available product may be used for the adhesive layer, and examples thereof include “CS9621T” manufactured by Nitto Denko Corporation.
  • an acrylic block copolymer (0) is used as the acrylic block copolymer (0). It is preferred to use II).
  • the above-mentioned pressure-sensitive adhesive layer (a) and pressure-sensitive adhesive layer (b) are within the range not impairing the effects of the present invention, and other polymers, softeners, curing agents, lubricants, plasticizers, pressure-sensitive adhesives, tackifying resins, and heat-stable.
  • An additive such as an agent, an antioxidant, a light stabilizer, an antistatic agent, a flame retardant, a foaming agent, a coloring agent, a dyeing agent, a refractive index adjusting agent, and a filler may be included.
  • These other polymers and additives may be included in one kind or in two or more kinds. As these other polymers and additives, those similar to those contained in the above-mentioned adhesive layer can be used.
  • the refractive index adjuster When the refractive index adjuster is contained in either or both of the adhesive layer (a) and the adhesive layer (b) in the transparent double-sided adhesive sheet, the adhesive layer (a) or the adhesive layer (b) and the base The difference in refractive index with the material layer or the difference in refractive index between the adhesive layer and the adherend can be reduced, and the visibility of the touch panel using such a transparent double-sided adhesive sheet can be increased.
  • the refractive index adjusting agent include aromatic organophosphorus compounds, silica-containing composite oxide spherical fine particles (see Patent Documents 6 and 7), and a tackifier resin excellent in compatibility with the adhesive layer. . Of these, aromatic organophosphorus compounds or tackifying resins are preferred from the viewpoint of transparency.
  • tackifying resins examples include rosins such as rosin, hydrogenated rosin, and disproportionated rosin; styrene resins and ⁇ -methylstyrene resins; terpene resins such as hydrogenated terpene resins and terpene phenols.
  • rosins are preferable from the viewpoint of improving adhesiveness, and disproportionated or hydrogenated rosin purified by operations such as distillation, recrystallization, and extraction from the viewpoint of suppressing light deterioration, coloring, and generation of bubbles due to impurities. Are more preferred.
  • rosins include Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, and Pine Crystal D-6250 (all manufactured by Arakawa Chemical Industries, Ltd.). It is done.
  • Specific examples of the styrenic resin include FTR6000 series and FTR7000 series (manufactured by Mitsui Chemicals, Inc.).
  • Specific examples of the terpene resin include Tamorol 901 (Arakawa Chemical Industries, Ltd.).
  • the content of the refractive index adjusting agent in the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer (b) can be adjusted according to the refractive index, but the cohesive force of the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer (b) can be adjusted. From the viewpoint of retention, the content is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass.
  • the refractive indexes of the adhesive layer (a) and the adhesive layer (b) are preferably 1.45 to 1.65.
  • the range of the refractive index difference defined in the present invention is easily satisfied, and reflection at the interface of the adhesive layer / base material layer is reduced, which is preferable in terms of improving visibility.
  • the method detailed in the below-mentioned Example is employ
  • the thicknesses of the adhesive layer (a) and the adhesive layer (b) are each preferably 10 ⁇ m or more and 200 ⁇ m or less, and are 25 ⁇ m from the viewpoint of balance between step absorbability, impact resistance, punching property, portability and foam resistance. More preferably, it is 100 ⁇ m or less.
  • the thickness of the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer (b) constituting the transparent double-sided pressure-sensitive adhesive sheet of the present invention is to selectively thicken the pressure-sensitive adhesive layer to be bonded to the stepped surface. It is preferable at the point which can thin the thickness of the whole transparent double-sided adhesive sheet.
  • the storage shear modulus of the adhesive layer on the side to be bonded to the stepped surface may be lowered.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention is provided with the pressure-sensitive adhesive layer (a) on one main surface of the base material layer and the pressure-sensitive adhesive layer (b) on the other main surface, the transparent double-sided pressure-sensitive adhesive having such a three-layer structure Two or more sheets may be stacked.
  • a three-layer structure is preferable from the viewpoint of enhancing the step absorbability and improving the productivity.
  • the adhesive layer (a) and the adhesive layer (b) contains the acrylic block copolymer (0).
  • (0) may be contained in both the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer (b), or may be contained in any one of the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer (b) and the base material layer. Also good.
  • the acrylic block copolymer (0) is contained in two or more layers, and when all the layers contain the acrylic block copolymer (0), the interlayer adhesion is high and the reworkability is excellent. And it is more preferable from the viewpoint of excellent transparency.
  • the refractive index difference between the pressure-sensitive adhesive layer (a) and the base material layer and the refractive index difference between the pressure-sensitive adhesive layer (b) and the base material layer are both 0.05 or less.
  • the refractive index difference is within this range, light scattering at the interface between layers is suppressed, and high transparency is obtained.
  • the refractive index adjusting agent described above is added to either or both of the pressure-sensitive adhesive layer and the base material layer in accordance with the pressure-sensitive adhesive layer or the base material layer to be used. (See Patent Documents 6 and 7) or a method of selecting an appropriate monomer (see Patent Document 8).
  • the acrylic block copolymer (0) used for the transparent double-sided pressure-sensitive adhesive sheet of the present invention preferably has the optical characteristics described above.
  • the molecular weight distribution of the acrylic block copolymer (0) is preferably close to 1.0.
  • a living polymerization method capable of highly controlling the molecular structure is preferable.
  • Living polymerization refers to polymerizing the monomer of the polymer block that constitutes the block copolymer, and then synthesizing the block copolymer by polymerizing other monomers before the polymerization is deactivated or stopped.
  • a method of living polymerization using an organic rare earth metal complex as a polymerization initiator see Patent Document 9
  • a mineral acid salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator
  • a living anion polymerization in the presence of see Patent Document 10
  • a living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound see Patent Document 11
  • an atom transfer radical examples thereof include a polymerization method (ATRP) (see Non-Patent Document 1).
  • the acrylic block copolymer (0) obtained has high transparency. Further, since the polymerization conversion rate of the monomer is high, the residual monomer is small and the odor is suppressed. Furthermore, when the monomer which comprises a polymer block (A) is a methacrylic ester, the molecular structure of the polymer block (A) obtained becomes high syndiotactic, and there exists an effect which improves heat resistance.
  • the acrylic block copolymer is preferably produced by a method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound.
  • organoaluminum compound for example, the following general formula (III) AlR 1 R 2 R 3 (III) (In the above formula (III), R 1 , R 2 and R 3 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent.
  • An arylene alkyl group which may have, an alkylenedioxy group which may have a substituent, and an aryleneoxy group which may have a substituent may be formed. The compound shown by these is mentioned.
  • organoaluminum compound represented by the above formula (III) examples include trialkylaluminum such as trimethylaluminum and triisobutylaluminum; dimethyl (2,6-di-tert-butylphenoxy) aluminum, diisobutyl (2,6-dioxy).
  • dialkylphenoxyaluminum such as diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum; methylbis (2,6-di-tert-butylphenoxy) aluminum, isobutylbis ( 2,6-di-tert-butylphenoxy) aluminum, isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6- ert-butylphenoxy)] alkyldiphenoxyaluminum such as aluminum; alkoxydiphenoxyaluminum such as methoxybis (2,6-di-tert-butylphenoxy) aluminum; tris (2,6-di-tert-butyl-4-methyl) Examples include phenoxy) aluminum, triphenoxyaluminum such as tris (2,6-diphenylphenoxy) aluminum.
  • isobutyl bis (2,6-di-tert-butylphenoxy) aluminum isobutyl bis (2,6-di-tert) are preferred from the standpoints of high livingness of polymerization and easy handling.
  • -Butyl-4-methylphenoxy) aluminum isobutyl [2,2'-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum are preferred.
  • an organic lithium compound can be preferably used as the organic alkali metal compound.
  • the organolithium compound include alkyllithium or alkylenedilithium such as n-butyllithium, sec-butyllithium, isobutyllithium, t-butyllithium and tetramethylenedilithium; aryllithium such as phenyllithium and xylyllithium.
  • aryl dilithium aralkyl lithium such as dilithium produced by the reaction of benzyl lithium, diisopropenylbenzene and butyl lithium or aralkyl dilithium; lithium amide such as lithium diisopropylamide; lithium alkoxide such as lithium methoxide;
  • t-butyllithium and sec-butyllithium are preferable because of high polymerization initiation efficiency, and sec-butyllithium is more preferable.
  • ethers such as dimethyl ether, dimethoxyethane, diethoxyethane, 12-crown-4; triethylamine, N, N, N ′, N′-tetramethylethylenediamine, N , N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, nitrogen-containing compounds such as 1,1,4,7,10,10-hexamethyltriethylenetetramine, pyridine, 2,2′-dipyridyl, etc.
  • the acrylic block copolymer (0) may be synthesized by further existing in the system.
  • the living anionic polymerization is usually performed in the presence of a solvent inert to the polymerization reaction.
  • a solvent inert examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride; ethers such as tetrahydrofuran and diethyl ether.
  • the method for producing the acrylic block copolymer (0) by living anion polymerization in the presence of an organoaluminum compound is further specifically exemplified.
  • a first step of polymerizing a monomer that forms a polymer block (A) with a polymerization initiator composed of an organic alkali metal compound a single amount that forms a polymer block (B)
  • the acrylic block copolymer (0) is subjected to a plurality of polymerization steps including a second step of polymerizing the polymer and a third step of polymerizing the monomer that forms the polymer block (A) if necessary. ) Can be manufactured.
  • a desired polymer block is formed at the end of the living polymer generated in each step in the next step. Therefore, for example, the polymer block (A)-is obtained by continuously reacting the active terminal of the obtained polymer with alcohol or the like through the above-described two-stage or three-stage polymerization process and stopping the polymerization reaction.
  • a binary block (diblock) copolymer comprising a polymer block (B) and a ternary block (triblock) copolymer comprising a polymer block (A) -polymer block (B) -polymer block (A)
  • a polymer can be produced.
  • the quaternary block copolymer is a desired polymer block (polymer block (A), polymer block (B), etc.) obtained by polymerizing monomers in addition to the above three-step process. Can be produced by adding the desired number of steps, reacting the active terminal of the obtained polymer with alcohol or the like, and stopping the polymerization reaction.
  • the polymerization temperature is preferably 0 to 100 ° C. when forming the polymer block (A), and ⁇ 50 to 50 ° C. when forming the polymer block (B).
  • the polymerization temperature is lower than the above range, the progress of the reaction is slow, and it takes a long time to complete the reaction.
  • the polymerization temperature is higher than the above range, deactivation increases, the molecular weight distribution becomes wide, and a desired block copolymer cannot be obtained.
  • the polymer block (A) and the polymer block (B) can be polymerized in the range of 1 second to 20 hours, respectively.
  • the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive sheet of the present invention can be produced by a hot melt molding method, a solution casting method, or the like.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention includes a base material layer
  • the base material layer can also be produced by the same method.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention includes three layers of a base material layer, a pressure-sensitive adhesive layer (a) and a pressure-sensitive adhesive layer (b), at least one of them is obtained by a hot melt molding method. May be.
  • the layer obtained by the hot melt molding method may be an adhesive layer or a base material layer.
  • all three layers of the adhesive layer (a), the base material layer, and the adhesive layer (b) may be obtained by a solution casting method.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention does not rely only on the solution casting method, it can be easily obtained with a thick, easy-to-carry, punchable, foam-resistant, and transparent material having different thicknesses. It is easy.
  • a thickness of 210 ⁇ m or more is preferable, and a thickness of 210 ⁇ m or more and 1000 ⁇ m or less is more preferable.
  • the thickness of 300 micrometers or more and 1000 micrometers or less is preferable, and the thickness of 500 micrometers or more and 1000 micrometers or less is more preferable.
  • the hot melt molding method is a method in which a resin is melted by heat to form, for example, a hot melt coating method, a T-die extrusion method, an inflation method, a calender molding method, etc.
  • the T die method or the inflation method is preferable from the viewpoint of processability and cost, and the T die method is more preferable from the viewpoint of excellent productivity and thickness accuracy.
  • the said composition containing an acrylic block copolymer (0) is fuse
  • the sheet or film is extruded from a die attached to the sheet, and the extruded sheet or film is taken into close contact with at least one cooling drum.
  • the layer structure may be formed at a time by co-extrusion of the adhesive layer and the base material layer.
  • the die is not particularly limited, and examples thereof include known dies such as a T die and a coat hanger die.
  • Examples of the material of the die include, but are not limited to, SCM steel and stainless steel such as SUS.
  • a general method used for manufacturing a film-like or sheet-like member can be used. Specifically, a heat resistant material such as polyethylene terephthalate or a flat plate or roll such as a steel belt is used as a support, and a bar coater, roll coater, die coater, comma coater, or the like is used on these. Examples include a method of applying a solution obtained by dissolving a composition containing the polymer (0) or the acrylic block copolymer (0) in a solvent, and removing the solvent by drying.
  • the method for removing the solvent by drying is not particularly limited, and a conventionally known method can be used, but it is preferable to perform drying in a plurality of stages.
  • the first stage of drying is performed at a relatively low temperature in order to suppress foaming due to rapid volatilization of the solvent.
  • a method of drying at a high temperature is more preferable.
  • examples of the solvent used for dissolving the acrylic block copolymer (0) or the composition containing the acrylic block copolymer (0) include toluene, ethyl acetate, ethylbenzene, methylene chloride, Examples include chloroform, tetrahydrofuran, methyl ethyl ketone, dimethyl sulfoxide, toluene-ethanol mixed solvent, and the like. Of these, toluene, ethylbenzene, ethyl acetate, and methyl ethyl ketone are preferable.
  • the concentration of the composition containing the acrylic block copolymer (0) or the acrylic block copolymer (0) in the solution is such that the acrylic block copolymer (0) or the acrylic block copolymer (0).
  • the method for laminating the pressure-sensitive adhesive layer and the base material layer obtained by the above method is not particularly limited.
  • each layer may be unwound from each roll, and may be wound on a roll while laminating an adhesive surface on both sides of the base material layer.
  • it may be obtained by cutting out to a required size and laminating the pressure-sensitive adhesive surfaces on both surfaces of the base material layer.
  • each of the pressure-sensitive adhesive layer (a) and the pressure-sensitive adhesive layer (b) is obtained by the above-described method, each of the pressure-sensitive adhesive layers is wound around a roll, and then the pressure-sensitive adhesive layer is unwound from each roll, and a hot melt extrusion molding method. May be wound on a roll while being laminated on both sides of the substrate layer extruded from the die.
  • a hot melt extrusion molding method May be wound on a roll while being laminated on both sides of the substrate layer extruded from the die.
  • the obtained transparent double-sided PSA sheet may be further subjected to a curing step by light or heat as necessary.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention can be used for various optical applications by utilizing its excellent transparency and flexibility.
  • it can be used for a flat or flexible image display device using an image display panel such as an LCD, EL, or PDP, such as electronic paper, PDA, TV, or game machine.
  • an adhesive layer is formed on a part or all of one surface or both surfaces of a surface protection panel, a touch panel, an image display panel, etc., and the panels are adhered to each other. be able to.
  • a member provided with a touch panel on one main surface of the transparent double-sided pressure-sensitive adhesive sheet of the present invention and an image display panel or a surface protection panel on the other main surface can be obtained.
  • the touch panel member is not limited to the above-described member having a touch panel on one main surface of the transparent double-sided pressure-sensitive adhesive sheet of the present invention and a member having an image display panel or a surface protection panel on the other main surface. . That is, the transparent double-sided pressure-sensitive adhesive sheet of the present invention can be used for sticking and fixing various layers of the touch panel member. Moreover, when each panel is formed by laminating a plurality of layers, they may be used for adhering and fixing those layers. Specifically, it can be used for sticking and fixing the following layers in the touch panel member.
  • surface protection layers such as anti-scattering films, glass, polycarbonate plates, and acrylic plates
  • surface protection layers such as surface protection sheets
  • Touch panel layers such as ITO protective layers
  • Layers that make up LCD panels such as color filters, sealing glass, LCD cells, organic EL cells, insulating films, electrodes, protective films; and layers that have these two or more functions at the same time, and other touch panel members It can be used for sticking and fixing any layer.
  • the touch panel member examples include an out-cell type, an in-cell type, an on-cell type, a cover glass integrated type, a cover sheet integrated type, and any other touch panel members.
  • the touch panel and the image display panel, or the surface protection panel and the touch panel may be integrated, or the panel portion may be formed of a film having each function.
  • the technical system of a touchscreen member For example, a resistive film type, an electrostatic capacitance type, an optical type, an ultrasonic type etc. are mentioned.
  • the total light transmittance of the transparent double-sided PSA sheet of the present invention is preferably 88% or more, and more preferably 90% or more.
  • the wavelength at the time of measuring the total light transmittance of the transparent double-sided pressure-sensitive adhesive sheet can be appropriately set within the range of visible light (360 to 730 nm).
  • the haze value of the transparent double-sided PSA sheet is preferably 3% or less, and more preferably 2% or less.
  • the wavelength at the time of measuring the haze value of the transparent double-sided pressure-sensitive adhesive sheet can be appropriately set within the range of visible light (360 to 730 nm).
  • a specific method for measuring the total light transmittance and the haze value a method described in detail in Examples described later is employed.
  • the extrapolation start temperature (Tgi) was defined as the glass transition temperature (Tg) in the curve obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121.
  • the acrylic block copolymer (II) (or composition of (II)) used for the adhesive layer was used.
  • a laminate in which an adhesive layer having a thickness of 1 mm produced in the same manner as in Example 12 described later is laminated to an acrylic adhesive sheet (C-1) used for the adhesive layer in the comparative example so as to have a thickness of 1 mm.
  • the release PET film on the other side of the test piece is peeled off and adhered to the glass plate or polycarbonate plate, which is an adherend, by reciprocating twice at a speed of 10 mm / second using a rubber roller with a load of 2 kg. I let you. This was stored for 24 hours at 23 ° C., 50% RH and atmospheric pressure, and then conditioned, and then peeled off at a peeling angle of 180 ° at a peeling speed of 30 mm / min and 300 mm / min in accordance with JIS Z0237. The adhesion was measured.
  • the release PET film on one side of the test piece was peeled off and adhered to a glass plate or a polycarbonate plate as an adherend by reciprocating twice at a speed of 10 mm / sec using a roller with a load of 2 kg. . Subsequently, this was autoclaved at 60 ° C. and 0.5 MPa for 30 minutes, stored in a constant temperature and humidity chamber at 60 ° C. and 95% RH for 200 hours, and then foamed using a calibrated loupe (10 times). The durability was evaluated based on the criteria described in Table 1.
  • Probe tack One side of the release PET film of the transparent double-sided pressure-sensitive adhesive sheet (having a release PET film on both sides) prepared in the examples or comparative examples is peeled off, and then a PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) Then, a test piece having a width of 25 mm and a length of 100 mm was cut out. Subsequently, the release PET film on the other side of the test piece was peeled off, and the probe tack was measured according to ASTM D2979.
  • a transparent conductive film “PG100-AB500H” (a film in which ITO is laminated on a PET film base material) manufactured by Teijin Chemicals Limited was cut into a width of 70 mm and a length of 50 mm.
  • a copper tape (made by Touch Panel Laboratories, made of copper foil and conductive acrylic adhesive, width 6 mm) having a conductive adhesive surface on one side was cut to a length of 80 mm on the surface on which this ITO was laminated.
  • the release PET film on one side is peeled off and bonded to a PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m), then cut into a width of 70 mm and a length of 50 mm, and the other release PET film is removed.
  • the test piece was obtained by peeling off and pasting on the surface of the transparent conductive film with the copper tape pasted thereon by reciprocating twice at a speed of 10 mm / second using a roller with a load of 2 kg. It was.
  • the obtained test piece was autoclaved at 60 ° C. and 0.5 MPa for 30 minutes, and then stored in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 200 hours.
  • the rate of change in ITO resistance value was calculated by measuring the resistance value before and after storage for 200 hours in a constant temperature and humidity chamber using the portion of the copper tape protruding from the test piece ([after storage for 200 hours Resistance value—resistance value before storage for 200 hours] / resistance value before storage for 200 hours). It shows that it is excellent in corrosion resistance, so that the change rate of ITO resistance value is small. (12) Initial Stress Value of Adhesive Layer A test piece was prepared in the same manner as in the above (4) storage shear modulus, and the initial stress value when stress was applied under the following conditions was measured.
  • the length of the longest portion of the portions (c) and (c ′) protruding from the punched section (b) of the transparent double-sided pressure-sensitive adhesive sheet (a) (such as the stringing portion of the material constituting the pressure-sensitive adhesive layer or the base material).
  • (C) is measured using a magnifying loupe (10 times), “ ⁇ ” for 0.25 cm or less, “ ⁇ ” for 0.25 cm or more and less than 0.55 cm, or 0.55 cm or more Was marked “x”.
  • Step absorbability A test piece having a width of 30 mm and a length of 30 mm was cut out from the transparent double-sided pressure-sensitive adhesive sheet (having a release PET film on both sides) prepared in Examples or Comparative Examples.
  • the release PET film on one side of the test piece was peeled off, and the adhesive surface was layered on the PET film with a step of 10 ⁇ m, and a rubber roller with a load of 2 kg was reciprocated twice at a speed of 10 mm / second and adhered. Subsequently, after autoclaving at 60 ° C. and 0.5 MPa for 30 minutes, the width of the air layer generated in the stepped portion was observed with a scaled loupe (10 times).
  • the resulting acrylic block copolymer (I-1) was subjected to 1 H-NMR measurement and GPC measurement. As a result, it was composed of polymethyl methacrylate-poly (n-butyl acrylate) -polymethyl methacrylate. It was a triblock copolymer, the weight average molecular weight (Mw) was 62,000, the number average molecular weight (Mn) was 56,000, and the molecular weight distribution (Mw / Mn) was 1.11. The content of each polymer block in the acrylic block copolymer (I-1) was 51.1% by mass for the methyl methacrylate polymer block and 48.9% by mass for the n-butyl acrylate polymer block. %Met.
  • the resulting acrylic block copolymer (I-2) was subjected to 1 H-NMR measurement and GPC measurement. As a result, polymethyl methacrylate-b-polyacrylate n-butyl-b-polymethacrylate was obtained. It is a triblock copolymer consisting of methyl acid, the weight average molecular weight (Mw) is 62,000, the number average molecular weight (Mn) is 57,400, and the molecular weight distribution (Mw / Mn) is 1.08. .
  • the content of each polymer block in the acrylic block copolymer (I-2) was 32.0% by mass for the methyl methacrylate polymer block and 68.0% by mass for the n-butyl acrylate polymer block. %Met.
  • the resulting acrylic block copolymer (II-2) was subjected to 1 H-NMR measurement and GPC measurement. As a result, it was composed of polymethyl methacrylate-poly (n-butyl acrylate) -polymethyl methacrylate. It was a triblock copolymer, the weight average molecular weight (Mw) was 115,000, the number average molecular weight (Mn) was 104,500, and the molecular weight distribution (Mw / Mn) was 1.10. The content of each polymer block in the acrylic block copolymer (II-2) was 22.5% by mass for the methyl methacrylate polymer block and 77.5% by mass for the n-butyl acrylate polymer block. %Met.
  • reaction solution was poured into 15 kg of methanol to precipitate an oily precipitate. Thereafter, an oily precipitate was collected by decantation and dried to obtain 310 g of a block copolymer [hereinafter referred to as “acrylic block copolymer (0-1)”].
  • the resulting acrylic block copolymer (0-1) was subjected to 1 H-NMR measurement and GPC measurement. As a result, a diblock copolymer comprising polymethyl methacrylate-n-butyl polyacrylate was obtained.
  • the weight average molecular weight (Mw) was 67,000
  • the number average molecular weight (Mn) was 55,400
  • the molecular weight distribution (Mw / Mn) was 1.21.
  • the content of each polymer block in the acrylic block copolymer (0-1) was 6.9% by mass for the methyl methacrylate polymer block, and 93.1% by mass for the n-butyl acrylate polymer block. %Met.
  • the obtained reaction mixture was cooled to ⁇ 30 ° C., and 60 ml of a toluene solution containing 0.6 mol / l isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added for 10 minutes. Stir to a homogeneous solution. While vigorously stirring this solution, 144 ml of n-butyl acrylate was added and polymerized at ⁇ 30 ° C. for 1 hour. Further, 2.4 ml of 1,6-hexanediol diacrylate was added and polymerized for 2 hours. Then about 1 ml of methanol was added to stop the polymerization. This reaction mixture was put into 8000 ml of methanol and reprecipitated to obtain a star block copolymer (E-3) with a yield of almost 100%.
  • E-3 star block copolymer
  • An acrylic thermoplastic resin composition (pellet shape) (D-1) was produced by melt-kneading at 230 ° C. with a shaft extruder. Further, this was subjected to extrusion molding at 190 ° C. to 210 ° C.
  • the adhesive layer (a) film obtained in (2) above is applied to one side of the substrate layer film obtained in (1) above on a laminator (Laboratory Laminator LL-100, manufactured by Chem Instruments). ), And then the adhesive layer (b) film obtained in (3) above is bonded to the other surface of the base film in the same manner, thereby releasing the PET film.
  • a double-sided transparent adhesive sheet having a structure of / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film layer was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 2 (1) Using the thermoplastic polymer composition (D-1) pellets obtained in Example 1 (1), a substrate layer film having a thickness of 300 ⁇ m was prepared in the same manner as in Example 1 (1). Produced. (2) The film for the adhesive layer (a) obtained in Example 1 (2) and the adhesive layer (b) obtained in Example 1 (3) were added to the base layer film obtained in (1) above. ) Film is laminated in the same manner as in Example 1 (4), so that the release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film has a layer structure. A double-sided transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 3 (1) Using the pellets of the thermoplastic polymer composition (D-1) obtained in Example 1 (1), a substrate layer film having a thickness of 100 ⁇ m was formed in the same manner as in Example 1 (1). Produced. (2) The acrylic block copolymer (II-1) obtained in Synthesis Example 3 was dissolved in a toluene solution to prepare a pressure-sensitive adhesive solution having a solid content of 35%, and this was used as a release PET film (Teijin DuPont). After coating on Purex A43 manufactured by Film Co., Ltd., having a thickness of 50 ⁇ m, it was dried at 60 ° C. for 30 minutes to obtain a film for an adhesive layer (a) having an adhesive layer thickness of 50 ⁇ m.
  • Example 4 Adhesive layer (a) having an adhesive layer thickness of 25 ⁇ m in the same manner as in Example 1 (2) using the acrylic block copolymer (II-2) obtained in Synthesis Example 4 A film was obtained. (2) A film for an adhesive layer (b) having an adhesive layer thickness of 25 ⁇ m was obtained by the same method as in (1) above. (3) For the film for the base layer obtained in Example 1 (1), for the adhesive layer (a) obtained in (1) above and for the adhesive layer (b) obtained in (2) above By sticking the film together in the same manner as in Example 1 (4), a double-sided transparent film comprising the structure of release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film An adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 5 (1) Using the acrylic block copolymer (I-1) obtained in Synthesis Example 1, T-die extrusion molding was carried out at 190 ° C to 210 ° C to produce a film for a substrate layer having a thickness of 125 ⁇ m. did. (2) The film for the adhesive layer (a) obtained in Example 1 (2) and the adhesive layer (b) obtained in Example 1 (3) were added to the base layer film obtained in (1) above. ) Film is laminated in the same manner as in Example 1 (4), thereby having a structure of release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film. A double-sided transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 6 The acrylic block copolymer (I-1) obtained in Synthesis Example 1 is dissolved in a toluene solution to prepare a solution having a solid concentration of 35%, and this is coated on the release PET film. Then, the film was dried at 60 ° C. for 30 minutes to prepare a film for a base material layer having a thickness of 50 ⁇ m.
  • the film for the adhesive layer (a) obtained in Example 1 (2) and the adhesive layer (b) obtained in Example 1 (3) were added to the base layer film obtained in (1) above.
  • Film is laminated in the same manner as in Example 1 (4), thereby having a structure of release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film.
  • a double-sided transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 7 (1) The acrylic block copolymer (I-1) obtained in Synthesis Example 1 is dissolved in a toluene solution to prepare a solution having a solid concentration of 35%, and this is coated on the release PET film. Then, it was dried at 60 ° C. for 30 minutes to obtain a film for a base material layer having a thickness of 100 ⁇ m. (2) The adhesive layer (b) obtained in Example 3 (3) and the adhesive layer (b) obtained in Example 3 (3) were added to the base layer film obtained in (1) above. ) Film is laminated in the same manner as in Example 1 (4), so that the release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film has a layer structure. A double-sided transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 8 (1) The acrylic block copolymer (I-2) obtained in Synthesis Example 2 is dissolved in a toluene solution to prepare a solution having a solid content of 35%, and this is coated on the release PET film. Then, the film was dried at 60 ° C. for 30 minutes to obtain a film for a base material layer having a thickness of 125 ⁇ m. (2) The film for the adhesive layer (a) obtained in Example 1 (2) and the adhesive layer (b) obtained in Example 1 (3) were added to the base layer film obtained in (1) above. ) Is bonded in the same manner as in Example 1 (4), whereby a double-sided transparent film having a structure of release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film. An adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 9 (1) 75% by mass of the methacrylic resin (E-1) obtained in Synthesis Example 5 and 25% by mass of the polyvinyl butyral resin (E-2) obtained in Synthesis Example 6 were transferred to a twin-screw extruder. The mixture was melt kneaded at 230 ° C. to produce an acrylic thermoplastic resin composition (pellet shape) (D-2). Using this pellet, a film for a substrate layer having a thickness of 125 ⁇ m was produced in the same manner as in Example 1 (1). (2) The film for the adhesive layer (a) obtained in Example 1 (2) and the adhesive layer (b) obtained in Example 1 (3) were added to the base layer film obtained in (1) above.
  • Example 2 Film is laminated in the same manner as in Example 1 (4), so that the release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film has a layer structure.
  • a double-sided transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 10 (1) Using the methacrylic resin composition (pellet shape) (D-3) obtained in Synthesis Example 8, a substrate layer film having a thickness of 125 ⁇ m was produced in the same manner as in Example 4 (1). . (2) The film for the adhesive layer (a) obtained in Example 1 (2) and the adhesive layer (b) obtained in Example 1 (3) were added to the base layer film obtained in (1) above. ) Film is laminated in the same manner as in Example 1 (4), so that the release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film has a layer structure. A double-sided transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 11 Film for adhesive layer (a) obtained in Example 1 (2) and Example 1 (3) on commercially available PET film (S100 manufactured by Mitsubishi Plastics, Inc., thickness 125 ⁇ m) (D-4) The film for the pressure-sensitive adhesive layer (b) obtained in 1 was bonded together in the same manner as in Example 1 (4), thereby releasing PET film / pressure-sensitive adhesive layer (a) / base material layer / pressure-sensitive adhesive layer (b) / A double-sided transparent adhesive sheet having a release PET film structure was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 12 (1) The acrylic block copolymer (II-2) obtained in Synthesis Example 4 is dissolved in a toluene solution to prepare a solution having a solid concentration of 35%, and this is coated on the release PET film. Then, it was dried at 60 ° C. for 30 minutes to obtain a film for an adhesive layer (a) having an adhesive layer thickness of 200 ⁇ m. (2) By attaching the release PET film to the adhesive layer (a) film obtained in (1) in the same manner as in Example 1 (4), a release PET film / adhesion layer ( a) A double-sided transparent adhesive sheet having a structure of a release PET film was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Example 13 (1) The acrylic block copolymer (II-1) obtained in Synthesis Example 3 and the acrylic block copolymer (0-1) obtained in Synthesis Example 5 at a ratio of 50:50 A solution having a solid content concentration of 35% was prepared by dissolving in a toluene solution, and this was coated on the above-mentioned release PET film, and then dried at 60 ° C. for 30 minutes. The pressure-sensitive adhesive layer had a thickness of 175 ⁇ m. A film for layer (a) was obtained.
  • Comparative Example 1 (1) Commercially available PET double-sided adhesive sheet (Nitto Denko Corporation CS9621T, thickness 25 ⁇ m) (C-1) on a commercially available PET film (Mitsubishi Resin Corporation S100, thickness 125 ⁇ m) (D-4) By bonding two sheets together in the same manner as in Example 1 (4), both surfaces having a structure of release PET film / adhesive layer (a) / base material layer / adhesive layer (b) / release PET film A transparent adhesive sheet was obtained. The various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • Comparative Example 2 >> (1) Two commercially available acrylic pressure-sensitive adhesive sheets (CS9621T manufactured by Nitto Denko Corporation, thickness 25 ⁇ m) (C-1) (C-1) were added to the base layer film obtained in Example 5 (1).
  • the various properties of the double-sided transparent adhesive sheet were measured or evaluated by the methods described above, and the results were as shown in Tables 3 to 5 below.
  • the transparent double-sided PSA sheets of Examples 1 to 13 containing the acrylic block copolymer (II) in the PSA layer have a small change rate of ITO resistance value. Corrosiveness is small and very excellent.
  • Comparative Examples 1 and 2 using an adhesive layer containing no acrylic block copolymer (II) had a large rate of change in ITO resistance, that is, ITO corrosivity was large.
  • each layer constituting the double-sided PSA sheet contains the acrylic block copolymer (0), there is no adhesive residue on the adherend in the measurement of 180 ° peel adhesion. Excellent reworkability.
  • the transparent double-sided pressure-sensitive adhesive sheets of Examples 12 and 13 composed of an adhesive layer containing the acrylic block copolymer (II) are excellent in step absorbability.
  • the transparent double-sided pressure-sensitive adhesive sheet of Example 13 containing acrylic block copolymers (II-1) and (0-1) in the adhesive layer contains acrylic block copolymer (II-2) in the adhesive layer. Since the storage shear modulus is lower, the probe tack is higher, and the initial stress value is lower than the transparent double-sided PSA sheet of Example 12, the step absorbability is excellent.
  • the transparent double-sided pressure-sensitive adhesive sheets of Examples 1 to 11 having a base material layer are excellent in punching property and excellent in portability.
  • the transparent double-sided PSA sheets of Examples 1 to 10 have a base material layer having a storage tensile modulus of 6.0 ⁇ 10 6 Pa to 3.3 ⁇ 10 9 Pa, and a storage shear modulus of 5.0. * 10 3 Pa or more and 2.0 ⁇ 10 6 Pa or less of the adhesive layer, and since the difference in refractive index between the base material layer and the adhesive layer is 0.05 or less, transparency, Excellent wet heat durability, punchability and step absorbability.
  • Comparative Example 1 in which the adhesive layer does not contain the acrylic block copolymer (0) has low transparency.
  • the comparative example 2 is inferior to the wet heat durability with respect to a polycarbonate.
  • the transparent double-sided PSA sheets of Examples 1 to 8 use the acrylic block copolymer having a storage tensile elastic modulus of 2.0 ⁇ 10 7 Pa or more and 1.0 ⁇ 10 9 Pa or less as a base material layer. Therefore, it has excellent wet heat durability.
  • the transparent double-sided pressure-sensitive adhesive sheet of Example 1 has a pressure-sensitive adhesive layer made of an acrylic block copolymer (II-1) having a content of polymer block B2 of 82% by mass or more. The wettability to the adherend is better and the wet heat durability is better than Example 4 having an adhesive layer made of an acrylic block copolymer (II-2) having a content of the combined block B2 of less than 82% by mass.
  • the adhesive layer contains the acrylic block copolymer (II-1)
  • the initial stress value is 6.1 ⁇ 10 4 Pa, and the probe tack is high, so that the step absorbability is excellent.
  • the transparent double-sided PSA sheets of Examples 1 to 7 using an acrylic block copolymer as the base material layer are excellent in reworkability because the adhesive layer is not transferred to the adherend.
  • the transparent double-sided pressure-sensitive adhesive sheet of Example 9 using an acrylic thermoplastic resin composition as a base material layer and Example 10 using a methacrylic resin composition the 180 ° peel adhesion measurement was performed at room temperature. Transfer of the pressure-sensitive adhesive layer to the adherend occurred, and adhesive residue was generated when measuring the adhesive force.
  • the transparent double-sided adhesive sheets of Example 9 and Example 10 when glass was used for the adherend, some peeling was observed at the end in the wet heat durability test.
  • the transparent double-sided pressure-sensitive adhesive sheets of Example 9 and Example 10 have excellent wet heat durability and can be used in these configurations if reworkability is not required. Can be used without problems. Moreover, since the transparent double-sided pressure-sensitive adhesive sheet of Example 11 uses a PET film having a high refractive index and high storage tensile modulus for the base material layer, the transparency is low and the step absorbability is poor, but the wet heat durability is excellent. . Therefore, the transparent double-sided pressure-sensitive adhesive sheet having this configuration can be used in applications where wet heat durability is required more strongly than transparency and step absorbability.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention has excellent transparency, adhesive strength, foam resistance, impact resistance, and images such as LCD, EL, PDP, etc., such as electronic paper, PDA, TV, game machine, etc. It can be suitably used when an optical member used in a flat type or flexible image display device using a display panel is bonded and fixed. Moreover, since the transparent double-sided adhesive sheet of this invention is excellent in corrosion resistance, punching property, and level

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  • Organic Chemistry (AREA)
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Abstract

[Problème] Fournir: une feuille adhésive transparente double face qui a d'excellentes résistance aux chocs et résistance à la corrosion; et un dispositif d'affichage d'image avec un panneau tactile, qui est équipé de la feuille adhésive transparente double face et a une excellente visibilité. [Solution] Une feuille adhésive transparente double face dans laquelle une couche adhésive contient un copolymère acrylique à blocs (0) qui contient : un bloc polymère (A) qui est obtenu par polymérisation d'au moins un monomère sélectionné parmi des esters d'acide méthacrylique et des esters d'acide acrylique et a une température de transition vitreuse de 50˚C ou plus; et un bloc polymère (B) qui est obtenu en polymérisant au moins un monomère choisi parmi des esters d'acide méthacrylique et des esters d'acide acrylique et a une température de transition vitreuse de 20˚C ou moins.
PCT/JP2011/077627 2011-03-31 2011-11-30 Feuille adhésive transparente double face et dispositif d'affichage d'image avec panneau tactile WO2012132115A1 (fr)

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JP2016508624A (ja) * 2013-02-20 2016-03-22 エルジー・ケム・リミテッド ディスプレイ装置用パッケージングフィルム
EP2889350A4 (fr) * 2013-06-19 2016-05-18 Lg Chemical Ltd Composition collante-adhésive
JP2016535409A (ja) * 2013-08-16 2016-11-10 エルジー・ケム・リミテッド 導電性フィルム及びその製造方法
JP2017065217A (ja) * 2015-10-02 2017-04-06 日東電工株式会社 積層体、タッチパネル、積層体形成キット、及び、透明導電性フィルムの屈曲耐性を向上する方法
WO2017061552A1 (fr) * 2015-10-07 2017-04-13 積水化学工業株式会社 Matériau de remplissage intercouche pour écrans tactiles, et stratifié d'écran tactile
WO2017061549A1 (fr) * 2015-10-07 2017-04-13 積水化学工業株式会社 Matériau de remplissage intercouche pour écrans tactiles, et stratifié d'écran tactile
JP2019506473A (ja) * 2015-12-22 2019-03-07 スリーエム イノベイティブ プロパティズ カンパニー 接着剤層を備えたアクリルポリビニルアセタールフィルム
CN110819258A (zh) * 2019-11-05 2020-02-21 新纶科技（常州）有限公司 压敏胶粘剂聚合物及其制备方法、压敏胶粘剂制品及其制备方法
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