WO2015132888A1 - 粘着剤および粘着シート - Google Patents

粘着剤および粘着シート Download PDF

Info

Publication number
WO2015132888A1
WO2015132888A1 PCT/JP2014/055513 JP2014055513W WO2015132888A1 WO 2015132888 A1 WO2015132888 A1 WO 2015132888A1 JP 2014055513 W JP2014055513 W JP 2014055513W WO 2015132888 A1 WO2015132888 A1 WO 2015132888A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
transparent conductive
monomer
Prior art date
Application number
PCT/JP2014/055513
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
隆行 荒井
祐樹 小澤
洋一 ▲高▼橋
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020167027263A priority Critical patent/KR102158457B1/ko
Priority to PCT/JP2014/055513 priority patent/WO2015132888A1/ja
Priority to CN202010177664.0A priority patent/CN111484809B/zh
Priority to CN201480076820.7A priority patent/CN106103631B/zh
Priority to JP2016505985A priority patent/JP6200065B2/ja
Priority to TW104106781A priority patent/TWI642739B/zh
Publication of WO2015132888A1 publication Critical patent/WO2015132888A1/ja

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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

Definitions

  • the present invention relates to an adhesive and an adhesive sheet that can be used for a touch panel or the like.
  • capacitive touch panels there are various configurations of capacitive touch panels.
  • a display module such as a liquid crystal module, a first film sensor laminated thereon with an adhesive layer thereon, The structure provided with the 2nd film sensor laminated
  • a frame-like printed layer may exist as a step on the display module side of the cover material. If the pressure-sensitive adhesive layer does not follow the step, the pressure-sensitive adhesive layer floats in the vicinity of the step, thereby causing light reflection loss. For this reason, the pressure-sensitive adhesive layer is required to have a step following ability.
  • the film sensor is usually composed of a base film and a transparent conductive film made of patterned tin-doped indium oxide (ITO).
  • ITO patterned tin-doped indium oxide
  • the touch panel having the patterned transparent conductive film as described above there is a problem of so-called bone appearance that the circuit pattern of the transparent conductive film is visible and the appearance is impaired. This problem tends to occur particularly noticeably when the touch panel is placed at a high temperature.
  • Patent Document 1 proposes a pressure-sensitive adhesive having a storage elastic modulus at 23 ° C.
  • Patent Document 2 has a pressure-sensitive adhesive having a storage elastic modulus and adhesive strength at 120 ° C. is suggesting.
  • Patent Document 3 proposes a pressure-sensitive adhesive layer in which an acrylic pressure-sensitive adhesive composition containing a predetermined amount of an acrylic polymer and a styrene-based oligomer is used and the refractive index and haze are defined.
  • Patent Documents 1 to 3 it has been difficult to sufficiently satisfy both effects of suppressing the appearance of bone and the ability to follow a step. Moreover, since the acrylic polymer of the adhesive used in the example of Patent Document 2 uses acrylic acid as a constituent monomer, it adversely affects the transparent conductive film.
  • the present invention has been made in view of the above circumstances, and can make it difficult to see the circuit pattern of the transparent conductive film on the capacitive touch panel, has excellent step following ability, and is transparent by the carboxyl group. It aims at providing the adhesive and adhesive sheet which do not have a bad influence on an electrically conductive film.
  • the present invention provides a pressure-sensitive adhesive used between two transparent conductive films or between a transparent conductive film and a cover material in a capacitive touch panel.
  • a pressure-sensitive adhesive having a refractive index of 1.45 to 1.54, a storage elastic modulus at 80 ° C. of 0.02 to 0.10 MPa, and containing no component having a carboxyl group is provided ( Invention 1).
  • the refractive index and the storage elastic modulus are defined as described above, it is possible to make it difficult to see the circuit pattern of the transparent conductive film in the capacitive touch panel. The effect is exerted even when it is placed at a high temperature such as 80 ° C.
  • the refractive index and the storage elastic modulus are defined as described above, the step followability with respect to the printing step or the like of the cover material is excellent. Furthermore, by not containing the component which has a carboxyl group, it can suppress that a transparent conductive film is corroded or changing the resistance value of a transparent conductive film.
  • the pressure-sensitive adhesive has 5 to 30% by mass of a monomer having a hydroxyl group as a monomer unit constituting the polymer, and an aromatic ring having a glass transition temperature of 70 ° C. or more as a homopolymer.
  • the (meth) acrylic acid ester copolymer (A) preferably has a weight average molecular weight of 200,000 to 1,000,000 (Invention 3).
  • the (meth) acrylic acid ester copolymer (A) includes, as the hard monomer, which is a monomer unit constituting the polymer, methyl methacrylate, isobornyl acrylate, and acryloylmorpholine. It is preferable to contain at least one selected from the group consisting of (Invention 4).
  • the adhesive preferably further contains a silane coupling agent (C) (Invention 5).
  • the present invention is an adhesive sheet used for adhesion of two transparent conductive films in a capacitive touch panel, or adhesion between a transparent conductive film and a cover material, the two release sheets, A pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer (Inventions 1 to 5), wherein the pressure-sensitive adhesive layer comprises the pressure-sensitive adhesive (Invention 1 to 5). (Invention 6).
  • the thickness of the pressure-sensitive adhesive layer is preferably 10 to 400 ⁇ m (Invention 7).
  • the pressure-sensitive adhesive and pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to the present invention it is possible to make it difficult to see the circuit pattern of the transparent conductive film on the capacitive touch panel. The effect is demonstrated even when the pressure-sensitive adhesive according to the present invention and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet are excellent in step following ability and do not contain a component having a carboxyl group, so that the transparent conductive film is corroded or the resistance value of the transparent conductive film is reduced. It can suppress changing.
  • the pressure-sensitive adhesive according to this embodiment has a refractive index of 1.45 to 1.54, a storage elastic modulus at 80 ° C. of 0.02 to 0.10 MPa, and does not contain a component having a carboxyl group. .
  • This adhesive is used between two transparent conductive films or between a transparent conductive film and a cover material in a capacitive touch panel.
  • the pressure-sensitive adhesive according to the present embodiment makes it difficult to see the circuit pattern of the transparent conductive film on the capacitive touch panel because the refractive index and the storage elastic modulus at 80 ° C. are in the above-described range. In particular, the effect is exhibited even when the touch panel is placed at a high temperature such as 80 ° C. Moreover, the adhesive which concerns on this embodiment is excellent also in level
  • the adhesive which concerns on this embodiment does not contain the component which has a carboxyl group, it can suppress corroding a transparent conductive film or changing the resistance value of a transparent conductive film.
  • the refractive index of the adhesive is less than 1.45, the circuit pattern of the transparent conductive film can be easily seen.
  • the refractive index of the pressure-sensitive adhesive is more than 1.54, the step following ability is inferior.
  • the storage elastic modulus at 80 ° C. is less than 0.02 MPa, the circuit pattern of the transparent conductive film becomes easy to see, and the visibility becomes particularly noticeable when placed at a high temperature such as 80 ° C.
  • the storage elastic modulus at 80 ° C. of the pressure-sensitive adhesive exceeds 0.10 MPa, the step following ability is inferior.
  • the refractive index of the pressure-sensitive adhesive is preferably 1.46 to 1.52, and particularly preferably 1.47 to 1.50.
  • the storage elastic modulus of the pressure-sensitive adhesive at 80 ° C. is preferably 0.015 to 0.09 MPa, and particularly preferably 0.02 to 0.07 MPa.
  • the refractive index in the present specification is a value measured according to JIS K0062-1992 using an Abbe refractometer.
  • the storage elastic modulus at 80 ° C. is a value measured by a torsional shear method shown in a test example described later.
  • the pressure-sensitive adhesive according to this embodiment is not particularly limited as long as it satisfies the above physical properties.
  • a monomer unit constituting the polymer a monomer having a hydroxyl group (hydroxyl group-containing monomer) 5 to 30% by mass, A (meth) acrylic acid ester copolymer (A) containing 5 to 40% by mass of a hard monomer having an aromatic ring having a glass transition temperature (Tg) of 70 ° C.
  • a pressure-sensitive adhesive obtained by cross-linking a pressure-sensitive adhesive composition (hereinafter sometimes referred to as “pressure-sensitive adhesive composition P”) containing a crosslinking agent (B) and preferably a silane coupling agent (C) is preferred.
  • pressure-sensitive adhesive composition P a pressure-sensitive adhesive composition containing a crosslinking agent (B) and preferably a silane coupling agent (C)
  • B crosslinking agent
  • C silane coupling agent
  • the adhesive composition P preferably contains the (meth) acrylic acid ester copolymer (A) as an adhesive main agent.
  • the content of the hydroxyl group-containing monomer and the hard monomer is in the range described above, so that the pressure-sensitive adhesive contains the (meth) acrylic acid ester copolymer (A).
  • the pressure-sensitive adhesive obtained from the composition P easily satisfies the above-described refractive index and storage elastic modulus.
  • the pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition P containing the (meth) acrylic acid ester copolymer (A) having a hydroxyl group-containing monomer content in the above range can be used under high temperature and high humidity conditions (for example, 85 Whitening is suppressed when the temperature is returned to room temperature and normal humidity, that is, excellent in heat-and-moisture whitening resistance.
  • high temperature and high humidity conditions for example, 85 Whitening is suppressed when the temperature is returned to room temperature and normal humidity, that is, excellent in heat-and-moisture whitening resistance.
  • the (meth) acrylic acid ester copolymer (A) contains a hydroxyl group-containing monomer in the above amount as a monomer unit, a predetermined amount of hydroxyl group remains in the resulting adhesive.
  • a hydroxyl group is a hydrophilic group, and when such a hydrophilic group is present in a pressure-sensitive adhesive, even if the pressure-sensitive adhesive is placed under a high temperature and high humidity condition, it penetrates into the pressure sensitive adhesive under the high temperature and high humidity condition. As a result, the whitening of the pressure-sensitive adhesive is suppressed.
  • the content of the hydroxyl group-containing monomer as the monomer unit in the (meth) acrylic acid ester copolymer (A) is less than 5% by mass, the wet heat and whitening resistance may be lowered, while the hydroxyl group-containing monomer is contained.
  • the amount exceeds 30% by mass the adhesion to the adherend is lowered, the durability may be lowered, and a desired adhesive force may not be obtained.
  • the refractive index and storage elastic modulus of an adhesive will become lower than the said range as content of the said hard monomer as a monomer unit in a (meth) acrylic acid ester copolymer (A) is less than 5 mass%.
  • content of the hard monomer exceeds 40% by mass, the step following ability may be deteriorated or a desired adhesive force may not be obtained.
  • the (meth) acrylic acid ester copolymer (A) preferably contains 5 to 30% by mass of a hydroxyl group-containing monomer as a monomer unit constituting the polymer, particularly 10 to 25% by mass. It is preferable to contain. Further, the (meth) acrylic acid ester copolymer (A) preferably contains 5 to 50% by mass of the hard monomer as a monomer unit constituting the polymer, particularly 10 to 30% by mass. Is preferred.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth And (meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of the reactivity of the hydroxyl group in the resulting (meth) acrylic acid ester polymer (A) with the crosslinking agent (B) and the copolymerizability with other monomers. Is preferred. These may be used alone or in combination of two or more.
  • the hard monomer is a monomer that does not contain an aromatic ring, and has a glass transition temperature of 70 ° C. or more, preferably 75 to 200 ° C., particularly preferably 80 to 200 ° C. as a homopolymer obtained by polymerizing only the hard monomer. It is a monomer at 180 ° C.
  • the hard monomer is preferably an acrylic monomer.
  • methyl methacrylate Tg 105 ° C.
  • isobornyl acrylate Tg 94 ° C.
  • isobornyl methacrylate Tg 180 ° C.
  • acryloylmorpholine Tg 145 ° C.
  • acrylic acid examples thereof include adamantyl (Tg 115 ° C.), adamantyl methacrylate (Tg 141 ° C.), dimethylacrylamide (Tg 89 ° C.), and acrylamide (Tg 165 ° C.). These may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester copolymer (A) is at least one selected from the group consisting of methyl methacrylate, isobornyl acrylate and acryloylmorpholine as the hard monomer which is a monomer unit constituting the polymer. It is preferable to contain.
  • (Meth) acrylic acid ester polymer (A) does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Thereby, even if the obtained adhesive is affixed on a transparent conductive film, those malfunctions by an acid can be suppressed. For example, it can suppress corroding the transparent conductive film or changing the resistance value of the transparent conductive film.
  • the (meth) acrylic acid ester polymer (A) contains a carboxyl group-containing monomer as a monomer unit in an amount of 0.1% by mass or less, preferably 0.01% by mass or less. It is acceptable.
  • the (meth) acrylic acid ester copolymer (A) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms (excluding the hard monomer described above) as a monomer unit constituting the polymer. It is preferable to contain. Thereby, the obtained adhesive can express preferable adhesiveness.
  • alkyl ester having 1 to 20 carbon atoms in the alkyl group examples include methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, ( N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate , Myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • (meth) acrylic acid esters having an alkyl group with 2 to 8 carbon atoms are preferred, and n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferred. .
  • these may be used independently and may be used in combination of 2 or more type.
  • the (meth) acrylic acid ester copolymer (A) contains 10 to 90% by mass of a (meth) acrylic acid alkyl ester having 2 to 20 carbon atoms as the monomer unit constituting the polymer.
  • the content is preferably 20 to 85% by mass, and more preferably 30 to 80% by mass.
  • the (meth) acrylic acid ester copolymer (A) may be referred to as a monomer that can increase the refractive index of the resulting pressure-sensitive adhesive (hereinafter referred to as “high refractive index monomer”) as a monomer unit constituting the polymer. .) May be contained.
  • a monomer containing an aromatic ring is preferable, and examples thereof include an aromatic monomer containing one or more aromatic rings and a monomer having a polycyclic aromatic skeleton.
  • the aromatic monomer containing one aromatic ring include benzyl (meth) acrylate, 2-phenoxyethyl acrylate, nonylphenoxypolyethylene glycol acrylate, and styryl (meth) acrylate.
  • the aromatic monomer containing two or more aromatic rings include a biphenyl group-containing monomer, a bisphenol A type monomer, and the like. From the viewpoint of handling, a biphenyl group-containing monomer is preferable.
  • the biphenyl group-containing monomer is preferably a biphenyl group-containing monofunctional acrylate. Examples of such a biphenyl group-containing monomer include ethoxylated o-phenylphenol acrylate, o-biphenyl (meth) acrylate, and the like.
  • Examples of the monomer having a polycyclic aromatic skeleton include a naphthalene skeleton, anthracene skeleton, triphenylene skeleton, tetraphen skeleton, tetracene skeleton, chrysene skeleton, pyrene skeleton, pentacene skeleton, hexacene skeleton, heptacene skeleton, coronene skeleton, and keklen skeleton.
  • Monomer Monomer.
  • a monomer having a naphthalene skeleton or an anthracene skeleton is preferable as the polycyclic aromatic skeleton, and a monomer having a naphthalene skeleton is more preferable.
  • Monomers having a naphthalene skeleton include 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 2- (1-naphthyloxy) ethyl acrylate, (4-methoxynaphthylene) -1-acrylate, vinyl naphthalene, etc. Is mentioned.
  • benzyl (meth) acrylate and ethoxylated o-phenylphenol acrylate are particularly preferable from the viewpoint of exhibiting a high refractive index and obtaining desired sticking suitability and handling properties.
  • the said high refractive index monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the (meth) acrylic acid ester copolymer (A) contains a high refractive index monomer as a monomer unit constituting the polymer, its content is preferably 1 to 30% by mass, particularly 2 to It is preferably 20% by mass.
  • the (meth) acrylic acid ester copolymer (A) may contain other monomers as monomer units constituting the polymer, if desired.
  • the other monomer is preferably a monomer that does not contain a reactive functional group in order not to interfere with the action of the hydroxyl group-containing monomer.
  • Such other monomers include, for example, (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, and aliphatic rings such as cyclohexyl (meth) acrylate (meta ) Acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, etc. (meth) acrylic acid ester having acetic acid tertiary amino group, acetic acid Examples include vinyl and styrene. These may be used alone or in combination of two or more.
  • the polymerization mode of the (meth) acrylic acid ester copolymer (A) may be a random copolymer or a block copolymer.
  • the (meth) acrylic acid ester copolymer (A) preferably has a weight average molecular weight of 200,000 to 1,000,000, particularly preferably 300,000 to 900,000, and more preferably 400,000 to 800,000. Is preferred.
  • the weight average molecular weight in this specification is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the obtained pressure-sensitive adhesive easily satisfies the storage elastic modulus described above.
  • the (meth) acrylic acid ester copolymer (A) may be used alone or in combination of two or more.
  • crosslinking agent (B) When the adhesive composition P is crosslinked, the crosslinking agent (B) reacts with a hydroxyl group derived from a hydroxyl group-containing monomer constituting the (meth) acrylic acid ester copolymer (A). Thereby, the structure where the (meth) acrylic acid ester copolymer (A) was bridge
  • Any crosslinking agent (B) may be used as long as it reacts with the reactive group (hydroxyl group of the hydroxyl group-containing monomer that is a monomer unit) of the (meth) acrylic acid ester copolymer (A).
  • Agent epoxy crosslinking agent, amine crosslinking agent, melamine crosslinking agent, aziridine crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline crosslinking agent, metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal A salt type crosslinking agent, an ammonium salt type crosslinking agent, etc. are mentioned.
  • an isocyanate-based crosslinking agent having excellent reactivity with a hydroxyl group.
  • a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.
  • the isocyanate-based crosslinking agent contains at least a polyisocyanate compound.
  • the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, etc.
  • biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • trimethylolpropane-modified aromatic polyisocyanate particularly trimethylolpropane-modified tolylene diisocyanate and trimethylolpropane-modified xylylene diisocyanate are preferable from the viewpoint of reactivity with hydroxyl groups.
  • the content of the crosslinking agent (B) in the pressure-sensitive adhesive composition P is preferably 0.01 to 2 parts by mass, particularly 100 parts by mass of the (meth) acrylic acid ester copolymer (A).
  • the amount is preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.5 part by mass.
  • the adhesive composition P preferably contains a silane coupling agent (C) from the viewpoint of improving the adhesive strength of the obtained adhesive.
  • the silane coupling agent (C) is an organosilicon compound having at least one alkoxysilyl group in the molecule, has good compatibility with the (meth) acrylic acid ester copolymer (A), and is light transmissive. Those having the following are preferred.
  • silane coupling agent (C) examples include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Mercapto groups such as silicon compounds having an epoxy structure such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane -Containing amino compounds, amino groups such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Silicon-containing compounds,
  • the content of the silane coupling agent (C) in the adhesive composition P is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). In particular, it is preferably 0.05 to 0.5 parts by mass, and more preferably 0.1 to 0.3 parts by mass.
  • additives for the adhesive composition P various additives usually used for acrylic pressure-sensitive adhesives, for example, refractive index adjusters, antistatic agents, tackifiers, antioxidants, ultraviolet rays, as desired. Absorbers, light stabilizers, softeners, fillers and the like can be added.
  • refractive index adjusting agent examples include benzyl benzoate, diphenyl sulfide, triphenyl phosphate, benzyl-n-butyl phthalate, diphenyl phthalate, diphenyl, diphenylmethane, tricresyl phosphate, diphenyl sulfoxide and the like.
  • the content thereof is preferably 1 to 30 parts by mass, particularly 5 to 5 parts per 100 parts by mass of the acrylate copolymer (A). It is preferably 20 parts by mass.
  • Adhesive composition P manufactured (meth) acrylic acid ester copolymer (A), and crosslinked to the obtained (meth) acrylic acid ester copolymer (A). It can be produced by adding the agent (B) and, if desired, the silane coupling agent (C) and additives.
  • the (meth) acrylic acid ester copolymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by an ordinary radical polymerization method.
  • the polymerization of the (meth) acrylic acid ester copolymer (A) can be carried out by a solution polymerization method or the like using a polymerization initiator as desired.
  • the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like, and two or more kinds may be used in combination.
  • Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more kinds may be used in combination.
  • Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
  • organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
  • organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
  • examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
  • the weight average molecular weight of the resulting polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
  • the solution of the (meth) acrylic acid ester copolymer (A) is added to the crosslinking agent (B), and optionally the silane coupling agent (C), A diluting solvent and an additive are added and mixed well to obtain an adhesive composition P (coating solution) diluted with a solvent.
  • the dilution solvent examples include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolve solvents such as ethyl cellosolve and the like are used.
  • aliphatic hydrocarbons such as hexane, heptane, and cyclohexane
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as methylene chloride and
  • the concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, dilution is performed so that the concentration of the adhesive composition P is 10 to 60% by mass.
  • a dilution solvent etc. is not a necessary condition, and if a viscosity etc. which can be coated with the adhesive composition P are not necessary, a dilution solvent does not need to be added.
  • the adhesive composition P becomes a coating solution using the polymerization solvent of the (meth) acrylic acid ester polymer (A) as a dilution solvent.
  • the pressure-sensitive adhesive according to the present embodiment is preferably one obtained by crosslinking the pressure-sensitive adhesive composition P.
  • the crosslinking of the pressure-sensitive adhesive composition P can be usually performed by heat treatment. In addition, this heat processing can also serve as the drying process at the time of volatilizing the dilution solvent of the adhesive composition P, etc.
  • the heating temperature is preferably 50 to 150 ° C., particularly preferably 70 to 120 ° C.
  • the heating time is preferably 30 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes.
  • a curing period of about 1 to 2 weeks may be provided at normal temperature (for example, 23 ° C., 50% RH).
  • the (meth) acrylic acid ester copolymer (A) is well crosslinked through the crosslinking agent (B), and the above-described physical properties can be exhibited.
  • the pressure-sensitive adhesive sheet 1 As shown in FIG. 1, the pressure-sensitive adhesive sheet 1 according to this embodiment includes two release sheets 12a and 12b and the two release sheets 12a so as to be in contact with the release surfaces of the two release sheets 12a and 12b. , 12b and an adhesive layer 11 sandwiched between the two layers.
  • the release surface of the release sheet in this specification refers to a surface having peelability in the release sheet, and includes both a surface that has been subjected to a release treatment and a surface that exhibits peelability without being subjected to a release treatment. .
  • Adhesive layer 11 is comprised from the adhesive mentioned above, Preferably it is comprised from the adhesive formed by bridge
  • FIG. 1 A Adhesive layer The adhesive layer 11 is comprised from the adhesive mentioned above, Preferably it is comprised from the adhesive formed by bridge
  • the thickness of the pressure-sensitive adhesive layer 11 is preferably 10 to 400 ⁇ m, particularly preferably 20 to 300 ⁇ m, and more preferably 25, depending on the height of the step. It is preferable that the thickness is ⁇ 250 ⁇ m. When the thickness of the pressure-sensitive adhesive layer 11 is 10 ⁇ m or more, good step followability is exhibited, and when the thickness of the pressure-sensitive adhesive layer 11 is 400 ⁇ m or less, workability is improved.
  • the pressure-sensitive adhesive layer 11 may be formed as a single layer or may be formed by laminating a plurality of layers.
  • release sheet examples of the release sheets 12a and 12b include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate. Phthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film A polyimide film, a fluororesin film, or the like is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.
  • the release surface of the release sheets 12a and 12b (particularly the surface in contact with the pressure-sensitive adhesive layer 11) is preferably subjected to a release treatment.
  • the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
  • one release sheet is preferably a heavy release release sheet having a high release force
  • the other release sheet is preferably a light release release sheet having a low release force.
  • the thickness of the release sheets 12a and 12b is not particularly limited, but is usually about 20 to 150 ⁇ m.
  • a coating liquid of the above-mentioned pressure-sensitive adhesive composition P is applied to the release surface of one release sheet 12a (or 12b), and heat treatment is performed for adhesion. After cross-linking the composition P and forming a coating layer, the release surface of the other release sheet 12b (or 12a) is overlaid on the coating layer.
  • a curing period is required, a curing period is set, and when the curing period is unnecessary, the coating layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained.
  • the conditions for the heat treatment and curing are as described above.
  • a coating liquid of the above-mentioned pressure-sensitive adhesive composition P is applied to the release surface of one release sheet 12 a, a heat treatment is performed to cross-link the pressure-sensitive adhesive composition P, and a coating layer To obtain a release sheet 12a with a coating layer.
  • the coating liquid of the said adhesive composition P is apply
  • a release sheet 12b is obtained. And the peeling sheet 12a with an application layer and the peeling sheet 12b with an application layer are bonded together so that both application layers may mutually contact.
  • the curing period is necessary, the curing period is set, and when the curing period is unnecessary, the above-mentioned laminated application layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained. According to this production example, even when the pressure-sensitive adhesive layer 11 is thick, it can be stably produced.
  • a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
  • a transparent conductive film made of tin-doped indium oxide (ITO) is provided on the pressure-sensitive adhesive layer 11 side of the laminate obtained by laminating the pressure-sensitive adhesive layer 11 on a base material made of a polyethylene terephthalate film having a thickness of 100 ⁇ m.
  • the adhesive strength of the laminate to the transparent conductive film is preferably 5 to 80 N / 25 mm, particularly 10 to 70 N / 25 mm. And more preferably 15 to 50 N / 25 mm.
  • the adhesive force here means the adhesive force measured by the 180 degree peeling method according to JIS200Z0237: 2009
  • the measurement sample has a width of 25 mm and a length of 100 mm, and the measurement sample is attached. After being applied to the body by applying pressure at 0.5 MPa and 50 ° C. for 20 minutes, the sample was left for 24 hours under conditions of normal pressure, 23 ° C. and 50% RH, and then measured at a peeling rate of 300 mm / min. To do.
  • the capacitive touch panel 2 shown in FIG. 2 can be manufactured.
  • the touch panel 2 includes a display module 3, a first film sensor 5 a laminated thereon via an adhesive layer 4, and a second film sensor 5 b laminated thereon via an adhesive layer 11. And the cover material 6 laminated
  • the two pressure-sensitive adhesive layers 11 in the touch panel 2 are the pressure-sensitive adhesive layers 11 of the pressure-sensitive adhesive sheet 1.
  • Examples of the display module 3 include a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper.
  • LCD liquid crystal
  • LED light emitting diode
  • organic EL organic electroluminescence
  • the pressure-sensitive adhesive layer 4 may be formed of the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 or may be formed of another pressure-sensitive adhesive or pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 4 includes an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, and a polyvinyl ether-based pressure-sensitive adhesive.
  • an acrylic pressure-sensitive adhesive is preferable.
  • the first film sensor 5a and the second film sensor 5b are each generally composed of a base film 51 and a patterned transparent conductive film 52, respectively.
  • a base film 51 For example, a polyethylene terephthalate film, a polycarbonate film, a polymethylmethacrylate film, a polycycloolefin film, a polyolefin film, a triacetylcellulose film etc. are used.
  • Examples of the transparent conductive film 52 include metals such as platinum, gold, silver and copper, oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
  • oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
  • Examples include composite oxides such as indium, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide, and non-oxidized compounds such as chalcogenide, lanthanum hexaboride, titanium nitride, and titanium carbide. Among these, those made of tin-doped indium oxide (ITO) are preferable.
  • One of the transparent conductive film 52 of the first film sensor 5a and the transparent conductive film 52 of the second film sensor 5b normally constitutes a circuit pattern in the X-axis direction, and the other constitutes a circuit pattern in the Y-axis direction. .
  • the transparent conductive film 52 of the first film sensor 5a in the present embodiment is located on the upper side (the cover material 6 side) of the first film sensor 5a in FIG. 2, but is not limited thereto.
  • the first film sensor 5a may be located below (the display module 3 side).
  • the transparent conductive film 52 of the second film sensor 5b is located below the second film sensor 5b in FIG. 2, but the present invention is not limited to this, and the second film sensor 5b. It may be located above.
  • the cover material 6 is mainly composed of a glass plate or a plastic plate.
  • the glass plate is not particularly limited. For example, chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass. Etc.
  • the plastic plate is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate and the like, and a polycarbonate plate.
  • a functional layer such as a hard coat layer, an antireflection layer, or an antiglare layer may be provided on one side or both sides of the glass plate or plastic plate, or a hard coat film, an antireflection film, or an antiglare film.
  • Such optical members may be laminated.
  • the cover material 6 has a step on the surface on the pressure-sensitive adhesive layer 11 side, and specifically has a step due to the presence or absence of the printing layer 7.
  • the print layer 7 is generally formed in a frame shape on the pressure-sensitive adhesive layer 11 side of the cover material 6.
  • the material constituting the printing layer 7 is not particularly limited, and a known material for printing is used.
  • the thickness of the printing layer 7, that is, the height of the step, is preferably 3 to 45 ⁇ m, more preferably 5 to 35 ⁇ m, particularly preferably 7 to 25 ⁇ m, and preferably 7 to 15 ⁇ m. Further preferred.
  • the thickness (height of the step) of the printing layer 7 is preferably 3 to 30% of the thickness of the pressure-sensitive adhesive layer 11, particularly preferably 3.2 to 20%, and more preferably 3 It is preferably 5 to 15%.
  • the pressure-sensitive adhesive layer 11 follows the step due to the printing layer 7 well, and the occurrence of floating, bubbles, etc. in the vicinity of the step is suppressed.
  • One release sheet 12a (or 12b) is peeled from the pressure-sensitive adhesive sheet 1, and the exposed pressure-sensitive adhesive layer 11 is bonded to the film sensor 5a so as to be in contact with the patterned transparent conductive film 52 of the film sensor 5a.
  • the other release sheet 12b (or 12a) is peeled from the pressure-sensitive adhesive sheet 1, and the exposed pressure-sensitive adhesive layer 11 is attached to the film sensor 5b so as to be in contact with the patterned transparent conductive film 52 of the film sensor 5b.
  • Match Thereby, the laminated body by which the film sensor 5a, the adhesive layer 11, and the film sensor 5b are laminated
  • the pressure-sensitive adhesive layer 4 provided on the release sheet is bonded to the film sensor 5a side surface (exposed surface of the base film 51 of the film sensor 5a) of the laminate.
  • the adhesive sheet 1 different from the said adhesive sheet 1 is prepared, one peeling sheet 12a (or 12b) is peeled from the said adhesive sheet 1, and the exposed adhesive layer 11 is adhesive with the said laminated body. It is bonded to the surface opposite to the side on which the layer 4 is laminated (exposed surface of the base film 51 of the film sensor 5b).
  • the other release sheet 12b (or 12a) is peeled from the other adhesive sheet 1, and the printed layer 7 side of the cover material 6 is in contact with the adhesive layer 11 with respect to the exposed adhesive layer 11.
  • the cover material 6 is bonded. Thereby, the structure by which the cover material 6, the adhesive layer 11, the film sensor 5b, the adhesive layer 11, the film sensor 5a, the adhesive layer 4, and a peeling sheet are laminated
  • the release sheet is peeled from the structure, and the structure is bonded to the display module 3 so that the exposed adhesive layer 4 is in contact with the display module 3. Thereby, the touch panel 2 shown in FIG. 2 is manufactured.
  • the pressure-sensitive adhesive layer 11 and the cover material 6 are bonded in the above process, since the pressure-sensitive adhesive layer 11 is excellent in step following ability, it is difficult to form a gap between the step formed by the printing layer 7 and the pressure-sensitive adhesive layer 11.
  • the agent layer 11 can fill the step.
  • the adhesive layer 11 has a predetermined refractive index and storage elastic modulus, it is difficult to see the circuit pattern of the transparent conductive film 52.
  • the touch panel 2 has a high temperature such as 80 ° C. The effect is also demonstrated when placed underneath.
  • the adhesive layer 11 is excellent in level
  • the adhesive layer 11 does not contain the component which has a carboxyl group, the transparent conductive film 52 which the adhesive layer 11 contacts is corroded, or the resistance value of the transparent conductive film 52 is changed. Is suppressed.
  • the pressure-sensitive adhesive layer 11 is formed by crosslinking the pressure-sensitive adhesive composition P, the pressure-sensitive adhesive layer 11 is excellent in moisture and heat whitening resistance, and returns to room temperature after the touch panel 2 is placed in a high temperature and high humidity condition. Whitening at the time is suppressed.
  • the pressure-sensitive adhesive layer 11 has the above-described storage elastic modulus and has cohesive strength derived from the hard monomer in the (meth) acrylic acid ester copolymer (A). In addition, foaming of the pressure-sensitive adhesive layer 11 due to outgas generated from the cover material 6 and bubble mixing (blister) are suppressed.
  • one of the release sheets 12a and 12b in the pressure-sensitive adhesive sheet 1 may be omitted.
  • Example 1 Preparation of (meth) acrylic acid ester copolymer 30 parts by weight of butyl acrylate, 30 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of methyl methacrylate and 20 parts by weight of 2-hydroxyethyl acrylate were copolymerized, A (meth) acrylic acid ester copolymer (A) was prepared. When the molecular weight of this (meth) acrylic acid ester copolymer (A) was measured by the method mentioned later, it was weight average molecular weight (Mw) 600,000.
  • Table 1 shows the composition of the adhesive composition. Details of the abbreviations and the like described in Table 1 are as follows.
  • (Meth) acrylic ester copolymer (A)] BA: n-butyl acrylate 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate (hard monomer) HEA: 2-hydroxyethyl acrylate IBXA: Isobornyl acrylate (hard monomer)
  • ACMO acryloylmorpholine (hard monomer)
  • A-LEN Ethoxylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • BzA benzyl acrylate AA: acrylic acid
  • V-3F 2,2,2-trifluoroethyl acrylate
  • TDI Trimethylolpropane-modified tolylene diisocyanate (manufactured by Soken Chemical Co.,
  • the heavy release type release sheet with the coating layer obtained above and the light release type release sheet with the coating layer obtained above were bonded so that both coating layers were in contact with each other.
  • a pressure-sensitive adhesive sheet having a structure of heavy release type release sheet / pressure-sensitive adhesive layer (thickness: 50 ⁇ m) / light release type release sheet was produced.
  • the thickness of the pressure-sensitive adhesive layer is a value measured using a constant pressure thickness measuring instrument (manufactured by Teclock, product name “PG-02”) in accordance with JIS K7130.
  • Examples 2 to 24, Comparative Examples 1 to 4 Kind of each monomer constituting the (meth) acrylic acid ester copolymer (A), ratio and polymerization average molecular weight (Mw), kind and blending amount of the crosslinking agent (B), and blending of the silane coupling agent (C)
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the amount was changed as shown in Table 1.
  • benzyl benzoate manufactured by Tokyo Chemical Industry Co., Ltd.
  • refractive index adjuster was further added to the adhesive composition.
  • the blending amounts are as shown in Table 1.
  • the above-mentioned weight average molecular weight (Mw) is a polystyrene-reduced weight average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
  • GPC measurement device manufactured by Tosoh Corporation, HLC-8020 GPC column (passed in the following order): TSK guard column HXL-H manufactured by Tosoh Corporation TSK gel GMHXL ( ⁇ 2) TSK gel G2000HXL ⁇ Measurement solvent: Tetrahydrofuran ⁇ Measurement temperature: 40 ° C.
  • a transparent conductive film (Oike Industry Co., Ltd., ITO film, thickness: 125 ⁇ m) in which a transparent conductive film (ITO film) made of tin-doped indium oxide (ITO) is provided on one side of a polyethylene terephthalate (PET) film
  • ITO film transparent conductive film
  • PET film polyethylene terephthalate
  • the heavy release type release sheet was peeled off from the sample, and the exposed adhesive layer was attached to the transparent conductive film. This pasting was performed by pressurizing at a pressure of 0.5 MPa for 20 minutes under a temperature condition of 50 ° C.
  • Test Example 2 Measurement of storage elastic modulus
  • the release sheet was peeled off from the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and a plurality of pressure-sensitive adhesive layers were laminated so as to have a thickness of 3 mm.
  • a cylindrical body (height 3 mm) having a diameter of 8 mm was punched out from the obtained laminate of the pressure-sensitive adhesive layer, and this was used as a sample.
  • the storage elastic modulus (MPa) of the above sample was measured according to JIS K7244-6 by a torsional shear method using a viscoelasticity measuring instrument (RENATRIC, DYNAMIC ANALAYZER) under the following conditions. The results are shown in Table 2. Measurement frequency: 1Hz Measurement temperature: 80 ° C
  • the obtained laminate was dipped in hydrochloric acid adjusted to 1 mol / l for 2 minutes to etch the ITO film portion on which the polyimide adhesive tape was not applied. Subsequently, the laminate was sufficiently washed with ion-exchanged water, dried at 120 ° C. for 10 minutes, and then the polyimide adhesive tape was peeled off from the transparent conductive film. As a result, a transparent conductive film was obtained in which the ITO film was patterned so that the 1 cm wide ITO film portion and the 1 cm wide ITO film non-existing portion were alternately repeated.
  • the transparent conductive film patterned with the ITO film as described above was annealed at 150 ° C. for 90 minutes to crystallize the patterned ITO film.
  • the light release type release sheet was peeled off from the pressure sensitive adhesive sheets obtained in Examples and Comparative Examples, and the exposed pressure sensitive adhesive layer was laminated on a PET film having a thickness of 100 ⁇ m. Then, the heavy release release sheet is peeled from the pressure-sensitive adhesive layer laminated on the PET film (thickness 100 ⁇ m), and the exposed pressure-sensitive adhesive layer is replaced with the patterned ITO film (crystals) of the transparent conductive film obtained above. Pasted together. Thus, an evaluation sample having a configuration of PET film (thickness 125 ⁇ m) / patterned ITO film / adhesive layer / PET film (thickness 100 ⁇ m) was obtained.
  • the pattern visibility by the pressure-sensitive adhesive layer was evaluated. The results are shown in Table 2.
  • Stepped glass plates having a thickness of 5 ⁇ m, 10 ⁇ m, 15 ⁇ m and 20 ⁇ m) were produced.
  • the light release type release sheet was peeled off from the pressure sensitive adhesive sheets obtained in Examples and Comparative Examples, and the exposed pressure sensitive adhesive layer was easily adhered to a polyethylene terephthalate film (PET100A4300, Toyobo Co., Ltd., thickness: 100 ⁇ m) having an easy adhesion layer. Bonded to the layer. Next, the heavy release type release sheet was peeled off to expose the pressure-sensitive adhesive layer.
  • Step followability is determined by whether or not the printing step is completely filled with the adhesive layer, and if gaps or bubbles are observed at the interface between the printing step and the adhesive layer, it cannot follow the printing step. It is judged that Here, the step following property was evaluated as a step following rate (%) according to the following criteria.
  • the sample for evaluation was put in an environment of 85 ° C. and 85% RH for 72 hours. Then, it returned to normal temperature normal humidity of 23 degreeC and 50% RH, and evaluated the level
  • the respective evaluation results are shown in Table 2.
  • Step follow-up rate% ⁇ (height of printed step filled without gaps or bubbles ( ⁇ m)) / (thickness of adhesive layer: 50 ⁇ m) ⁇ ⁇ 100
  • the laminate was stored for 72 hours under wet heat conditions of 85 ° C. and 85% RH. Then, it returned to normal temperature normal humidity of 23 degreeC and 50% RH, and about the said laminated body, using a haze meter (the Nippon Denshoku Industries Co., Ltd. product name "NDH2000”), a haze value (according to JIS K7136: 2000) %). In addition, the said haze value was measured within 30 minutes after returning a laminated body to normal temperature normal humidity.
  • a haze value increase (point) after the wet heat condition was calculated by subtracting the haze value before the wet heat condition from the haze value after the wet heat condition.
  • Humidity and heat-whitening resistance is good when the haze value rises after a moist heat condition is less than 1.0 point (A), and heat haze resistance increases when the haze value rise after a moist heat condition is 1.0 point or more and less than 5.0 points
  • ⁇ suitability value
  • x heat and heat whitening resistance
  • the adhesive layer of the adhesive sheets obtained in the examples and comparative examples is made of a transparent conductive film (made by Oike Kogyo Co., Ltd., ITO film) provided with a transparent conductive film made of tin-doped indium oxide (ITO) on one side of a PET film. , Thickness: 125 ⁇ m) and a polycarbonate plate (Mitsubishi Gas Chemical Co., Ltd., Iupilon sheet MR58, thickness: 1 mm) to obtain a laminate.
  • a transparent conductive film made by Oike Kogyo Co., Ltd., ITO film
  • ITO tin-doped indium oxide
  • the obtained laminate was autoclaved for 30 minutes at 50 ° C. and 0.5 MPa, and then allowed to stand for 15 hours. Subsequently, it was stored for 72 hours under 85 ° C. and 85% RH durability conditions. Thereafter, it was visually confirmed whether or not the pressure-sensitive adhesive layer had bubbles, floats or peeling. As a result, no bubble, no lift or peeling was evaluated as ⁇ , only a bubble having a diameter of 0.2 mm or less was generated, ⁇ , a bubble having a diameter of more than 0.2 mm, float or peeling was evaluated as ⁇ . (Evaluation of blister resistance). The results are shown in Table 2.
  • the pressure-sensitive adhesive sheets obtained in the examples it was difficult to see the pattern of the transparent conductive film, and excellent level difference followability and blister resistance were achieved.
  • the pressure-sensitive adhesive sheets obtained in Examples 1 to 23 were also excellent in moisture and heat whitening resistance, and the pressure-sensitive adhesive sheets obtained in Examples 1 to 22 and 24 also had excellent adhesive strength. .
  • the pressure-sensitive adhesive and pressure-sensitive adhesive sheet of the present invention are very useful for forming a pressure-sensitive adhesive layer used for a capacitive touch panel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
PCT/JP2014/055513 2014-03-04 2014-03-04 粘着剤および粘着シート WO2015132888A1 (ja)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020167027263A KR102158457B1 (ko) 2014-03-04 2014-03-04 점착제 및 점착 시트
PCT/JP2014/055513 WO2015132888A1 (ja) 2014-03-04 2014-03-04 粘着剤および粘着シート
CN202010177664.0A CN111484809B (zh) 2014-03-04 2014-03-04 触摸面板
CN201480076820.7A CN106103631B (zh) 2014-03-04 2014-03-04 粘着剂及粘着片
JP2016505985A JP6200065B2 (ja) 2014-03-04 2014-03-04 粘着剤および粘着シート
TW104106781A TWI642739B (zh) 2014-03-04 2015-03-04 Touch panel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/055513 WO2015132888A1 (ja) 2014-03-04 2014-03-04 粘着剤および粘着シート

Publications (1)

Publication Number Publication Date
WO2015132888A1 true WO2015132888A1 (ja) 2015-09-11

Family

ID=54054726

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/055513 WO2015132888A1 (ja) 2014-03-04 2014-03-04 粘着剤および粘着シート

Country Status (5)

Country Link
JP (1) JP6200065B2 (zh)
KR (1) KR102158457B1 (zh)
CN (2) CN111484809B (zh)
TW (1) TWI642739B (zh)
WO (1) WO2015132888A1 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017110074A (ja) * 2015-12-15 2017-06-22 住友化学株式会社 粘着剤層付光学フィルム及び光学積層体
JP6371922B1 (ja) * 2017-03-28 2018-08-08 バンドー化学株式会社 光学透明粘着シート、光学透明粘着シートの製造方法、積層体、及び、貼り合わせ構造物
WO2018179608A1 (ja) * 2017-03-28 2018-10-04 バンドー化学株式会社 光学透明粘着シート、光学透明粘着シートの製造方法、積層体、及び、貼り合わせ構造物
JP2019048973A (ja) * 2017-09-07 2019-03-28 積水化学工業株式会社 粘着剤及び粘着テープ
JP2021059617A (ja) * 2019-10-03 2021-04-15 王子ホールディングス株式会社 粘着シート
WO2021192423A1 (ja) * 2020-03-25 2021-09-30 リンテック株式会社 粘着シートおよび積層体
WO2021225038A1 (ja) * 2020-05-07 2021-11-11 リンテック株式会社 粘着性組成物、粘着剤、粘着シートおよび積層体

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200192510A1 (en) * 2016-12-14 2020-06-18 3M Innovative Properties Company Touch sensor assembly and planarization tape
CN108795341A (zh) * 2018-06-05 2018-11-13 江西和信化研纳米材料有限公司 一种粘着性组合物
KR102133279B1 (ko) 2018-06-20 2020-07-13 주식회사 엘지화학 회절 격자 도광판용 몰드의 제조방법 및 회절 격자 도광판의 제조방법
JP7304683B2 (ja) * 2018-07-24 2023-07-07 リンテック株式会社 粘着シートおよび積層体
CN109237434A (zh) * 2018-09-29 2019-01-18 江苏锐阳照明电器设备有限公司 一种矿用照明灯具防尘涂层
JP7224138B2 (ja) * 2018-10-23 2023-02-17 株式会社ダイセル 半導体装置製造方法
JP7428494B2 (ja) * 2019-09-18 2024-02-06 リンテック株式会社 繰り返し屈曲積層部材および繰り返し屈曲デバイス

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009035708A (ja) * 2007-07-06 2009-02-19 Nippon Shokubai Co Ltd 溶剤型再剥離用粘着剤組成物および再剥離用粘着製品
JP2010077287A (ja) * 2008-09-26 2010-04-08 Nitto Denko Corp 光学部材貼り合わせ用粘着シート
WO2011040022A1 (ja) * 2009-09-30 2011-04-07 日本ケミコン株式会社 負極活物質、この負極活物質の製造方法、及びこの負極活物質を用いたリチウムイオン二次電池
JP2013082772A (ja) * 2011-10-06 2013-05-09 Nitto Denko Corp 光学用粘着剤、粘着剤層、光学フィルム、及び、画像表示装置

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5379410B2 (ja) * 2008-03-14 2013-12-25 日東電工株式会社 光学フィルム用粘着剤組成物、粘着型光学フィルムおよび画像表示装置
TWI486415B (zh) * 2009-09-29 2015-06-01 Lintec Corp 黏著劑及黏著片
JP5529720B2 (ja) * 2010-12-15 2014-06-25 日東電工株式会社 粘着剤層付き透明導電性フィルム、その製造方法及びタッチパネル
JP5844996B2 (ja) 2011-05-11 2016-01-20 日東電工株式会社 透明導電性積層体及びタッチパネル
JP5764435B2 (ja) * 2011-08-29 2015-08-19 綜研化学株式会社 粘着剤組成物、粘着シートおよびタッチパネル用積層体
JP6001255B2 (ja) * 2011-11-15 2016-10-05 日東電工株式会社 粘着シート
JP5887118B2 (ja) 2011-12-05 2016-03-16 日東電工株式会社 透明導電性フィルム用粘着剤層、粘着剤層付き透明導電性フィルム、透明導電性積層体、およびタッチパネル

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009035708A (ja) * 2007-07-06 2009-02-19 Nippon Shokubai Co Ltd 溶剤型再剥離用粘着剤組成物および再剥離用粘着製品
JP2010077287A (ja) * 2008-09-26 2010-04-08 Nitto Denko Corp 光学部材貼り合わせ用粘着シート
WO2011040022A1 (ja) * 2009-09-30 2011-04-07 日本ケミコン株式会社 負極活物質、この負極活物質の製造方法、及びこの負極活物質を用いたリチウムイオン二次電池
JP2013082772A (ja) * 2011-10-06 2013-05-09 Nitto Denko Corp 光学用粘着剤、粘着剤層、光学フィルム、及び、画像表示装置

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017110074A (ja) * 2015-12-15 2017-06-22 住友化学株式会社 粘着剤層付光学フィルム及び光学積層体
JP6371922B1 (ja) * 2017-03-28 2018-08-08 バンドー化学株式会社 光学透明粘着シート、光学透明粘着シートの製造方法、積層体、及び、貼り合わせ構造物
WO2018179608A1 (ja) * 2017-03-28 2018-10-04 バンドー化学株式会社 光学透明粘着シート、光学透明粘着シートの製造方法、積層体、及び、貼り合わせ構造物
JP2019048973A (ja) * 2017-09-07 2019-03-28 積水化学工業株式会社 粘着剤及び粘着テープ
JP7176897B2 (ja) 2017-09-07 2022-11-22 積水化学工業株式会社 粘着剤及び粘着テープ
JP2021059617A (ja) * 2019-10-03 2021-04-15 王子ホールディングス株式会社 粘着シート
WO2021192423A1 (ja) * 2020-03-25 2021-09-30 リンテック株式会社 粘着シートおよび積層体
CN115315496A (zh) * 2020-03-25 2022-11-08 琳得科株式会社 粘着片及层叠体
WO2021225038A1 (ja) * 2020-05-07 2021-11-11 リンテック株式会社 粘着性組成物、粘着剤、粘着シートおよび積層体
CN115516054A (zh) * 2020-05-07 2022-12-23 琳得科株式会社 粘着性组合物、粘着剂、粘着片及层叠体

Also Published As

Publication number Publication date
TW201540794A (zh) 2015-11-01
JP6200065B2 (ja) 2017-09-20
CN111484809A (zh) 2020-08-04
CN106103631A (zh) 2016-11-09
CN106103631B (zh) 2020-03-31
KR20160130799A (ko) 2016-11-14
TWI642739B (zh) 2018-12-01
JPWO2015132888A1 (ja) 2017-03-30
CN111484809B (zh) 2022-07-01
KR102158457B1 (ko) 2020-09-22

Similar Documents

Publication Publication Date Title
JP6200065B2 (ja) 粘着剤および粘着シート
JP6196781B2 (ja) 粘着性組成物、粘着剤および粘着シート
JP5789350B1 (ja) 粘着シートおよび積層体
JP6356786B2 (ja) 粘着シートおよび積層体
JP6310062B2 (ja) 両面粘着シート
JP6290377B2 (ja) 積層体
JP6374485B2 (ja) 粘着シート
JP6368410B2 (ja) タッチパネル
WO2016063405A1 (ja) 粘着剤、粘着シートおよび表示体
JP6325653B2 (ja) 粘着性組成物、粘着剤および粘着シート
JP6290466B2 (ja) 粘着シート
JP6145568B2 (ja) 粘着剤および粘着シート
JP7008467B2 (ja) 粘着シートおよび表示体
JP6500077B2 (ja) 積層体
JP6343717B2 (ja) 粘着剤、粘着シートおよび表示体
JP6934443B2 (ja) 粘着剤および粘着シート

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14884618

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016505985

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167027263

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14884618

Country of ref document: EP

Kind code of ref document: A1