WO2015132888A1 - Adhesive agent and adhesive sheet - Google Patents
Adhesive agent and adhesive sheet Download PDFInfo
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- 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
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- pressure
- sensitive adhesive
- meth
- transparent conductive
- monomer
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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.
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Abstract
Description
〔粘着剤〕
本実施形態に係る粘着剤は、屈折率が1.45~1.54であり、80℃における貯蔵弾性率が0.02~0.10MPaであり、カルボキシル基を有する成分を含有しないものである。この粘着剤は、静電容量方式のタッチパネルにおいて、2つの透明導電膜の間、または透明導電膜とカバー材との間に使用される。 Hereinafter, embodiments of the present invention will be described.
[Adhesive]
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.
粘着性組成物Pは、(メタ)アクリル酸エステル共重合体(A)を粘着主剤として含有することが好ましい。(メタ)アクリル酸エステル共重合体(A)において、水酸基含有モノマーおよび上記ハードモノマーの含有量が前述した範囲にあることで、(メタ)アクリル酸エステル共重合体(A)を含有する粘着性組成物Pから得られる粘着剤が前述した屈折率および貯蔵弾性率を満たし易くなる。 (1) (Meth) acrylic acid ester copolymer (A)
The adhesive composition P preferably contains the (meth) acrylic acid ester copolymer (A) as an adhesive main agent. In the (meth) acrylic acid ester copolymer (A), 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.
粘着性組成物Pを架橋すると、架橋剤(B)は、(メタ)アクリル酸エステル共重合体(A)を構成する水酸基含有モノマー由来の水酸基と反応する。これにより、架橋剤(B)によって(メタ)アクリル酸エステル共重合体(A)が架橋された構造が形成される。 (2) 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 | crosslinked with the crosslinking agent (B) is formed.
粘着性組成物Pは、得られる粘着剤の粘着力を改善する観点から、シランカップリング剤(C)を含有することが好ましい。シランカップリング剤(C)としては、分子内にアルコキシシリル基を少なくとも1個有する有機ケイ素化合物であって、(メタ)アクリル酸エステル共重合体(A)との相溶性がよく、光透過性を有するものが好ましい。 (3) Silane coupling agent (C)
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.
粘着性組成物Pには、所望により、アクリル系粘着剤に通常使用されている各種添加剤、例えば屈折率調整剤、帯電防止剤、粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、軟化剤、充填剤などを添加することができる。 (4) Various 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.
粘着性組成物Pは、(メタ)アクリル酸エステル共重合体(A)を製造し、得られた(メタ)アクリル酸エステル共重合体(A)に、架橋剤(B)、および所望により、シランカップリング剤(C)、添加剤を加えることで製造することができる。 (5) Manufacture of adhesive composition 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.
本実施形態に係る粘着剤は、粘着性組成物Pを架橋してなるものであることが好ましい。粘着性組成物Pの架橋は、通常は加熱処理により行うことができる。なお、この加熱処理は、粘着性組成物Pの希釈溶剤等を揮発させる際の乾燥処理で兼ねることもできる。 (6) Production of pressure-sensitive adhesive 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.
図1に示すように、本実施形態に係る粘着シート1は、2枚の剥離シート12a,12bと、それら2枚の剥離シート12a,12bの剥離面と接するように当該2枚の剥離シート12a,12bに挟持された粘着剤層11とから構成される。なお、本明細書における剥離シートの剥離面とは、剥離シートにおいて剥離性を有する面をいい、剥離処理を施した面および剥離処理を施さなくても剥離性を示す面のいずれをも含むものである。 [Adhesive sheet]
As shown in FIG. 1, the pressure-
粘着剤層11は、前述した粘着剤から構成され、好ましくは粘着性組成物Pを架橋してなる粘着剤から構成される。 (1) Adhesive layer The
剥離シート12a,12bとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニルフィルム、アイオノマー樹脂フィルム、エチレン・(メタ)アクリル酸共重合体フィルム、エチレン・(メタ)アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルム等が用いられる。また、これらの架橋フィルムも用いられる。さらに、これらの積層フィルムであってもよい。 (2) Release sheet Examples of the
粘着シート1の一製造例としては、一方の剥離シート12a(または12b)の剥離面に、上記粘着性組成物Pの塗布液を塗布し、加熱処理を行って粘着性組成物Pを架橋し、塗布層を形成した後、その塗布層に他方の剥離シート12b(または12a)の剥離面を重ね合わせる。養生期間が必要な場合は養生期間をおくことにより、養生期間が不要な場合はそのまま、上記塗布層が粘着剤層11となる。これにより、上記粘着シート1が得られる。加熱処理および養生の条件については、前述した通りである。 (3) Production of pressure-sensitive adhesive sheet As one production example of the pressure-
粘着剤層11を厚さ100μmのポリエチレンテレフタレートフィルムからなる基材上に積層した積層体の粘着剤層11側の面を、スズドープ酸化インジウム(ITO)からなる透明導電膜が設けられた透明導電性フィルムの当該透明導電膜に貼付した場合における、当該積層体の透明導電性フィルムに対する粘着力は、5~80N/25mmであることが好ましく、特に10~70N/25mmであることが好ましく、さらには15~50N/25mmであることが好ましい。粘着力が上記範囲にあることにより、タッチパネルの構成部材が確実に接着される。 (4) Adhesive strength A transparent conductive film made of tin-doped indium oxide (ITO) is provided on the pressure-
上記粘着シート1を使用することにより、例えば、図2に示す静電容量方式のタッチパネル2を製造することができる。タッチパネル2は、表示体モジュール3と、その上に粘着剤層4を介して積層された第1のフィルムセンサー5aと、その上に粘着剤層11を介して積層された第2のフィルムセンサー5bと、その上に粘着剤層11を介して積層されたカバー材6とを備えて構成される。 (5) Use of pressure-sensitive adhesive sheet By using the pressure-
粘着シート1から一方の剥離シート12a(又は12b)を剥離し、露出した粘着剤層11を、フィルムセンサー5aのパターニングされた透明導電膜52と接するように、当該フィルムセンサー5aと貼合する。次いで、上記粘着シート1から他方の剥離シート12b(又は12a)を剥離し、露出した粘着剤層11を、フィルムセンサー5bのパターニングされた透明導電膜52と接するように、当該フィルムセンサー5bと貼合する。これにより、フィルムセンサー5a、粘着剤層11およびフィルムセンサー5bが順次積層されてなる積層体が得られる。 An example of the manufacturing method of the
One
1.(メタ)アクリル酸エステル共重合体の調製
アクリル酸ブチル30質量部、アクリル酸2-エチルヘキシル30質量部、メタクリル酸メチル20質量部およびアクリル酸2-ヒドロキシエチル20質量部を共重合させて、(メタ)アクリル酸エステル共重合体(A)を調製した。この(メタ)アクリル酸エステル共重合体(A)の分子量を後述する方法で測定したところ、重量平均分子量(Mw)60万であった。 [Example 1]
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.
上記工程(1)で得られた(メタ)アクリル酸エステル共重合体(A)100質量部(固形分換算値;以下同じ)と、架橋剤(B)としてのトリメチロールプロパン変性トリレンジイソシアネート(綜研化学社製,製品名「L-45」)0.25質量部と、シランカップリング剤としての3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製,製品名「KBM-403」)0.2質量部とを混合し、十分に撹拌して、メチルエチルケトンで希釈することにより、固形分濃度40質量%の粘着性組成物の塗布溶液を得た。 2. Preparation of adhesive composition (Meth) acrylate copolymer (A) 100 parts by mass (in terms of solid content; the same applies hereinafter) obtained in the above step (1), and trimethylol as a crosslinking agent (B) 0.25 parts by mass of propane-modified tolylene diisocyanate (manufactured by Soken Chemical Co., Ltd., product name “L-45”) and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name) as a silane coupling agent “KBM-403”) was mixed with 0.2 part by mass, sufficiently stirred, and diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition having a solid content concentration of 40% by mass.
[(メタ)アクリル酸エステル共重合体(A)]
BA:アクリル酸n-ブチル
2EHA:アクリル酸2-エチルヘキシル
MMA:メタクリル酸メチル(ハードモノマー)
HEA:アクリル酸2-ヒドロキシエチル
IBXA:アクリル酸イソボルニル(ハードモノマー)
ACMO:アクリロイルモルホリン(ハードモノマー)
A-LEN:エトキシ化o-フェニルフェノールアクリレート(新中村化学工業社製)
BzA:アクリル酸ベンジル
AA:アクリル酸
V-3F:2,2,2-トリフルオロエチルアクリレート
[架橋剤(B)]
TDI:トリメチロールプロパン変性トリレンジイソシアネート(綜研化学社製,製品名「L-45」)
XDI:トリメチロールプロパン変性キシリレンレンジイソシアネート(綜研化学社製,製品名「TD-75」)
エポキシ:1,3-ビス(ジグリシジルアミノメチル)シクロヘキサン(三菱ガス化学社製,製品名「TETRAD-C」) Here, 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
[Crosslinking agent (B)]
TDI: Trimethylolpropane-modified tolylene diisocyanate (manufactured by Soken Chemical Co., Ltd., product name “L-45”)
XDI: Trimethylolpropane-modified xylylene diisocyanate (manufactured by Soken Chemical Co., Ltd., product name “TD-75”)
Epoxy: 1,3-bis (diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, product name “TETRAD-C”)
得られた粘着性組成物の塗布溶液を、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した重剥離型剥離シート(リンテック社製,製品名「SP-PET752150」)の剥離処理面に、乾燥後の厚さが25μmになるようにナイフコーターで塗布したのち、100℃で4分間加熱処理して塗布層を形成した。同様に、得られた粘着性組成物の塗布溶液を、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した軽剥離型剥離シート(リンテック社製,製品名「SP-PET382120」)の剥離処理面に、乾燥後の厚さが25μmになるようにナイフコーターで塗布したのち、100℃で4分間加熱処理して塗布層を形成した。 3. Manufacture of pressure-sensitive adhesive sheet Peeling of a heavy-peelable release sheet (product name “SP-PET752150”, manufactured by Lintec Corporation) from a polyethylene terephthalate film with a silicone-based release agent. The treated surface was coated with a knife coater so that the thickness after drying was 25 μm, and then heated at 100 ° C. for 4 minutes to form a coated layer. Similarly, a release treatment of a light release type release sheet (product name “SP-PET382120” manufactured by Lintec Co., Ltd.) in which one side of a polyethylene terephthalate film was release-treated with a silicone-based release agent was applied to the obtained adhesive composition coating solution. The surface was coated with a knife coater so that the thickness after drying was 25 μm, and then heated at 100 ° C. for 4 minutes to form a coating layer.
(メタ)アクリル酸エステル共重合体(A)を構成する各モノマーの種類、割合および重合平均分子量(Mw)、架橋剤(B)の種類および配合量、ならびにシランカップリング剤(C)の配合量を表1に示すように変更する以外、実施例1と同様にして粘着シートを製造した。なお、実施例7~9については、粘着性組成物に、さらに屈折率調整剤としての安息香酸ベンジル(東京化成工業社製)を配合した。配合量は表1に示す通りである。 [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. In Examples 7 to 9, benzyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a refractive index adjuster was further added to the adhesive composition. The blending amounts are as shown in Table 1.
<測定条件>
・GPC測定装置:東ソー社製,HLC-8020
・GPCカラム(以下の順に通過):東ソー社製
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
・測定溶媒:テトラヒドロフラン
・測定温度:40℃ Here, 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).
<Measurement conditions>
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.
実施例および比較例で得られた粘着シートから軽剥離型剥離シートを剥がし、露出した粘着剤層を、易接着層を有するポリエチレンテレフタレートフィルム(東洋紡社製,PETA4300,厚さ:100μm)の易接着層に貼合した。その積層体を、幅25mm、長さ100mmに裁断し、これをサンプルとした。 [Test Example 1] (Measurement of adhesive strength)
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 (Toyobo Co., Ltd., PETA4300, thickness: 100 μm) having an easy-adhesion layer. Bonded to the layer. The laminate was cut into a width of 25 mm and a length of 100 mm, and this was used as a sample.
実施例および比較例で得られた粘着シートから剥離シートを剥がし、粘着剤層を厚さ3mmになるように複数層積層した。得られた粘着剤層の積層体から、直径8mmの円柱体(高さ3mm)を打ち抜き、これをサンプルとした。 [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 (
測定周波数:1Hz
測定温度:80℃ 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
実施例および比較例で得られた粘着シートの粘着剤層の屈折率を、アッベ屈折計(アタゴ社製,品名「アッベ屈折計DR-M2」,Na光源,波長:589nm)を使用して、JIS K0062-1992に準じて測定した。結果を表2に示す。 [Test Example 3] (Measurement of refractive index)
The refractive index of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples was measured using an Abbe refractometer (manufactured by Atago Co., Ltd., product name “Abbe refractometer DR-M2”, Na light source, wavelength: 589 nm). The measurement was performed according to JIS K0062-1992. The results are shown in Table 2.
厚さ125μmのPETフィルムの片面にスズドープ酸化インジウム(ITO)からなる透明導電膜(ITO膜)が設けられた透明導電性フィルム(尾池工業社製,ITOフィルム)のITO膜上に、複数のポリイミド粘着テープ(幅1cm)を、1cm間隔でそれぞれ平行に配列されるように貼り合わせた。 [Test Example 4] (Evaluation of pattern visibility)
On the ITO film of a transparent conductive film (Oike Industry Co., Ltd., ITO film) in which a transparent conductive film (ITO film) made of tin-doped indium oxide (ITO) is provided on one side of a 125 μm thick PET film, A polyimide adhesive tape (
◎:パターンが見えない。
○:パターンがうっすら見える。
×:パターンが見える。 By visually observing the patterned ITO film under the fluorescent lamp from the transparent conductive film side of the obtained evaluation sample, that is, the PET film side having a thickness of 125 μm, the pattern visibility by the pressure-sensitive adhesive layer according to the following criteria ( The difficulty in viewing the pattern of the transparent conductive film) was evaluated. The results are shown in Table 2.
A: The pattern is not visible.
○: The pattern is slightly visible.
X: A pattern is visible.
(a)評価用サンプルの作製
ガラス板(NSGプレシジョン社製,製品名「コーニングガラス イーグルXG」,縦90mm×横50mm×厚み0.5mm)の表面に、紫外線硬化型インク(帝国インキ社製,製品名「POS-911墨」)を塗布厚が5μm、10μm、15μm及び20μmとなるように額縁状(外形:縦90mm×横50mm,幅5mm)にスクリーン印刷した。次いで、紫外線を照射(80W/cm2,メタルハライドランプ2灯,ランプ高さ15cm,ベルトスピード10~15m/分)して、印刷した上記紫外線硬化型インクを硬化させ、印刷による段差(段差の高さ:5μm、10μm、15μm及び20μm)を有する段差付ガラス板を作製した。 [Test Example 5] (Evaluation of step following ability)
(A) Preparation of sample for evaluation On the surface of a glass plate (manufactured by NSG Precision, product name “Corning Glass Eagle XG”, length 90 mm × width 50 mm × thickness 0.5 mm), an ultraviolet curable ink (made by Teikoku Ink, The product name “POS-911 Black”) was screen-printed in a frame shape (outside: 90 mm long × 50 mm wide, 5 mm wide) so that the coating thickness was 5 μm, 10 μm, 15 μm and 20 μm. Next, irradiation with ultraviolet rays (80 W / cm 2 , 2 metal halide lamps, lamp height 15 cm, belt speed 10 to 15 m / min) is performed to cure the printed ultraviolet curable ink, and a level difference due to printing (level difference) Stepped glass plates having a thickness of 5 μm, 10 μm, 15 μm and 20 μm) were produced.
上記評価用サンプルについて、最初に、評価用サンプルが得られた段階での段差追従性を「初期」として評価した。段差追従性は、粘着剤層により印刷段差が完全に埋められたか否かで判断し、印刷段差と粘着剤層との界面で隙間や気泡などが観察された場合は、印刷段差に追従できなかったと判断される。ここでは、段差追従性は、下記の基準にしたがって段差追従率(%)として評価した。 (B) Evaluation of Evaluation Sample For the evaluation sample, first, the step following property at the stage where the evaluation sample was obtained was evaluated as “initial”. 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.
◎:段差追従率40%
○:段差追従率10%~30%
×:段差追従率10%未満 Step follow-up rate% = {(height of printed step filled without gaps or bubbles (μm)) / (thickness of adhesive layer: 50 μm)} × 100
A: Step following rate 40%
○: Step following rate 10% to 30%
×: Step following rate less than 10%
実施例および比較例で得られた粘着シートの粘着剤層を、2枚のソーダライムガラス(厚さ:1.1mm)で挟み、積層体を得た。その積層体について、ヘイズメーター(日本電色工業社製,製品名「NDH2000」)を用いて、JIS K7136:2000に準じてヘイズ値(%)を測定した。 [Test Example 6] (Moisture and heat whitening evaluation)
The pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were sandwiched between two soda lime glasses (thickness: 1.1 mm) to obtain a laminate. About the laminated body, haze value (%) was measured according to JISK7136: 2000 using the haze meter (The Nippon Denshoku Industries Co., Ltd. make, product name "NDH2000").
実施例および比較例で得られた粘着シートの粘着剤層を、PETフィルムの片面にスズドープ酸化インジウム(ITO)からなる透明導電膜が設けられた透明導電性フィルム(尾池工業社製,ITOフィルム,厚さ:125μm)の透明導電膜と、ポリカーボネート板(三菱ガス化学社製,ユーピロン・シート MR58,厚さ:1mm)とで挟み、積層体を得た。 [Test Example 7] (Blister resistance evaluation)
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 μm) and a polycarbonate plate (Mitsubishi Gas Chemical Co., Ltd., Iupilon sheet MR58, thickness: 1 mm) to obtain a laminate.
11…粘着剤層
12a,12b…剥離シート
2…タッチパネル
3…表示体モジュール
4…粘着剤層
5a…第1のフィルムセンサー
5b…第2のフィルムセンサー
51…基材フィルム
52…透明導電膜
6…カバー材
7…印刷層 DESCRIPTION OF
Claims (8)
- 静電容量方式のタッチパネルにおいて、2つの透明導電膜の間、または透明導電膜とカバー材との間に使用される粘着剤であって、
屈折率が、1.45~1.54であり、
80℃における貯蔵弾性率が、0.02~0.10MPaであり、
カルボキシル基を有する成分を含有しない
ことを特徴とする粘着剤。 In the capacitive touch panel, an adhesive used between two transparent conductive films, or between a transparent conductive film and a cover material,
The refractive index is 1.45 to 1.54,
The storage elastic modulus at 80 ° C. is 0.02 to 0.10 MPa,
A pressure-sensitive adhesive characterized by not containing a component having a carboxyl group. - 前記粘着剤は、
重合体を構成するモノマー単位として、水酸基を有するモノマー5~30質量%と、ホモポリマーとしてのガラス転移温度が70℃以上の芳香族環を有しないハードモノマー5~40質量%とを含有し、カルボキシル基を有するモノマーを含有しない(メタ)アクリル酸エステル共重合体(A)と、
架橋剤(B)と
を含む粘着性組成物を架橋してなるものである
ことを特徴とする請求項1に記載の粘着剤。 The adhesive is
As monomer units constituting the polymer, 5 to 30% by mass of a monomer having a hydroxyl group and 5 to 40% by mass of a hard monomer having no glass transition temperature of 70 ° C. or higher as a homopolymer and having no aromatic ring, (Meth) acrylic acid ester copolymer (A) not containing a monomer having a carboxyl group;
The pressure-sensitive adhesive according to claim 1, wherein the pressure-sensitive adhesive composition is obtained by crosslinking a pressure-sensitive adhesive composition containing the crosslinking agent (B). - 前記(メタ)アクリル酸エステル共重合体(A)の重量平均分子量は、20万~100万であることを特徴とする請求項2に記載の粘着剤。 The pressure-sensitive adhesive according to claim 2, wherein the (meth) acrylic acid ester copolymer (A) has a weight average molecular weight of 200,000 to 1,000,000.
- 前記(メタ)アクリル酸エステル共重合体(A)は、当該重合体を構成するモノマー単位である前記ハードモノマーとして、メタクリル酸メチル、アクリル酸イソボルニルおよびアクリロイルモルホリンからなる群から選ばれる少なくとも1種を含有することを特徴とする請求項2または3に記載の粘着剤。 The (meth) acrylic acid ester copolymer (A) contains 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 contains, The adhesive of Claim 2 or 3 characterized by the above-mentioned.
- 前記粘着剤は、さらにシランカップリング剤(C)を含有することを特徴とする請求項2~4のいずれか一項に記載の粘着剤。 The pressure-sensitive adhesive according to any one of claims 2 to 4, wherein the pressure-sensitive adhesive further contains a silane coupling agent (C).
- 静電容量方式のタッチパネルにおける2つの透明導電膜の接着、または透明導電膜とカバー材との接着に使用される粘着シートであって、
2枚の剥離シートと、
前記2枚の剥離シートの剥離面と接するように前記剥離シートに挟持された粘着剤層とを備え、
前記粘着剤層は、請求項1~5のいずれか一項に記載の粘着剤からなる
ことを特徴とする粘着シート。 A pressure-sensitive adhesive sheet used for bonding two transparent conductive films in a capacitive touch panel, or bonding a transparent conductive film and a cover material,
Two release sheets,
An adhesive layer sandwiched between the release sheets so as to be in contact with the release surfaces of the two release sheets;
The pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer comprises the pressure-sensitive adhesive according to any one of claims 1 to 5. - 前記粘着剤層の厚さは、10~400μmであることを特徴とする請求項6に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 6, wherein the pressure-sensitive adhesive layer has a thickness of 10 to 400 µm.
- 前記粘着剤層を厚さ100μmのポリエチレンテレフタレートフィルムからなる基材上に積層した積層体の前記粘着剤層側の面をソーダライムガラスに貼付した場合における、前記積層体の前記ソーダライムガラスに対する粘着力は、5~50N/25mmであることを特徴とする請求項6または7に記載の粘着シート。 Adhesion of the laminate to the soda lime glass when the adhesive layer side surface of the laminate obtained by laminating the adhesive layer on a substrate made of a polyethylene terephthalate film having a thickness of 100 μm is attached to soda lime glass The pressure-sensitive adhesive sheet according to claim 6 or 7, wherein the force is 5 to 50 N / 25 mm.
Priority Applications (6)
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CN202010177664.0A CN111484809B (en) | 2014-03-04 | 2014-03-04 | Touch panel |
CN201480076820.7A CN106103631B (en) | 2014-03-04 | 2014-03-04 | Adhesive and adhesive sheet |
KR1020167027263A KR102158457B1 (en) | 2014-03-04 | 2014-03-04 | Adhesive agent and adhesive sheet |
JP2016505985A JP6200065B2 (en) | 2014-03-04 | 2014-03-04 | Adhesive and adhesive sheet |
PCT/JP2014/055513 WO2015132888A1 (en) | 2014-03-04 | 2014-03-04 | Adhesive agent and adhesive sheet |
TW104106781A TWI642739B (en) | 2014-03-04 | 2015-03-04 | Touch panel |
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PCT/JP2014/055513 WO2015132888A1 (en) | 2014-03-04 | 2014-03-04 | Adhesive agent and adhesive sheet |
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KR (1) | KR102158457B1 (en) |
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JP2017110074A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Optical film with adhesive layer and optical laminate |
JP6371922B1 (en) * | 2017-03-28 | 2018-08-08 | バンドー化学株式会社 | Optical transparent adhesive sheet, optical transparent adhesive sheet manufacturing method, laminate, and bonded structure |
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JP2021059617A (en) * | 2019-10-03 | 2021-04-15 | 王子ホールディングス株式会社 | Adhesive sheet |
WO2021192423A1 (en) * | 2020-03-25 | 2021-09-30 | リンテック株式会社 | Adhesive sheet and laminate |
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JPWO2015132888A1 (en) | 2017-03-30 |
CN106103631A (en) | 2016-11-09 |
KR20160130799A (en) | 2016-11-14 |
JP6200065B2 (en) | 2017-09-20 |
CN106103631B (en) | 2020-03-31 |
CN111484809B (en) | 2022-07-01 |
CN111484809A (en) | 2020-08-04 |
KR102158457B1 (en) | 2020-09-22 |
TWI642739B (en) | 2018-12-01 |
TW201540794A (en) | 2015-11-01 |
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