WO2019004107A1 - Composition adhésive, feuille adhésive et stratifié - Google Patents

Composition adhésive, feuille adhésive et stratifié Download PDF

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Publication number
WO2019004107A1
WO2019004107A1 PCT/JP2018/023957 JP2018023957W WO2019004107A1 WO 2019004107 A1 WO2019004107 A1 WO 2019004107A1 JP 2018023957 W JP2018023957 W JP 2018023957W WO 2019004107 A1 WO2019004107 A1 WO 2019004107A1
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pressure
sensitive adhesive
polymer
adhesive composition
adhesive layer
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PCT/JP2018/023957
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English (en)
Japanese (ja)
Inventor
貴迪 山口
山本　真之
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王子ホールディングス株式会社
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Priority to JP2019526877A priority Critical patent/JPWO2019004107A1/ja
Publication of WO2019004107A1 publication Critical patent/WO2019004107A1/fr

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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
    • 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
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • 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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet and a laminate.
  • LCDs liquid crystal displays
  • touch panels touch panels
  • input devices capacitive touch panels are rapidly spreading due to their functionality.
  • a pressure-sensitive adhesive sheet is used for bonding optical members, and a pressure-sensitive adhesive sheet is also used for bonding a display device and an input device.
  • Patent Document 1 discloses a pressure-sensitive adhesive that can realize a pressure-sensitive adhesive layer having a low relative dielectric constant. Specifically, Patent Document 1 is obtained by polymerizing a monomer component containing 19 to 99.5% by weight of alkyl (meth) acrylate having a branched alkyl group having 10 to 24 carbon atoms at the end of the ester group. An adhesive comprising a (meth) acrylic polymer is described.
  • the problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition which can reduce the relative dielectric constant in the case of forming a pressure-sensitive adhesive layer and can make the step following property excellent.
  • an active energy ray-curable pressure-sensitive adhesive composition or a heat-curable pressure-sensitive adhesive composition containing a base polymer is used.
  • Acrylic polymer units such as alkyl (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates and the like because they are excellent in transparency etc. as a base polymer
  • An acrylic base polymer containing is used.
  • the present inventors found that when the relative dielectric constant of the pressure-sensitive adhesive layer is lowered, the step followability is inferior, and when the step followability is improved, the relative dielectric constant is increased, and the structure of the base polymer is changed. It has been found that it is difficult to improve both the relative dielectric constant and the step followability simply by As a result of intensive studies to solve the above problems, the present inventors found that hydrocarbon polymers having a number average molecular weight within a predetermined range and liquid or oily at 20 ° C. are crosslinkable acrylic polymers. In addition to the above, it has been found that the relative dielectric constant in the case of forming the pressure-sensitive adhesive layer can be lowered and the step followability can be made excellent, and the present invention has been completed.
  • a pressure-sensitive adhesive composition comprising a crosslinkable acrylic polymer, a crosslinking agent and a hydrocarbon polymer, Containing 50% by mass or more of a crosslinkable acrylic polymer based on the pressure-sensitive adhesive composition, The number average molecular weight of the hydrocarbon polymer is 250 to 15,000, The hydrocarbon polymer is liquid or oily at 20 ° C., A pressure-sensitive adhesive composition in which the relative dielectric constant at a frequency of 1 MHz of the pressure-sensitive adhesive layer is 3.5 or less when a pressure-sensitive adhesive layer which is a cured product of the pressure-sensitive adhesive composition is formed.
  • a hydrocarbon polymer is a polymer having unsaturated hydrocarbon in its molecule, The polymer having unsaturated hydrocarbons has a number average molecular weight of 250 to 15,000, The pressure-sensitive adhesive composition according to [1], wherein the polymer having unsaturated hydrocarbon is liquid or oily at 20 ° C. [3] The pressure-sensitive adhesive composition according to [2], wherein the polymer having an unsaturated hydrocarbon is a styrenic polymer, polyisoprene or polybutadiene.
  • the hydrocarbon polymer is a linear saturated hydrocarbon polymer, The number average molecular weight of the linear saturated hydrocarbon polymer is 250 to 5000, The pressure-sensitive adhesive composition according to [1], wherein the linear saturated hydrocarbon polymer is liquid or oily at 20 ° C. [5] The pressure-sensitive adhesive composition according to [4], wherein the linear saturated hydrocarbon polymer is polybutene. [6] The crosslinkable functional group possessed by the crosslinkable acrylic polymer is one or more selected from any of a carboxy group, a hydroxy group, an amino group, an amide group, an epoxy group and an isocyanate group [1 ] The pressure-sensitive adhesive composition according to any one of [5].
  • Agent composition [8] The pressure-sensitive adhesive composition according to any one of [1] to [7], which contains a hydrocarbon polymer in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer. [9] The pressure-sensitive adhesive composition according to any one of [1] to [8], containing 5 to 15 parts by mass of a hydrocarbon polymer based on 100 parts by mass of the crosslinkable acrylic polymer.
  • a pressure-sensitive adhesive sheet wherein the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition according to any one of [1] to [9].
  • a first release sheet is provided on one surface of the pressure-sensitive adhesive layer
  • a second release sheet is provided on the other surface of the pressure-sensitive adhesive layer
  • a pressure-sensitive adhesive composition capable of reducing the relative dielectric constant in the case of forming a pressure-sensitive adhesive layer and also making the step following property excellent.
  • a pressure-sensitive adhesive sheet having a low relative dielectric constant and excellent step difference followability.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of the pressure-sensitive adhesive sheet of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of the configuration of the laminate of the present invention.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a crosslinkable acrylic polymer, a crosslinking agent and a hydrocarbon polymer, and the crosslinkable acrylic polymer is contained in an amount of 50% by mass or more based on the pressure-sensitive adhesive composition. Containing a hydrocarbon polymer having a number average molecular weight of 250 to 15,000, a hydrocarbon polymer liquid or oil at 20 ° C., and forming a pressure-sensitive adhesive layer which is a cured product of the pressure-sensitive adhesive composition The relative dielectric constant at a frequency of 1 MHz of the agent layer is 3.5 or less.
  • the pressure-sensitive adhesive composition of the present invention can lower the relative dielectric constant when the pressure-sensitive adhesive layer is formed, and can make the step following property excellent.
  • the component for lowering the relative dielectric constant is added not as a copolymerization component of the crosslinkable acrylic polymer but as a separate material having a low molecular weight. Since another material having a low molecular weight can improve the step followability, such a material also plays a role of a plasticizer that makes the step followability good, in addition to the role of lowering the relative dielectric constant.
  • the relative dielectric constant at a frequency of 1 MHz of the pressure-sensitive adhesive layer may be 3.5 or less, preferably 3.1 or less. It is more preferably 3.0 or less, and particularly preferably 2.9 or less.
  • the pressure-sensitive adhesive composition may contain a solvent as described later.
  • the solid concentration is preferably 20 to 60% by mass, and more preferably 30 to 50% by mass.
  • the hydrocarbon polymer contained in the pressure-sensitive adhesive composition is a polymer containing a hydrocarbon group and is a polymer having no acryloyl group.
  • the hydrocarbon polymer is a polymer having unsaturated hydrocarbons in the molecule.
  • the number average molecular weight of the polymer having unsaturated hydrocarbon is 250 to 15,000, and the polymer having unsaturated hydrocarbon is preferably liquid or oily at 20 ° C.
  • the hydrocarbon polymer is a linear saturated hydrocarbon polymer.
  • the number average molecular weight of the linear saturated hydrocarbon polymer is 250 to 5,000, and the linear saturated hydrocarbon polymer is preferably liquid or oily at 20 ° C.
  • the crosslinkable acrylic polymer is a (meth) acrylic monomer having a unit (a1) derived from a non-crosslinkable (meth) acrylic acid ester having a branched alkyl group having 5 to 9 carbon atoms and a crosslinkable functional group It is preferred to contain a unit (a2) derived from In the (meth) acrylic monomer having a crosslinkable functional group and a unit (a1) derived from a non-crosslinkable (meth) acrylic acid ester having a branched alkyl group having 5 to 9 carbon atoms, and the crosslinkable acrylic polymer
  • a pressure-sensitive adhesive layer having a sufficiently low dielectric constant can be formed from a pressure-sensitive adhesive composition containing a crosslinkable acrylic polymer.
  • the unit (a1) derived from the non-crosslinkable (meth) acrylate having a branched alkyl group having 5 to 9 carbon atoms contained in the crosslinkable acrylic polymer has an alkyl group having 5 or more carbon atoms, And since such an alkyl group is a branched structure, its molar volume is large and its density is small. Therefore, the molar volume of the crosslinkable acrylic polymer can be increased, and the density can be reduced.
  • the unit (a1) has an alkyl group having 9 or less carbon atoms, it is possible to suppress the volume shrinkage when made into a polymer, and to maintain a large molar volume of the crosslinkable acrylic polymer Conceivable.
  • the crosslinkable acrylic polymer is preferably one having transparency to such an extent that the visibility of the display device is not reduced.
  • the "unit” is a repeating unit (monomer unit) constituting the polymer.
  • the unit (a1) derived from the non-crosslinkable (meth) acrylic acid ester is a repeating unit derived from a (meth) acrylic acid alkyl ester having a branched alkyl group having 5 to 9 carbon atoms.
  • (meth) acrylic acid alkyl ester isopentyl (meth) acrylate, isohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, And (meth) acrylic acid isononyl and the like.
  • 2-ethylhexyl (meth) acrylate is preferably used as the non-crosslinkable (meth) acrylic acid ester unit (a1), and 2-ethylhexyl acrylate (2-EHA) and 2-ethylhexyl methacrylate (2-EHMA) It is more preferable to use
  • the carbon number of the branched alkyl group possessed by the unit (a1) derived from the non-crosslinkable (meth) acrylic acid ester may be 5 or more and 9 or less, preferably 7 or more and 9 or less.
  • the content of the units (a1) derived from the non-crosslinkable (meth) acrylic acid ester in the crosslinkable acrylic polymer is preferably 60% by mass or more based on the total mass of the crosslinkable acrylic polymer, and 80 It is more preferable that it is mass% or more, and it is further more preferable that it is 90 mass% or more.
  • one or at least one crosslinkable functional group possessed by the crosslinkable acrylic polymer is selected from any of a carboxy group, a hydroxy group, an amino group, an amide group, an epoxy group (preferably glycidyl group) and an isocyanate group. It is preferable that it is 2 or more types.
  • a unit (a2) derived from a (meth) acrylic monomer having a crosslinkable functional group a carboxy group-containing monomer unit, a hydroxy group-containing monomer unit, an amino group-containing monomer unit
  • examples thereof include amide group-containing monomer units, epoxy group (preferably glycidyl group) -containing monomer units, and isocyanate group-containing monomer units.
  • the methacrylic acid monomer is preferable to the acrylic acid monomer from the viewpoint of not increasing the relative dielectric constant.
  • a unit (a2) derived from a (meth) acrylic monomer having a crosslinkable functional group a carboxy group-containing monomer unit, a hydroxy group-containing monomer unit, an amino group-containing monomer unit, a glycidyl group-containing Monomer units are preferred, and hydroxy group-containing monomer units are more preferred. These monomer units may be of one type or of two or more types.
  • the hydroxy group-containing monomer unit is a repeating unit derived from a hydroxy group-containing monomer.
  • hydroxy group-containing monomer for example, hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.
  • (Meth) acrylic acid [(mono, di or poly) alkylene glycol] such as (meth) acrylic acid mono (diethylene glycol) and (meth) acrylic acid lactone such as (meth) acrylic acid monocaprolactone.
  • the amino group-containing monomer unit include repeating units derived from an amino group-containing monomer such as (meth) acrylamide and allylamine.
  • the glycidyl group-containing monomer unit includes a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth) acrylate.
  • a glycidyl group-containing monomer such as glycidyl (meth) acrylate.
  • carboxy group-containing monomer unit acrylic acid and methacrylic acid can be mentioned.
  • the content of the unit (a2) derived from the (meth) acrylic monomer having a crosslinkable functional group in the crosslinkable acrylic polymer is 0.01% by mass or more based on the total mass of the crosslinkable acrylic polymer
  • the content is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the content of the unit (a2) is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. If content of a unit (a2) is more than the lower limit of the said range, it has crosslinking property enough, and if it is below the upper limit of the said range, necessary adhesion physical property can be maintained, and a relative dielectric constant Is sufficiently low to form a pressure-sensitive adhesive layer.
  • the crosslinkable acrylic polymer is, if necessary, a unit (a1) derived from a non-crosslinkable (meth) acrylic acid ester and a single monomer other than the (meth) acrylic monomer unit (a2) having a crosslinkable functional group. It may have a monomeric unit. Examples of the other monomer include (meth) acrylic acid ester units having 4 or less carbon atoms or 10 or more carbon atoms.
  • n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, etc. Can be mentioned.
  • acrylic acid ester units (meth) acrylic acid ester units having a cyclic group such as cyclohexyl (meth) acrylate and benzyl (meth) acrylate, (meth) acrylonitrile, vinyl acetate, Styrene, vinyl chloride, vinyl pyrrolidone, vinyl pyridine and the like can be mentioned.
  • the content of the other monomer units in the crosslinkable acrylic polymer is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total mass of the crosslinkable acrylic polymer. It is particularly preferable that the content is 1% by mass or less.
  • the weight average molecular weight of the crosslinkable acrylic polymer is preferably 100,000 or more and 2,000,000 or less, and more preferably 300,000 or more and 1.5 million or less. By setting the weight average molecular weight within the above range, it is possible to ensure sufficient step-following performance.
  • the weight average molecular weight of the crosslinkable acrylic polymer is a value before being crosslinked by the crosslinking agent.
  • the weight average molecular weight is a value determined by gel permeation chromatography (GPC) and determined on the basis of polystyrene.
  • GPC gel permeation chromatography
  • the glass transition temperature (Tg) of the crosslinkable acrylic polymer is preferably ⁇ 80 ° C. or more and ⁇ 15 ° C. or less, more preferably ⁇ 75 ° C. or more and ⁇ 18 ° C. or less, and ⁇ 70 ° C. or more and ⁇ 18 ° C. It is more preferable that it is the following.
  • Tg glass transition temperature
  • the specific dielectric constant of the crosslinkable acrylic polymer alone is preferably 4.0 or less, more preferably 3.8 or less.
  • the hydrocarbon polymer is a polymer having unsaturated hydrocarbons in the molecule.
  • the number average molecular weight of the polymer having unsaturated hydrocarbon is 250 to 15,000
  • the polymer having unsaturated hydrocarbon is liquid or oily at 20 ° C.
  • the liquid or oil state of the polymer having unsaturated hydrocarbon at 20 ° C. means that the viscosity measured by the B-type viscometer at 20 ° C. is 10,000 mPa ⁇ s or less.
  • the polymer having unsaturated hydrocarbon does not have a polar group from the viewpoint of lowering the relative dielectric constant. It is preferable that the polymer having an unsaturated hydrocarbon is linear from the viewpoint of lowering the relative dielectric constant and the viewpoint of making the step followability favorable.
  • polystyrenic polymers examples include polybutadiene, polyisoprene, and styrenic polymers.
  • the polymer having unsaturated hydrocarbon is preferably at least one selected from polybutadiene and styrenic polymers.
  • styrenic polymer As a polymer having an unsaturated hydrocarbon, one type of styrene polymer may be contained alone, or two or more types different in composition, number average molecular weight, etc. of the styrenic polymer may be contained.
  • styrene-based monomer which can constitute a styrene-based polymer
  • styrene alkylstyrene (methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, butylstyrene, hexylstyrene, octylstyrene) And monomers having a styrene skeleton such as halogenated styrene (chlorostyrene, bromostyrene) and the like.
  • styrene is preferably used as the styrene-based monomer from the viewpoint of having no functional group capable of reacting with the crosslinking agent and being easy to obtain.
  • a commercial item can be used as a styrene-type polymer.
  • Examples of commercially available products include Piccolastic A5 (trade name, styrene homopolymer, number average molecular weight: 300) manufactured by EASTMAN CHEMICAL.
  • polybutadiene As a polymer having unsaturated hydrocarbon, one type of polybutadiene may be contained alone, or two or more types different in composition, number average molecular weight, etc. of polybutadiene may be contained.
  • a commercial item can be used as polybutadiene.
  • Examples of commercially available products include Kuraray Co. (part number: “LBR-302” and “LBR-307”), Total Cray Valley (trade names “Ricon 130”, “Ricon 131”, “Ricon 142” and “Ricon 156” "Ricon 157”) etc. are mentioned.
  • the number average molecular weight of the polymer having unsaturated hydrocarbon is 15000 or less, preferably 10000 or less, more preferably 7000 or less, and particularly preferably 5000 or less. Further, the number average molecular weight of the unsaturated hydrocarbon-containing polymer is 250 or more, preferably 280 or more, and more preferably 300 or more.
  • the agent layer can be formed.
  • step difference tracking property can be formed by carrying out the number average molecular weight of the polymer which has unsaturated hydrocarbon in the said range.
  • the number average molecular weight of the polymer having unsaturated hydrocarbon is a value determined by gel permeation gel permeation chromatography (GPC) and determined on the basis of polystyrene.
  • the hydrocarbon polymer is a linear saturated hydrocarbon polymer.
  • the number average molecular weight of the linear saturated hydrocarbon polymer is 250 to 5,000, and the linear saturated hydrocarbon polymer is liquid or oily at 20 ° C.
  • the linear saturated hydrocarbon polymer is liquid or oily at 20 ° C., it means that the viscosity measured by the B-type viscometer at 20 ° C. is 10,000 mPa ⁇ s or less.
  • the linear saturated hydrocarbon polymer does not have a polar group from the viewpoint of lowering the relative dielectric constant.
  • linear saturated hydrocarbon polymers examples include polyethylene, polypropylene and polybutene.
  • the linear saturated hydrocarbon polymer is preferably polybutene.
  • polybutene As the linear saturated hydrocarbon polymer, one type of polybutene may be contained alone, or two or more types having different polybutene composition, number average molecular weight, etc. may be contained.
  • butene monomer which can constitute polybutene, 1-butene, cis-2-butene, trans-2-butene and isobutene can be mentioned.
  • a commercial item can be used as polybutene.
  • a commercial item "made by NOF Corporation (brand name” polybutene TM grade 0N ”) etc. is mentioned.
  • the number average molecular weight of the linear saturated hydrocarbon polymer is 5,000 or less, preferably 1,000 or less, more preferably 700 or less, and particularly preferably 500 or less. Moreover, the number average molecular weight of the linear saturated hydrocarbon polymer is 250 or more, preferably 280 or more, and more preferably 300 or more.
  • the number average molecular weight of the linear saturated hydrocarbon polymer is a value determined by gel permeation gel permeation chromatography (GPC) and determined on the basis of polystyrene.
  • the hydrocarbon polymer is preferably contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • the content of the hydrocarbon polymer is more preferably 3% by mass or more, particularly preferably 5% by mass or more based on the total mass of the crosslinkable acrylic polymer.
  • the content of the hydrocarbon polymer is more preferably 15% by mass or less, and particularly preferably 12% by mass or less, based on the total mass of the crosslinkable acrylic polymer.
  • the production method is not particularly limited, and can be appropriately selected from commonly used polymerization methods.
  • the polymerization method a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and the like can be mentioned.
  • the crosslinking agent is preferably a crosslinking agent that reacts with the crosslinkable acrylic polymer by heat.
  • the crosslinking agent for example, among known crosslinking agents such as isocyanate compound, epoxy compound, oxazoline compound, aziridine compound, metal chelate compound, butylated melamine compound, and the crosslinkable functional group possessed by the crosslinkable acrylic polymer It can be selected appropriately in consideration of the reactivity. For example, when it contains a hydroxy group as a crosslinkable functional group, an isocyanate compound can be used because of the reactivity of the hydroxy group.
  • the crosslinking agent is preferably one or more selected from any of a difunctional or higher epoxy compound and a difunctional or higher isocyanate compound, and is a difunctional or higher isocyanate compound. Is more preferred.
  • isocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
  • an epoxy compound for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycid
  • a commercial item can be used as a crosslinking agent.
  • Examples of commercially available products include xylylene diisocyanate compound (manufactured by Mitsui Chemicals, Inc., Takenate D-110N) and the like.
  • the crosslinking agent one type may be used alone, or two or more types may be used in combination.
  • the content of the crosslinking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired adhesive physical properties and the like, and is not particularly limited, but 0.01 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer. It can be made into parts or less, and can be made into 0.03 to 3 parts by mass.
  • the content of the crosslinking agent can be 0.01% by mass or more and 5.0% by mass or less with respect to the total mass of the pressure-sensitive adhesive composition, and 0.02% by mass or more and 2.0% by mass or less can do.
  • the pressure-sensitive adhesive composition may further contain a solvent.
  • the solvent is used to improve the coating suitability of the pressure-sensitive adhesive composition.
  • solvents include, for example, hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene and dichloropropane; methanol Alcohols such as ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran etc.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone etc Methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl acetate and the like; Ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyols and derivatives thereof such as propylene glycol monomethyl ether acetate.
  • a solvent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but can be 25 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the crosslinkable acrylic polymer, and is 30 parts by mass or more and 400 parts by mass or less It can be done.
  • content of a solvent can be 10 mass% or more and 90 mass% or less with respect to the total mass of an adhesive composition, and can be 20 mass% or more and 80 mass% or less.
  • the pressure-sensitive adhesive composition of the present invention may contain a plasticizer other than the hydrocarbon polymer.
  • a plasticizer is contained, the content of the plasticizer can be 50 parts by mass or less, can be 30 parts by mass or less, and 10 parts by mass or less with respect to 100 parts by mass of the crosslinkable acrylic polymer. It can also be done.
  • a nonfunctional acrylic polymer can be used as a plasticizer.
  • a nonfunctional acrylic polymer is a polymer consisting only of an acrylic monomer unit having no functional group other than an acrylate group, or an acrylic monomer unit having no functional group other than an acrylate group and no functional group It means a polymer consisting of non-acrylic monomer units.
  • an acrylic monomer unit which does not have functional groups other than an acrylate group the thing similar to a non-crosslinkable (meth) acrylic acid ester unit (a1) is mentioned, for example.
  • non-acrylic monomer unit having no functional group for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, stearin
  • vinyl acid esters of vinyl acid such as vinyl acid, vinyl cyclohexanecarboxylic acid and vinyl benzoate, and styrene.
  • the pressure-sensitive adhesive composition may contain other components other than the above as long as the effects of the present invention are not impaired.
  • components known as additives for adhesives such as antioxidants, metal corrosion inhibitors, tackifiers, silane coupling agents, ultraviolet absorbers, light stabilizers such as hindered amine compounds, etc. You can choose among them as needed.
  • the antioxidant include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • benzotriazole resin can be mentioned.
  • tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
  • silane coupling agent a silane coupling agent, a mercapto alkoxysilane compound (for example, a mercapto group substituted alkoxy oligomer etc.) etc. are mentioned, for example.
  • the UV absorber include benzotriazole compounds and benzophenone compounds.
  • the pressure-sensitive adhesive composition of the present invention is preferably a pressure-sensitive adhesive composition which substantially does not contain a polymer monomer or a polymerization initiator in addition to the crosslinking agent and the hydrocarbon polymer (after-cureless).
  • After cure is a pressure-sensitive adhesive layer of a semi-cured product after providing a pressure-sensitive adhesive layer on the surface of an adherend using a semi-cured product of a pressure-sensitive adhesive layer which is a cured product of a pressure-sensitive adhesive composition.
  • After cureless means that the after cure after providing the adhesive layer on the surface of the adherend is unnecessary.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive sheet of the present invention is preferably used for bonding of an optical member constituting a display device having a touch panel mounted thereon, because the pressure-sensitive adhesive sheet has a low relative dielectric constant and is excellent in step followability.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet may be a single-layer pressure-sensitive adhesive sheet composed only of a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive sheet or a double-sided pressure-sensitive adhesive sheet.
  • the single-sided pressure-sensitive adhesive sheet includes a multilayer sheet in which a pressure-sensitive adhesive layer is laminated on a support. In addition, another layer may be provided between the support and the pressure-sensitive adhesive layer.
  • a double-sided pressure-sensitive adhesive sheet As a double-sided pressure-sensitive adhesive sheet, a single-layer pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer, a multilayer pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated, and a multilayer pressure-sensitive adhesive layer in which another pressure-sensitive adhesive layer is laminated between the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer
  • stacked the support body between the adhesive layer and the adhesive layer is mentioned.
  • the double-sided pressure-sensitive adhesive sheet has a support, one using a transparent support as the support is preferred.
  • Such a double-sided pressure-sensitive adhesive sheet is also excellent in transparency as the entire pressure-sensitive adhesive sheet, and thus can be suitably used for bonding optical members.
  • the non-carrier type is preferable, and a single-layer pressure-sensitive adhesive sheet consisting of a pressure-sensitive adhesive layer or a multilayer pressure-sensitive adhesive sheet obtained by laminating a plurality of pressure-sensitive adhesive layers is preferable. Double-sided PSA sheets are particularly preferred.
  • the support include plastics such as polystyrene, styrene-acrylic copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyetheretherketone, and triacetylcellulose. Films; optical films such as antireflective films, electromagnetic wave shielding films, etc. may be mentioned.
  • the surface of the pressure-sensitive adhesive layer is preferably covered by a release sheet. That is, the adhesive sheet may be a release sheet-attached adhesive sheet.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of a release sheet-attached pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet 11 shown in FIG. 1 has a release sheet (12a, 12b).
  • the adhesive sheet 11 of FIG. 1 is a non-carrier type single layer adhesive sheet, and is a double-sided adhesive sheet.
  • a release sheet a peelable laminate sheet having a release sheet substrate and a release agent layer provided on one side of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity substrate
  • Papers and polymer films are used for the release sheet base in the release laminate sheet.
  • the release agent constituting the release agent layer for example, a general-purpose addition type or condensation type silicone release agent or a long chain alkyl group-containing compound is used. In particular, an addition-type silicone release agent having high reactivity is preferably used.
  • silicone release agents include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3600 manufactured by Shin-Etsu Chemical Co., Ltd., KS-774 and X62-2600, etc. Can be mentioned.
  • a silicone resin which is an organic silicon compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 CHCH (CH 3 ) SiO 1/2 unit in a silicone-based release agent preferable.
  • Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.
  • the first release sheet is provided on one surface of the pressure-sensitive adhesive layer
  • the second release sheet is provided on the other surface of the pressure-sensitive adhesive layer
  • the release force of the first release sheet and the second release sheet are preferably different.
  • the release sheet 12 it is preferable to make the release properties of the release sheet 12 a and the release sheet 12 b different in order to facilitate release. That is, when the releasability from one side is different from the releasability from the other, it becomes easy to peel off only the release sheet 12 having the higher releasability first. In that case, the releasability of the release sheet 12 of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately set depending on the application and is not particularly limited, but usually, it is preferably in the range of 10 ⁇ m to 500 ⁇ m, more preferably 20 ⁇ m to 450 ⁇ m, and more preferably 30 ⁇ m to 450 ⁇ m. Is more preferably 40 ⁇ m or more and 400 ⁇ m or less, still more preferably 40 ⁇ m or more and 350 ⁇ m or less, and particularly preferably 40 ⁇ m or more and 300 ⁇ m or less.
  • the step following property can be sufficiently secured, and the durability can be further enhanced.
  • manufacture of a double-sided adhesive sheet becomes easy by carrying out the thickness of an adhesive layer in the said range.
  • the relative dielectric constant at a frequency of 1 MHz of the pressure-sensitive adhesive layer may be 3.5 or less, preferably 3.1 or less, more preferably 3.0 or less, and 2.9 or less Particularly preferred.
  • the relative dielectric constant is a relative dielectric constant at a specific frequency.
  • a relative dielectric constant at a frequency of 1 MHz which is a value calculated by the method defined in JIS C 2138 is used.
  • the adhesive strength of the pressure-sensitive adhesive sheet is preferably 10 N / 25 mm or more, more preferably 15 N / 25 mm or more.
  • the adhesive force of the adhesive sheet with respect to the to-be-adhered body mentioned above is the value which peeled 180 degrees with respect to each to-be-adhered body, and measured the adhesive force according to JISZ0237.
  • the method for producing the pressure-sensitive adhesive sheet is not particularly limited.
  • the pressure-sensitive adhesive sheet of the present invention may be composed of a pressure-sensitive adhesive layer and another layer, but is preferably composed only of a pressure-sensitive adhesive layer.
  • the adhesive layer formed from the adhesive composition of that excepting the above, a support body, a release sheet etc. are mentioned, for example.
  • the support for example, plastic films such as polystyrene, styrene-acrylic copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyetheretherketone, triacetylcellulose, etc .; optical films such as antireflection film, electromagnetic wave shielding film, etc. Can be mentioned.
  • the manufacturing process of an adhesive sheet includes the process of coating an adhesive composition on a peeling sheet, and forming a coating film, and the process of making this coating film into a hardened
  • the step of applying a pressure-sensitive adhesive composition on a release sheet to form a coating and the step of heating the coating to form a cured product will be described as a representative.
  • Coating of the adhesive composition which forms an adhesive sheet can be implemented using a well-known coating apparatus.
  • a coating apparatus a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater etc. are mentioned, for example.
  • the coating film can be heated using a known heating device such as a heating furnace or an infrared lamp. By heating the coating, the reaction between the crosslinkable acrylic polymer and the crosslinking agent proceeds to form a cured product (pressure-sensitive adhesive sheet).
  • a known heating device such as a heating furnace or an infrared lamp.
  • the reaction between the crosslinkable acrylic polymer and the crosslinking agent proceeds to form a cured product (pressure-sensitive adhesive sheet).
  • an aging treatment may be performed in which the pressure-sensitive adhesive sheet is allowed to stand at a constant temperature for a fixed period. The aging treatment can be carried out, for example, by leaving at 23 ° C. for 7 days.
  • the adhesive layer of an adhesive sheet is made to contact an adherend surface.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet contains a hydrocarbon polymer having a small relative dielectric constant, even if the adherend has a step portion, the pressure-sensitive adhesive layer can follow the unevenness of the step portion .
  • the laminate of the present invention has an adherend on at least one surface of the pressure-sensitive adhesive sheet of the present invention, and the adherend has a stepped portion.
  • the adherend is preferably an optical member constituting an image display apparatus having a liquid crystal module or an optical member constituting a touch panel.
  • the laminate is preferably obtained through the step of bringing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet into contact with the adherend surface.
  • FIG. 2 is a cross-sectional view showing an example of the configuration of a laminate 20 in which the pressure-sensitive adhesive sheet 21 of the present invention is bonded to the adherend 22 and the adherend 24.
  • the adherends 22 and 24 have stepped portions (27a, 27b, 27c, 27d or 27a and 27b, or only one side of 27c and 27d).
  • the adherend 22 has stepped portions (27a, 27b), and the adherend 24 has stepped portions (27c, 27d).
  • the thickness of the step portions (27a, 27b, 27c, 27d) is usually 5 ⁇ m to 60 ⁇ m.
  • the adhesive sheet 21 of this invention can be bonded to the member which has a level
  • the adherend is preferably an optical member.
  • an optical member each structural member in optical products, such as a touch panel and an image display device, can be mentioned.
  • an ITO film in which an ITO film is provided on a transparent resin film an ITO glass in which an ITO film is provided on the surface of a glass plate, a transparent conductive film obtained by coating a conductive polymer on a transparent resin film Hard coat films, fingerprint resistant films and the like can be mentioned.
  • the pressure-sensitive adhesive sheet of the present invention is preferably for sensor lamination of a touch panel, and more preferably for sensor lamination of a touch panel using a touch pen.
  • an ITO film in which an ITO film is provided on a transparent resin film an ITO glass in which an ITO film is provided on the surface of a glass plate, a conductive polymer for a transparent resin film A transparent conductive film coated with is preferred.
  • the antireflection film used for a liquid crystal display device an orientation film, a polarizing film, retardation film, a brightness improvement film etc. are mentioned, for example.
  • Examples of the material used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, and cellulose acylate.
  • the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, it can be used for bonding two adherends.
  • the pressure-sensitive adhesive sheet according to the present invention comprises bonding of ITO films to each other in the inside of a touch panel, bonding of ITO film and ITO glass, bonding of an ITO film on a touch panel and liquid crystal panel, and a cover glass and an ITO film. It is used for pasting, pasting of a cover glass and a decoration film, etc.
  • the present invention also relates to a method of manufacturing a laminate. It is preferable that the manufacturing method of a laminated body includes the process of making the surface of an adherend contact the adhesive sheet mentioned above.
  • Example 1 Preparation of Pressure-Sensitive Adhesive Composition> 2-ethylhexyl acrylate (2-EHA), 2-ethylhexyl methacrylate (2-EHMA), 2-hydroxyethyl acrylate (2-HEA) in a mass ratio of 30:60:10, and a radical polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain a crosslinkable acrylic polymer (A). The weight average molecular weight of the crosslinkable acrylic polymer (A) was 500,000.
  • the number average molecular weight or weight average molecular weight is a value determined by gel permeation chromatography (GPC) and determined on the basis of polystyrene.
  • the measurement conditions of gel permeation chromatography (GPC) are as follows. Solvent: Tetrahydrofuran column: Shodex KF801, KF803L, KF800L, KF800D (Showa Denko KK made four connection) Column temperature: 40 ° C Sample concentration: 0.5 mass% Detector: RI-2031 plus (made by JASCO) Pump: RI-2080plus (made by JASCO) Flow rate (flow rate): 0.8 ml / min Injection volume: 10 ⁇ l
  • Polystyrene compound (Piccolastic A5 manufactured by EASTMAN CHEMICAL Co., Ltd. Number average molecular weight 300 as a polymer having an unsaturated hydrocarbon with respect to 100 parts by mass of the solid content of the acrylic polymer of the crosslinkable acrylic polymer (A) obtained above 10 parts by mass) and 0.15 parts by mass of xylylene diisocyanate compound (Takenate D-110N, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent, and ethyl acetate is added so that the solid content concentration is 40 mass%. Thus, a pressure-sensitive adhesive composition was obtained.
  • the polystyrene compound (Piccolastic A5 number average molecular weight 300 manufactured by EASTMAN CHEMICAL Co., Ltd.) used as the polymer having unsaturated hydrocarbon was oily at 20 ° C.
  • first release sheet a release sheet manufactured by Oji F-TEX, Inc .: 38RL-07
  • release agent layer treated with a silicone-based release agent
  • the surface of (2) was uniformly coated by an applicator such that the coated amount after drying was 150 ⁇ m / m 2 . Then, it dried in 100 degreeC of air circulation type thermostatic ovens for 3 minutes, and formed the adhesive layer on the surface of a 1st peeling sheet.
  • a second release sheet (manufactured by Oji F-TEX Co., Ltd .: 38RL-07 (L)) having a thickness of 38 ⁇ m is attached to the surface of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer has a pair of peeling force differences.
  • interposed into the peeling sheet was obtained.
  • the pressure-sensitive adhesive sheet was subjected to an aging treatment in which it was allowed to stand for 7 days under conditions of 23 ° C. and a relative humidity of 50%.
  • a UV curable ink was screen printed on the surface of a glass plate (90 mm long ⁇ 50 mm wide ⁇ 0.5 mm thick) in a frame shape (90 mm long ⁇ 50 mm wide, 5 mm wide) so that the coating thickness would be 5 ⁇ m.
  • ultraviolet rays were irradiated to cure the printed ultraviolet curable ink. This process was repeated eight times to obtain a printed stepped glass having a 40 ⁇ m stepped portion.
  • the obtained pressure-sensitive adhesive sheet is cut into a shape of 90 mm long ⁇ 50 mm wide, the first release sheet is peeled off, and the pressure-sensitive adhesive layer is a printed step glass using a laminator (IKO-650EMT manufactured by Eubon Co., Ltd.) It stuck so that the frame-like printing whole surface might be covered. Thereafter, the second release sheet is peeled off, and a glass plate (90 mm long ⁇ 50 mm wide ⁇ 0.5 mm thick) is bonded to the surface of the exposed pressure-sensitive adhesive layer with the above laminator, and autoclaved (40 ° C., 0. 0. 5 MPa for 30 minutes) to obtain a laminate (1).
  • a laminator IKO-650EMT manufactured by Eubon Co., Ltd.
  • Laminate (2) ⁇ Production of Laminate (2)>
  • the obtained adhesive sheet is cut into a shape of 90 mm long ⁇ 50 mm wide, the first release sheet is peeled off, and a laminate (1) is prepared using a laminator (IKO-650 EMT, manufactured by Eubon Co., Ltd.) It bonded so that the frame-like printing whole surface of the printing level-difference glass which has a used 40-micrometer level
  • a laminator IKO-650 EMT, manufactured by Eubon Co., Ltd.
  • a polarizing plate manufactured by Polatechno Co., Ltd., SKN-18243T
  • a glass plate 90 mm long ⁇ 50 mm wide ⁇ 0.5 mm thick
  • central particles are formed on the surface of the polarizing plate.
  • a dispersion of about 0.05 mg of glass beads of 30 ⁇ m in diameter was prepared.
  • the second release sheet of the laminate integrated with the printed step glass was peeled off, and the laminate was bonded to the surface of the adherend's polarizing plate to which the glass beads were dispersed by a laminator. Thereafter, autoclave treatment (40 ° C., 0.5 MPa, 30 minutes) was performed to obtain a laminate (2).
  • Example 2 The polymer having an unsaturated hydrocarbon is replaced by a polybutadiene compound (Kuraray (product number: “LBR-302” number average molecular weight 5500) ”in place of polystyrene compound (Piccolastic A5 number average molecular weight 300 manufactured by EASTMAN CHEMICAL)
  • a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet and a laminate were obtained in the same manner as in Example 1.
  • the polybutadiene compound (Kuraray Co., Ltd. (product number: “LBR-302 number average molecular weight 5500”)) used as the polymer having unsaturated hydrocarbon was oily at 20 ° C.
  • Comparative Example 1 A pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and a laminate were obtained in the same manner as in Example 1 except that the unsaturated hydrocarbon-containing polymer was not blended.
  • Comparative Example 2 A pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and a laminate were obtained in the same manner as in Comparative Example 1 except that the crosslinkable acrylic polymer (B) was used instead of the crosslinkable acrylic polymer (A).
  • the crosslinkable acrylic polymer (B) uses n-butyl acrylate (BA) instead of 2-EHMA so that the mass ratio of BA, 2-EHA, 2-HEA is 70:20:10.
  • BA n-butyl acrylate
  • 2-EHMA 2-EHMA
  • a crosslinkable acrylic polymer (B) was obtained in the same manner as in Example 1 except that the composition was blended.
  • the weight average molecular weight of the crosslinkable acrylic polymer (B) was 700,000.
  • Comparative Example 3 The same as Example 1 except using the crosslinkable acrylic polymer (C) instead of the crosslinkable acrylic polymer (A) and changing the compounding amount of the crosslinking agent from 0.15 parts by mass to 0.7 parts by mass Thus, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet and a laminate were obtained.
  • the crosslinkable acrylic polymer (C) is obtained by using ISTA, 2-EHA and HBA using isostearyl acrylate (ISTA) instead of 2-EHMA and 4-hydroxybutyl acrylate (HBA) instead of 2-EHA.
  • a crosslinkable acrylic polymer (C) was obtained in the same manner as in Example 1 except that it was used.
  • the weight average molecular weight of the crosslinkable acrylic polymer (C) was 700,000.
  • Example 101 ⁇ Preparation of Pressure-Sensitive Adhesive Composition> 2-ethylhexyl acrylate (2-EHA), 2-ethylhexyl methacrylate (2-EHMA), 2-hydroxyethyl acrylate (2-HEA) in a mass ratio of 30:60:10, and a radical polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain a crosslinkable acrylic polymer (A). The weight average molecular weight of the crosslinkable acrylic polymer (A) was 500,000.
  • the number average molecular weight or weight average molecular weight is a value determined by gel permeation chromatography (GPC) and determined on the basis of polystyrene.
  • the measurement conditions of gel permeation chromatography (GPC) are as follows. Solvent: Tetrahydrofuran column: Shodex KF801, KF803L, KF800L, KF800D (Showa Denko KK made four connection) Column temperature: 40 ° C Sample concentration: 0.5 mass% Detector: RI-2031 plus (made by JASCO) Pump: RI-2080plus (made by JASCO) Flow rate (flow rate): 0.8 ml / min Injection volume: 10 ⁇ l
  • NOF Corporation (trade name “polybutene TM grade 0 N") as a linear saturated hydrocarbon polymer relative to 100 parts by mass of the solid content of the acrylic polymer of the crosslinkable acrylic polymer (A) obtained above 10 parts by mass, and 0.15 parts by mass of xylylene diisocyanate compound (manufactured by Mitsui Chemicals, Inc., Takenate D-110N) as a crosslinking agent, and ethyl acetate is added so that the solid content concentration is 40 mass%.
  • the pressure-sensitive adhesive composition was obtained.
  • NOF Corporation (trade name “polybutene TM grade 0 N") used as a linear saturated hydrocarbon polymer was oily at 20 ° C.
  • Comparative Example 101 A pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and a laminate were obtained in the same manner as in Example 101 except that the linear saturated hydrocarbon polymer was not blended.
  • a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and a laminate were obtained in the same manner as in Comparative Example 1 except that the crosslinkable acrylic polymer (B) was used instead of the crosslinkable acrylic polymer (A).
  • the crosslinkable acrylic polymer (B) uses n-butyl acrylate (BA) instead of 2-EHMA so that the mass ratio of BA, 2-EHA, 2-HEA is 70:20:10.
  • BA n-butyl acrylate
  • 2-EHMA 2-EHMA
  • a crosslinkable acrylic polymer (B) was obtained in the same manner as in Example 101 except that the composition was blended.
  • the weight average molecular weight of the crosslinkable acrylic polymer (B) was 700,000.
  • Example 10 is the same as Example 101 except using the crosslinkable acrylic polymer (C) instead of the crosslinkable acrylic polymer (A) and changing the compounding amount of the crosslinking agent from 0.15 parts by mass to 0.7 parts by mass.
  • a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet and a laminate were obtained.
  • the crosslinkable acrylic polymer (C) is obtained by using ISTA, 2-EHA and HBA using isostearyl acrylate (ISTA) instead of 2-EHMA and 4-hydroxybutyl acrylate (HBA) instead of 2-EHA.
  • a crosslinkable acrylic polymer (C) was obtained in the same manner as in Example 101 except that it was used.
  • the weight average molecular weight of the crosslinkable acrylic polymer (C) was 700,000.
  • ⁇ Step followability> The printed stepped portions of the laminate (1) and the laminated body (2) were observed with a microscope (magnification: 25 times), and the step followability of the pressure-sensitive adhesive sheet was evaluated based on the following criteria. ⁇ : The step is completely filled. Fair: Air remains in part of the step portion. X: Air remains in the entire stepped portion.
  • the pressure-sensitive adhesive composition obtained in the examples can lower the relative dielectric constant when the pressure-sensitive adhesive layer is formed, and can make the step following property excellent.
  • the adhesion to glass of the pressure-sensitive adhesive sheets of Examples 1, 2 and 101 was 18 N / 25 mm or more.
  • the pressure-sensitive adhesive sheet obtained in Comparative Example 1 of an embodiment in which the pressure-sensitive adhesive composition does not contain a polymer having an unsaturated hydrocarbon and Comparative Example 101 of an embodiment in which the pressure-sensitive adhesive composition does not contain a linear saturated hydrocarbon polymer is Although the relative dielectric constant could be lowered, the step followability was inferior, and the relative dielectric constant and the step followability could not be compatible.
  • the pressure-sensitive adhesive sheet obtained in Comparative Example 2 of the embodiment in which the pressure-sensitive adhesive composition does not contain a polymer having an unsaturated hydrocarbon and Comparative Example 102 in which the pressure-sensitive adhesive composition does not contain a linear saturated hydrocarbon polymer is Although the step followability can be made good, the relative dielectric constant is high, and the relative permittivity and the step followability can not both be achieved.
  • Comparative Example 3 of an embodiment in which the pressure-sensitive adhesive composition does not contain a polymer having an unsaturated hydrocarbon and Comparative Example 103 in which the pressure-sensitive adhesive composition does not contain a linear saturated hydrocarbon polymer is Although the relative dielectric constant could be lowered, the step followability was inferior, and the relative dielectric constant and the step followability could not be compatible. Comparative Examples 3 and 103 are examples in which Example 4 of JP-A-2016-172865 is referred to.
  • Adhesive sheet with release sheet 11 Adhesive sheet (adhesive layer) 12a, 12b Peeling sheet 20 laminate 21 adhesive sheet (adhesive layer) 22 adherend 24 adherend 27a, 27b, 27c, 27d step portion

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Abstract

L'invention concerne une composition adhésive qui réduit la constante diélectrique et présente une meilleure conformité de contour lors de la formation d'une couche adhésive. La présente invention concerne une composition adhésive comprenant un polymère acrylique réticulable, un agent de réticulation et un polymère hydrocarboné : le pourcentage en masse du polymère acrylique réticulable dans la composition adhésive est d'au moins 50 %; le polymère hydrocarboné a un poids moléculaire moyen en nombre compris entre 250 et 15 000; le polymère hydrocarboné passe à un état liquide ou un état huileux à 20 °C; et lorsque la couche adhésive, qui est un produit durci de la composition adhésive, est formée, ladite couche adhésive a une constante diélectrique inférieure ou égale à 3,5 à une fréquence de 1 MHz. La présente invention concerne également une feuille adhésive et un stratifié qui sont formés à partir de la composition adhésive.
PCT/JP2018/023957 2017-06-30 2018-06-25 Composition adhésive, feuille adhésive et stratifié WO2019004107A1 (fr)

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JP2020111629A (ja) * 2019-01-08 2020-07-27 王子ホールディングス株式会社 粘着シート、剥離シート付き粘着シート及び積層体
JP7346822B2 (ja) 2019-01-08 2023-09-20 王子ホールディングス株式会社 粘着シート、剥離シート付き粘着シート及び積層体

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