WO2015098965A1 - Adhesive composition, adhesive sheet, and method for processing adhesive sheet - Google Patents

Adhesive composition, adhesive sheet, and method for processing adhesive sheet Download PDF

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Publication number
WO2015098965A1
WO2015098965A1 PCT/JP2014/084147 JP2014084147W WO2015098965A1 WO 2015098965 A1 WO2015098965 A1 WO 2015098965A1 JP 2014084147 W JP2014084147 W JP 2014084147W WO 2015098965 A1 WO2015098965 A1 WO 2015098965A1
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Prior art keywords
pressure
sensitive adhesive
adhesive composition
component
mass
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PCT/JP2014/084147
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French (fr)
Japanese (ja)
Inventor
翔 大高
宮田　壮
征太郎 山口
貴洋 植田
小野　義友
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リンテック株式会社
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Priority to JP2015554958A priority Critical patent/JPWO2015098965A1/en
Publication of WO2015098965A1 publication Critical patent/WO2015098965A1/en

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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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and a method for processing the pressure-sensitive adhesive sheet.
  • pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition have been widely used for industrial, commercial, and household use, and are used for application of parts and for surface protection of parts. Yes.
  • the pressure-sensitive adhesive sheet used for industrial use may be processed into a predetermined shape by applying cutting or punching with a blade in a state of being attached to the adherend or before being attached to the adherend. is there.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing a urethane polymer is suitable for surface protection of an adherend because the pressure-sensitive adhesive layer has excellent elasticity.
  • the pressure-sensitive adhesive layer containing a urethane polymer has high elasticity, it is easily stretched and easily deformed. Therefore, when the adhesive sheet having the pressure-sensitive adhesive layer is subjected to cutting processing, punching processing, or the like, generation of a blade residue in which a part of the pressure-sensitive adhesive layer adheres to the blade, or the substrate that the pressure-sensitive adhesive sheet has on the cut surface In some cases, the adhesive layer oozes out from the adherend.
  • Patent Document 1 proposes a pressure-sensitive adhesive composition containing a gelling agent composed of an optically active amino acid derivative having a specific structure together with a urethane-based polymer as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive composition described in Patent Document 1 contains a specific gelling agent as an essential component, the gelling agent causes a decrease in the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition.
  • any pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition disclosed as an example of Patent Document 1 has low adhesive strength. Therefore, the pressure-sensitive adhesive composition described in Patent Document 1 is unsuitable as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet used for applications requiring high adhesive strength.
  • the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition described in Patent Document 1 sufficiently suppresses the pressure-sensitive adhesive layer from exuding to the base material at the cut surface when the punching process is performed. It cannot be said that it was done.
  • the present invention has a pressure-sensitive adhesive composition that can be a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet having excellent adhesive strength and excellent punching workability, and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. It aims at providing the processing method of an adhesive sheet and an adhesive sheet.
  • the present inventors have solved the above problem by adjusting the average aspect ratio of the filler dispersed in the pressure-sensitive adhesive composition to a specific range.
  • the present invention was completed. That is, the present invention provides the following [1] to [16].
  • [1] A pressure-sensitive adhesive composition comprising a urethane-based polymer (A) and a filler (B), wherein the average aspect ratio of the filler (B) in the pressure-sensitive adhesive composition is 5 to 350. .
  • the shape of the component (B) includes at least one shape selected from the group consisting of a columnar shape, a cylindrical shape, a weight shape, a fiber shape, and an oblate shape, according to the above [1] or [2] Adhesive composition.
  • the component constituting the component (B) includes one or more components selected from the group consisting of carbon nanomaterials, boehmite, aluminum hydroxide, and diaspore Item 2.
  • the pressure-sensitive adhesive composition according to item 1.
  • Item 2 The pressure-sensitive adhesive composition according to item 1.
  • [6] The pressure-sensitive adhesive composition according to any one of [1] to [5] above, wherein the component (A) comprises a urethane polymer having a polyoxyalkylene structure.
  • C tackifier resin
  • the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a good adhesive force and has excellent punching workability.
  • production of the oozing-out of an adhesive layer with respect to the base material or adherend of an adhesive sheet in a cut surface can be suppressed.
  • mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically measured based on the method described in the examples. It is the value.
  • the resin component means a polymer having a mass average molecular weight (Mw) of 10,000 or more (however, the filler (B) is not included in the resin component).
  • (meth) acrylate” is used as a term indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms.
  • the “active ingredient” in the pressure-sensitive adhesive composition means a component excluding the dilution solvent contained in the pressure-sensitive adhesive composition, and specifically includes the following components (A) to (F), (A) The resin component other than a component and other additives are pointed out.
  • the pressure-sensitive adhesive composition of the present invention contains a urethane-based polymer (A) and a filler (B). From the viewpoint of developing higher pressure-sensitive physical properties, a tackifier resin (C), a crosslinking agent (D), and a curing agent are further included. It is preferable that 1 or more types chosen from a promoter (E) and a crosslinking adjuvant (F) are included.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention may contain a resin component other than the component (A) and other additives other than those described above as long as the effects are not impaired.
  • each component contained in the pressure-sensitive adhesive composition of one embodiment of the present invention will be described.
  • urethane polymer used in the present invention is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of a main chain and a side chain.
  • polyol (a1) A chain extension reaction using a chain extender (a3) is further performed on the urethane prepolymer ( ⁇ ) obtained by reacting the polyisocyanate compound (a2) with the urethane prepolymer ( ⁇ ).
  • Examples thereof include urethane polymer ( ⁇ ) obtained.
  • the component (A) may be used alone or in combination of two or more.
  • polyol (a1) examples include polyol compounds such as alkylene diols, polyether type polyols, polyester type polyols, and polycarbonate type polyols, but are not particularly limited as long as they are polyols. May be a triol.
  • diols are preferable from the viewpoints of availability, reactivity, and the like.
  • diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol; ethylene Alkylene glycols such as glycol, propylene glycol, diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxybutylene glycol And the like.
  • alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol
  • these diols individually or in combination of 2 or more types.
  • a glycol having a mass average molecular weight of 1000 to 3000 is preferable from the viewpoint of suppressing gelation in the reaction.
  • Examples of the polyvalent isocyanate compound (a2) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxy
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca.
  • HMDI hexamethylene diisocyanate
  • pentamethylene diisocyanate 1,2-propylene diisocyanate
  • 2,3-butylene diisocyanate 1,3-butylene diisocyanate
  • dodeca examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.
  • IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • polyisocyanate compounds (a2) are a trimethylolpropane adduct type modified product of the above polyisocyanate, a burette type modified product reacted with water, and an isocyanurate type modified product containing an isocyanurate ring. Also good.
  • polyisocyanate compounds (a2) 4,4′-diphenylmethane diisocyanate (MDI) and 2,4-tolylene diisocyanate (2,4-TDI) are used from the viewpoint of obtaining a urethane polymer having excellent adhesive properties.
  • 2,6-tolylene diisocyanate (2,6-TDI) hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) and their modified products
  • HMDI hexamethylene diisocyanate
  • IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
  • One or more selected are preferable, and one or more selected from HMDI, IPDI, and modified products thereof are more preferable from the viewpoint of weather resistance.
  • the chain extender (a3) is preferably a compound having two functional groups selected from a hydroxyl group and an amino group, or a compound having three or more functional groups selected from a hydroxyl group and an amino group.
  • the compound having two functional groups selected from a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
  • aliphatic diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
  • alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
  • Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
  • Examples of bisphenol include bisphenol A and the like.
  • Examples of the aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
  • Examples of the compound having three or more functional groups selected from a hydroxyl group and an amino group include, for example, polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1-amino-2,3-propanediol, Examples thereof include amino alcohols such as methylamino-2,3-propanediol and N- (2-hydroxypropylethanolamine), ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine, and the like.
  • polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1-amino-2,3-propanediol
  • amino alcohols such as methylamino-2,3-propanediol and N- (2-hydroxypropylethanolamine
  • the method for synthesizing the urethane-based prepolymer ( ⁇ ) is not particularly limited.
  • a polyol (a1) and a polyvalent isocyanate compound (a2), a catalyst added as necessary, and a solvent are charged into a reactor.
  • the catalyst to be used is not particularly limited, and examples thereof include tertiary amine compounds and organometallic compounds.
  • the molar ratio of NCO group to OH group is preferably 1.1 to 3.0, more preferably The reaction is preferably carried out so as to be 1.2 to 2.5.
  • the isocyanate group content (NCO%) in the urethane-based prepolymer ( ⁇ ) to be obtained is preferably 0.5 to 12% by mass, more preferably 1 to 1% in a value measured according to JIS K 1603. 4% by mass.
  • the method for synthesizing the urethane polymer ( ⁇ ) obtained by further subjecting the urethane prepolymer ( ⁇ ) to a chain extension reaction using a chain extender (a3) is not particularly limited.
  • the method is mentioned.
  • a method in which a solution obtained by diluting a urethane-based prepolymer ( ⁇ ) with a solvent is charged into a reactor, and a predetermined amount of a chain extender is charged into the reactor in a batch to cause a reaction.
  • a terminal terminator such as a compound having only one active hydrogen capable of reacting with an isocyanate group or a compound having only one amino group may be used.
  • the compound having only one active hydrogen capable of reacting with an isocyanate group include monool compounds such as methanol and ethanol.
  • the compound having only one amino group include diethylamine and morpholine.
  • silyl group-containing urethane polymer In this invention, you may contain a silyl group containing urethane type polymer as (A) component.
  • the silyl group-containing urethane polymer has at least one of a urethane bond and a urea bond in at least one of a main chain and a side chain, and is represented by the following general formula (1) at both ends of the main chain.
  • a polymer having a decomposable silyl group is preferred.
  • X 1 and X 2 each independently represent a hydroxy group or an unsubstituted or substituted alkoxy group.
  • R 1 represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.
  • the number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 1, from the viewpoint of hydrolytic dehydration condensation reactivity. 6, more preferably 1 to 3, and still more preferably 1 to 2.
  • the number of carbon atoms of the alkyl group represented by R 1 is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 1, from the viewpoint of the hydrolytic dehydration condensation reactivity. 3, more preferably 1 to 2.
  • carbon number of the above-mentioned alkoxy group and alkyl group does not include the carbon number of the substituent which these groups may have.
  • the alkoxy group or alkyl group selected as X 1 , X 2 , or R 1 has a substituent
  • examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, and an amino group. .
  • FIG. 2A shows a synthesis example of the silyl group-containing urethane polymer 30.
  • a urethane prepolymer 10 having isocyanate groups 14a and 14b is prepared at the terminal or side chain (not shown) of the main chain 12 of the polymer.
  • the urethane prepolymer 10 is a urethane prepolymer ( ⁇ ) obtained by reacting the polyol (a1) with the polyvalent isocyanate compound (a2), and the synthesis method is also as described above.
  • an active hydrogen group 22 that can react with the isocyanate groups 14a and 14b of the urethane-based prepolymer 10 is present at one end of the main chain 26 of the molecule, and the above-mentioned general A silylating agent 20 having a hydrolyzable silyl group 24 represented by the formula (1) is prepared.
  • FIG. 2 shows a case where X 1 and X 2 in the general formula (1) are methoxy groups and R 1 is a methyl group.
  • the silyl group containing urethane type polymer 30 is compoundable by making it react at 80 degreeC for 1 hour, for example in nitrogen atmosphere. The reaction is preferably carried out until the disappearance of the isocyanate group absorption peak (2265 cm ⁇ 1 ) measured by infrared spectroscopy (IR) is confirmed.
  • the silyl group-containing urethane polymer 30 ′′ is cured by a crosslinking reaction via hydrolysis of the hydrolyzable silyl group represented by the general formula (1). It is a so-called moisture-curing polymer having a dimensional network structure.
  • silyl group containing urethane type polymer which has a predetermined silyl group only in the both ends of a principal chain
  • the terminal silyl group-containing urethane polymer having a hydrolyzable silyl group represented by the general formula (1) may be used at the end of the side chain.
  • a silyl group-containing urethane polymer may be synthesized by reacting an silylating agent having an isocyanate group with a polymer having an active hydrogen group.
  • the active hydrogen in the urethane bond or urea bond introduced into the main chain or side chain may be substituted with an organic group as shown below. Therefore, allophanate bonds are also included in the category of urethane bonds, and burette bonds are also included in the category of urea bonds.
  • terminal portions 32a and 32b of the silyl group-containing urethane polymer shown in FIG. 2A are represented by the following general formulas (2) to (8) (terminal portions -A to G). It preferably has a structure, and more preferably has a structure represented by the following general formula (2).
  • X 1 , X 2 and R 1 are the same as those in the general formula (1).
  • R 2 and R 3 each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and the alkyl group has Preferably, it is 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, and still more preferably 1 to 3.
  • carbon number of said alkyl group does not include carbon number of the substituent which the said alkyl group may have.
  • examples of the substituent include a halogen atom, a cyano group, and a nitro group. Is mentioned.
  • A represents an alkylene group, and the alkylene group preferably has 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6.
  • B represents an organic group having 1 to 20 carbon atoms.
  • Examples of such an organic group include unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms, A substituted or substituted alkylamino group having 1 to 20 carbon atoms, an unsubstituted or substituted arylamino group having 6 to 20 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, no Substituted or substituted aryloxy group having 6 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted or substituted heterocyclic ring having 2 to 20 carbon atoms Group, unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms, unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms, unsubstituted or substituted carbon group having 3 to 2 carbon atoms It includes cycloalkyl groups such as of.
  • the number of carbon atoms in each of the above groups does not include the number of carbon atoms of the substituent that these groups may have.
  • examples of the substituent include a halogen atom, a cyano group, and a nitro group.
  • the silyl group-containing urethane polymer used in the present invention is a polyoxyalkylene as a main chain from the viewpoint of imparting appropriate flexibility to the obtained pressure-sensitive adhesive composition and improving adhesion to an adherend.
  • a silyl group-containing urethane polymer having a structure is preferable.
  • polyoxyalkylene polyoxypropylene and polyoxyethylene are preferable from the above viewpoint, and polyoxypropylene is more preferable.
  • the silyl group-containing urethane polymer having such a structure the crosslinking density between the polymers is adjusted to a suitable range, and both the adhesive force and the cohesive force in the adhesive composition after crosslinking can be improved. it can.
  • the weight average molecular weight (Mw) of the component (A) is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, still more preferably 20,000 to 70,000.
  • Mw of the component (A) is 10,000 or more, the molecular structure can be prevented from becoming too dense, and the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive composition can be improved. Moreover, the fall of workability (coating property) by the viscosity of the said adhesive composition becoming low too much can be avoided.
  • Mw of (A) component is 200,000 or less, the workability (applicability
  • the content of the component (A) with respect to the total amount (100% by mass) of the active ingredient in the pressure-sensitive adhesive composition of one embodiment of the present invention is preferably 15 to from the viewpoint of improving the pressure-sensitive adhesive properties of the resulting pressure-sensitive adhesive composition. It is 85% by mass, more preferably 20 to 80% by mass, still more preferably 25 to 75% by mass, and still more preferably 30 to 70% by mass.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention is a resin component other than the component (A) (a polymer having a mass average molecular weight (Mw) of 10,000 or more) within a range not impairing the effects of the present invention. One or more of these may be contained.
  • the component (A) with respect to the total amount of the resin component in the pressure-sensitive adhesive composition (total amount (100% by mass) of the resin component other than the component (A) and the component (A))
  • the content of is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 95 to 100% by mass. is there.
  • the resin component other than the component (A) is contained, the resin component other than the component (A) is preferably blended so that the content of the component (A) is within the above range.
  • content of the resin component containing (A) component with respect to the whole quantity (100 mass%) of the active ingredient in an adhesive composition is the adhesive physical property of the obtained adhesive composition. From the viewpoint of improving the quality, it is preferably 30 to 85% by mass, more preferably 35 to 80% by mass, still more preferably 40 to 75% by mass, and still more preferably 43 to 70% by mass.
  • an acrylic polymer is preferable from the viewpoint of adjusting the adhesive physical properties.
  • an acrylic polymer having a structural unit (p1) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms is preferable, and together with the structural unit (p1), further containing a functional group (
  • An acrylic copolymer having a structural unit (p2) derived from (meth) acrylate is more preferred.
  • the said acrylic polymer may have the structural unit (p3) derived from monomers other than the above in addition to the structural units (p1) and (p2).
  • alkyl (meth) acrylate constituting the structural unit (p1) examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like. In addition, you may use these alkyl (meth) acrylates individually or in combination of 2 or more types.
  • alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is preferable, and butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable.
  • said functional group containing (meth) acrylate which comprises a structural unit (p2), a hydroxyl group containing monomer, a carboxy group containing monomer, an epoxy group containing monomer, an amino group containing monomer, a cyano group containing monomer, keto group containing, for example And monomers, monomers having a nitrogen atom-containing ring, and alkoxysilyl group-containing monomers.
  • a hydroxyl group-containing monomer, a carboxy group-containing monomer, and a monomer having a nitrogen atom-containing ring are preferable.
  • hydroxy-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) )
  • hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • carboxy group-containing monomer examples include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine and the like can be mentioned.
  • Examples of other monomers constituting the structural unit (p3) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and dicyclopentenyloxyethyl.
  • Examples include (meth) acrylates having a cyclic structure such as acrylate and imide acrylate, acrylonitrile, and styrene. In addition, you may use these monomers individually or in combination of 2 or more types.
  • the content of the structural unit (p1) is preferably 50 to 99% by mass, more preferably 60 to 97% by mass, and still more preferably 70 to 95% by mass with respect to all the structural units (100% by mass) of the acrylic polymer. %, More preferably 75 to 92% by mass.
  • the content of the structural unit (p2) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, and still more preferably 5 to 30% by weight with respect to all the structural units (100% by weight) of the acrylic polymer. %, More preferably 8 to 25% by mass.
  • the content of the structural unit (p3) is preferably 0 to 20% by weight, more preferably 0 to 15% by weight, and still more preferably 0 to 10% by weight with respect to the total structural unit (100% by weight) of the acrylic polymer. %, More preferably 0 to 5% by mass.
  • the mass average molecular weight (Mw) of the acrylic polymer is preferably 50,000 to 1,500,000, more preferably 150,000 to 1,200,000, still more preferably 300,000 to 1,100,000.
  • the form of copolymerization of the acrylic polymer is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the content of the acrylic polymer is preferably 0 to 100 parts by mass, more preferably 0 to 70 parts by mass, still more preferably 0 to 60 parts by mass, and still more preferably 0 to 100 parts by mass with respect to 100 parts by mass of the component (A).
  • the amount is 25 parts by mass, more preferably 0 to 8 parts by mass.
  • the filler (B) used in the present invention is not particularly limited as long as it can be dispersed in the pressure-sensitive adhesive composition so as to have an average aspect ratio of 5 to 350.
  • the “aspect ratio” is the ratio of the long side length (H) to the short side length (L) of the target filler (B), that is, “long side length (H) / It is a value calculated from the “short side length (L)”.
  • the “average aspect ratio” is an average value of the “aspect ratio” calculated for 10 target fillers.
  • the “long side length (H)” of the filler means the length in the height direction (longitudinal direction) of the filler.
  • the “short side length (L)” of the filler is a cross section having the maximum area among the cut surfaces perpendicular to the height direction (longitudinal direction) of the filler, and the cross section is a circle or an ellipse. If the cross section is a polygon, it means the length of the longest side among the sides of the polygon.
  • the values of “long side length (H)”, “short side length (L)”, and “aspect ratio” of the specific filler (B) are measured by the method described in the examples. Means the calculated value.
  • the shape of the filler (B) preferably includes one shape selected from the group consisting of a columnar shape, a cylindrical shape, a weight shape, a fiber shape, and an oblate shape. That is, the shape of the filler (B) may have only one type selected from the above group, or may be a combination of two or more types selected from the above group.
  • . 3 (a) to 3 (k) are diagrams showing an example of the shape of the filler (B) used in the pressure-sensitive adhesive composition of the present invention. Hereinafter, “long side length (H)” and “short side length (L)” in each shape will be described.
  • the length in the height direction of the filler corresponds to the “long side length (H)”, and the length of the cut surface perpendicular to the height direction.
  • the diameter (or major axis) of the cross section (the hatched portion in FIG. 3A) having the largest area corresponds to the “short side length (L)”.
  • the length in the height direction of the filler corresponds to the “long side length (H)”, and the cutting is perpendicular to the height direction.
  • the length of the longest side of the polygonal side of the cross section corresponds to the “long side length (H)
  • the “short side length (L)” refers to the length of one side of the square if the polygon is a square, and the two parallel sets of the rectangle if the polygon is a rectangle.
  • the length of the longer side is indicated (the same applies to the following description).
  • the “columnar shape” means a shape that extends in a predetermined plane (for example, an XY plane, a YZ plane, a ZX plane, etc.) and has a height in a direction orthogonal to the predetermined plane.
  • a predetermined plane for example, an XY plane, a YZ plane, a ZX plane, etc.
  • the length in the longest direction among the X direction, the Y direction, and the Z direction is defined as “long side length (H)”, and the area of the cut surface orthogonal to the direction is the largest.
  • the length of the remaining two directions is the “short side length (L)”.
  • L short side length
  • the solid has an extension in the XY plane and has a height in a direction (Z direction) orthogonal to the XY plane.
  • the length in the Z direction is longer than the lengths in both the X direction and the Y direction, so the length in the Z direction corresponds to the “long side length (H)”.
  • the longer length of the X direction and the Y direction is “the length of the short side”. (L) ".
  • the ZX plane has a spread, and has a height in a direction (Y direction) orthogonal to the ZX plane.
  • the length in the Z direction corresponds to the “long side length (H)”.
  • the longer length in the X direction and the Y direction corresponds to “short side length (L)”.
  • the “columnar shape” referred to in the present invention includes a solid having a hemispherical shape at least at one end of the column as shown in FIG.
  • the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”
  • this height direction (Z) The diameter (or major axis) of the cross section (the hatched portion in FIG. 3C) having the largest area among the cut surfaces orthogonal to the (direction) corresponds to the “short side length (L)”.
  • the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height direction (Z
  • the diameter (or major axis) of the outermost circle of the cross section (the hatched portion in FIG. 3D) having the largest area among the cut surfaces orthogonal to the (direction) corresponds to the “short side length (L)”.
  • the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height.
  • the length of the longest side of the outermost polygonal side of the cross section (hatched portion in FIG. 3E) having the largest area among the cut surfaces orthogonal to the direction (Z direction) is “the length of the short side. (L) ".
  • the “cylindrical shape” means that at least one end in the longitudinal direction is open with respect to the columnar shape described above, and the inside is hollow.
  • the shape of the opening at the opened end is a polygon such as a circle, an ellipse, a hexagon or a quadrangle, and may be the same as or different from the shape of the bottom of the column.
  • the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height direction (Z
  • the diameter (or major axis) of the cross section (the hatched portion in FIG. 3 (f)) having the largest area among the cut surfaces orthogonal to the (direction) corresponds to the “short side length (L)”.
  • the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”.
  • the length of the longest side of the polygonal side of the cross section (hatched portion in FIG. 3G) having the largest area among the cut planes orthogonal to the length corresponds to the “short side length (L)”.
  • the term “conical” means that a predetermined plane (for example, an XY plane, a YZ plane, a ZX plane, etc.) extends and has a height in a direction perpendicular to the predetermined plane. It means various shapes whose cross-sectional area becomes gradually smaller toward. Therefore, in the present invention, the “conical shape” includes not only the shape in which the top portion is a point as shown in FIGS. 3F and 3G but also the top portion as shown in FIG. , An elliptical shape, or a frustum shape that is polygonal. In the frustum filler as shown in FIG.
  • the length of the filler in the height direction (Z direction) corresponds to the “long side length (H)”.
  • the diameter (or major axis) of the cross section (the hatched portion in FIG. 3 (h)) having the largest area among the cut surfaces orthogonal to the (Z direction) or the length of the largest side of the polygonal side is “short”. This corresponds to the “length of side (L)”.
  • the length in the longitudinal direction (Z direction) of the filler corresponds to “long side length (H)”, and this longitudinal direction (Z direction).
  • the “fibrous” is a shape extending in the longitudinal direction, and the length of the primary particles in the extending direction is larger than the length in the direction perpendicular to the extending direction. means.
  • the length in the longitudinal direction (Z direction) of the filler corresponds to the “long side length (H)”, and this longitudinal direction (Z direction).
  • the diameter (or major axis) of the cross section (the hatched portion in FIG. 4 (j)) having the largest area among the cut planes orthogonal to the “corresponding to the length of the short side (L)”.
  • “oblate shape” is a rotating body obtained when an ellipse is rotated about its short axis as a rotation axis, and the length in the longitudinal direction of the primary particles of the filler (long side length).
  • the shape of the filler before dispersion is not particularly limited as long as it is a filler that can be dispersed in the pressure-sensitive adhesive composition so as to have an average aspect ratio of 5 to 350, but a columnar filler, a cylindrical filler
  • a columnar filler Preferably, one or more selected from the group consisting of spindle-shaped fillers, fibrous fillers, and oblate fillers, and one or more selected from the group consisting of columnar fillers, cylindrical fillers, and fibrous fillers Is more preferable.
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing fillers of these shapes
  • the fillers easily form a network in the pressure-sensitive adhesive layer, and the fillers are intertwined even after being subjected to a punching process. It is considered that the remaining is difficult to occur, and bleeding of the pressure-sensitive adhesive layer is suppressed, and the punching processability is improved.
  • the adhesive force of an adhesive layer can also be kept favorable by formation of the network of fillers, and adhesive force can be improved depending on the kind of (A) component and the shape of a filler.
  • the average aspect ratio [long side length (H) / short side length (L)] of the filler (B) in the pressure-sensitive adhesive composition of the present invention is 5 to 350, preferably 6 to 350, More preferably, it is 15 to 340, more preferably 25 to 330, still more preferably 35 to 320, still more preferably 50 to 310, still more preferably 60 to 300.
  • the average aspect ratio is less than 5
  • the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is inferior in punching processability. Occurrence of the pressure-sensitive adhesive layer and bleeding of the pressure-sensitive adhesive layer to the substrate or adherend of the pressure-sensitive adhesive sheet are observed on the cut surface. Moreover, the adhesive force of the said adhesive sheet may fall.
  • the average aspect ratio exceeds 350 the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive composition are lowered, which is not preferable.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention may contain a filler having the shape of (l) in FIG. 5, but the “average” aspect ratio of the filler contained in the pressure-sensitive adhesive composition is 5 to 350.
  • the average of the length (H) of the long side of the filler (B) in the pressure-sensitive adhesive composition is preferably 0.05 to 2000 ⁇ m, more preferably 0.05 to 1000 ⁇ m, and more preferably Is 0.05 to 500 ⁇ m, more preferably 0.05 to 100 ⁇ m, and still more preferably 0.07 to 20 ⁇ m.
  • the average of the short side length (L) of the filler (B) in the pressure-sensitive adhesive composition is preferably 1.0 to 2000 nm, more preferably 2.0 to 1000 nm. More preferably, it is 3.0 to 500 nm, still more preferably 5.0 to 100 nm, and still more preferably 7.0 to 50 nm.
  • the average aspect ratio [long side length (H) / short side length (L)] of the filler (B) before dispersion used in one embodiment of the present invention is preferably 5 to 450, more preferably. Is 6 to 420, more preferably 15 to 400, more preferably 25 to 370, still more preferably 35 to 350, still more preferably 50 to 330, and still more preferably 60 to 310.
  • the average of the long side length (H) of the filler (B) before dispersion used in one embodiment of the present invention is preferably 0.05 to 2500 ⁇ m, more preferably 0.05 to 1800 ⁇ m, more preferably 0.05. It is ⁇ 800 ⁇ m, more preferably 0.05 to 150 ⁇ m, still more preferably 0.07 to 30 ⁇ m.
  • the average length (L) of the short side of the filler (B) before dispersion used in one embodiment of the present invention is preferably 1.0 to 2000 nm, more preferably 2.0 to 1000 nm, and more preferably 3.0. It is ⁇ 500 nm, more preferably 5.0 to 100 nm, and still more preferably 7.0 to 50 nm.
  • the “average aspect ratio of the filler (B) in the pressure-sensitive adhesive composition” means the filler (B) dispersed in the pressure-sensitive adhesive composition containing the urethane-based polymer (A). It is distinguished from the average aspect ratio of the filler (B) before dispersion (before mixing with the urethane polymer).
  • the component constituting the filler (B) is not particularly limited, but from the viewpoint of improving the processability of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition and maintaining good adhesive strength, the carbon nanomaterial, It is preferable to include at least one component selected from the group consisting of boehmite, aluminum hydroxide, and diaspore, and more preferable to include at least one of a carbon nanomaterial and boehmite.
  • the carbon nanomaterial is composed of a material including a graphite sheet having a six-membered ring arrangement as a main structure, but the graphite structure may contain elements other than carbon such as boron and nitrogen.
  • the material may be in a form including another substance, and further, the carbon nanomaterial may be modified with another conductive substance.
  • the carbon nanotube which is a cylindrical carbon nanomaterial.
  • the carbon nanotube is a cylindrical carbon polyhedron having a structure in which a graphite (graphite) sheet mainly having a carbon 6-membered ring structure is closed in a cylindrical shape.
  • the carbon nanotube includes a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape, a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape, and a three-layered graphite sheet
  • a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape
  • a three-layered graphite sheet There are multi-walled carbon nanotubes having a multi-layered structure concentrically closed as described above, and any two or more of these can be used in combination.
  • a carbon nanomaterial having an average aspect ratio before dispersion of 450 or less should be used.
  • the average aspect ratio before dispersion of the carbon nanomaterial is preferably 6 to 420, more preferably 15 to 400, more preferably 25 to 370, still more preferably 35 to 350, still more preferably 50 to 330, and still more.
  • it is 60-310.
  • Boehmite is one of the naturally occurring alumina hydrates and is an alumina compound represented by AlO (OH) .H 2 O.
  • Diaspore is one of naturally occurring minerals and is an alumina-based compound represented by AlO (OH). -
  • the said carbon nanomaterial is a form of a dispersion liquid from a viewpoint of adjusting the average aspect-ratio of the filler in an adhesive composition so that it may become the said range, It is preferable to mix
  • blend in a pressure-sensitive adhesive composition containing a urethane polymer in the form of a dispersion containing a carbon nanomaterial it can be mixed in a low-viscosity state. This is because the punching processability is improved by being formed.
  • Examples of the solvent for the dispersion include water and an organic solvent, and an organic solvent is preferable.
  • Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
  • Examples of the method for preparing the dispersion containing the carbon nanomaterial include a method in which the filler (B) is added to the solvent, and the filler (B) is dispersed in the solvent by applying vibration by ultrasonic waves or the like. Can be mentioned.
  • the solid content concentration of the dispersion containing the carbon nanomaterial is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 3% by mass.
  • the content of the component (B) with respect to the total amount (100% by mass) of the active ingredients in the pressure-sensitive adhesive composition is preferably 0.2 to 70.0% by mass, more preferably 0.3 to 50.0% by mass, More preferably 0.4 to 15.0% by mass, still more preferably 0.5 to 10.0% by mass, still more preferably 0.7 to 6.0% by mass, and still more preferably 2.0 to 5.%. 5% by mass. If content of (B) component is 0.2 mass% or more, the punching property of the adhesive sheet using the obtained adhesive composition can be improved. On the other hand, if content of (B) component is 70.0 mass% or less, the adhesive physical property of the obtained adhesive composition can be kept favorable.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention preferably further contains a tackifier resin (C).
  • the tackifier resin (C) used in the present invention means a resin having adhesiveness that can be mixed with the urethane polymer (A).
  • the mass average molecular weight (Mw) of the tackifying resin is usually less than 10,000, and is distinguished from the resin component containing the component (A).
  • the mass average molecular weight (Mw) of the tackifier resin (C) is preferably 400 to 4000, more preferably 800 to 1500, from the viewpoint of improving the adhesive properties of the resulting adhesive composition.
  • the softening point of the tackifying resin (C) is preferably 110 ° C. or more, more preferably 110 to 180 ° C., more preferably from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B).
  • the temperature is preferably 115 to 175 ° C, more preferably 120 to 170 ° C.
  • the “softening point” of the tackifier resin means a value measured in accordance with JIS K2531.
  • tackifier resin (C) examples include rosin resins such as rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins and aromatic modified terpene resins.
  • Terpene resins such as terpene phenol resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; and C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha.
  • C5 petroleum resin obtained by polymerization and hydrogenated resin of this C5 petroleum resin C9 fraction such as indene, vinyltoluene, ⁇ - or ⁇ -methylstyrene produced by thermal decomposition of petroleum naphtha is copolymerized Examples thereof include C9 petroleum resin obtained and hydrogenated resin of this C9 petroleum resin.
  • tackifying resin (C) individually or in combination of 2 or more types from which a softening point and a structure differ.
  • terpene phenol resins are preferable and hydrogenated terpene phenol resins are more preferable from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B).
  • the terpene phenolic resin used in the present invention is a copolymer of terpene resin and phenol, which is an essential oil component obtained from natural products such as pine crabs and orange peels, and is at least part of the copolymer. Alternatively, a fully hydrogenated hydrogenated terpene phenol resin is also included.
  • the hydrogenation ratio of the hydrogenated terpene phenol resin is 100 mol% of the unsaturated bond of the terpene phenol resin from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B). On the other hand, it is preferably 50 mol% or more, more preferably 65 mol% or more, and still more preferably 80 mol% or more.
  • the content of the terpene phenol tackifying resin in the component (C) is the total amount of the component (C) (100% by mass) from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B). ) Is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the content of the component (C) in the pressure-sensitive adhesive composition is the component (A) from the viewpoint of improving the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition containing the components (A) and (B).
  • the amount is preferably 30 to 180 parts by mass, more preferably 40 to 170 parts by mass, more preferably 50 to 160 parts by mass, still more preferably 70 to 150 parts by mass, and still more preferably 85 to 130 parts by mass with respect to 100 parts by mass. Part.
  • the content of the component (C) with respect to the total amount (100% by mass) of the active ingredients in the pressure-sensitive adhesive composition is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and still more preferably It is 20 to 60% by mass, more preferably 25 to 55% by mass.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention preferably further contains a crosslinking agent (D) from the viewpoint of expressing higher pressure-sensitive adhesive properties.
  • a crosslinking agent (D) include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, amine crosslinking agents, amino resin crosslinking agents, and the like. These crosslinking agents may be used alone or in combination of two or more. Among these, the isocyanate type crosslinking agent is preferable from the viewpoint of further improving the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive composition.
  • isocyanate-based crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanate compounds such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate Is mentioned.
  • the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the content of the crosslinking agent (D) is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Part by mass.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention contains a silyl group-containing urethane polymer as the component (A), it promotes the crosslinking reaction between the silyl groups of the silyl group-containing urethane polymer, From the viewpoint of further improving the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition, it is preferable to further contain a curing accelerator (E).
  • This hardening accelerator (E) functions as a catalyst.
  • the curing accelerator (E) the pressure-sensitive adhesive composition after crosslinking is facilitated by accelerating the crosslinking reaction between the silyl groups of the silyl group-containing urethane polymer contained as the component (A) and easily controlling the crosslinking density. From the viewpoint of further improving the physical properties of the adhesive, it is preferably at least one selected from the group consisting of an aluminum catalyst, a titanium catalyst, a zirconium catalyst, and a boron trifluoride catalyst.
  • aluminum catalyst aluminum alkoxide, aluminum chelate, and aluminum chloride (III) are preferable.
  • titanium-based catalyst titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferable.
  • zirconium-based catalyst zirconium alkoxide, zirconium chelate, and zirconium (IV) chloride are preferable.
  • boron trifluoride-based catalyst an amine complex of boron trifluoride such as boron trifluoride monoethylamine complex or an alcohol complex is preferable.
  • the content of the curing accelerator (E) is preferably 0.001 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the silyl group-containing urethane polymer contained as the component (A) from the viewpoint of catalytic action. Is 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass.
  • ⁇ (F) component crosslinking aid>
  • the adhesive composition of 1 aspect of this invention contains a silyl group containing urethane type polymer as (A) component, it combines a crosslinking adjuvant (F) with said hardening accelerator (E). It is preferable to contain.
  • the crosslinking aid (F) an amino group-containing alkoxysilane is preferable. Examples of the amino group-containing alkoxysilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl).
  • the content of the crosslinking aid (F) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 6 parts by mass with respect to 100 parts by mass of the silyl group-containing urethane polymer contained as the component (A). Part, more preferably 0.1 to 3 parts by weight.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention may contain other additives depending on the use of the pressure-sensitive adhesive sheet as long as the effects of the present invention are not impaired.
  • additives include ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, and dyes.
  • the amount of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of component (A). is there.
  • the adhesive sheet of this invention has an adhesive layer formed from the above-mentioned adhesive composition, the structure will not be specifically limited, The structure where the adhesive layer was pinched
  • FIG. 1 is a cross-sectional view of an adhesive sheet showing an example of the configuration of the adhesive sheet of the present invention.
  • a pressure-sensitive adhesive sheet with a substrate 1a having a pressure-sensitive adhesive layer 3 on one surface of the substrate 2 is used. Is mentioned.
  • FIG. 1B the pressure-sensitive adhesive sheet 1b with the base material having the pressure-sensitive adhesive layer 3 and the pressure-sensitive adhesive layer 3 ′ on both surfaces of the base material 2, respectively, and FIG.
  • Examples thereof include a pressure-sensitive adhesive sheet 1c with a base material in which a release sheet 4 is further laminated on the pressure-sensitive adhesive layer 3 formed on one side of the base material 2.
  • a release sheet 4 is further laminated on the pressure-sensitive adhesive layer 3 formed on one side of the base material 2.
  • a baseless adhesive sheet 1d having a structure in which the adhesive layer 3 is sandwiched between the release sheet 4 and another release sheet 4 ′ without using a base material.
  • the material of the release sheets 4 and 4 ′ of the pressure-sensitive adhesive sheet 1d may be the same or different, but may be a material adjusted so that the release force between the release sheet 4 and the release sheet 4 ′ is different. preferable.
  • the adhesive sheet etc. which have the structure which wound what provided the adhesive layer on the single side
  • the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately adjusted depending on the application and the like, but is preferably 0.5 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and still more preferably 3 to 40 ⁇ m. is there. When the thickness of the pressure-sensitive adhesive layer is 0.5 ⁇ m or more, good adhesive force can be expressed regardless of the type of adherend.
  • the thickness of the pressure-sensitive adhesive layer is 100 ⁇ m or less, there are advantages in terms of productivity, and when the sheet is used as a wound body, winding slippage due to deformation of the pressure-sensitive adhesive layer, or pressure-sensitive adhesive Since the protrusion from the edge part of a layer can be suppressed, it can become a favorable adhesive sheet also in terms of handleability.
  • the base material of the pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately selected according to the purpose of use of the pressure-sensitive adhesive sheet, but may be an insulating base material including an insulating material, or a conductive material such as metal. It may be a conductive substrate containing
  • the insulating base material examples include various types of paper such as fine paper, art paper, coated paper, glassine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; Material: Polyolefin resin such as polyethylene resin and polypropylene resin, polybutylene terephthalate resin, polyester resin such as polyethylene terephthalate resin, plastic film or sheet formed from acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc .; these resins A plastic film or sheet formed from a mixture of the above; a multilayer plastic film or sheet having a laminate of these plastic films or sheets.
  • a thermoplastic resin such as polyethylene on these paper base materials
  • Material Polyolefin resin such as polyethylene resin and polypropylene resin, polybutylene terephthalate resin, polyester resin such as polyethylene terephthalate resin, plastic film or sheet formed from acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc .;
  • the base material such as a plastic film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as longitudinal or lateral. Further, the base material used in the present invention may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant and the like.
  • the conductive substrate for example, a metal foil, a film or sheet obtained by laminating a metal foil with a resin or the like that forms the above-described insulating substrate, a film obtained by performing metal vapor deposition on the surface of the above-described insulating substrate, or Examples thereof include a sheet, a film or sheet obtained by performing antistatic treatment on the surface of the above-described insulating substrate, and a sheet in which a metal wire is knitted in a mesh shape.
  • a metal used for an electroconductive base material aluminum, copper, silver, gold
  • the thickness of the substrate is not particularly limited, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoint of ease of handling.
  • the surface of the base material is subjected to a surface treatment such as an oxidation method or an unevenness method as necessary.
  • the oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • a corona discharge treatment method for example, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • corrugated method For example, a sandblasting method, a solvent processing method, etc. are mentioned.
  • These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the pressure-sensitive adhesive layer and operability.
  • primer treatment can also be performed.
  • the adhesive sheet of 1 aspect of this invention may be an adhesive sheet which does not have a base material as above-mentioned.
  • a release sheet is used instead of the above-described base material, and the release sheet is removed when the pressure-sensitive adhesive sheet is used.
  • a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used.
  • Examples include a release sheet coated on a release sheet substrate.
  • the release sheet base material include paper base materials such as glassine paper, coated paper, and high-quality paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials, or polyethylene terephthalate resin, polybutylene terephthalate.
  • plastic films such as resins, polyester resin films such as polyethylene naphthalate resin, and polyolefin resin films such as polypropylene resin and polyethylene resin.
  • the release agent examples include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release sheet is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • Method for producing adhesive sheet There is no restriction
  • Examples of the organic solvent added to the pressure-sensitive adhesive composition include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, Examples thereof include dimethyl sulfoxide.
  • combination of (A) component, the organic solvent used when (B) component was prepared in the form of the dispersion liquid may be used as it is, and this adhesive You may add 1 or more types of organic solvents other than the organic solvent used at the time of the synthesis
  • the solid content concentration of the pressure-sensitive adhesive composition solution is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass. If the said solid content concentration is 5 mass% or more, the usage-amount of a solvent is enough, and when apply
  • Examples of the method for applying the pressure-sensitive adhesive composition onto the substrate or release sheet include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, and die coating. Method, gravure coating method and the like.
  • the pressure-sensitive adhesive sheet 1a having the pressure-sensitive adhesive layer 3 on one side of the base material 2 as shown in FIG. 1A is obtained by, for example, directly applying the above-mentioned pressure-sensitive adhesive composition solution on one side of the base material 2. It can be produced by forming the pressure-sensitive adhesive layer 3. Moreover, the adhesive sheet 1a can also be produced by removing the release sheet 4 after producing the adhesive sheet 1c of FIG.
  • the pressure-sensitive adhesive sheet 1b having the pressure-sensitive adhesive layers 3 and 3 ′ on both surfaces of the base material 2 as shown in FIG. 1B is obtained by directly applying a pressure-sensitive adhesive composition solution on both surfaces of the base material 2, for example. 3, 3 ′ can be formed.
  • the pressure-sensitive adhesive sheet 1b can be prepared by preparing two sheets in which a pressure-sensitive adhesive layer is previously formed on a release sheet and bonding the two pressure-sensitive adhesive layers to both surfaces of the substrate 2. In this case, a pressure-sensitive adhesive layer provided on a release sheet is bonded to one surface of the substrate 2, and a solution of the pressure-sensitive adhesive composition is directly applied to the other surface of the substrate 2. Then, an adhesive layer may be formed and produced.
  • the pressure-sensitive adhesive sheet 1c having the pressure-sensitive adhesive layer 3 and the release sheet 4 in this order on the substrate 2 as shown in FIG. 1C is formed on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet 1a obtained as described above, for example.
  • the release sheet 4 can be laminated.
  • the adhesive layer 3 and the base material 2 which were formed by directly applying the solution of the above-mentioned adhesive composition to the release-treated surface of the release sheet 4 can be produced.
  • a pressure-sensitive adhesive sheet 1d having a configuration in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4 ′ without using a substrate as shown in FIG.
  • the adhesive layer 3 formed by directly applying the solution of the above-mentioned adhesive composition and the release sheet 4 ′ can be bonded to each other. As described above, it is preferable to adjust the release sheet 4 and the release sheet 4 ′ so that the release forces are different.
  • the solution of an adhesive composition on a base material or a peeling sheet and forming a coating film it is preferable to dry-process and remove the solvent contained in a coating film. Further, in order to improve the adhesive strength, after the drying treatment, for example, it was allowed to stand for 7 days to 30 days in an environment of 23 ° C. and 50% RH (relative humidity) to form the adhesive composition. It is preferable to sufficiently crosslink the pressure-sensitive adhesive layer (coating film).
  • the pressure-sensitive adhesive sheet of the present invention has excellent adhesive strength.
  • the adhesive strength of the adhesive sheet according to one embodiment of the present invention in which the thickness of the adhesive layer is 25 ⁇ m is preferably 7.0 N / 25 mm or more, more preferably 10.0 N / 25 mm or more. More preferably, it is 15.0 N / 25 mm or more, and still more preferably 20.0 N / 25 mm or more.
  • the pressure-sensitive adhesive sheet has a structure such as the pressure-sensitive adhesive sheet 1d in FIG. 1 (d)
  • the pressure-sensitive adhesive force when backing a polyethylene terephthalate film with a thickness of 50 ⁇ m is in the above range. It is preferable to adjust to.
  • the adhesive force of said adhesive sheet means the value measured by the method as described in an Example.
  • the processing method of the pressure-sensitive adhesive sheet of the present invention includes a step of punching the pressure-sensitive adhesive sheet of the present invention into a predetermined size. Since the pressure-sensitive adhesive sheet of the present invention is excellent in punching workability, according to the above-described processing method, when the punching process is performed, generation of a blade residue and the substrate or adherend of the pressure-sensitive adhesive sheet on the cut surface On the other hand, it is possible to suppress the occurrence of bleeding of the pressure-sensitive adhesive layer. For this reason, the pressure-sensitive adhesive sheet processing method of the present invention is excellent in productivity, and is particularly suitable as a pressure-sensitive adhesive sheet processing method included in the manufacture of electronic material parts that require precision and downsizing.
  • the pressure-sensitive adhesive sheet attached to the adherend may be subjected to a punching process, or the pressure-sensitive adhesive sheet before the sticking to the adherend may be subjected to a punching process. Good.
  • Synthesis of silyl group-containing urethane polymer (1) Synthesis of silylating agent In a reaction vessel, 100 parts by mass of N-aminoethyl- ⁇ -aminopropylmethyldimethoxysilane and 83.5 parts by mass of methyl acrylate were charged, and 10% at 80 ° C. in a nitrogen atmosphere. The mixture was stirred for a time to obtain a silane compound to be a silylating agent.
  • the silyl group-containing urethane-based polymer used N-aminoethyl- ⁇ -aminopropylmethyldimethoxysilane as a raw material for the silylating agent at the time of synthesis. Therefore, the terminal is represented by the following formula (9). As shown, a bifunctional silyl group has been introduced.
  • Examples 1 to 25, Comparative Examples 1 to 12 (1) Preparation of pressure-sensitive adhesive composition For 100 parts by mass (solid content) of the urethane-based polymers of the types shown in Table 1 and Table 2, fillers of the types and blending amounts (solid content ratio) shown in Table 1 and Table 2, Add tackifier resin and various additives (crosslinking agent, curing accelerator, crosslinking aid), add ethyl acetate as solvent, stir until uniform, and pressure sensitive adhesive composition with a solid content concentration of 55% by mass A solution of was prepared. The average aspect ratio and long side length (H) of the filler (B) dispersed in the pressure-sensitive adhesive composition were as shown in Tables 1 and 2.
  • BA / MA / ACMO / HEA 80.0 / 2.0 / 16.0 / 2.0 (parts by mass), Mw: 600,000, solid content concentration: 33.6% by mass.
  • CNT (1) trade name “NC 7000”, manufactured by Nanosil Co., Ltd., cylindrical multi-walled carbon nanotube shown in FIG. 3D, average aspect ratio (H / L): 150, long side length ( H): 1.5 ⁇ m, short side length (L): 10 nm.
  • CNT (2) trade name “VGCF-X”, manufactured by Showa Denko KK, cylindrical multi-walled carbon nanotube shown in Fig. 3 (d), average aspect ratio (H / L): 200, long side Length (H): 3.0 ⁇ m, short side length (L): 15 nm.
  • Boehmite trade name "CAM 9010", manufactured by Saint-Gobain, fibrous AlO (OH) .H 2 O shown in Fig. 4 (i), average aspect ratio (H / L): 7.2, long side Length (H): 0.09 ⁇ m, short side length (L): 12.5 nm.
  • "Boron nitride” trade name "UHP-2", manufactured by Showa Denko KK, scaly boron nitride shown in Fig. 4 (k), average aspect ratio (H / L): 3.9, long side Length (H): 11.8 ⁇ m, short side length (L): 3.0 ⁇ m.
  • the fillers Of these fillers, only carbon nanotubes were dispersed in ethyl acetate by applying ultrasonic vibration with an ultrasonic cleaner (42 kHz, 125 W) for 1 hour to obtain a solid content concentration of 0.3% by mass. Added as a liquid. About fillers other than a carbon nanotube, the dispersion liquid was not produced but it was added together with the other component directly. Moreover, the compounding quantity of the filler of Table 1 and 2 has shown the quantity of the solid content (filler) in the said dispersion liquid. Moreover, the average aspect-ratio of said filler, the length (H) of a long side, and the length (L) of a short side are the values before dispersion
  • ⁇ Tackifying resin (C)> "YS Polystar NH”: Yasuhara Chemical Co., Ltd., hydrogenated terpene phenol resin (80 mol% or more is hydrogenated in 100 mol% of unsaturated bonds in the molecule), softening point 125 ° C, Mw: 820. “YS Polystar G125”: manufactured by Yashara Chemical Co., Ltd., terpene phenol resin, softening point 125 ° C., Mw: 1080.
  • Crosslinking agent manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HX”, isocyanate-based crosslinking agent (isocyanurate-type modified product of hexamethylene diisocyanate).
  • Crosslinking agent manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HX”, isocyanate-based crosslinking agent (isocyanurate-type modified product of hexamethylene diisocyanate).
  • Crosslinking agent Boron trifluoride monoethylamine complex.
  • Crosslinking aid 3-aminopropyltrimethoxysilane.
  • FIG. 6 is a photograph when the cut surface of each adhesive sheet after cutting the adhesive sheet with scissors is observed with a digital microscope (manufactured by Keyence Corporation, product name “VHX-2000”). 8 is a photograph of a cut surface of the pressure-sensitive adhesive sheet produced in Comparative Example 11, and FIG. In any of the photographs (a) to (c) in FIG. 6, the right side is an adhesive sheet and the left side is a pedestal, and the cut portion is photographed from the base material.
  • the boundary between the base material and the pressure-sensitive adhesive layer is clear, and a state in which a part of the pressure-sensitive adhesive layer oozes out is not seen. It can be seen that the pressure-sensitive adhesive sheet has good punchability.
  • the cut surfaces of the pressure-sensitive adhesive sheets prepared in Comparative Examples 3 and 11 of FIGS. 6B and 6C are such that part of the pressure-sensitive adhesive layer oozes out to the base material portion, and these pressure-sensitive adhesive sheets Shows that the punching processability is inferior.
  • the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has excellent adhesive strength and excellent punching workability. It can be suitably used in applications that require punching.

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Abstract

Provided is an adhesive composition including a urethane-based polymer (A) and a filler (B), wherein the average aspect ratio of the filler (B) in the adhesive composition is from 5 to 350. Also provided are: an adhesive sheet having an adhesive layer formed from said adhesive composition; and a method for processing said adhesive sheet. This adhesive sheet having an adhesive layer formed from said adhesive composition has excellent adhesive strength and excellent punchability.

Description

粘着剤組成物、粘着シート、及び粘着シートの加工方法Adhesive composition, adhesive sheet, and processing method of adhesive sheet
　本発明は、粘着剤組成物、及び当該粘着剤組成物から形成された粘着剤層を有する粘着シート、並びに粘着シートの加工方法に関する。 The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and a method for processing the pressure-sensitive adhesive sheet.
　従来、粘着剤組成物から形成された粘着剤層を有する粘着シートは、工業用、商業用、家庭用に広く使用されており、部品の貼着用途や部品の表面保護用途等に使用されている。
　特に、工業用に用いられる粘着シートは、被着体に貼付した状態で、もしくは被着体に貼付する前に、刃による切断加工や抜き加工等を施し、所定の形状に加工される場合がある。 Conventionally, pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition have been widely used for industrial, commercial, and household use, and are used for application of parts and for surface protection of parts. Yes.
In particular, the pressure-sensitive adhesive sheet used for industrial use may be processed into a predetermined shape by applying cutting or punching with a blade in a state of being attached to the adherend or before being attached to the adherend. is there.
　ところで、ウレタン系ポリマーを含む粘着剤組成物から形成された粘着剤層を有する粘着シートは、当該粘着剤層が優れた弾性力を有するため、被着体の表面保護用途として好適である。
　しかしながら、ウレタン系ポリマーを含む粘着剤層は、弾性力が高いため、伸び易く、変形し易い。そのため、当該粘着剤層を有する粘着シートに、切断加工や抜き加工等を施した際、刃に粘着剤層の一部が付着する刃残りの発生や、切断面において、粘着シートが有する基材や被着体に対して粘着剤層の染み出しが発生する場合等がある。
　このような粘着剤層の一部が付着する刃残りの発生は、刃の洗浄回数が増大する等の生産性を低下させる要因となる。また、切断面における基材や被着体への粘着剤層の染み出しの発生は、特に精密化及び小型化等が要求される電子材料部品においては、製品の品質低下に繋がる大きな問題である。
　このような問題に対して、特許文献１では、粘着シートの粘着剤層の形成材料として、ウレタン系ポリマーと共に、特定構造を有する光学活性アミノ酸誘導体からなるゲル化剤を含む粘着剤組成物が提案されている。 Incidentally, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing a urethane polymer is suitable for surface protection of an adherend because the pressure-sensitive adhesive layer has excellent elasticity.
However, since the pressure-sensitive adhesive layer containing a urethane polymer has high elasticity, it is easily stretched and easily deformed. Therefore, when the adhesive sheet having the pressure-sensitive adhesive layer is subjected to cutting processing, punching processing, or the like, generation of a blade residue in which a part of the pressure-sensitive adhesive layer adheres to the blade, or the substrate that the pressure-sensitive adhesive sheet has on the cut surface In some cases, the adhesive layer oozes out from the adherend.
Generation | occurrence | production of the blade residue to which a part of such adhesive layer adheres becomes a factor which reduces productivity, such as the frequency | count of washing | cleaning of a blade increasing. In addition, the occurrence of bleeding of the pressure-sensitive adhesive layer on the substrate or adherend on the cut surface is a major problem that leads to a reduction in product quality, particularly in electronic material parts that require precision and downsizing. .
For such a problem, Patent Document 1 proposes a pressure-sensitive adhesive composition containing a gelling agent composed of an optically active amino acid derivative having a specific structure together with a urethane-based polymer as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet. Has been.
特開２０１１－２５６２６４号公報JP 2011-256264 A
　しかしながら、特許文献１記載の粘着剤組成物は、特定のゲル化剤を必須成分としているが、当該ゲル化剤は、粘着剤組成物の粘着物性の低下を招くものである。現に、特許文献１の実施例として開示された当該粘着剤組成物から形成された粘着剤層を有する粘着シートは、いずれも粘着力が低いものである。そのため、特許文献１に記載の粘着剤組成物は、高粘着力が求められる用途に使用される粘着シートの粘着剤層の形成材料としては不適当である。
　また、特許文献１に記載の粘着剤組成物から形成された粘着剤層を有する粘着シートは、抜き加工を施した際に、切断面における基材への粘着剤層の染み出しが十分に抑制されたものとはいえない。 However, although the pressure-sensitive adhesive composition described in Patent Document 1 contains a specific gelling agent as an essential component, the gelling agent causes a decrease in the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition. In fact, any pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition disclosed as an example of Patent Document 1 has low adhesive strength. Therefore, the pressure-sensitive adhesive composition described in Patent Document 1 is unsuitable as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet used for applications requiring high adhesive strength.
In addition, the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition described in Patent Document 1 sufficiently suppresses the pressure-sensitive adhesive layer from exuding to the base material at the cut surface when the punching process is performed. It cannot be said that it was done.
　本発明は、優れた粘着力を有すると共に、優れた抜き加工性を有する粘着シートの粘着剤層の形成材料となり得る粘着剤組成物、及び当該粘着剤組成物から形成された粘着剤層を有する粘着シート、並びに粘着シートの加工方法を提供することを目的とする。 The present invention has a pressure-sensitive adhesive composition that can be a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet having excellent adhesive strength and excellent punching workability, and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. It aims at providing the processing method of an adhesive sheet and an adhesive sheet.
　本発明者らは、ウレタン系ポリマー及びフィラーを含む粘着剤組成物において、当該粘着剤組成物中に分散しているフィラーの平均アスペクト比を特定の範囲に調整することで、上記課題を解決し得ることを見出し、本発明を完成させた。
　すなわち、本発明は、下記〔１〕～〔１６〕を提供するものである。
〔１〕ウレタン系ポリマー（Ａ）及びフィラー（Ｂ）を含む粘着剤組成物であって、前記粘着剤組成物中のフィラー（Ｂ）の平均アスペクト比が５～３５０である、粘着剤組成物。
〔２〕前記粘着剤組成物中の（Ｂ）成分の長辺の長さの平均が、０．０５～２０００μｍである、上記〔１〕に記載の粘着剤組成物。
〔３〕（Ｂ）成分の形状が、柱状、筒状、錘状、繊維状、及び扁球状からなる群より選ばれる１種以上の形状を含む、上記〔１〕又は〔２〕に記載の粘着剤組成物。
〔４〕（Ｂ）成分を構成する成分が、カーボンナノ材料、ベーマイト、水酸化アルミニウム、及びダイアスポアからなる群から選ばれる１種以上の成分を含む、上記〔１〕～〔３〕のいずれか１項に記載の粘着剤組成物。
〔５〕（Ｂ）成分の含有量が、前記粘着剤組成物中の有効成分の全量に対して、０．２～７０．０質量％である、上記〔１〕～〔４〕のいずれか１項に記載の粘着剤組成物。
〔６〕（Ａ）成分が、ポリオキシアルキレン構造を有するウレタン系ポリマーを含む、上記〔１〕～〔５〕のいずれか１項に記載の粘着剤組成物。
〔７〕（Ａ）成分が、シリル基含有ウレタン系ポリマーを含む、上記〔１〕～〔６〕のいずれか１項に記載の粘着剤組成物。
〔８〕さらに粘着付与樹脂（Ｃ）を含む、上記〔１〕～〔７〕のいずれか１項に記載の粘着剤組成物。
〔９〕（Ｃ）成分が、水素化テルペンフェノール系樹脂を含む、上記〔８〕に記載の粘着剤組成物。
〔１０〕（Ｃ）成分の含有量が、（Ａ）成分１００質量部に対して、３０～１８０質量部である、上記〔８〕又は〔９〕に記載の粘着剤組成物。
〔１１〕前記粘着剤組成物中に含まれる樹脂成分の全量に対する（Ａ）成分の含有量が４０～１００質量％である、上記〔１〕～〔１０〕のいずれか１項に記載の粘着剤組成物。
〔１２〕上記〔１〕～〔１１〕のいずれか１項に記載の粘着剤組成物から形成された粘着剤層を有する、粘着シート。
〔１３〕２枚の剥離シートにより前記粘着剤層が挟持された構造を有する、上記〔１２〕に記載の粘着シート。
〔１４〕基材の少なくとも片面に、前記粘着剤層を有する、上記〔１２〕に記載の粘着シート。
〔１５〕基材の両面に、前記粘着剤層を有する、上記〔１２〕に記載の粘着シート。
〔１６〕上記〔１２〕～〔１５〕のいずれか１項に記載の粘着シートを、所定の大きさに抜き加工する工程を有する、粘着シートの加工方法。 In the pressure-sensitive adhesive composition containing a urethane-based polymer and a filler, the present inventors have solved the above problem by adjusting the average aspect ratio of the filler dispersed in the pressure-sensitive adhesive composition to a specific range. The present invention was completed.
That is, the present invention provides the following [1] to [16].
[1] A pressure-sensitive adhesive composition comprising a urethane-based polymer (A) and a filler (B), wherein the average aspect ratio of the filler (B) in the pressure-sensitive adhesive composition is 5 to 350. .
[2] The pressure-sensitive adhesive composition according to the above [1], wherein the average length of the long side of the component (B) in the pressure-sensitive adhesive composition is 0.05 to 2000 μm.
[3] The shape of the component (B) includes at least one shape selected from the group consisting of a columnar shape, a cylindrical shape, a weight shape, a fiber shape, and an oblate shape, according to the above [1] or [2] Adhesive composition.
[4] Any of the above [1] to [3], wherein the component constituting the component (B) includes one or more components selected from the group consisting of carbon nanomaterials, boehmite, aluminum hydroxide, and diaspore Item 2. The pressure-sensitive adhesive composition according to item 1.
[5] Any of [1] to [4] above, wherein the content of the component (B) is 0.2 to 70.0% by mass with respect to the total amount of the active ingredients in the pressure-sensitive adhesive composition. Item 2. The pressure-sensitive adhesive composition according to item 1.
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5] above, wherein the component (A) comprises a urethane polymer having a polyoxyalkylene structure.
[7] The pressure-sensitive adhesive composition according to any one of the above [1] to [6], wherein the component (A) includes a silyl group-containing urethane polymer.
[8] The pressure-sensitive adhesive composition according to any one of [1] to [7], further including a tackifier resin (C).
[9] The pressure-sensitive adhesive composition according to [8], wherein the component (C) includes a hydrogenated terpene phenol resin.
[10] The pressure-sensitive adhesive composition according to the above [8] or [9], wherein the content of the component (C) is 30 to 180 parts by mass with respect to 100 parts by mass of the component (A).
[11] The pressure-sensitive adhesive according to any one of [1] to [10], wherein the content of the component (A) is 40 to 100% by mass with respect to the total amount of the resin component contained in the pressure-sensitive adhesive composition. Agent composition.
[12] A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of [1] to [11].
[13] The pressure-sensitive adhesive sheet according to the above [12], which has a structure in which the pressure-sensitive adhesive layer is sandwiched between two release sheets.
[14] The pressure-sensitive adhesive sheet according to the above [12], which has the pressure-sensitive adhesive layer on at least one surface of the substrate.
[15] The pressure-sensitive adhesive sheet according to the above [12], which has the pressure-sensitive adhesive layer on both surfaces of the substrate.
[16] A method for processing an adhesive sheet, comprising a step of punching the adhesive sheet according to any one of [12] to [15] into a predetermined size.
　本発明の粘着剤組成物から形成された粘着剤層を有する粘着シートは、良好な粘着力を有すると共に、優れた抜き加工性を有するため、切断加工や抜き加工等を施した際に、粘着剤層の刃残りの発生や、切断面において粘着シートの基材や被着体に対して粘着剤層の染み出しの発生を抑制することができる。 The pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a good adhesive force and has excellent punching workability. Generation | occurrence | production of the blade residue of an adhesive layer and generation | occurrence | production of the oozing-out of an adhesive layer with respect to the base material or adherend of an adhesive sheet in a cut surface can be suppressed.
本発明の粘着シートの構成の一例を示す粘着シートの断面図である。It is sectional drawing of the adhesive sheet which shows an example of a structure of the adhesive sheet of this invention. シリル基含有ウレタン系ポリマーの合成法及び構造を示す図である。It is a figure which shows the synthesis method and structure of a silyl group containing urethane type polymer. 本発明の粘着剤組成物で用いるフィラー（Ｂ）の形状の一例を示す図である。It is a figure which shows an example of the shape of the filler (B) used with the adhesive composition of this invention. 本発明の粘着剤組成物で用いるフィラー（Ｂ）の形状の一例を示す図である。It is a figure which shows an example of the shape of the filler (B) used with the adhesive composition of this invention. 比較例で使用したフィラーの形状を示す図である。It is a figure which shows the shape of the filler used by the comparative example. （ａ）実施例８で作製の粘着シート、（ｂ）比較例３で作製の粘着シート、（ｃ）比較例１１で作製の粘着シートについて、各粘着シートをはさみで切断した後の各粘着シートの切断面をデジタル顕微鏡（キーエンス社製、製品名「ＶＨＸ－２０００」）で観察した際の写真である。(A) About the adhesive sheet produced in Example 8, (b) About the adhesive sheet produced in Comparative Example 3, (c) About the adhesive sheet produced in Comparative Example 11, each adhesive sheet after cutting each adhesive sheet with scissors This is a photograph when the cut surface of is observed with a digital microscope (manufactured by Keyence Corporation, product name “VHX-2000”).
　以下の記載において、「質量平均分子量（Ｍｗ）」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法に基づいて測定した値である。
　また、本発明において、樹脂成分とは、質量平均分子量（Ｍｗ）が１万以上の重合体を示す（ただし、フィラー（Ｂ）は、当該樹脂成分には含まれない）。
　さらに、例えば「（メタ）アクリレート」とは、「アクリレート」及び「メタクリレート」の双方を示す語として用いており、他の類似用語についても同様である。
　そして、粘着剤組成物中の「有効成分」とは、粘着剤組成物中に含まれる希釈溶媒を除いた成分を意味し、具体的には、以下に示す（Ａ）～（Ｆ）成分、（Ａ）成分以外の他の樹脂成分、その他の添加剤を指す。 In the following description, “mass average molecular weight (Mw)” is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically measured based on the method described in the examples. It is the value.
In the present invention, the resin component means a polymer having a mass average molecular weight (Mw) of 10,000 or more (however, the filler (B) is not included in the resin component).
Furthermore, for example, “(meth) acrylate” is used as a term indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms.
The “active ingredient” in the pressure-sensitive adhesive composition means a component excluding the dilution solvent contained in the pressure-sensitive adhesive composition, and specifically includes the following components (A) to (F), (A) The resin component other than a component and other additives are pointed out.
〔粘着剤組成物〕
　本発明の粘着剤組成物は、ウレタン系ポリマー（Ａ）及びフィラー（Ｂ）を含むものであるが、より高い粘着物性を発現させる観点から、さらに粘着付与樹脂（Ｃ）、架橋剤（Ｄ）、硬化促進剤（Ｅ）、及び架橋助剤（Ｆ）から選ばれる１種以上を含むことが好ましい。
　なお、本発明の一態様の粘着剤組成物は、効果を損なわない範囲において、上記（Ａ）成分以外の樹脂成分や、上記以外のその他の添加剤を含有してもよい。
　以下、本発明の一態様の粘着剤組成物に含まれる各成分について説明する。 [Adhesive composition]
The pressure-sensitive adhesive composition of the present invention contains a urethane-based polymer (A) and a filler (B). From the viewpoint of developing higher pressure-sensitive physical properties, a tackifier resin (C), a crosslinking agent (D), and a curing agent are further included. It is preferable that 1 or more types chosen from a promoter (E) and a crosslinking adjuvant (F) are included.
Note that the pressure-sensitive adhesive composition of one embodiment of the present invention may contain a resin component other than the component (A) and other additives other than those described above as long as the effects are not impaired.
Hereinafter, each component contained in the pressure-sensitive adhesive composition of one embodiment of the present invention will be described.
＜（Ａ）成分：ウレタン系ポリマー＞
　本発明で用いるウレタン系ポリマー（Ａ）としては、主鎖及び側鎖の少なくとも一方に、ウレタン結合及び尿素結合の少なくとも一種を有する重合体であれば、特に制限されず、例えば、ポリオール（ａ１）と多価イソシアネート化合物（ａ２）とを反応して得られるウレタン系プレポリマー（α）や、当該ウレタン系プレポリマー（α）に対して、更に鎖延長剤（ａ３）を用いた鎖延長反応を行い得られるウレタン系ポリマー（β）等が挙げられる。
　これらの中でも、（Ａ）成分として、ポリオキシアルキレン構造を有するウレタン系ポリマーを含むことが好ましい。
　なお、本発明において、（Ａ）成分は、単独で又は２種以上を組み合わせて用いてもよい。 <(A) component: urethane polymer>
The urethane polymer (A) used in the present invention is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of a main chain and a side chain. For example, polyol (a1) A chain extension reaction using a chain extender (a3) is further performed on the urethane prepolymer (α) obtained by reacting the polyisocyanate compound (a2) with the urethane prepolymer (α). Examples thereof include urethane polymer (β) obtained.
Among these, it is preferable to include a urethane-based polymer having a polyoxyalkylene structure as the component (A).
In the present invention, the component (A) may be used alone or in combination of two or more.
　ポリオール（ａ１）としては、例えば、アルキレンジオール、ポリエーテル型ポリオール、ポリエステル型ポリオール、ポリカーボネート型ポリオール等のポリオール化合物が挙げられるが、ポリオールであれば特に限定はされず、２官能のジオール、３官能のトリオールであってもよい。これらのポリオール（ａ１）の中でも、入手の容易性、反応性等の観点から、ジオールが好ましい。 Examples of the polyol (a1) include polyol compounds such as alkylene diols, polyether type polyols, polyester type polyols, and polycarbonate type polyols, but are not particularly limited as long as they are polyols. May be a triol. Among these polyols (a1), diols are preferable from the viewpoints of availability, reactivity, and the like.
　ジオールとしては、例えば、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，６－ヘキサンジオール、１，７－ヘプタンジオール等のアルカンジオール；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレングリコール；ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリアルキレングリコール；ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシブチレングリコール等のポリオキシアルキレングリコール；等が挙げられる。なお、これらのジオールは、単独で又は２種以上組み合わせて用いてもよい。
　これらのジオールの中でも、さらに鎖延長剤（ａ３）との反応を行う場合、当該反応においてゲル化を抑制する観点から、質量平均分子量１０００～３０００のグリコールが好ましい。 Examples of the diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol; ethylene Alkylene glycols such as glycol, propylene glycol, diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxybutylene glycol And the like. In addition, you may use these diols individually or in combination of 2 or more types.
Among these diols, when a reaction with the chain extender (a3) is further performed, a glycol having a mass average molecular weight of 1000 to 3000 is preferable from the viewpoint of suppressing gelation in the reaction.
　多価イソシアネート化合物（ａ２）としては、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネート等が挙げられる。
　芳香族ポリイソシアネートとしては、例えば、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、２，４－トリレンジイソシアネート（２，４－ＴＤＩ）、２，６－トリレンジイソシアネート（２，６－ＴＤＩ）、４，４’－トルイジンジイソシアネート、２，４，６－トリイソシアネートトルエン、１，３，５－トリイソシアネートベンゼン、ジアニシジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、４，４’，４”－トリフェニルメタントリイソシアネート、１，４－テトラメチルキシリレンジイソシアネート、１，３－テトラメチルキシリレンジイソシアネート等が挙げられる。
　脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＭＤＩ）、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート等が挙げられる。
　脂環式ポリイソシアネートとしては、例えば、３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（ＩＰＤＩ）、１，３－シクロペンタンジイソシアネート、１，３－シクロヘキサンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、１，４－ビス（イソシアネートメチル）シクロヘキサン、１，４－ビス（イソシアネートメチル）シクロヘキサン等が挙げられる。
　なお、これらの多価イソシアネート化合物（ａ２）は、上記ポリイソシアネートのトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含有させたイソシアヌレート型変性体であってもよい。 Examples of the polyvalent isocyanate compound (a2) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.
These polyisocyanate compounds (a2) are a trimethylolpropane adduct type modified product of the above polyisocyanate, a burette type modified product reacted with water, and an isocyanurate type modified product containing an isocyanurate ring. Also good.
　これらの多価イソシアネート化合物（ａ２）の中でも、粘着物性に優れたウレタン系ポリマーを得る観点から、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、２，４－トリレンジイソシアネート（２，４－ＴＤＩ）、２，６－トリレンジイソシアネート（２，６－ＴＤＩ）、ヘキサメチレンジイソシアネート（ＨＭＤＩ）、３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（別名イソホロンジイソシアネート、ＩＰＤＩ）及びこれらの変性体から選ばれる１種以上が好ましく、耐候性の観点から、ＨＭＤＩ、ＩＰＤＩ及びこれらの変性体から選ばれる１種以上がより好ましい。 Among these polyisocyanate compounds (a2), 4,4′-diphenylmethane diisocyanate (MDI) and 2,4-tolylene diisocyanate (2,4-TDI) are used from the viewpoint of obtaining a urethane polymer having excellent adhesive properties. 2,6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) and their modified products One or more selected are preferable, and one or more selected from HMDI, IPDI, and modified products thereof are more preferable from the viewpoint of weather resistance.
　鎖延長剤（ａ３）としては、水酸基及びアミノ基から選ばれる官能基を２つ有する化合物、又は、水酸基及びアミノ基から選ばれる官能基を３つ以上有する化合物が好ましい。 The chain extender (a3) is preferably a compound having two functional groups selected from a hydroxyl group and an amino group, or a compound having three or more functional groups selected from a hydroxyl group and an amino group.
　水酸基及びアミノ基から選ばれる官能基を２つ有する化合物としては、脂肪族ジオール、脂肪族ジアミン、アルカノールアミン、ビスフェノール、及び芳香族ジアミンからなる群より選ばれる少なくとも１種の化合物が好ましい。
　脂肪族ジオールとしては、例えば、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，６－ヘキサンジオール、１，７－ヘプタンジオール等のアルカンジオール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレングリコールが挙げられる。
　脂肪族ジアミンとしては、例えば、エチレンジアミン、１，３－プロパンジアミン、１，４－ブタンジアミン、１，５－ペンタンジアミン、１，６－ヘキサンジアミン等が挙げられる。
　アルカノールアミンとしては、例えば、モノエタノールアミン、モノプロパノールアミン、イソプロパノールアミン等が挙げられる。
　ビスフェノールとしては、例えば、ビスフェノールＡ等が挙げられる。
　芳香族ジアミンとしては、例えば、ジフェニルメタンジアミン、トリレンジアミン、キシリレンジアミン等が挙げられる。 The compound having two functional groups selected from a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
Examples of the aliphatic diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol. And alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
Examples of bisphenol include bisphenol A and the like.
Examples of the aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
　水酸基及びアミノ基から選ばれる官能基を３つ以上有する化合物としては、例えば、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等のポリオール、１－アミノ－２，３－プロパンジオール、１－メチルアミノ－２，３－プロパンジオール、Ｎ－（２－ヒドロキシプロピルエタノールアミン）等のアミノアルコール、テトラメチルキシリレンジアミンのエチレンオキシド又はプロピレンオキシド付加物等が挙げられる。 Examples of the compound having three or more functional groups selected from a hydroxyl group and an amino group include, for example, polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1-amino-2,3-propanediol, Examples thereof include amino alcohols such as methylamino-2,3-propanediol and N- (2-hydroxypropylethanolamine), ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine, and the like.
　ウレタン系プレポリマー（α）の合成方法としては特に制限されず、例えば、ポリオール（ａ１）及び多価イソシアネート化合物（ａ２）と、必要に応じて添加される触媒と、溶剤とを反応器に仕込んで反応させる方法等が挙げられる。
　使用する触媒としては、特に制限はないが、３級アミン系化合物、有機金属系化合物等が挙げられる。
　（ａ１）成分と（ａ２）成分の配合比については、ＮＣＯ基とＯＨ基とのモル比（〔ＮＣＯ基〕／〔ＯＨ基〕）が、好ましくは１．１～３．０、より好ましくは１．２～２．５となるように反応させることが好ましい。
　また、得られるウレタン系プレポリマー（α）中のイソシアネート基含有量（ＮＣＯ％）は、ＪＩＳ　Ｋ　１６０３に準じて測定された値において、好ましくは０．５～１２質量％、より好ましくは１～４質量％である。 The method for synthesizing the urethane-based prepolymer (α) is not particularly limited. For example, a polyol (a1) and a polyvalent isocyanate compound (a2), a catalyst added as necessary, and a solvent are charged into a reactor. And the like.
The catalyst to be used is not particularly limited, and examples thereof include tertiary amine compounds and organometallic compounds.
Regarding the blending ratio of the component (a1) and the component (a2), the molar ratio of NCO group to OH group ([NCO group] / [OH group]) is preferably 1.1 to 3.0, more preferably The reaction is preferably carried out so as to be 1.2 to 2.5.
In addition, the isocyanate group content (NCO%) in the urethane-based prepolymer (α) to be obtained is preferably 0.5 to 12% by mass, more preferably 1 to 1% in a value measured according to JIS K 1603. 4% by mass.
　上記のウレタン系プレポリマー（α）に対して、更に鎖延長剤（ａ３）を用いた鎖延長反応を行い得られるウレタン系ポリマー（β）の合成方法としては、特に制限されず、例えば、下記の方法が挙げられる。
・ウレタン系プレポリマー（α）の溶液を反応器に仕込み、その反応器に鎖延長剤（ａ３）を滴下して反応させる方法。
・鎖延長剤（ａ３）を反応器に仕込み、そこにウレタン系プレポリマー（α）の溶液を滴下して反応させる方法。
・ウレタン系プレポリマー（α）を溶剤で希釈した溶液を反応器に仕込み、そこに鎖延長剤を所定量一括投入して反応させる方法。 The method for synthesizing the urethane polymer (β) obtained by further subjecting the urethane prepolymer (α) to a chain extension reaction using a chain extender (a3) is not particularly limited. The method is mentioned.
A method in which a solution of a urethane prepolymer (α) is charged into a reactor, and a chain extender (a3) is dropped into the reactor to cause a reaction.
A method in which a chain extender (a3) is charged into a reactor, and a solution of a urethane prepolymer (α) is added dropwise to react therewith.
A method in which a solution obtained by diluting a urethane-based prepolymer (α) with a solvent is charged into a reactor, and a predetermined amount of a chain extender is charged into the reactor in a batch to cause a reaction.
　なお、鎖延長反応の停止のために、イソシアネート基と反応可能な活性水素を１つだけ有する化合物や、アミノ基を１つだけ有する化合物等の末端停止剤を用いてもよい。
　イソシアネート基と反応可能な活性水素を１つだけ有する化合物としては、例えば、メタノール、エタノール等のモノオール化合物等が挙げられる。
　アミノ基を１つだけ有する化合物としては、例えば、ジエチルアミン、モルホリン等が挙げられる。 In order to terminate the chain extension reaction, a terminal terminator such as a compound having only one active hydrogen capable of reacting with an isocyanate group or a compound having only one amino group may be used.
Examples of the compound having only one active hydrogen capable of reacting with an isocyanate group include monool compounds such as methanol and ethanol.
Examples of the compound having only one amino group include diethylamine and morpholine.
（シリル基含有ウレタン系ポリマー）
　本発明において、（Ａ）成分として、シリル基含有ウレタン系ポリマーを含有してもよい。
　シリル基含有ウレタン系ポリマーとしては、主鎖及び側鎖の少なくとも一方に、ウレタン結合及び尿素結合の少なくとも一種を有し、且つ、主鎖の両末端に下記一般式（１）で表される加水分解性シリル基を有するポリマーが好ましい。 (Silyl group-containing urethane polymer)
In this invention, you may contain a silyl group containing urethane type polymer as (A) component.
The silyl group-containing urethane polymer has at least one of a urethane bond and a urea bond in at least one of a main chain and a side chain, and is represented by the following general formula (1) at both ends of the main chain. A polymer having a decomposable silyl group is preferred.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記一般式（１）中、Ｘ１、Ｘ２は、それぞれ独立に、ヒドロキシ基、又は、無置換もしくは置換基を有するアルコキシ基を示す。Ｒ１は、無置換もしくは置換基を有する炭素数１～２０のアルキル基を示す。
　上記一般式（１）中のＸ１、Ｘ２がアルコキシ基である場合の当該アルコキシ基の炭素数は、加水分解脱水縮合の反応性の観点から、好ましくは１～１２、より好ましくは１～６、更に好ましくは１～３、より更に好ましくは１～２である。
　また、一般式（１）中、Ｒ１で示されるアルキル基の炭素数は、加水分解脱水縮合の反応性の観点から、好ましくは１～１２、より好ましくは１～６、更に好ましくは１～３、より更に好ましくは１～２である。
　なお、上記のアルコキシ基及びアルキル基の炭素数には、これらの基が有してもよい置換基の炭素数は含まれない。
　Ｘ１、Ｘ２、Ｒ１として選択されるアルコキシ基又はアルキル基が置換基を有する場合、当該置換基としては、例えば、ハロゲン原子、ヒドロキシル基、シアノ基、ニトロ基及びアミノ基等が挙げられる。 In the general formula (1), X 1 and X 2 each independently represent a hydroxy group or an unsubstituted or substituted alkoxy group. R 1 represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.
When X 1 and X 2 in the general formula (1) are alkoxy groups, the number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 1, from the viewpoint of hydrolytic dehydration condensation reactivity. 6, more preferably 1 to 3, and still more preferably 1 to 2.
In general formula (1), the number of carbon atoms of the alkyl group represented by R 1 is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 1, from the viewpoint of the hydrolytic dehydration condensation reactivity. 3, more preferably 1 to 2.
In addition, carbon number of the above-mentioned alkoxy group and alkyl group does not include the carbon number of the substituent which these groups may have.
When the alkoxy group or alkyl group selected as X 1 , X 2 , or R 1 has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, and an amino group. .
　次いで、図２を用いて、シリル基含有ウレタン系ポリマーが有する分子構造について説明する。
　図２（ａ）には、シリル基含有ウレタン系ポリマー３０の合成例が示してある。
　まず、ポリマーの主鎖１２の末端又は側鎖（図示せず）に、イソシアネート基１４ａ、１４ｂを有するウレタン系プレポリマー１０を用意する。
　ウレタン系プレポリマー１０は、上述のポリオール（ａ１）と多価イソシアネート化合物（ａ２）とを反応して得られるウレタン系プレポリマー（α）であって、合成方法も上述のとおりである。
　次に、分子の主鎖２６の一方の末端に、ウレタン系プレポリマー１０のイソシアネート基１４ａ、１４ｂと反応可能な活性水素基２２を有すると共に、分子の主鎖２６の他方の末端に、上記一般式（１）で表される加水分解性シリル基２４を有するシリル化剤２０を用意する。（なお、図２では、前記一般式（１）中のＸ１及びＸ２がメトキシ基、Ｒ１がメチル基とした場合を示している。）
　そして、ウレタン系プレポリマー１０及びシリル化剤２０を混合した後、例えば、窒素雰囲気下、８０℃で１時間反応させることで、シリル基含有ウレタン系ポリマー３０を合成することができる。なお、当該反応は、赤外分光法（ＩＲ）にて測定したイソシアネート基の吸収ピーク（２２６５ｃｍ－１）の消失を確認するまで行うことが好ましい。 Next, the molecular structure of the silyl group-containing urethane polymer will be described with reference to FIG.
FIG. 2A shows a synthesis example of the silyl group-containing urethane polymer 30.
First, a urethane prepolymer 10 having isocyanate groups 14a and 14b is prepared at the terminal or side chain (not shown) of the main chain 12 of the polymer.
The urethane prepolymer 10 is a urethane prepolymer (α) obtained by reacting the polyol (a1) with the polyvalent isocyanate compound (a2), and the synthesis method is also as described above.
Next, an active hydrogen group 22 that can react with the isocyanate groups 14a and 14b of the urethane-based prepolymer 10 is present at one end of the main chain 26 of the molecule, and the above-mentioned general A silylating agent 20 having a hydrolyzable silyl group 24 represented by the formula (1) is prepared. (Note that FIG. 2 shows a case where X 1 and X 2 in the general formula (1) are methoxy groups and R 1 is a methyl group.)
And after mixing the urethane type prepolymer 10 and the silylating agent 20, the silyl group containing urethane type polymer 30 is compoundable by making it react at 80 degreeC for 1 hour, for example in nitrogen atmosphere. The reaction is preferably carried out until the disappearance of the isocyanate group absorption peak (2265 cm −1 ) measured by infrared spectroscopy (IR) is confirmed.
　また、図２（ｂ）に示すように、シリル基含有ウレタン系ポリマー３０’’は、前記一般式（１）で表わされる加水分解性シリル基の加水分解を経由した架橋反応により硬化して３次元網目構造をとる、いわゆる、湿気硬化型のポリマーである。 Further, as shown in FIG. 2 (b), the silyl group-containing urethane polymer 30 ″ is cured by a crosslinking reaction via hydrolysis of the hydrolyzable silyl group represented by the general formula (1). It is a so-called moisture-curing polymer having a dimensional network structure.
　なお、図２（ａ）においては、主鎖の両末端のみに所定のシリル基を有する両末端シリル基含有ウレタン系ポリマーを例に挙げて説明したが、本発明で用いるシリル基含有ウレタン系ポリマーとしては、側鎖の末端に、前記一般式（１）で表される加水分解性シリル基を有する末端シリル基含有ウレタン系ポリマーであってもよい。
　また、図２（ａ）の場合とは逆に、イソシアネート基を有するシリル化剤と、活性水素基を有するポリマーとを反応させて、シリル基含有ウレタン系ポリマーを合成してもよい。
　さらに、シリル基含有ウレタン系ポリマーは、主鎖又は側鎖に導入されているウレタン結合あるいは尿素結合における活性水素は、以下に例を示すように有機基で置換されていてもよい。
　したがって、アロファネート結合もウレタン結合の範疇に含まれ、ビュレット結合も尿素結合の範疇に含まれることになる。 In addition, in FIG. 2 (a), although demonstrated taking the example of the both-ends silyl group containing urethane type polymer which has a predetermined silyl group only in the both ends of a principal chain, the silyl group containing urethane type polymer used by this invention is demonstrated. The terminal silyl group-containing urethane polymer having a hydrolyzable silyl group represented by the general formula (1) may be used at the end of the side chain.
In contrast to the case of FIG. 2A, a silyl group-containing urethane polymer may be synthesized by reacting an silylating agent having an isocyanate group with a polymer having an active hydrogen group.
Furthermore, in the silyl group-containing urethane polymer, the active hydrogen in the urethane bond or urea bond introduced into the main chain or side chain may be substituted with an organic group as shown below.
Therefore, allophanate bonds are also included in the category of urethane bonds, and burette bonds are also included in the category of urea bonds.
　図２（ａ）に示す、シリル基含有ウレタン系ポリマーの末端部分３２ａ、３２ｂの具体的な構造としては、下記一般式（２）～（８）（末端部分－Ａ～Ｇ）に表される構造を有することが好ましく、下記一般式（２）で表される構造を有することがより好ましい。 Specific structures of the terminal portions 32a and 32b of the silyl group-containing urethane polymer shown in FIG. 2A are represented by the following general formulas (2) to (8) (terminal portions -A to G). It preferably has a structure, and more preferably has a structure represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記一般式（２）～（８）中、Ｘ１、Ｘ２及びＲ１は上記一般式（１）と同様である。
　上記一般式（２）～（５）中、Ｒ２及びＲ３は、それぞれ独立して、無置換もしくは置換基を有する炭素数１～２０のアルキル基を示し、当該アルキル基の炭素数としては、好ましくは１～１２、より好ましくは１～８、更に好ましくは１～６、より更に好ましくは１～３である。
　なお、上記のアルキル基の炭素数には、当該アルキル基が有してもよい置換基の炭素数は含まれない。
　また、上記一般式（２）～（５）中のＲ２及びＲ３として選択されるアルキル基が置換基を有する場合、当該置換基としては、例えば、ハロゲン原子、シアノ基、及びニトロ基等が挙げられる。 In the general formulas (2) to (8), X 1 , X 2 and R 1 are the same as those in the general formula (1).
In the general formulas (2) to (5), R 2 and R 3 each independently represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and the alkyl group has Preferably, it is 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, and still more preferably 1 to 3.
In addition, carbon number of said alkyl group does not include carbon number of the substituent which the said alkyl group may have.
When the alkyl group selected as R 2 and R 3 in the general formulas (2) to (5) has a substituent, examples of the substituent include a halogen atom, a cyano group, and a nitro group. Is mentioned.
　また、上記一般式（８）中、Ａはアルキレン基を示し、当該アルキレン基の炭素数は、好ましくは１～２０、より好ましくは１～１２、更に好ましくは１～６である。
　一方、上記一般式（８）中、Ｂは炭素数１～２０の有機基を示し、そのような有機基としては、例えば、無置換もしくは置換基を有する炭素数１～２０のアルキル基、無置換もしくは置換基を有する炭素数１～２０のアルキルアミノ基、無置換もしくは置換基を有する炭素数６～２０のアリールアミノ基、無置換もしくは置換基を有する炭素数１～２０のアルコキシ基、無置換もしくは置換基を有する炭素数６～２０のアリールオキシ基、無置換もしくは置換基を有する炭素数６～２０の芳香族炭化水素基、無置換もしくは置換基を有する炭素数２～２０の複素環基、無置換もしくは置換基を有する炭素数２～２０のアルケニル基、無置換もしくは置換基を有する炭素数２～２０のアルキニル基、無置換もしくは置換基を有する炭素数３～２０のシクロアルキル基等が挙げられる。
　上記の各基の炭素数には、これらの基が有してもよい置換基の炭素数は含まれない。
　なお、上記一般式（８）中のＢとして選択される上述の基が置換基を有する場合、当該置換基としては、例えば、ハロゲン原子、シアノ基、及びニトロ基等が挙げられる。 In the general formula (8), A represents an alkylene group, and the alkylene group preferably has 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6.
On the other hand, in the above general formula (8), B represents an organic group having 1 to 20 carbon atoms. Examples of such an organic group include unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms, A substituted or substituted alkylamino group having 1 to 20 carbon atoms, an unsubstituted or substituted arylamino group having 6 to 20 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms, no Substituted or substituted aryloxy group having 6 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted or substituted heterocyclic ring having 2 to 20 carbon atoms Group, unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms, unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms, unsubstituted or substituted carbon group having 3 to 2 carbon atoms It includes cycloalkyl groups such as of.
The number of carbon atoms in each of the above groups does not include the number of carbon atoms of the substituent that these groups may have.
In addition, when the above-mentioned group selected as B in the general formula (8) has a substituent, examples of the substituent include a halogen atom, a cyano group, and a nitro group.
　また、図２（ａ）に示す、シリル基含有ウレタン系ポリマー３０の主鎖１２又は側鎖（図示せず）の構造としては、適宜選択し得る。
　ただし、得られる粘着剤組成物に対して、適度な柔軟性を付与し、被着体に対する密着性を向上させる観点から、本発明で用いるシリル基含有ウレタン系ポリマーは、主鎖としてポリオキシアルキレン構造を有するシリル基含有ウレタン系ポリマーであることが好ましい。
　当該ポリオキシアルキレンとしては、上記観点から、ポリオキシプロピレン、ポリオキシエチレンが好ましく、ポリオキシプロピレンがより好ましい。 The structure of the main chain 12 or the side chain (not shown) of the silyl group-containing urethane polymer 30 shown in FIG.
However, the silyl group-containing urethane polymer used in the present invention is a polyoxyalkylene as a main chain from the viewpoint of imparting appropriate flexibility to the obtained pressure-sensitive adhesive composition and improving adhesion to an adherend. A silyl group-containing urethane polymer having a structure is preferable.
As the polyoxyalkylene, polyoxypropylene and polyoxyethylene are preferable from the above viewpoint, and polyoxypropylene is more preferable.
　また、以上のようなシリル基含有ウレタン系ポリマーの中でも、図２（ａ）に示されたシリル基含有ウレタン系ポリマー３０ように、側鎖に上記一般式（１）で表される加水分解性シリル基を有さず、主鎖の両末端のみに上記一般式（１）で表される加水分解性シリル基を有するシリル基含有ウレタン系ポリマーであることが好ましい。
　このような構造を有する当該シリル基含有ウレタン系ポリマーであれば、ポリマー同士の架橋密度が好適な範囲に調節され、架橋後の粘着剤組成物における粘着力と凝集力とを共に向上させることができる。 Among the silyl group-containing urethane polymers as described above, the hydrolyzability represented by the above general formula (1) in the side chain as in the silyl group-containing urethane polymer 30 shown in FIG. It is preferable that it is a silyl group containing urethane type polymer which does not have a silyl group and has a hydrolyzable silyl group represented by the said General formula (1) only in the both ends of a principal chain.
With the silyl group-containing urethane polymer having such a structure, the crosslinking density between the polymers is adjusted to a suitable range, and both the adhesive force and the cohesive force in the adhesive composition after crosslinking can be improved. it can.
　（Ａ）成分の質量平均分子量（Ｍｗ）は、好ましくは１万～２０万、より好ましくは１．２万～１５万、更に好ましくは１．５万～１０万、より更に好ましくは２万～７万である。
　（Ａ）成分のＭｗが１万以上であれば、分子構造が密になり過ぎることを防ぎ、得られる粘着剤組成物の粘着物性を良好とすることができる。また、当該粘着剤組成物の粘度が低くなり過ぎることによる加工性（塗布性）の低下を避けることができる。
　一方、（Ａ）成分のＭｗが２０万以下であれば、得られる粘着剤組成物の加工性（塗布性）を良好とすることができる。また、架橋密度を過度な範囲とすることができ、当該粘着剤組成物から形成された粘着剤層の耐ブリスター性を良好にすることができる。 The weight average molecular weight (Mw) of the component (A) is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, still more preferably 20,000 to 70,000.
When the Mw of the component (A) is 10,000 or more, the molecular structure can be prevented from becoming too dense, and the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive composition can be improved. Moreover, the fall of workability (coating property) by the viscosity of the said adhesive composition becoming low too much can be avoided.
On the other hand, if Mw of (A) component is 200,000 or less, the workability (applicability | paintability) of the obtained adhesive composition can be made favorable. Moreover, a crosslinking density can be made into an excessive range, and the blister resistance of the adhesive layer formed from the said adhesive composition can be made favorable.
　本発明の一態様の粘着剤組成物中の有効成分の全量（１００質量％）に対する（Ａ）成分の含有量は、得られる粘着剤組成物の粘着物性を向上させる観点から、好ましくは１５～８５質量％、より好ましくは２０～８０質量％、更に好ましくは２５～７５質量％、より更に好ましくは３０～７０質量％である。 The content of the component (A) with respect to the total amount (100% by mass) of the active ingredient in the pressure-sensitive adhesive composition of one embodiment of the present invention is preferably 15 to from the viewpoint of improving the pressure-sensitive adhesive properties of the resulting pressure-sensitive adhesive composition. It is 85% by mass, more preferably 20 to 80% by mass, still more preferably 25 to 75% by mass, and still more preferably 30 to 70% by mass.
＜（Ａ）成分以外の他の樹脂成分＞
　なお、本発明の一態様の粘着剤組成物は、本発明の効果を損なわない範囲において、上記（Ａ）成分以外の他の樹脂成分（質量平均分子量（Ｍｗ）が１万以上の重合体）を１種以上含有してもよい。
　本発明の一態様としては、粘着剤組成物中の樹脂成分の全量（（Ａ）成分と（Ａ）成分以外の他の樹脂成分との合計量（１００質量％））に対する、（Ａ）成分の含有量は、好ましくは４０～１００質量％、より好ましくは５０～１００質量％、更に好ましくは７０～１００質量％、更に好ましくは８０～１００質量％、より更に好ましくは９５～１００質量％である。
　（Ａ）成分以外の他の樹脂成分を含有する場合、（Ａ）成分の含有量が上記範囲内となるように、（Ａ）成分以外の他の樹脂成分を配合することが好ましい。
　また、本発明の一態様としては、粘着剤組成物中の有効成分の全量（１００質量％）に対する、（Ａ）成分を含む樹脂成分の含有量は、得られる粘着剤組成物の粘着物性を良好とする観点から、好ましくは３０～８５質量％、より好ましくは３５～８０質量％、更に好ましくは４０～７５質量％、より更に好ましくは４３～７０質量％である。 <Resin component other than component (A)>
The pressure-sensitive adhesive composition of one embodiment of the present invention is a resin component other than the component (A) (a polymer having a mass average molecular weight (Mw) of 10,000 or more) within a range not impairing the effects of the present invention. One or more of these may be contained.
As one aspect of the present invention, the component (A) with respect to the total amount of the resin component in the pressure-sensitive adhesive composition (total amount (100% by mass) of the resin component other than the component (A) and the component (A)) The content of is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 95 to 100% by mass. is there.
When the resin component other than the component (A) is contained, the resin component other than the component (A) is preferably blended so that the content of the component (A) is within the above range.
Moreover, as one aspect | mode of this invention, content of the resin component containing (A) component with respect to the whole quantity (100 mass%) of the active ingredient in an adhesive composition is the adhesive physical property of the obtained adhesive composition. From the viewpoint of improving the quality, it is preferably 30 to 85% by mass, more preferably 35 to 80% by mass, still more preferably 40 to 75% by mass, and still more preferably 43 to 70% by mass.
　（Ａ）成分以外の他の樹脂としては、粘着物性の調整の観点から、アクリル系ポリマーが好ましい。
　アクリル系ポリマーとしては、炭素数１～２０のアルキル基を有するアルキル（メタ）アクリレートに由来する構成単位（ｐ１）を有するアクリル系重合体が好ましく、構成単位（ｐ１）と共に、さらに官能基含有（メタ）アクリレートに由来する構成単位（ｐ２）を有するアクリル系共重合体がより好ましい。なお、当該アクリル系ポリマーは、構成単位（ｐ１）、（ｐ２）以外に、上記以外のモノマー由来の構成単位（ｐ３）を有していてもよい。 As the resin other than the component (A), an acrylic polymer is preferable from the viewpoint of adjusting the adhesive physical properties.
As the acrylic polymer, an acrylic polymer having a structural unit (p1) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms is preferable, and together with the structural unit (p1), further containing a functional group ( An acrylic copolymer having a structural unit (p2) derived from (meth) acrylate is more preferred. In addition, the said acrylic polymer may have the structural unit (p3) derived from monomers other than the above in addition to the structural units (p1) and (p2).
　構成単位（ｐ１）を構成する上記アルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。なお、これらのアルキル（メタ）アクリレートは、単独で又は２種以上を組み合わせて用いてもよい。
　これらの中でも、炭素数１～８のアルキル基を有するアルキル（メタ）アクリレートが好ましく、ブチル（メタ）アクリレート、及び２－エチルヘキシル（メタ）アクリレートがより好ましい。 Examples of the alkyl (meth) acrylate constituting the structural unit (p1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like. In addition, you may use these alkyl (meth) acrylates individually or in combination of 2 or more types.
Among these, an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is preferable, and butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable.
　構成単位（ｐ２）を構成する上記官能基含有（メタ）アクリレートとしては、例えば、ヒドロキシ基含有モノマー、カルボキシ基含有モノマー、エポキシ基含有モノマー、アミノ基含有物モノマー、シアノ基含有モノマー、ケト基含有モノマー、窒素原子含有環を有するモノマー、アルコキシシリル基含有モノマー等が挙げられる。なお、これらの官能基含有モノマーは、単独で又は２種以上組み合わせて用いてもよい。
　これらの中でも、ヒドロキシ基含有モノマー、カルボキシ基含有モノマー、窒素原子含有環を有するモノマーが好ましい。 As said functional group containing (meth) acrylate which comprises a structural unit (p2), a hydroxyl group containing monomer, a carboxy group containing monomer, an epoxy group containing monomer, an amino group containing monomer, a cyano group containing monomer, keto group containing, for example And monomers, monomers having a nitrogen atom-containing ring, and alkoxysilyl group-containing monomers. In addition, you may use these functional group containing monomers individually or in combination of 2 or more types.
Among these, a hydroxyl group-containing monomer, a carboxy group-containing monomer, and a monomer having a nitrogen atom-containing ring are preferable.
　ヒドロキシ含有モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；ビニルアルコール、アリルアルコール等の不飽和アルコール類等が挙げられる。 Examples of the hydroxy-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) ) And hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
　カルボキシ基含有モノマーとしては、（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸等が挙げられる。 Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and the like.
　窒素原子含有環を有するモノマーとしては、例えば、Ｎ－ビニル－２－ピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピペリドン、Ｎ－ビニルピペラジン、Ｎ－ビニルピラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、Ｎ－ビニルモルホリン、Ｎ－ビニルカプロラクタム、Ｎ－（メタ）アクリロイルモルホリン等が挙げられる。 Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine and the like can be mentioned.
　構成単位（ｐ３）を構成する上記以外のモノマーとしては、例えば、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニルオキシエチルアクリレート、イミドアクリレート等の環状構造を有する（メタ）アクリレートや、アクリロニトリル、スチレン等が挙げられる。なお、これらのモノマーは、単独で又は２種以上を組み合わせて用いてもよい。 Examples of other monomers constituting the structural unit (p3) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and dicyclopentenyloxyethyl. Examples include (meth) acrylates having a cyclic structure such as acrylate and imide acrylate, acrylonitrile, and styrene. In addition, you may use these monomers individually or in combination of 2 or more types.
　構成単位（ｐ１）の含有割合は、アクリル系ポリマーの全構成単位（１００質量％）に対して、好ましくは５０～９９質量％、より好ましくは６０～９７質量％、更に好ましくは７０～９５質量％、より更に好ましくは７５～９２質量％である。
　構成単位（ｐ２）の含有割合は、アクリル系ポリマーの全構成単位（１００質量％）に対して、好ましくは１～５０質量％、より好ましくは３～４０質量％、更に好ましくは５～３０質量％、より更に好ましくは８～２５質量％である。
　構成単位（ｐ３）の含有割合は、アクリル系ポリマーの全構成単位（１００質量％）に対して、好ましくは０～２０質量％、より好ましくは０～１５質量％、更に好ましくは０～１０質量％、より更に好ましくは０～５質量％である。 The content of the structural unit (p1) is preferably 50 to 99% by mass, more preferably 60 to 97% by mass, and still more preferably 70 to 95% by mass with respect to all the structural units (100% by mass) of the acrylic polymer. %, More preferably 75 to 92% by mass.
The content of the structural unit (p2) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, and still more preferably 5 to 30% by weight with respect to all the structural units (100% by weight) of the acrylic polymer. %, More preferably 8 to 25% by mass.
The content of the structural unit (p3) is preferably 0 to 20% by weight, more preferably 0 to 15% by weight, and still more preferably 0 to 10% by weight with respect to the total structural unit (100% by weight) of the acrylic polymer. %, More preferably 0 to 5% by mass.
　アクリル系ポリマーの質量平均分子量（Ｍｗ）は、好ましくは５万～１５０万、より好ましくは１５万～１２０万、更に好ましくは３０万～１１０万である。
　また、アクリル系ポリマーの共重合の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、グラフト共重合体のいずれであってもよい。 The mass average molecular weight (Mw) of the acrylic polymer is preferably 50,000 to 1,500,000, more preferably 150,000 to 1,200,000, still more preferably 300,000 to 1,100,000.
The form of copolymerization of the acrylic polymer is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
　アクリル系ポリマーの含有量は、（Ａ）成分１００質量部に対して、好ましくは０～１００質量部、より好ましくは０～７０質量部、更に好ましくは０～６０質量部、更に好ましくは０～２５質量部、より更に好ましくは０～８質量部である。 The content of the acrylic polymer is preferably 0 to 100 parts by mass, more preferably 0 to 70 parts by mass, still more preferably 0 to 60 parts by mass, and still more preferably 0 to 100 parts by mass with respect to 100 parts by mass of the component (A). The amount is 25 parts by mass, more preferably 0 to 8 parts by mass.
＜（Ｂ）成分：フィラー＞
　本発明で用いるフィラー（Ｂ）は、粘着剤組成物中にて、平均アスペクト比が５～３５０となるように分散し得るフィラーであれば特に制限はされない。
　本発明において、「アスペクト比」とは、対象となるフィラー（Ｂ）の短辺の長さ（Ｌ）に対する長辺の長さ（Ｈ）の割合、つまり「長辺の長さ（Ｈ）／短辺の長さ（Ｌ）」より算出される値である。また、「平均アスペクト比」とは、対象となるフィラー１０個の算出した当該「アスペクト比」の平均値である。 <(B) component: filler>
The filler (B) used in the present invention is not particularly limited as long as it can be dispersed in the pressure-sensitive adhesive composition so as to have an average aspect ratio of 5 to 350.
In the present invention, the “aspect ratio” is the ratio of the long side length (H) to the short side length (L) of the target filler (B), that is, “long side length (H) / It is a value calculated from the “short side length (L)”. Further, the “average aspect ratio” is an average value of the “aspect ratio” calculated for 10 target fillers.
　ここで、フィラーの「長辺の長さ（Ｈ）」とは、フィラーの高さ方向（長手方向）の長さを意味する。
　また、フィラーの「短辺の長さ（Ｌ）」とは、フィラーの高さ方向（長手方向）と直交する切断面のうち面積が最大となる断面において、当該断面が円又は楕円であれば、直径又は長径であり、当該断面が多角形であれば、当該多角形の辺のうち最長の辺の長さを意味する。
　なお、具体的なフィラー（Ｂ）の「長辺の長さ（Ｈ）」、「短辺の長さ（Ｌ）」、及び「アスペクト比」の値は、実施例に記載の方法により測定又は算出された値を意味する。 Here, the “long side length (H)” of the filler means the length in the height direction (longitudinal direction) of the filler.
In addition, the “short side length (L)” of the filler is a cross section having the maximum area among the cut surfaces perpendicular to the height direction (longitudinal direction) of the filler, and the cross section is a circle or an ellipse. If the cross section is a polygon, it means the length of the longest side among the sides of the polygon.
The values of “long side length (H)”, “short side length (L)”, and “aspect ratio” of the specific filler (B) are measured by the method described in the examples. Means the calculated value.
　フィラー（Ｂ）の形状としては、柱状、筒状、錘状、繊維状、及び扁球状からなる群より選ばれる１種の形状を含むものであることが好ましい。
　つまり、フィラー（Ｂ）の形状は、上述の群より選ばれる１種の形状のみを有するものであってもよく、上述の群より選ばれる２種以上の形状を組み合わせたものであってもよい。
　図３、４の（ａ）～（ｋ）は、本発明の粘着剤組成物で用いるフィラー（Ｂ）の形状の一例を示す図である。以下、それぞれの形状における「長辺の長さ（Ｈ）」及び「短辺の長さ（Ｌ）」について説明する。 The shape of the filler (B) preferably includes one shape selected from the group consisting of a columnar shape, a cylindrical shape, a weight shape, a fiber shape, and an oblate shape.
That is, the shape of the filler (B) may have only one type selected from the above group, or may be a combination of two or more types selected from the above group. .
3 (a) to 3 (k) are diagrams showing an example of the shape of the filler (B) used in the pressure-sensitive adhesive composition of the present invention. Hereinafter, “long side length (H)” and “short side length (L)” in each shape will be described.
　図３の（ａ）のような円柱状のフィラーにおいては、当該フィラーの高さ方向の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向と直交する切断面のうち面積が最大となる断面（図３（ａ）の斜線部分）の直径（又は長径）が「短辺の長さ（Ｌ）」に該当する。
　また、図３の（ｂ）のような角柱状のフィラーにおいては、当該フィラーの高さ方向の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向と直交する切断面のうち面積が最大となる断面（図３（ｂ）の斜線部分）の多角形の辺のうち最長の辺の長さが「短辺の長さ（Ｌ）」に該当する。
　なお、「短辺の長さ（Ｌ）」は、当該多角形が正方形であれば当該正方形の一辺の長さを指し、当該多角形が長方形であれば当該長方形を構成する２組の平行な辺のうち長い方の長さを指す（なお、以下の記載においても同様である）。 In the cylindrical filler as shown in FIG. 3 (a), the length in the height direction of the filler corresponds to the “long side length (H)”, and the length of the cut surface perpendicular to the height direction. Of these, the diameter (or major axis) of the cross section (the hatched portion in FIG. 3A) having the largest area corresponds to the “short side length (L)”.
Further, in the prismatic filler as shown in FIG. 3B, the length in the height direction of the filler corresponds to the “long side length (H)”, and the cutting is perpendicular to the height direction. The length of the longest side of the polygonal side of the cross section (the hatched portion in FIG. 3B) having the maximum area in the surface corresponds to the “short side length (L)”.
The “short side length (L)” refers to the length of one side of the square if the polygon is a square, and the two parallel sets of the rectangle if the polygon is a rectangle. The length of the longer side is indicated (the same applies to the following description).
　また、本発明において、「柱状」とは、所定平面（例えば、ＸＹ平面、ＹＺ平面、ＺＸ平面等）に広がりを有し、前記所定平面と直交する方向に高さを有する形状を意味する。この「柱状」の場合、Ｘ方向、Ｙ方向、Ｚ方向のうち、最も長い方向の長さを「長辺の長さ（Ｈ）」とし、当該方向と直交する切断面のうち面積が最大となる断面において、残りの２方向のうち長い方向の長さを「短辺の長さ（Ｌ）」とする。
　例えば、図３の（ａ）、（ｂ）に示されたような立体の場合は、ＸＹ平面に広がりを有し、当該ＸＹ平面と直交する方向（Ｚ方向）に高さを有する。これらの立体においては、Ｚ方向の長さが、Ｘ方向及びＹ方向の両方向の長さよりも長いため、Ｚ方向の長さが「長辺の長さ（Ｈ）」に該当する。一方、Ｚ方向と直交する切断面のうち面積が最大となる断面（図３（ａ）（ｂ）の斜線部分）において、Ｘ方向及びＹ方向のうち長い方の長さが「短辺の長さ（Ｌ）」に該当する。
　また、図４の（ｋ）に示されたような立体の場合は、ＺＸ平面に広がりを有し、当該ＺＸ平面と直交する方向（Ｙ方向）に高さを有する。当該立体においては、Ｚ方向の長さが、Ｘ方向及びＹ方向の両方向の長さよりも長いため、Ｚ方向の長さが「長辺の長さ（Ｈ）」に該当する。一方、Ｚ方向と直交する切断面のうち面積が最大となる断面（図４（ｋ）の斜線部分）において、Ｘ方向及びＹ方向のうち長い方の長さ（図４の（ｋ）ではＸ方向）が「短辺の長さ（Ｌ）」に該当する。 In the present invention, the “columnar shape” means a shape that extends in a predetermined plane (for example, an XY plane, a YZ plane, a ZX plane, etc.) and has a height in a direction orthogonal to the predetermined plane. In the case of this “columnar shape”, the length in the longest direction among the X direction, the Y direction, and the Z direction is defined as “long side length (H)”, and the area of the cut surface orthogonal to the direction is the largest. In the cross section, the length of the remaining two directions is the “short side length (L)”.
For example, in the case of a solid as shown in FIGS. 3A and 3B, the solid has an extension in the XY plane and has a height in a direction (Z direction) orthogonal to the XY plane. In these three-dimensional objects, the length in the Z direction is longer than the lengths in both the X direction and the Y direction, so the length in the Z direction corresponds to the “long side length (H)”. On the other hand, in the cross section (the hatched portion in FIGS. 3 (a) and 3 (b)) having the largest area among the cut surfaces orthogonal to the Z direction, the longer length of the X direction and the Y direction is “the length of the short side”. (L) ".
In addition, in the case of a solid as shown in FIG. 4K, the ZX plane has a spread, and has a height in a direction (Y direction) orthogonal to the ZX plane. In the three-dimensional object, since the length in the Z direction is longer than the length in both the X direction and the Y direction, the length in the Z direction corresponds to the “long side length (H)”. On the other hand, in the cross section having the largest area among the cut surfaces orthogonal to the Z direction (shaded portion in FIG. 4K), the longer length in the X direction and the Y direction (X in FIG. 4K). Direction) corresponds to “short side length (L)”.
　また、本発明でいう「柱状」には、図３の（ｃ）のような、柱の少なくとも一端に半球形状を有する立体も含まれる。
　この図３の（ｃ）のような立体のフィラーにおいては、当該フィラーの高さ方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図３（ｃ）の斜線部分）の直径（又は長径）が「短辺の長さ（Ｌ）」に該当する。 In addition, the “columnar shape” referred to in the present invention includes a solid having a hemispherical shape at least at one end of the column as shown in FIG.
In the three-dimensional filler as shown in FIG. 3C, the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height direction (Z The diameter (or major axis) of the cross section (the hatched portion in FIG. 3C) having the largest area among the cut surfaces orthogonal to the (direction) corresponds to the “short side length (L)”.
　図３の（ｄ）のような円筒状のフィラーにおいては、当該フィラーの高さ方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図３（ｄ）の斜線部分）の最外円の直径（又は長径）が「短辺の長さ（Ｌ）」に該当する。
　また、図３の（ｅ）のような角筒状のフィラーにおいては、当該フィラーの高さ方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図３（ｅ）の斜線部分）の最外側の多角形の辺のうち最長の辺の長さが「短辺の長さ（Ｌ）」に該当する。 In the cylindrical filler as shown in FIG. 3D, the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height direction (Z The diameter (or major axis) of the outermost circle of the cross section (the hatched portion in FIG. 3D) having the largest area among the cut surfaces orthogonal to the (direction) corresponds to the “short side length (L)”.
In addition, in the rectangular tubular filler as shown in FIG. 3E, the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height. The length of the longest side of the outermost polygonal side of the cross section (hatched portion in FIG. 3E) having the largest area among the cut surfaces orthogonal to the direction (Z direction) is “the length of the short side. (L) ".
　なお、本発明において、「筒状」とは、上述の柱状に対して、長手方向の少なくとも一方の端部が開口しており、内部が中空になっているものである。開口した端部の開口部の形状は、円、楕円、六角形や四角形等の多角形であって、柱の底辺の形状と同じであっても、異なっていてもよい。 In the present invention, the “cylindrical shape” means that at least one end in the longitudinal direction is open with respect to the columnar shape described above, and the inside is hollow. The shape of the opening at the opened end is a polygon such as a circle, an ellipse, a hexagon or a quadrangle, and may be the same as or different from the shape of the bottom of the column.
　図３の（ｆ）のような円錐状のフィラーにおいては、当該フィラーの高さ方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図３（ｆ）の斜線部分）の直径（又は長径）が「短辺の長さ（Ｌ）」に該当する。
　また、図３の（ｇ）のような角錐状のフィラーにおいては、当該フィラーの高さ方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向と直交する切断面のうち面積が最大となる断面（図３（ｇ）の斜線部分）の多角形の辺のうち最長の辺の長さが「短辺の長さ（Ｌ）」に該当する。 In the conical filler as shown in FIG. 3 (f), the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”, and this height direction (Z The diameter (or major axis) of the cross section (the hatched portion in FIG. 3 (f)) having the largest area among the cut surfaces orthogonal to the (direction) corresponds to the “short side length (L)”.
Further, in the pyramidal filler as shown in FIG. 3G, the length in the height direction (Z direction) of the filler corresponds to the “long side length (H)”. The length of the longest side of the polygonal side of the cross section (hatched portion in FIG. 3G) having the largest area among the cut planes orthogonal to the length corresponds to the “short side length (L)”. .
　なお、本発明において、「錘状」とは、所定平面（例えば、ＸＹ平面、ＹＺ平面、ＺＸ平面等）に広がりを有し、前記所定平面と直交する方向に高さを有し、頂上部分に向かって断面積が次第に小さくなる種々の形状を意味する。
　そのため、本発明において、「錘状」には、図３の（ｆ）、（ｇ）のような頂上部分が点となる形状だけでなく、図３の（ｈ）のような頂上部分が円、楕円、又は多角形となるような錐台状の形状も含まれる。
　この図３の（ｈ）のような錐台のフィラーにおいては、当該フィラーの高さ方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この高さ方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図３（ｈ）の斜線部分）の直径（又は長径）、もしくは多角形の辺のうち最大の辺の長さが、「短辺の長さ（Ｌ）」に該当する。 In the present invention, the term “conical” means that a predetermined plane (for example, an XY plane, a YZ plane, a ZX plane, etc.) extends and has a height in a direction perpendicular to the predetermined plane. It means various shapes whose cross-sectional area becomes gradually smaller toward.
Therefore, in the present invention, the “conical shape” includes not only the shape in which the top portion is a point as shown in FIGS. 3F and 3G but also the top portion as shown in FIG. , An elliptical shape, or a frustum shape that is polygonal.
In the frustum filler as shown in FIG. 3 (h), the length of the filler in the height direction (Z direction) corresponds to the “long side length (H)”. The diameter (or major axis) of the cross section (the hatched portion in FIG. 3 (h)) having the largest area among the cut surfaces orthogonal to the (Z direction) or the length of the largest side of the polygonal side is “short”. This corresponds to the “length of side (L)”.
　図４の（ｉ）のような繊維状のフィラーにおいては、当該フィラーの長手方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この長手方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図４（ｉ）の斜線部分）の直径（又は長径）が「短辺の長さ（Ｌ）」に該当する。
　なお、本発明において、「繊維状」とは、長手方向に伸張している形状であって、一次粒子の伸長方向の長さが、伸長方向に垂直な方向の長さに比べて大きいものを意味する。
　また、図４の（ｉ）のように長手方向に対して曲面を有していてもよい。 In the fibrous filler as in (i) of FIG. 4, the length in the longitudinal direction (Z direction) of the filler corresponds to “long side length (H)”, and this longitudinal direction (Z direction). The diameter (or major axis) of the cross section (the hatched portion in FIG. 4 (i)) having the largest area among the cut planes orthogonal to the “corresponding to the length (L) of the short side”.
In the present invention, the “fibrous” is a shape extending in the longitudinal direction, and the length of the primary particles in the extending direction is larger than the length in the direction perpendicular to the extending direction. means.
Moreover, you may have a curved surface with respect to a longitudinal direction like (i) of FIG.
　図４の（ｊ）のような扁球状のフィラーにおいては、当該フィラーの長手方向（Ｚ方向）の長さが「長辺の長さ（Ｈ）」に該当し、この長手方向（Ｚ方向）と直交する切断面のうち面積が最大となる断面（図４（ｊ）の斜線部分）の直径（又は長径）が「短辺の長さ（Ｌ）」に該当する。
　なお、本発明において、「扁球状」とは、楕円をその短軸を回転軸として回転したときに得られる回転体であって、フィラーの一次粒子の長手方向の長さ（長辺の長さ（Ｈ））が、長手方向に垂直な方向の長さ（短辺の長さ（Ｌ））に比べて大きいものを意味する。
　そのため、本発明で使用するフィラー（Ｂ）からは、図５の（ｌ）のような、長手方向の長さ（長辺の長さ（Ｈ））と長手方向に垂直な方向の長さ（短辺の長さ（Ｌ））とが同じである真球状のフィラーは除外される。 In the oblate filler as shown in FIG. 4J, the length in the longitudinal direction (Z direction) of the filler corresponds to the “long side length (H)”, and this longitudinal direction (Z direction). The diameter (or major axis) of the cross section (the hatched portion in FIG. 4 (j)) having the largest area among the cut planes orthogonal to the “corresponding to the length of the short side (L)”.
In the present invention, “oblate shape” is a rotating body obtained when an ellipse is rotated about its short axis as a rotation axis, and the length in the longitudinal direction of the primary particles of the filler (long side length). (H)) is larger than the length in the direction perpendicular to the longitudinal direction (the length of the short side (L)).
Therefore, from the filler (B) used in the present invention, the length in the longitudinal direction (long side length (H)) and the length in the direction perpendicular to the longitudinal direction ((l) in FIG. 5) ( A spherical filler having the same short side length (L)) is excluded.
　本発明において、粘着剤組成物中にて平均アスペクト比が５～３５０となるように分散し得るフィラーであれば、分散前のフィラーの形状は特に制限されないが、柱状のフィラー、筒状のフィラー、錘状のフィラー、繊維状のフィラー及び扁球状のフィラーからなる群より選ばれる１種以上が好ましく、柱状のフィラー、筒状のフィラー、及び繊維状のフィラーからなる群より選ばれる１種以上がより好ましい。
　これらの形状のフィラーを含む粘着剤組成物から粘着剤層を形成した場合、粘着剤層中でフィラー同士がネットワークを形成しやすく、抜き加工を施してもフィラー同士が絡み合っているために、刃残りが生じ難く、また、粘着剤層の染み出しが抑制され、抜き加工性が向上するものと考えられる。また、フィラー同士のネットワークの形成により、粘着剤層の粘着力も良好に保つことができ、（Ａ）成分の種類やフィラーの形状によっては粘着力を向上させることができる。 In the present invention, the shape of the filler before dispersion is not particularly limited as long as it is a filler that can be dispersed in the pressure-sensitive adhesive composition so as to have an average aspect ratio of 5 to 350, but a columnar filler, a cylindrical filler Preferably, one or more selected from the group consisting of spindle-shaped fillers, fibrous fillers, and oblate fillers, and one or more selected from the group consisting of columnar fillers, cylindrical fillers, and fibrous fillers Is more preferable.
When the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing fillers of these shapes, the fillers easily form a network in the pressure-sensitive adhesive layer, and the fillers are intertwined even after being subjected to a punching process. It is considered that the remaining is difficult to occur, and bleeding of the pressure-sensitive adhesive layer is suppressed, and the punching processability is improved. Moreover, the adhesive force of an adhesive layer can also be kept favorable by formation of the network of fillers, and adhesive force can be improved depending on the kind of (A) component and the shape of a filler.
　本発明の粘着剤組成物中のフィラー（Ｂ）の平均アスペクト比〔長辺の長さ（Ｈ）／短辺の長さ（Ｌ）〕は、５～３５０であり、好ましくは６～３５０、より好ましくは１５～３４０、より好ましくは２５～３３０、更に好ましくは３５～３２０、更に好ましくは５０～３１０、より更に好ましくは６０～３００である。
　当該平均アスペクト比が５未満であると、得られる粘着剤組成物から形成された粘着剤層を有する粘着シートの抜き加工性が劣り、当該粘着シートに抜き加工等を施した際に、刃残りの発生や、切断面において粘着シートの基材や被着体に対して粘着剤層の染み出しの発生が見られる。また、当該粘着シートの粘着力が低下する場合もある。
　一方、当該平均アスペクト比が３５０を超えると、得られる粘着剤組成物の粘着物性が低下するため好ましくない。 The average aspect ratio [long side length (H) / short side length (L)] of the filler (B) in the pressure-sensitive adhesive composition of the present invention is 5 to 350, preferably 6 to 350, More preferably, it is 15 to 340, more preferably 25 to 330, still more preferably 35 to 320, still more preferably 50 to 310, still more preferably 60 to 300.
When the average aspect ratio is less than 5, the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is inferior in punching processability. Occurrence of the pressure-sensitive adhesive layer and bleeding of the pressure-sensitive adhesive layer to the substrate or adherend of the pressure-sensitive adhesive sheet are observed on the cut surface. Moreover, the adhesive force of the said adhesive sheet may fall.
On the other hand, when the average aspect ratio exceeds 350, the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive composition are lowered, which is not preferable.
　なお、図４の（ｌ）の形状のフィラーのように、長辺の長さ（Ｈ）と、短辺の長さ（Ｌ）とが同じである真球状のフィラーの場合、当該フィラーの上記アスペクト比は１となる。
　本発明の一態様の粘着剤組成物においては、図５の（ｌ）の形状のフィラーを含有してもよいが、当該粘着剤組成物中に含まれるフィラーの「平均」アスペクト比が５～３５０であることを要する。 In addition, in the case of a true spherical filler having the same long side length (H) and short side length (L) as in the filler having the shape of (l) in FIG. The aspect ratio is 1.
The pressure-sensitive adhesive composition of one embodiment of the present invention may contain a filler having the shape of (l) in FIG. 5, but the “average” aspect ratio of the filler contained in the pressure-sensitive adhesive composition is 5 to 350.
　本発明の一態様としては、粘着剤組成物中のフィラー（Ｂ）の長辺の長さ（Ｈ）の平均は、好ましくは０．０５～２０００μｍ、より好ましくは０．０５～１０００μｍ、より好ましくは０．０５～５００μｍ、更に好ましくは０．０５～１００μｍ、より更に好ましくは０．０７～２０μｍである。 In one embodiment of the present invention, the average of the length (H) of the long side of the filler (B) in the pressure-sensitive adhesive composition is preferably 0.05 to 2000 μm, more preferably 0.05 to 1000 μm, and more preferably Is 0.05 to 500 μm, more preferably 0.05 to 100 μm, and still more preferably 0.07 to 20 μm.
　また、本発明の一態様としては、粘着剤組成物中のフィラー（Ｂ）の短辺の長さ（Ｌ）の平均は、好ましくは１．０～２０００ｎｍ、より好ましくは２．０～１０００ｎｍ、より好ましくは３．０～５００ｎｍ、更に好ましくは５．０～１００ｎｍ、より更に好ましくは７．０～５０ｎｍである。 In one embodiment of the present invention, the average of the short side length (L) of the filler (B) in the pressure-sensitive adhesive composition is preferably 1.0 to 2000 nm, more preferably 2.0 to 1000 nm. More preferably, it is 3.0 to 500 nm, still more preferably 5.0 to 100 nm, and still more preferably 7.0 to 50 nm.
　本発明の一態様で用いる分散前のフィラー（Ｂ）の平均アスペクト比〔長辺の長さ（Ｈ）／短辺の長さ（Ｌ）〕としては、好ましくは５～４５０であり、より好ましくは６～４２０、より好ましくは１５～４００、より好ましくは２５～３７０、更に好ましくは３５～３５０、更に好ましくは５０～３３０、より更に好ましくは６０～３１０である。
　本発明の一態様で用いる分散前のフィラー（Ｂ）の長辺の長さ（Ｈ）の平均は、好ましくは０．０５～２５００μｍ、より好ましくは０．０５～１８００μｍ、より好ましくは０．０５～８００μｍ、更に好ましくは０．０５～１５０μｍ、より更に好ましくは０．０７～３０μｍである。
　本発明の一態様で用いる分散前のフィラー（Ｂ）の短辺の長さ（Ｌ）の平均は、好ましくは１．０～２０００ｎｍ、より好ましくは２．０～１０００ｎｍ、より好ましくは３．０～５００ｎｍ、更に好ましくは５．０～１００ｎｍ、より更に好ましくは７．０～５０ｎｍである。 The average aspect ratio [long side length (H) / short side length (L)] of the filler (B) before dispersion used in one embodiment of the present invention is preferably 5 to 450, more preferably. Is 6 to 420, more preferably 15 to 400, more preferably 25 to 370, still more preferably 35 to 350, still more preferably 50 to 330, and still more preferably 60 to 310.
The average of the long side length (H) of the filler (B) before dispersion used in one embodiment of the present invention is preferably 0.05 to 2500 μm, more preferably 0.05 to 1800 μm, more preferably 0.05. It is ˜800 μm, more preferably 0.05 to 150 μm, still more preferably 0.07 to 30 μm.
The average length (L) of the short side of the filler (B) before dispersion used in one embodiment of the present invention is preferably 1.0 to 2000 nm, more preferably 2.0 to 1000 nm, and more preferably 3.0. It is ˜500 nm, more preferably 5.0 to 100 nm, and still more preferably 7.0 to 50 nm.
　なお、本明細書において、例えば、「粘着剤組成物中のフィラー（Ｂ）の平均アスペクト比」とは、ウレタン系ポリマー（Ａ）を含む粘着剤組成物中に分散しているフィラー（Ｂ）の平均アスペクト比を意味し、分散前（ウレタン系ポリマーと混合前）のフィラー（Ｂ）の平均アスペクト比ものとは区別される。 In the present specification, for example, the “average aspect ratio of the filler (B) in the pressure-sensitive adhesive composition” means the filler (B) dispersed in the pressure-sensitive adhesive composition containing the urethane-based polymer (A). It is distinguished from the average aspect ratio of the filler (B) before dispersion (before mixing with the urethane polymer).
　フィラー（Ｂ）を構成する成分としては、特に制限はないが、得られる粘着剤組成物を用いた粘着シートの抜き加工性を向上させると共に、粘着力を良好に保つ観点から、カーボンナノ材料、ベーマイト、水酸化アルミニウム、及びダイアスポアからなる群から選ばれる成分を１種以上含むことが好ましく、カーボンナノ材料及びベーマイトの少なくとも一方を含むことがより好ましい。 The component constituting the filler (B) is not particularly limited, but from the viewpoint of improving the processability of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition and maintaining good adhesive strength, the carbon nanomaterial, It is preferable to include at least one component selected from the group consisting of boehmite, aluminum hydroxide, and diaspore, and more preferable to include at least one of a carbon nanomaterial and boehmite.
　カーボンナノ材料は、六員環配列構造を主構造とするグラファイトシートを含む物質からなるものであるが、グラファイト構造中にホウ素や窒素等の炭素以外の元素を含有していてもよく、カーボンナノ材料が他の物質を内包している形態であってもよく、さらに、カーボンナノ材料が他の導電性物質に修飾されている形態であってもよい。
　なお、（Ｂ）成分としてカーボンナノ材料を用いる場合、筒状形状のカーボンナノ材料である、カーボンナノチューブ（ＣＮＴ）を用いることが好ましい。
　カーボンナノチューブは、炭素６員環構造を主構造とするグラファイト（黒鉛）シートが円筒状に閉じた構造を有する筒状の炭素多面体である。
　カーボンナノチューブには、１層の黒鉛シートが円筒状に閉じた構造を有する単層カーボンナノチューブと、２層の黒鉛シートが円筒状に閉じた構造を有する二層カーボンナノチューブと、黒鉛シートが３層以上同心筒状に閉じた多層構造を有する多層カーボンナノチューブとがあり、これらのうちのいずれか２つ以上を併用することもできる。 The carbon nanomaterial is composed of a material including a graphite sheet having a six-membered ring arrangement as a main structure, but the graphite structure may contain elements other than carbon such as boron and nitrogen. The material may be in a form including another substance, and further, the carbon nanomaterial may be modified with another conductive substance.
In addition, when using a carbon nanomaterial as (B) component, it is preferable to use the carbon nanotube (CNT) which is a cylindrical carbon nanomaterial.
The carbon nanotube is a cylindrical carbon polyhedron having a structure in which a graphite (graphite) sheet mainly having a carbon 6-membered ring structure is closed in a cylindrical shape.
The carbon nanotube includes a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape, a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape, and a three-layered graphite sheet There are multi-walled carbon nanotubes having a multi-layered structure concentrically closed as described above, and any two or more of these can be used in combination.
　なお、フィラー（Ｂ）として、分散前の平均アスペクト比が、例えば５００以上の高アスペクト比のカーボンナノ材料を用いる場合、粘着剤組成物の一般的な調製法では、ウレタン系ポリマー（Ａ）中の高アスペクト比のカーボンナノ材料は互いに絡み易く、アスペクト比が５未満の球状の凝集体を形成し易い。そのため、分散前の平均アスペクト比が５００以上のカーボンナノ材料を用いた粘着剤組成物は、フィラー（Ｂ）の分散形状が本発明の粘着剤組成物と異なる傾向にある。
　そのため、粘着剤組成物中に分散しているカーボンナノ材料からなるフィラー（Ｂ）の平均アスペクト比を５以上と調整する観点から、分散前の平均アスペクト比が４５０以下のカーボンナノ材料を用いることが好ましい。
　当該カーボンナノ材料の分散前の平均アスペクト比としては、好ましくは６～４２０、より好ましくは１５～４００、より好ましくは２５～３７０、更に好ましくは３５～３５０、更に好ましくは５０～３３０、より更に好ましくは６０～３１０である。
　なお、フィラー（Ｂ）として、分散前の平均アスペクト比が５００以上のカーボンナノ材料を用いる場合、例えば、ウレタン系ポリマー（Ａ）と混合後に、撹拌機を用いて、高回転数にて（例えば、３０００ｒｐｍ以上）撹拌することで、上記の凝集体の形成を避けることができる。 In addition, when using a carbon nanomaterial having a high aspect ratio of, for example, 500 or more as an average aspect ratio before dispersion as the filler (B), in a general preparation method of the pressure-sensitive adhesive composition, in the urethane polymer (A) These high aspect ratio carbon nanomaterials tend to be entangled with each other and form a spherical aggregate having an aspect ratio of less than 5. Therefore, the pressure-sensitive adhesive composition using the carbon nanomaterial having an average aspect ratio before dispersion of 500 or more tends to have a different dispersion shape of the filler (B) from the pressure-sensitive adhesive composition of the present invention.
Therefore, from the viewpoint of adjusting the average aspect ratio of the filler (B) made of the carbon nanomaterial dispersed in the pressure-sensitive adhesive composition to 5 or more, a carbon nanomaterial having an average aspect ratio before dispersion of 450 or less should be used. Is preferred.
The average aspect ratio before dispersion of the carbon nanomaterial is preferably 6 to 420, more preferably 15 to 400, more preferably 25 to 370, still more preferably 35 to 350, still more preferably 50 to 330, and still more. Preferably it is 60-310.
When a carbon nanomaterial having an average aspect ratio before dispersion of 500 or more is used as the filler (B), for example, after mixing with the urethane polymer (A), using a stirrer at a high rotational speed (for example, The above-mentioned aggregate formation can be avoided by stirring (3000 rpm or more).
　なお、ベーマイトは、天然に存在するアルミナ水和物の一つであり、ＡｌＯ（ＯＨ）・Ｈ２Ｏで表されるアルミナ系化合物である。
　また、ダイアスポアは、天然に存在する鉱物の一つであり、ＡｌＯ（ＯＨ）で表されるアルミナ系化合物である。- Boehmite is one of the naturally occurring alumina hydrates and is an alumina compound represented by AlO (OH) .H 2 O.
Diaspore is one of naturally occurring minerals and is an alumina-based compound represented by AlO (OH). -
　なお、フィラー（Ｂ）として、カーボンナノ材料を用いる場合、当該カーボンナノ材料は、粘着剤組成物中のフィラーの平均アスペクト比を上記範囲となるように調整する観点から、分散液の形態で、ウレタン系ポリマー（Ａ）を含む粘着剤組成物中に配合されることが好ましい。
　カーボンナノ材料を含む分散液の形態でウレタン系ポリマーを含む粘着剤組成物中に配合されると、低粘度の状態で混合することが出来るため、フィラー同士が近接しやすくなり、フィラーのネットワークが形成されることにより抜き加工性が良好となるためである。 In addition, when using carbon nanomaterial as a filler (B), the said carbon nanomaterial is a form of a dispersion liquid from a viewpoint of adjusting the average aspect-ratio of the filler in an adhesive composition so that it may become the said range, It is preferable to mix | blend in the adhesive composition containing a urethane type polymer (A).
When blended in a pressure-sensitive adhesive composition containing a urethane polymer in the form of a dispersion containing a carbon nanomaterial, it can be mixed in a low-viscosity state. This is because the punching processability is improved by being formed.
　当該分散液の溶媒としては、水又は有機溶媒が挙げられるが、有機溶媒が好ましい。
　有機溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサン、ｎ－ヘキサン、トルエン、キシレン、ｎ－プロパノール、イソプロパノール、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド等が挙げられる。
　カーボンナノ材料含む分散液の調製方法としては、例えば、上記溶媒中にフィラー（Ｂ）を添加し、超音波等により振動を与えて、フィラー（Ｂ）を溶媒中に分散させて得る方法等が挙げられる。
　カーボンナノ材料を含む分散液の固形分濃度としては、好ましくは０．０１～６０質量％、より好ましくは０．０５～１０質量％、更に好ましくは０．１～３質量％である。 Examples of the solvent for the dispersion include water and an organic solvent, and an organic solvent is preferable.
Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
Examples of the method for preparing the dispersion containing the carbon nanomaterial include a method in which the filler (B) is added to the solvent, and the filler (B) is dispersed in the solvent by applying vibration by ultrasonic waves or the like. Can be mentioned.
The solid content concentration of the dispersion containing the carbon nanomaterial is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 3% by mass.
　粘着剤組成物中の有効成分の全量（１００質量％）に対する（Ｂ）成分の含有量は、好ましくは０．２～７０．０質量％、より好ましくは０．３～５０．０質量％、より好ましくは０．４～１５．０質量％、更に好ましくは０．５～１０．０質量％、より更に好ましくは０．７～６．０質量％、より更に好ましくは２．０～５．５質量％である。
　（Ｂ）成分の含有量が０．２質量％以上であれば、得られる粘着剤組成物を用いた粘着シートの抜き加工性を向上させることができる。
　一方、（Ｂ）成分の含有量が７０．０質量％以下であれば、得られる粘着剤組成物の粘着物性を良好に保つことができる。 The content of the component (B) with respect to the total amount (100% by mass) of the active ingredients in the pressure-sensitive adhesive composition is preferably 0.2 to 70.0% by mass, more preferably 0.3 to 50.0% by mass, More preferably 0.4 to 15.0% by mass, still more preferably 0.5 to 10.0% by mass, still more preferably 0.7 to 6.0% by mass, and still more preferably 2.0 to 5.%. 5% by mass.
If content of (B) component is 0.2 mass% or more, the punching property of the adhesive sheet using the obtained adhesive composition can be improved.
On the other hand, if content of (B) component is 70.0 mass% or less, the adhesive physical property of the obtained adhesive composition can be kept favorable.
＜（Ｃ）成分：粘着付与樹脂＞
　本発明の一態様の粘着剤組成物は、さらに粘着付与樹脂（Ｃ）を含むことが好ましい。
　本発明で用いる粘着付与樹脂（Ｃ）は、ウレタン系ポリマー（Ａ）と混合することが可能な粘着性を有する樹脂を意味する。当該粘着付与樹脂の質量平均分子量（Ｍｗ）は、通常１万未満であり、（Ａ）成分を含む樹脂成分とは区別されるものである。
　なお、粘着付与樹脂（Ｃ）の質量平均分子量（Ｍｗ）は、得られる粘着剤組成物の粘着物性を向上させる観点から、好ましくは４００～４０００、より好ましくは８００～１５００である。 <(C) component: tackifying resin>
The pressure-sensitive adhesive composition of one embodiment of the present invention preferably further contains a tackifier resin (C).
The tackifier resin (C) used in the present invention means a resin having adhesiveness that can be mixed with the urethane polymer (A). The mass average molecular weight (Mw) of the tackifying resin is usually less than 10,000, and is distinguished from the resin component containing the component (A).
The mass average molecular weight (Mw) of the tackifier resin (C) is preferably 400 to 4000, more preferably 800 to 1500, from the viewpoint of improving the adhesive properties of the resulting adhesive composition.
　粘着付与樹脂（Ｃ）の軟化点としては、（Ａ）及び（Ｂ）成分を含む粘着剤組成物の粘着物性を向上させる観点から、好ましくは１１０℃以上、より好ましくは１１０～１８０℃、更に好ましくは１１５～１７５℃、より更に好ましくは１２０～１７０℃である。
　なお、本発明において、粘着付与樹脂の「軟化点」は、ＪＩＳ　Ｋ　２５３１に準拠して測定した値を意味する。 The softening point of the tackifying resin (C) is preferably 110 ° C. or more, more preferably 110 to 180 ° C., more preferably from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B). The temperature is preferably 115 to 175 ° C, more preferably 120 to 170 ° C.
In the present invention, the “softening point” of the tackifier resin means a value measured in accordance with JIS K2531.
　粘着付与樹脂（Ｃ）としては、例えば、ロジン樹脂、ロジンフェノール樹脂、及びそのエステル化合物等のロジン系樹脂；これらロジン系樹脂を水素化した水素化ロジン系樹脂；テルペン樹脂、芳香族変性テルペン樹脂、テルペンフェノール系樹脂等のテルペン系樹脂；これらテルペン系樹脂を水素化した水素化テルペン樹脂；石油ナフサの熱分解で生成するペンテン、イソプレン、ピペリン、１．３－ペンタジエン等のＣ５留分を共重合して得られるＣ５系石油樹脂及びこのＣ５系石油樹脂の水素化樹脂；石油ナフサの熱分解で生成するインデン、ビニルトルエン、α－又はβ－メチルスチレン等のＣ９留分を共重合して得られるＣ９系石油樹脂及びこのＣ９系石油樹脂を水素化樹脂；等が挙げられる。
　なお、本発明において、粘着付与樹脂（Ｃ）は、単独で又は軟化点や構造が異なる２種以上を組み合わせて用いてもよい。 Examples of the tackifier resin (C) include rosin resins such as rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins and aromatic modified terpene resins. Terpene resins such as terpene phenol resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; and C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha. C5 petroleum resin obtained by polymerization and hydrogenated resin of this C5 petroleum resin; C9 fraction such as indene, vinyltoluene, α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha is copolymerized Examples thereof include C9 petroleum resin obtained and hydrogenated resin of this C9 petroleum resin.
In addition, in this invention, you may use tackifying resin (C) individually or in combination of 2 or more types from which a softening point and a structure differ.
　これらの粘着付与樹脂（Ｃ）の中でも、（Ａ）及び（Ｂ）成分を含む粘着剤組成物の粘着物性を向上させる観点から、テルペンフェノール系樹脂が好ましく、水素化テルペン系フェノール樹脂がより好ましい。
　本発明で用いるテルペンフェノール系樹脂とは、松ヤニやオレンジの皮等の天然物から得られる精油成分であるテルペン系樹脂とフェノールとの共重合体であって、当該共重合体の少なくとも一部又は完全に水素化した水素化テルペンフェノール系樹脂も含まれる。
　なお、水素化テルペンフェノール系樹脂の水素化の割合は、（Ａ）及び（Ｂ）成分を含む粘着剤組成物の粘着物性を向上させる観点から、テルペンフェノール系樹脂の不飽和結合１００モル％に対して、好ましくは５０モル％以上、より好ましくは６５モル％以上、更に好ましくは８０モル％以上である。 Among these tackifier resins (C), terpene phenol resins are preferable and hydrogenated terpene phenol resins are more preferable from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B). .
The terpene phenolic resin used in the present invention is a copolymer of terpene resin and phenol, which is an essential oil component obtained from natural products such as pine crabs and orange peels, and is at least part of the copolymer. Alternatively, a fully hydrogenated hydrogenated terpene phenol resin is also included.
In addition, the hydrogenation ratio of the hydrogenated terpene phenol resin is 100 mol% of the unsaturated bond of the terpene phenol resin from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B). On the other hand, it is preferably 50 mol% or more, more preferably 65 mol% or more, and still more preferably 80 mol% or more.
　（Ｃ）成分中のテルペンフェノール系粘着付与樹脂の含有量は、（Ａ）及び（Ｂ）成分を含む粘着剤組成物の粘着物性を向上させる観点から、（Ｃ）成分の全量（１００質量％）に対して、好ましくは７０～１００質量％、より好ましくは８０～１００質量％、更に好ましくは９０～１００質量％、より更に好ましくは９５～１００質量％である。 The content of the terpene phenol tackifying resin in the component (C) is the total amount of the component (C) (100% by mass) from the viewpoint of improving the adhesive properties of the adhesive composition containing the components (A) and (B). ) Is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
　本発明の一態様としては、粘着剤組成物中の（Ｃ）成分の含有量は、（Ａ）及び（Ｂ）成分を含む粘着剤組成物の粘着物性を向上させる観点から、（Ａ）成分１００質量部に対して、好ましくは３０～１８０質量部、より好ましくは４０～１７０質量部、より好ましくは５０～１６０質量部、更に好ましくは７０～１５０質量部、より更に好ましくは８５～１３０質量部である。 As one aspect of the present invention, the content of the component (C) in the pressure-sensitive adhesive composition is the component (A) from the viewpoint of improving the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition containing the components (A) and (B). The amount is preferably 30 to 180 parts by mass, more preferably 40 to 170 parts by mass, more preferably 50 to 160 parts by mass, still more preferably 70 to 150 parts by mass, and still more preferably 85 to 130 parts by mass with respect to 100 parts by mass. Part.
　粘着剤組成物中の有効成分の全量（１００質量％）に対する（Ｃ）成分の含有量としては、上記観点から、好ましくは１０～７０質量％、より好ましくは１５～６５質量％、更に好ましくは２０～６０質量％、より更に好ましくは２５～５５質量％である。 From the above viewpoint, the content of the component (C) with respect to the total amount (100% by mass) of the active ingredients in the pressure-sensitive adhesive composition is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and still more preferably It is 20 to 60% by mass, more preferably 25 to 55% by mass.
＜（Ｄ）成分：架橋剤＞
　本発明の一態様の粘着剤組成物は、より高い粘着物性を発現させる観点から、さらに架橋剤（Ｄ）を含むすることが好ましい。
　架橋剤（Ｄ）としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤、アミン系架橋剤、アミノ樹脂系架橋剤等が挙げられる。これらの架橋剤は、単独で又は２種以上組み合わせて用いてもよい。
　これらの中でも、得られる粘着剤組成物の粘着物性をより向上させる観点から、イソシアネート系架橋剤が好ましい。 <(D) component: cross-linking agent>
The pressure-sensitive adhesive composition of one embodiment of the present invention preferably further contains a crosslinking agent (D) from the viewpoint of expressing higher pressure-sensitive adhesive properties.
Examples of the crosslinking agent (D) include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, amine crosslinking agents, amino resin crosslinking agents, and the like. These crosslinking agents may be used alone or in combination of two or more.
Among these, the isocyanate type crosslinking agent is preferable from the viewpoint of further improving the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive composition.
　イソシアネート系架橋剤としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルメタン－２，４’－ジイソシアネート、３－メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、ジシクロヘキシルメタン－２，４’－ジイソシアネート、リジンイソシアネート等の多価イソシアネート化合物が挙げられる。
　また、多価イソシアネート化合物は、上記化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含むイソシアヌレート型変性体であってもよい。 Examples of the isocyanate-based crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanate compounds such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate Is mentioned.
Further, the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
　架橋剤（Ｄ）の含有量は、（Ａ）成分１００質量部に対して、好ましくは０．０１～２０質量部、より好ましくは０．０５～１５質量部、更に好ましくは０．１～１０質量部である。 The content of the crosslinking agent (D) is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Part by mass.
＜（Ｅ）成分：硬化促進剤＞
　本発明の一態様の粘着剤組成物は、（Ａ）成分として、シリル基含有ウレタン系ポリマーを含有する場合、当該シリル基含有ウレタン系ポリマーのシリル基同士の架橋反応を促進させ、架橋後の粘着剤組成物の粘着物性をより向上させる観点から、さらに硬化促進剤（Ｅ）を含むことが好ましい。この硬化促進剤（Ｅ）は、触媒として機能する。
　硬化促進剤（Ｅ）としては、（Ａ）成分して含有するシリル基含有ウレタン系ポリマーのシリル基同士の架橋反応を促進させ、架橋密度の制御が容易であり、架橋後の粘着剤組成物の粘着物性をより向上させる観点から、アルミ系触媒、チタン系触媒、ジルコニウム系触媒、及び三フッ化ホウ素系触媒からなる群から選ばれる少なくとも一種であることが好ましい。 <(E) component: hardening accelerator>
When the pressure-sensitive adhesive composition of one embodiment of the present invention contains a silyl group-containing urethane polymer as the component (A), it promotes the crosslinking reaction between the silyl groups of the silyl group-containing urethane polymer, From the viewpoint of further improving the pressure-sensitive adhesive properties of the pressure-sensitive adhesive composition, it is preferable to further contain a curing accelerator (E). This hardening accelerator (E) functions as a catalyst.
As the curing accelerator (E), the pressure-sensitive adhesive composition after crosslinking is facilitated by accelerating the crosslinking reaction between the silyl groups of the silyl group-containing urethane polymer contained as the component (A) and easily controlling the crosslinking density. From the viewpoint of further improving the physical properties of the adhesive, it is preferably at least one selected from the group consisting of an aluminum catalyst, a titanium catalyst, a zirconium catalyst, and a boron trifluoride catalyst.
　アルミ系触媒としては、アルミニウムのアルコキシド、アルミニウムキレート、塩化アルミニウム（III）が好ましい。
　チタン系触媒としては、チタンのアルコキシド、チタンキレート、塩化チタン（IV）が好ましい。
　ジルコニウム系触媒としては、ジルコニウムのアルコキシド、ジルコニウムキレート、塩化ジルコニウム（IV）が好ましい。
　三フッ化ホウ素系触媒としては、三フッ化ホウ素モノエチルアミン錯体等の三フッ化ホウ素のアミン錯体や、アルコール錯体が好ましい。 As the aluminum catalyst, aluminum alkoxide, aluminum chelate, and aluminum chloride (III) are preferable.
As the titanium-based catalyst, titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferable.
As the zirconium-based catalyst, zirconium alkoxide, zirconium chelate, and zirconium (IV) chloride are preferable.
As the boron trifluoride-based catalyst, an amine complex of boron trifluoride such as boron trifluoride monoethylamine complex or an alcohol complex is preferable.
　硬化促進剤（Ｅ）の含有量としては、触媒作用の観点から、（Ａ）成分として含有するシリル基含有ウレタン系ポリマー１００質量部に対して、好ましくは０．００１～２０質量部、より好ましくは０．０１～１０質量部、更に好ましくは０．０３～５質量部である。 The content of the curing accelerator (E) is preferably 0.001 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the silyl group-containing urethane polymer contained as the component (A) from the viewpoint of catalytic action. Is 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass.
＜（Ｆ）成分：架橋助剤＞
　また、本発明の一態様の粘着剤組成物は、（Ａ）成分として、シリル基含有ウレタン系ポリマーを含有する場合、上記の硬化促進剤（Ｅ）と共に、架橋助剤（Ｆ）を組み合わせて含有することが好ましい。
　架橋助剤（Ｆ）としては、アミノ基含有アルコキシシランが好ましい。
　アミノ基含有アルコキシシランとしては、例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン等が挙げられる。 <(F) component: crosslinking aid>
Moreover, when the adhesive composition of 1 aspect of this invention contains a silyl group containing urethane type polymer as (A) component, it combines a crosslinking adjuvant (F) with said hardening accelerator (E). It is preferable to contain.
As the crosslinking aid (F), an amino group-containing alkoxysilane is preferable.
Examples of the amino group-containing alkoxysilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl). ) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like.
　架橋助剤（Ｆ）の含有量は、（Ａ）成分として含有するシリル基含有ウレタン系ポリマー１００質量部に対して、好ましくは０．０１～１０質量部、より好ましくは０．０５～６質量部、更に好ましくは０．１～３質量部である。 The content of the crosslinking aid (F) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 6 parts by mass with respect to 100 parts by mass of the silyl group-containing urethane polymer contained as the component (A). Part, more preferably 0.1 to 3 parts by weight.
＜その他の添加剤＞
　本発明の一態様の粘着剤組成物は、本発明の効果を損なわない範囲において、粘着シートの用途に応じて、その他の添加剤を含有させてもよい。
　その他の添加剤としては、例えば、紫外線吸収剤、酸化防止剤、軟化剤（可塑剤）、充填剤、防錆剤、顔料、染料等が挙げられる。
　これらの添加剤を配合する場合、添加剤のそれぞれの配合量は、（Ａ）成分１００質量部に対して、好ましくは０．０１～６質量部、より好ましくは０．０１～２質量部である。 <Other additives>
The pressure-sensitive adhesive composition of one embodiment of the present invention may contain other additives depending on the use of the pressure-sensitive adhesive sheet as long as the effects of the present invention are not impaired.
Examples of other additives include ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, and dyes.
When these additives are blended, the amount of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of component (A). is there.
〔粘着シート〕
　本発明の粘着シートは、上述の粘着剤組成物から形成された粘着剤層を有するものであれば、その構成は特に限定されず、２枚の剥離シートにより粘着剤層が挟持された構造を有する粘着シートであってもよく、基材の少なくとも片面に粘着剤層を有する粘着シートであってもよい。 [Adhesive sheet]
If the adhesive sheet of this invention has an adhesive layer formed from the above-mentioned adhesive composition, the structure will not be specifically limited, The structure where the adhesive layer was pinched | interposed by two peeling sheets The adhesive sheet which has may be sufficient and the adhesive sheet which has an adhesive layer in the at least single side | surface of a base material may be sufficient.
　図１は、本発明の粘着シートの構成の一例を示す粘着シートの断面図である。
　本発明の一態様の粘着シートの具体的な構成として、例えば、図１（ａ）に示されたような、基材２の片面上に、粘着剤層３を有する、基材付き粘着シート１ａが挙げられる。
　また、図１（ｂ）に示されたような、基材２の両面上にそれぞれ粘着剤層３及び粘着剤層３’を有する基材付き粘着シート１ｂや、図１（ｃ）に示されたような、基材２の片面に形成した粘着剤層３上に、さらに剥離シート４が積層された基材付き粘着シート１ｃ等も挙げられる。なお、粘着シート１ｂの構成において、粘着剤層３及び３’上に、さらに剥離シートを積層した粘着シートとしてもよい。 FIG. 1 is a cross-sectional view of an adhesive sheet showing an example of the configuration of the adhesive sheet of the present invention.
As a specific configuration of the pressure-sensitive adhesive sheet of one embodiment of the present invention, for example, as shown in FIG. 1A, a pressure-sensitive adhesive sheet with a substrate 1a having a pressure-sensitive adhesive layer 3 on one surface of the substrate 2 is used. Is mentioned.
Further, as shown in FIG. 1B, the pressure-sensitive adhesive sheet 1b with the base material having the pressure-sensitive adhesive layer 3 and the pressure-sensitive adhesive layer 3 ′ on both surfaces of the base material 2, respectively, and FIG. Examples thereof include a pressure-sensitive adhesive sheet 1c with a base material in which a release sheet 4 is further laminated on the pressure-sensitive adhesive layer 3 formed on one side of the base material 2. In addition, in the structure of the adhesive sheet 1b, it is good also as an adhesive sheet which laminated | stacked the peeling sheet further on the adhesive layers 3 and 3 '.
　また、図１（ｄ）に示されたような、基材を用いずに、剥離シート４と別の剥離シート４’により粘着剤層３が挟持された構造を有する基材無し粘着シート１ｄとしてもよい。
　この粘着シート１ｄの剥離シート４、４’の素材は、同じものでもよく、異なるものでもよいが、剥離シート４と剥離シート４’との剥離力が異なるように調整された素材であることが好ましい。
　他にも、表面が剥離処理された剥離シートの片面に粘着剤層を設けたものをロール状に巻いた構成を有する粘着シート等も挙げられる。 Further, as shown in FIG. 1 (d), as a baseless adhesive sheet 1d having a structure in which the adhesive layer 3 is sandwiched between the release sheet 4 and another release sheet 4 ′ without using a base material. Also good.
The material of the release sheets 4 and 4 ′ of the pressure-sensitive adhesive sheet 1d may be the same or different, but may be a material adjusted so that the release force between the release sheet 4 and the release sheet 4 ′ is different. preferable.
In addition, the adhesive sheet etc. which have the structure which wound what provided the adhesive layer on the single side | surface of the peeling sheet by which the surface was peeling-processed in roll shape are mentioned.
　本発明の一態様の粘着シートの粘着剤層の厚さは、用途等に応じて適宜調整されるが、好ましくは０．５～１００μｍ、より好ましくは１～６０μｍ、更に好ましくは３～４０μｍである。
　当該粘着剤層の厚さが０．５μｍ以上であれば、被着体の種類に依らずに、良好な粘着力を発現させることができる。
　一方、当該粘着剤層の厚さが１００μｍ以下であれば、生産性の面で利点があると共に、シートを巻回体とした際に、粘着剤層が変形することによる巻きずれや、粘着剤層の端部からのはみ出しを抑制することができるため取扱性の面でも良好な粘着シートとなり得る。 The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately adjusted depending on the application and the like, but is preferably 0.5 to 100 μm, more preferably 1 to 60 μm, and still more preferably 3 to 40 μm. is there.
When the thickness of the pressure-sensitive adhesive layer is 0.5 μm or more, good adhesive force can be expressed regardless of the type of adherend.
On the other hand, when the thickness of the pressure-sensitive adhesive layer is 100 μm or less, there are advantages in terms of productivity, and when the sheet is used as a wound body, winding slippage due to deformation of the pressure-sensitive adhesive layer, or pressure-sensitive adhesive Since the protrusion from the edge part of a layer can be suppressed, it can become a favorable adhesive sheet also in terms of handleability.
＜基材＞
　本発明の一態様の粘着シートが有する基材としては、粘着シートの使用目的に応じて適宜選択されるが、絶縁性材料を含む絶縁性基材であってもよく、金属等の導電性材料を含む導電性基材であってもよい。 <Base material>
The base material of the pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately selected according to the purpose of use of the pressure-sensitive adhesive sheet, but may be an insulating base material including an insulating material, or a conductive material such as metal. It may be a conductive substrate containing
　絶縁性基材としては、例えば、上質紙、アート紙、コート紙、グラシン紙等やこれらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙等の各種紙類；不織布等の多孔質材料；ポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂等のポリエステル樹脂、アセテート樹脂、ＡＢＳ樹脂、ポリスチレン樹脂、塩化ビニル樹脂等から形成されたプラスチックフィルム又はシート；これらの樹脂の混合物から形成されたプラスチックフィルム又はシート；これらのプラスチックフィルム又はシートの積層体を有する複層プラスチックフィルム又はシート等が挙げられる。
　なお、プラスチックフィルム又はシート等の基材は、未延伸でもよいし、縦又は横等の一軸方向あるいは二軸方向に延伸されていてもよい。
　また、本発明で用いる基材は、さらに紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、スリップ剤、アンチブロッキング剤、着色剤等が含有されていてもよい。 Examples of the insulating base material include various types of paper such as fine paper, art paper, coated paper, glassine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; Material: Polyolefin resin such as polyethylene resin and polypropylene resin, polybutylene terephthalate resin, polyester resin such as polyethylene terephthalate resin, plastic film or sheet formed from acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc .; these resins A plastic film or sheet formed from a mixture of the above; a multilayer plastic film or sheet having a laminate of these plastic films or sheets.
The base material such as a plastic film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as longitudinal or lateral.
Further, the base material used in the present invention may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant and the like.
　導電性基材としては、例えば、金属箔、金属箔を上述の絶縁性基材を形成する樹脂等でラミネートしたフィルム又はシート、上述の絶縁性基材の表面に金属蒸着処理を行ったフィルム又はシート、上述の絶縁性基材の表面に帯電防止処理を行ったフィルム又はシート、メッシュ状に金属線を編んだシート等が挙げられる。
　なお、導電性基材に用いられる金属としては、例えば、アルミニウム、銅、銀、金等が挙げられる。 As the conductive substrate, for example, a metal foil, a film or sheet obtained by laminating a metal foil with a resin or the like that forms the above-described insulating substrate, a film obtained by performing metal vapor deposition on the surface of the above-described insulating substrate, or Examples thereof include a sheet, a film or sheet obtained by performing antistatic treatment on the surface of the above-described insulating substrate, and a sheet in which a metal wire is knitted in a mesh shape.
In addition, as a metal used for an electroconductive base material, aluminum, copper, silver, gold | metal | money etc. are mentioned, for example.
　基材の厚さは、特に制限はないが、取り扱い易さの観点から、好ましくは１０～２５０μｍ、より好ましくは１５～２００μｍ、更に好ましくは２０～１５０μｍである。 The thickness of the substrate is not particularly limited, but is preferably 10 to 250 μm, more preferably 15 to 200 μm, and still more preferably 20 to 150 μm from the viewpoint of ease of handling.
　基材がプラスチックフィルム又はシートである場合、基材と粘着剤層との密着性を向上させる観点から、必要に応じて、基材の表面に対し酸化法や凹凸化法等の表面処理を施すことが好ましい。
　酸化法としては、特に限定されず、例えば、コロナ放電処理法、プラズマ処理法、クロム酸酸化（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理等が挙げられる。また、凹凸化法としては、特には限定されず、例えば、サンドブラスト法、溶剤処理法等が挙げられる。これらの表面処理は、基材の種類に応じて適宜選定されるが、粘着剤層との密着性の向上効果や操作性の観点から、コロナ放電処理法が好ましい。また、プライマー処理を施すこともできる。 When the base material is a plastic film or sheet, from the viewpoint of improving the adhesion between the base material and the pressure-sensitive adhesive layer, the surface of the base material is subjected to a surface treatment such as an oxidation method or an unevenness method as necessary. It is preferable.
The oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment. Moreover, it does not specifically limit as an uneven | corrugated method, For example, a sandblasting method, a solvent processing method, etc. are mentioned. These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the pressure-sensitive adhesive layer and operability. Moreover, primer treatment can also be performed.
＜剥離シート＞
　また、本発明の一態様の粘着シートは、上述のとおり、基材を有さない粘着シートであってもよい。
　基材を有さない粘着シートは、上述の基材の代わりに剥離シートが用いられ、粘着シートの使用時には、当該剥離シートは除去される。 <Peeling sheet>
Moreover, the adhesive sheet of 1 aspect of this invention may be an adhesive sheet which does not have a base material as above-mentioned.
For the pressure-sensitive adhesive sheet having no base material, a release sheet is used instead of the above-described base material, and the release sheet is removed when the pressure-sensitive adhesive sheet is used.
　剥離シートとしては、両面剥離処理をされた剥離シートや、片面剥離処理された剥離シート等が用いられ、剥離シート用基材上に剥離剤を塗布したもの等が挙げられる。
　剥離シート用基材としては、例えば、グラシン紙、コート紙、上質紙等の紙基材、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙、又はポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂等のポリエステル樹脂フィルム、ポリプロピレン樹脂、ポリエチレン樹脂等のポリオレフィン樹脂フィルム等のプラスチックフィルム等が挙げられる。
　剥離剤としては、例えば、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂等が挙げられる。
　剥離シートの厚さは、特に制限ないが、好ましくは１０～２００μｍ、より好ましくは２５～１５０μｍである。 As the release sheet, a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release sheet coated on a release sheet substrate.
Examples of the release sheet base material include paper base materials such as glassine paper, coated paper, and high-quality paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials, or polyethylene terephthalate resin, polybutylene terephthalate. Examples thereof include plastic films such as resins, polyester resin films such as polyethylene naphthalate resin, and polyolefin resin films such as polypropylene resin and polyethylene resin.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
The thickness of the release sheet is not particularly limited, but is preferably 10 to 200 μm, more preferably 25 to 150 μm.
〔粘着シートの製造方法〕
　本発明の粘着シートの製造方法としては、特に制限はなく、公知の方法により製造することができる。例えば、上記の粘着剤組成物に、有機溶媒を添加して、粘着剤組成物の溶液の形態とした後、当該溶液を上述の基材又は剥離シート上に公知の塗布方法により塗布して製造することができる。
　ただし、粘着剤組成物の溶液を調整する際には、当該粘着剤組成物中に分散するフィラー（Ｂ）の平均アスペクト比が上記範囲となるように調整する必要がある。 [Method for producing adhesive sheet]
There is no restriction | limiting in particular as a manufacturing method of the adhesive sheet of this invention, It can manufacture by a well-known method. For example, an organic solvent is added to the above pressure-sensitive adhesive composition to form a solution of the pressure-sensitive adhesive composition, and then the solution is applied onto the substrate or release sheet by a known coating method. can do.
However, when adjusting the solution of an adhesive composition, it is necessary to adjust so that the average aspect-ratio of the filler (B) disperse | distributed in the said adhesive composition may become the said range.
　粘着剤組成物に添加される有機溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサン、ｎ－ヘキサン、トルエン、キシレン、ｎ－プロパノール、イソプロパノール、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド等が挙げられる。
　なお、これらの有機溶媒は、（Ａ）成分の合成時に使用した有機溶媒や、（Ｂ）成分を分散液の形態に調製した際に用いた有機溶媒をそのまま用いてもよいし、該粘着剤溶液を均一に塗布できるように、（Ａ）成分の合成時や（Ｂ）成分の分散液に使用している有機溶媒以外の１種以上の有機溶媒を加えてもよい。 Examples of the organic solvent added to the pressure-sensitive adhesive composition include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, Examples thereof include dimethyl sulfoxide.
In addition, as for these organic solvents, the organic solvent used at the time of the synthesis | combination of (A) component, the organic solvent used when (B) component was prepared in the form of the dispersion liquid may be used as it is, and this adhesive You may add 1 or more types of organic solvents other than the organic solvent used at the time of the synthesis | combination of (A) component, or the dispersion liquid of (B) component so that a solution can be apply | coated uniformly.
　粘着剤組成物の溶液の固形分濃度としては、好ましくは５～９０質量％、より好ましくは１０～８０質量％、更に好ましくは１５～７０質量％である。当該固形分濃度が５質量％以上であれば、溶媒の使用量としては十分であり、基材や剥離シート上に塗布する際、塗布及び乾燥の効率が向上し、生産性が良好となる。一方、当該固形分濃度が９０質量％以下であれば、適度な粘度となり、塗布作業が容易となり、生産性が良好となる。 The solid content concentration of the pressure-sensitive adhesive composition solution is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass. If the said solid content concentration is 5 mass% or more, the usage-amount of a solvent is enough, and when apply | coating on a base material or a peeling sheet, the efficiency of application | coating and drying will improve and productivity will become favorable. On the other hand, when the solid content concentration is 90% by mass or less, an appropriate viscosity is obtained, the coating operation is facilitated, and productivity is improved.
　基材や剥離シート上への粘着剤組成物の塗布方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等が挙げられる。 Examples of the method for applying the pressure-sensitive adhesive composition onto the substrate or release sheet include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, and die coating. Method, gravure coating method and the like.
　具体的な製造方法としては、粘着シートの構成により以下の方法が挙げられる。
　図１（ａ）のような基材２の片面に粘着剤層３を有する粘着シート１ａは、例えば、基材２の一方の面上に、上述の粘着剤組成物の溶液を直接塗布して粘着剤層３を形成して作製することができる。また、粘着シート１ａは、図１（ｃ）の粘着シート１ｃを作製後に、剥離シート４を除去して作製することもできる。 As a specific manufacturing method, the following method is mentioned by the structure of an adhesive sheet.
The pressure-sensitive adhesive sheet 1a having the pressure-sensitive adhesive layer 3 on one side of the base material 2 as shown in FIG. 1A is obtained by, for example, directly applying the above-mentioned pressure-sensitive adhesive composition solution on one side of the base material 2. It can be produced by forming the pressure-sensitive adhesive layer 3. Moreover, the adhesive sheet 1a can also be produced by removing the release sheet 4 after producing the adhesive sheet 1c of FIG.
　図１（ｂ）のような基材２の両面に粘着剤層３、３’を有する粘着シート１ｂは、例えば、基材２の両面に粘着剤組成物の溶液を直接塗布して粘着剤層３、３’を形成して作製することができる。また、粘着シート１ｂは、予め剥離シート上に粘着剤層を形成したものを２つ用意し、２つの粘着剤層を基材２の両面に貼り合わせて作製することもできる。なお、この場合に、基材２の一方の面上には、剥離シート上に設けた粘着剤層を貼り合わせ、基材２の他方の面上には、粘着剤組成物の溶液を直接塗布して粘着剤層を形成して作製してもよい。 The pressure-sensitive adhesive sheet 1b having the pressure-sensitive adhesive layers 3 and 3 ′ on both surfaces of the base material 2 as shown in FIG. 1B is obtained by directly applying a pressure-sensitive adhesive composition solution on both surfaces of the base material 2, for example. 3, 3 ′ can be formed. Alternatively, the pressure-sensitive adhesive sheet 1b can be prepared by preparing two sheets in which a pressure-sensitive adhesive layer is previously formed on a release sheet and bonding the two pressure-sensitive adhesive layers to both surfaces of the substrate 2. In this case, a pressure-sensitive adhesive layer provided on a release sheet is bonded to one surface of the substrate 2, and a solution of the pressure-sensitive adhesive composition is directly applied to the other surface of the substrate 2. Then, an adhesive layer may be formed and produced.
　図１（ｃ）のような基材２上に、粘着剤層３及び剥離シート４をこの順で有する粘着シート１ｃは、例えば、上述のようにして得られた粘着シート１ａの粘着剤面に剥離シート４をラミネートして作製することができる。また、剥離シート４の剥離処理面に上述の粘着剤組成物の溶液を直接塗布して形成した粘着剤層３と基材２とを貼り合わせて作製することができる。 The pressure-sensitive adhesive sheet 1c having the pressure-sensitive adhesive layer 3 and the release sheet 4 in this order on the substrate 2 as shown in FIG. 1C is formed on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet 1a obtained as described above, for example. The release sheet 4 can be laminated. Moreover, the adhesive layer 3 and the base material 2 which were formed by directly applying the solution of the above-mentioned adhesive composition to the release-treated surface of the release sheet 4 can be produced.
　図１（ｄ）のような、基材を用いずに、２つの剥離シート４、４’により粘着剤層３が挟持された構成を有する粘着シート１ｄは、例えば、剥離シート４の剥離処理面に上述の粘着剤組成物の溶液を直接塗布して形成した粘着剤層３と剥離シート４’とを貼り合わせて作製することができる。なお、前述のように、剥離シート４と剥離シート４’とは、剥離力が異なるように調整することが好ましい。 A pressure-sensitive adhesive sheet 1d having a configuration in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4 ′ without using a substrate as shown in FIG. The adhesive layer 3 formed by directly applying the solution of the above-mentioned adhesive composition and the release sheet 4 ′ can be bonded to each other. As described above, it is preferable to adjust the release sheet 4 and the release sheet 4 ′ so that the release forces are different.
　また、基材や剥離シート上に粘着剤組成物の溶液を塗布し塗布膜を形成した後、乾燥処理をし、塗布膜中に含まれる溶媒を除去することが好ましい。
　さらに、粘着力を向上させるために、当該乾燥処理の後、例えば、２３℃、５０％ＲＨ（相対湿度）の環境下で７日間～３０日程度放置して、粘着剤組成物から形成された粘着剤層（塗布膜）を十分に架橋させることが好ましい。 Moreover, after apply | coating the solution of an adhesive composition on a base material or a peeling sheet and forming a coating film, it is preferable to dry-process and remove the solvent contained in a coating film.
Further, in order to improve the adhesive strength, after the drying treatment, for example, it was allowed to stand for 7 days to 30 days in an environment of 23 ° C. and 50% RH (relative humidity) to form the adhesive composition. It is preferable to sufficiently crosslink the pressure-sensitive adhesive layer (coating film).
〔粘着シートの物性〕
　本発明の粘着シートは、優れた粘着力を有する。
　被着体がステンレスである場合、粘着剤層の厚さが２５μｍである本発明の一態様の粘着シートの粘着力は、好ましくは７．０Ｎ／２５ｍｍ以上、より好ましくは１０．０Ｎ／２５ｍｍ以上、更に好ましくは１５．０Ｎ／２５ｍｍ以上、より更に好ましくは２０．０Ｎ／２５ｍｍ以上である。
　なお、粘着シートが、図１（ｄ）の粘着シート１ｄのような、基材を有しない構成である場合は、厚み５０μｍのポリエチレンテレフタレートフィルムに裏打ちした際の粘着力が、上記範囲となるように調整することが好ましい。また、上記の粘着シートの粘着力は、実施例に記載の方法により測定した値を意味する。 [Physical properties of adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has excellent adhesive strength.
When the adherend is stainless steel, the adhesive strength of the adhesive sheet according to one embodiment of the present invention in which the thickness of the adhesive layer is 25 μm is preferably 7.0 N / 25 mm or more, more preferably 10.0 N / 25 mm or more. More preferably, it is 15.0 N / 25 mm or more, and still more preferably 20.0 N / 25 mm or more.
When the pressure-sensitive adhesive sheet has a structure such as the pressure-sensitive adhesive sheet 1d in FIG. 1 (d), the pressure-sensitive adhesive force when backing a polyethylene terephthalate film with a thickness of 50 μm is in the above range. It is preferable to adjust to. Moreover, the adhesive force of said adhesive sheet means the value measured by the method as described in an Example.
〔粘着シートの加工方法〕
　本発明の粘着シートの加工方法は、本発明の粘着シートを所定の大きさに抜き加工する工程を有する。
　本発明の粘着シートは、抜き加工性が優れているため、上記の加工方法によれば、抜き加工を施した際に、刃残りの発生や、切断面において粘着シートの基材や被着体に対して粘着剤層の染み出しの発生を抑制することができる。そのため、本発明の粘着シートの加工方法は、生産性に優れ、特に精密化及び小型化等が要求される電子材料部品の製造に含まれる粘着シートの加工方法として適している。
　なお、本発明の一態様の粘着シートの加工方法において、被着体に貼付した粘着シートに抜き加工を施してもよく、また、被着体に貼付前の粘着シートに抜き加工を施してもよい。 [Processing method of adhesive sheet]
The processing method of the pressure-sensitive adhesive sheet of the present invention includes a step of punching the pressure-sensitive adhesive sheet of the present invention into a predetermined size.
Since the pressure-sensitive adhesive sheet of the present invention is excellent in punching workability, according to the above-described processing method, when the punching process is performed, generation of a blade residue and the substrate or adherend of the pressure-sensitive adhesive sheet on the cut surface On the other hand, it is possible to suppress the occurrence of bleeding of the pressure-sensitive adhesive layer. For this reason, the pressure-sensitive adhesive sheet processing method of the present invention is excellent in productivity, and is particularly suitable as a pressure-sensitive adhesive sheet processing method included in the manufacture of electronic material parts that require precision and downsizing.
In the pressure-sensitive adhesive sheet processing method of one embodiment of the present invention, the pressure-sensitive adhesive sheet attached to the adherend may be subjected to a punching process, or the pressure-sensitive adhesive sheet before the sticking to the adherend may be subjected to a punching process. Good.
　以下の実施例及び比較例で用いた各成分の物性については、以下に記載の方法により測定した値を使用した。 For the physical properties of each component used in the following examples and comparative examples, values measured by the methods described below were used.
＜フィラーのアスペクト比、及び長辺又は粒径＞
　走査型電子顕微鏡（日立ハイテクノロジーズ社製、製品名「Ｓ－４７００」）を用いて、無作為に抽出したフィラーの粒子１０個を観察して、それぞれの長辺の長さ及び短辺の長さを測定し、粒子１０個の平均値を、そのフィラーの「長辺の長さ（Ｈ）」及び「短辺の長さ（Ｌ）」とした。また、アスペクト比は、「長辺の長さ（Ｈ）／短辺の長さ（Ｌ）」より算出した。 <Aspect ratio of filler and long side or particle size>
Using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, product name “S-4700”), 10 randomly extracted filler particles were observed, and the length of each long side and the length of the short side were observed. The thickness was measured, and the average value of 10 particles was defined as “long side length (H)” and “short side length (L)” of the filler. The aspect ratio was calculated from “long side length (H) / short side length (L)”.
＜質量平均分子量（Ｍｗ）＞
　ゲル浸透クロマトグラフ装置（東ソー株式会社製、製品名「ＨＬＣ－８０２０」）を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
（測定条件）
・カラム：「ＴＳＫ　ｇｕａｒｄ　ｃｏｌｕｍｎ　ＨＸＬ－Ｈ」「ＴＳＫ　ｇｅｌ　ＧＭＨＸＬ（×２）」「ＴＳＫ　ｇｅｌ　Ｇ２０００ＨＸＬ」（いずれも東ソー株式会社製）
・カラム温度：４０℃
・展開溶媒：テトラヒドロフラン
・流速：１．０ｍＬ／ｍｉｎ <Mass average molecular weight (Mw)>
Using a gel permeation chromatograph (product name “HLC-8020” manufactured by Tosoh Corporation), measurement was performed under the following conditions, and values measured in terms of standard polystyrene were used.
(Measurement condition)
・ Column: “TSK guard column HXL-H” “TSK gel GMHXL (× 2)” “TSK gel G2000HXL” (both manufactured by Tosoh Corporation)
-Column temperature: 40 ° C
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min
＜軟化点＞
　ＪＩＳ　Ｋ　２５３１に準拠して測定した値を用いた。 <Softening point>
A value measured according to JIS K 2531 was used.
製造例１（シリル基含有ウレタン系ポリマーの合成）
（１）シリル化剤の合成
　反応容器内に、Ｎ－アミノエチル－γ－アミノプロピルメチルジメトキシシラン１００質量部、アクリル酸メチル８３．５質量部を仕込み、窒素雰囲気下にて、８０℃で１０時間撹拌し、シリル化剤となるシラン化合物を得た。
（２）ウレタンプレポリマーの合成
　上記（１）で使用したものとは別の反応容器内に、ポリオキシプロピレンジオール（旭硝子（株）製、製品名「ＰＭＬ　Ｓ４０１５」、質量平均分子量：１５，０００）１００質量部、イソホロンジイソシアネート２．４６質量部（ＮＣＯ／ＯＨ比＝１．７）、ジブチルスズジラウレート０．００５質量部を仕込み、窒素雰囲気下にて、８５℃で７時間反応させ、ウレタンプレポリマーを得た。
（３）シリル基含有ウレタン系ポリマーの合成
　上記（２）で得たウレタンプレポリマー１００質量部に対し、シリル化剤として、上記（１）で得たシラン化合物４．２１質量部を添加し、窒素雰囲気下にて、８０℃で１時間反応させた。ＩＲにて、イソシアネート基の吸収（２２６５ｃｍ－１）の消失を確認した後、反応を終了し、ポリマーを得た。
　得られた当該ポリマーは、主鎖であるポリオキシプロピレンの両末端に、下記式（９）で表される末端部分を有し、質量平均分子量（Ｍｗ）が４０，０００のシリル基含有ウレタン系ポリマーであった。
　なお、当該シリル基含有ウレタン系ポリマーは、合成の際に、シリル化剤の原料として、Ｎ－アミノエチル－γ－アミノプロピルメチルジメトキシシランを用いたため、末端には、下記式（９）で表されるように、２官能のシリル基が導入されている。 Production Example 1 (Synthesis of silyl group-containing urethane polymer)
(1) Synthesis of silylating agent In a reaction vessel, 100 parts by mass of N-aminoethyl-γ-aminopropylmethyldimethoxysilane and 83.5 parts by mass of methyl acrylate were charged, and 10% at 80 ° C. in a nitrogen atmosphere. The mixture was stirred for a time to obtain a silane compound to be a silylating agent.
(2) Synthesis of urethane prepolymer In a reaction vessel different from that used in (1) above, polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., product name “PML S4015”, mass average molecular weight: 15,000 ) 100 parts by weight, isophorone diisocyanate 2.46 parts by weight (NCO / OH ratio = 1.7), and dibutyltin dilaurate 0.005 parts by weight were reacted in a nitrogen atmosphere at 85 ° C. for 7 hours to obtain a urethane prepolymer. Got.
(3) Synthesis of silyl group-containing urethane-based polymer To 100 parts by mass of the urethane prepolymer obtained in (2) above, 4.21 parts by mass of the silane compound obtained in (1) above was added as a silylating agent. The reaction was carried out at 80 ° C. for 1 hour under a nitrogen atmosphere. After confirming the disappearance of isocyanate group absorption (2265 cm −1 ) by IR, the reaction was terminated to obtain a polymer.
The obtained polymer has a silyl group-containing urethane system having terminal portions represented by the following formula (9) at both ends of polyoxypropylene as a main chain and a mass average molecular weight (Mw) of 40,000. It was a polymer.
The silyl group-containing urethane-based polymer used N-aminoethyl-γ-aminopropylmethyldimethoxysilane as a raw material for the silylating agent at the time of synthesis. Therefore, the terminal is represented by the following formula (9). As shown, a bifunctional silyl group has been introduced.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
実施例１～２５、比較例１～１２
（１）粘着剤組成物の調製
　表１及び表２に示す種類のウレタン系ポリマー１００質量部（固形分）に対し、表１及び表２に示す種類及び配合量（固形分比）のフィラー、粘着付与樹脂、及び各種添加剤（架橋剤、硬化促進剤、架橋助剤）を添加し、溶媒として酢酸エチルを加え、均一になるまで攪拌して、固形分濃度５５質量％の粘着剤組成物の溶液を調製した。なお、当該粘着剤組成物中に分散しているフィラー（Ｂ）の平均アスペクト比及び長辺の長さ（Ｈ）の平均は、表１及び表２に示すとおりであった。 Examples 1 to 25, Comparative Examples 1 to 12
(1) Preparation of pressure-sensitive adhesive composition For 100 parts by mass (solid content) of the urethane-based polymers of the types shown in Table 1 and Table 2, fillers of the types and blending amounts (solid content ratio) shown in Table 1 and Table 2, Add tackifier resin and various additives (crosslinking agent, curing accelerator, crosslinking aid), add ethyl acetate as solvent, stir until uniform, and pressure sensitive adhesive composition with a solid content concentration of 55% by mass A solution of was prepared. The average aspect ratio and long side length (H) of the filler (B) dispersed in the pressure-sensitive adhesive composition were as shown in Tables 1 and 2.
（２）粘着シートの作製
　基材として、厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東レ（株）製、商品名「ルミラー」）を用いて、当該基材の片面上に、調製した粘着剤組成物の酢酸エチル溶液を、乾燥後の膜厚が２５μｍになるように塗布して塗布膜を形成した。
　そして、当該塗布膜を乾燥させ、２３℃、５０％ＲＨ（相対湿度）の環境下で１４日間放置して、粘着剤組成物から形成された塗布膜を十分に架橋させ、図１（ａ）の粘着シート１ａと同じ構成を有する、粘着シートを作製した。 (2) Production of pressure-sensitive adhesive sheet A 50 μm-thick polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., trade name “Lumirror”) was used as a base material, and the pressure-sensitive adhesive prepared on one side of the base material. The ethyl acetate solution of the composition was applied so that the film thickness after drying was 25 μm to form a coating film.
Then, the coating film is dried and left in an environment of 23 ° C. and 50% RH (relative humidity) for 14 days to sufficiently crosslink the coating film formed from the pressure-sensitive adhesive composition. A pressure-sensitive adhesive sheet having the same configuration as that of the pressure-sensitive adhesive sheet 1a was prepared.
　なお、表１及び表２中に記載の実施例及び比較例で調製した粘着剤組成物中の各成分の詳細は、以下のとおりである。
＜ウレタン系ポリマー（Ａ）＞
・「ＵＳ－９０２Ａ」：商品名、一方社油脂工業（株）製、ウレタン系ポリマー、Ｍｗ＝５６，０００。
・「シリル基含有ウレタン系ポリマー」：製造例１で得たシリル基含有ウレタン系ポリマー、Ｍｗ＝４０，０００。 In addition, the detail of each component in the adhesive composition prepared by the Example and comparative example as described in Table 1 and Table 2 is as follows.
<Urethane-based polymer (A)>
“US-902A”: trade name, manufactured by Yushi Kogyo Co., Ltd., urethane polymer, Mw = 56,000.
“Silyl group-containing urethane polymer”: Silyl group-containing urethane polymer obtained in Production Example 1, Mw = 40,000.
＜他の樹脂成分＞
・「アクリル系ポリマー（１）」：ｎ－ブチルアクリレート（ＢＡ）及びアクリル酸（ＡＡ）を共重合させて得られるアクリル系ポリマーの酢酸メチル溶液、ＢＡ／ＡＡ＝９０．０／１０．０（質量部）、Ｍｗ：７０万、固形分濃度：３３．６質量％。
・「アクリル系ポリマー（２）」：ｎ－ブチルアクリレート（ＢＡ）、メチルアクリレート（ＭＡ）、Ｎ－アクリロイルモルホリン（ＡＣＭＯ）、及び２－ヒドロキシエチルアクリレート（ＨＥＡ）を共重合させて得られるアクリル系ポリマーの酢酸メチル溶液、ＢＡ／ＭＡ／ＡＣＭＯ／ＨＥＡ＝８０．０／２．０／１６．０／２．０（質量部）、Ｍｗ：６０万、固形分濃度：３３．６質量％。 <Other resin components>
"Acrylic polymer (1)": methyl acetate solution of acrylic polymer obtained by copolymerizing n-butyl acrylate (BA) and acrylic acid (AA), BA / AA = 90.0 / 10.0 ( Part by mass), Mw: 700,000, solid content concentration: 33.6% by mass.
"Acrylic polymer (2)": an acrylic polymer obtained by copolymerizing n-butyl acrylate (BA), methyl acrylate (MA), N-acryloylmorpholine (ACMO), and 2-hydroxyethyl acrylate (HEA) Methyl acetate solution of polymer, BA / MA / ACMO / HEA = 80.0 / 2.0 / 16.0 / 2.0 (parts by mass), Mw: 600,000, solid content concentration: 33.6% by mass.
＜フィラー（Ｂ）＞
・「ＣＮＴ（１）」：商品名「ＮＣ　７０００」、ナノシル社製、図３（ｄ）に示す円筒状の多層カーボンナノチューブ、平均アスペクト比（Ｈ／Ｌ）：１５０、長辺の長さ（Ｈ）：１．５μｍ、短辺の長さ（Ｌ）：１０ｎｍ。
・「ＣＮＴ（２）」：商品名「ＶＧＣＦ－Ｘ」、昭和電工（株）製、図３（ｄ）に示す円筒状の多層カーボンナノチューブ、平均アスペクト比（Ｈ／Ｌ）：２００、長辺の長さ（Ｈ）：３．０μｍ、短辺の長さ（Ｌ）：１５ｎｍ。
・「ベーマイト」：商品名「ＣＡＭ　９０１０」、サンゴバン社製、図４（ｉ）に示す繊維状のAlO(OH)・H2O、平均アスペクト比（Ｈ／Ｌ）：７．２、長辺の長さ（Ｈ）：０．０９μｍ、短辺の長さ（Ｌ）：１２．５ｎｍ。
・「窒化ホウ素」：商品名「ＵＨＰ－２」、昭和電工（株）製、図４（ｋ）に示す鱗片状の窒化ホウ素、平均アスペクト比（Ｈ／Ｌ）：３．９、長辺の長さ（Ｈ）：１１．８μｍ、短辺の長さ（Ｌ）：３．０μｍ。
・「アルミナ」：商品名「ＡＳ－２０」、昭和電工（株）製、図５（ｌ）に示す真球状のアルミナ、平均アスペクト比（Ｈ／Ｌ）：１．０、平均粒径（＝長辺の長さ（Ｈ）＝短辺の長さ（Ｌ））：２２．０μｍ。
・「モンモリロナイト（１）」：商品名「オルガナイト」、ホージュン社製、図５（ｌ）に示す真球状のモンモリロナイト、平均アスペクト比（Ｈ／Ｌ）：１．０、平均粒径（＝長辺の長さ（Ｈ）＝短辺の長さ（Ｌ））：２．０μｍ。
・「モンモリロナイト（２）」：商品名「エスベンＮＸ」、ホージュン社製、図５（ｌ）に示す真球状のモンモリロナイト、平均アスペクト比（Ｈ／Ｌ）：１．０、平均粒径（＝長辺の長さ（Ｈ）＝短辺の長さ（Ｌ））：１．６μｍ。
・「シリカ」：商品名「ＭＥＫ－ＳＴ－ＵＰ」、日産化学社製、図５（ｌ）に示す真球状の有機ベントナイト、平均アスペクト比（Ｈ／Ｌ）：１．０、平均粒径（＝長辺の長さ（Ｈ）＝短辺の長さ（Ｌ））：１２．５ｎｍ。 <Filler (B)>
“CNT (1)”: trade name “NC 7000”, manufactured by Nanosil Co., Ltd., cylindrical multi-walled carbon nanotube shown in FIG. 3D, average aspect ratio (H / L): 150, long side length ( H): 1.5 μm, short side length (L): 10 nm.
"CNT (2)": trade name "VGCF-X", manufactured by Showa Denko KK, cylindrical multi-walled carbon nanotube shown in Fig. 3 (d), average aspect ratio (H / L): 200, long side Length (H): 3.0 μm, short side length (L): 15 nm.
"Boehmite": trade name "CAM 9010", manufactured by Saint-Gobain, fibrous AlO (OH) .H 2 O shown in Fig. 4 (i), average aspect ratio (H / L): 7.2, long side Length (H): 0.09 μm, short side length (L): 12.5 nm.
"Boron nitride": trade name "UHP-2", manufactured by Showa Denko KK, scaly boron nitride shown in Fig. 4 (k), average aspect ratio (H / L): 3.9, long side Length (H): 11.8 μm, short side length (L): 3.0 μm.
“Alumina”: trade name “AS-20”, Showa Denko KK, true spherical alumina shown in FIG. 5 (l), average aspect ratio (H / L): 1.0, average particle size (= Long side length (H) = short side length (L)): 22.0 μm.
“Montmorillonite (1)”: trade name “Organite”, manufactured by Hojun Co., Ltd., true spherical montmorillonite shown in FIG. 5 (l), average aspect ratio (H / L): 1.0, average particle diameter (= long) Side length (H) = short side length (L)): 2.0 μm.
“Montmorillonite (2)”: trade name “Esven NX”, manufactured by Hojun Co., Ltd., spherical montmorillonite shown in FIG. Side length (H) = short side length (L)): 1.6 μm.
“Silica”: trade name “MEK-ST-UP”, manufactured by Nissan Chemical Co., Ltd., spherical organic bentonite shown in FIG. 5 (l), average aspect ratio (H / L): 1.0, average particle diameter ( = Long side length (H) = Short side length (L): 12.5 nm.
　なお、これらのフィラーのうち、カーボンナノチューブのみ、酢酸エチル中で、超音波洗浄機（４２ｋＨｚ、１２５Ｗ）による超音波で振動を１時間与えて分散させて、固形分濃度０．３質量％の分散液として添加した。カーボンナノチューブ以外のフィラーについては、分散液を作製せず、直接他の成分と一緒に添加した。また、表１及び２に記載のフィラーの配合量は、当該分散液中の固形分（フィラー）の量を示している。
　また、上記のフィラーの平均アスペクト比、長辺の長さ（Ｈ）、及び短辺の長さ（Ｌ）は、粘着剤組成物中に分散前（配合前）の値である。 Of these fillers, only carbon nanotubes were dispersed in ethyl acetate by applying ultrasonic vibration with an ultrasonic cleaner (42 kHz, 125 W) for 1 hour to obtain a solid content concentration of 0.3% by mass. Added as a liquid. About fillers other than a carbon nanotube, the dispersion liquid was not produced but it was added together with the other component directly. Moreover, the compounding quantity of the filler of Table 1 and 2 has shown the quantity of the solid content (filler) in the said dispersion liquid.
Moreover, the average aspect-ratio of said filler, the length (H) of a long side, and the length (L) of a short side are the values before dispersion | distribution (before mixing | blending) in an adhesive composition.
＜粘着付与樹脂（Ｃ）＞
・「ＹＳポリスターＮＨ」：ヤスハラケミカル（株）製、水素化テルペンフェノール系樹脂（分子中の不飽和結合１００モル％中、８０モル％以上が水素化）、軟化点１２５℃、Ｍｗ：８２０。
・「ＹＳポリスターＧ１２５」：ヤスハラケミカル（株）製、テルペンフェノール系樹脂、軟化点１２５℃、Ｍｗ：１０８０。 <Tackifying resin (C)>
"YS Polystar NH": Yasuhara Chemical Co., Ltd., hydrogenated terpene phenol resin (80 mol% or more is hydrogenated in 100 mol% of unsaturated bonds in the molecule), softening point 125 ° C, Mw: 820.
“YS Polystar G125”: manufactured by Yashara Chemical Co., Ltd., terpene phenol resin, softening point 125 ° C., Mw: 1080.
＜架橋剤（Ｄ）、硬化促進剤（Ｅ）、架橋助剤（Ｆ）＞
・「架橋剤」：日本ポリウレタン工業（株）製、商品名「コロネートＨＸ」、イソシアネート系架橋剤（ヘキサメチレンジイソシアネートのイソシアヌレート型変性体）。
・「硬化促進剤」：三フッ化ホウ素モノエチルアミン錯体。
・「架橋助剤」：３－アミノプロピルトリメトキシシラン。 <Crosslinking agent (D), curing accelerator (E), crosslinking aid (F)>
“Crosslinking agent”: manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HX”, isocyanate-based crosslinking agent (isocyanurate-type modified product of hexamethylene diisocyanate).
"Curing accelerator": Boron trifluoride monoethylamine complex.
“Crosslinking aid”: 3-aminopropyltrimethoxysilane.
　実施例及び比較例で作製した粘着シートの粘着力及び抜き加工性について、以下の方法により測定及び評価した。その結果を表１及び表２に示す。 The adhesive strength and punching workability of the pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were measured and evaluated by the following methods. The results are shown in Tables 1 and 2.
＜粘着力＞
　作製した粘着シートを２５ｍｍ×３００ｍｍに切断したものを試験片として使用した。
　当該試験片を２３℃、５０％ＲＨ（相対湿度）の環境下で、ステンレス板（ＳＵＳ３０４、３６０番研磨）に貼付し、同じ環境下で２４時間放置し、貼付後２４時間後に、ＪＩＳ　Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、粘着シートの粘着力を測定した。 <Adhesive strength>
What produced the adhesive sheet cut | disconnected to 25 mm x 300 mm was used as a test piece.
The test piece was applied to a stainless steel plate (SUS304, No. 360 polishing) in an environment of 23 ° C. and 50% RH (relative humidity), left in the same environment for 24 hours, and 24 hours after application, JIS Z0237: Based on 2000, the adhesive strength of the adhesive sheet was measured by a 180 ° peeling method at a pulling speed of 300 mm / min.
＜抜き加工性＞
　作製した粘着シートをはさみで切断し、粘着シートの断面を、デジタル顕微鏡（キーエンス社製、製品名「ＶＨＸ－２０００」）を用いて観察し、以下の基準により評価した。
　Ａ：粘着シートの切断に用いたはさみに、粘着剤層の付着が見られず、基材と粘着剤層の境界が明確で、基材部分への粘着剤層の染み出しが見られない。
　Ｂ：粘着シートの切断に用いたはさみに、粘着剤層の付着が確認され、さらに粘着剤層の剥がれや、基材部分への粘着剤層の染み出しがわずかに確認された。
　Ｃ：粘着シートの切断に用いたはさみに、粘着剤層の付着が確認され、さらに粘着剤層の剥がれや、基材部分への粘着剤層の染み出しが多く確認された。 <Punching workability>
The produced pressure-sensitive adhesive sheet was cut with scissors, and the cross-section of the pressure-sensitive adhesive sheet was observed with a digital microscope (manufactured by Keyence Corporation, product name “VHX-2000”) and evaluated according to the following criteria.
A: Adhesion of the pressure-sensitive adhesive layer is not observed in the scissors used for cutting the pressure-sensitive adhesive sheet, the boundary between the base material and the pressure-sensitive adhesive layer is clear, and no sticking-out of the pressure-sensitive adhesive layer to the base material portion is observed.
B: Adhesion of the pressure-sensitive adhesive layer was confirmed on the scissors used for cutting the pressure-sensitive adhesive sheet, and peeling of the pressure-sensitive adhesive layer and bleeding of the pressure-sensitive adhesive layer to the substrate portion were slightly confirmed.
C: Adhesion of the pressure-sensitive adhesive layer was confirmed on the scissors used for cutting the pressure-sensitive adhesive sheet. Further, peeling of the pressure-sensitive adhesive layer and bleeding of the pressure-sensitive adhesive layer to the base material part were confirmed.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表１より、実施例１～２５で作製した粘着シートは、粘着力及び抜き加工性に優れる結果となった。
　一方、表２に示すとおり、比較例１～１２で作製した粘着シートは、いずれも抜き加工性が劣る結果となった。
　図６は、粘着シートをはさみで切断した後の各粘着シートの切断面をデジタル顕微鏡（キーエンス社製、製品名「ＶＨＸ－２０００」）で観察した際の写真であり、（ａ）は実施例８で作製の粘着シート、（ｂ）は比較例３で作製の粘着シート、（ｃ）は比較例１１で作製の粘着シートの切断面の写真である。図６の（ａ）～（ｃ）のいずれの写真についても、右側が粘着シート、左側が台座であり、切断箇所を基材から撮影している。
　図６（ａ）の実施例８で作製した粘着シートの切断面は、基材と粘着剤層の境界が明確であり、粘着剤層の一部が外側へ染み出す等といった状態は見られず、当該粘着シートは抜き加工性が良好であることがわかる。
　一方、図６（ｂ）及び（ｃ）の比較例３及び１１で作製した粘着シートの切断面は、外側に粘着剤層の一部が基材部分への染み出しており、これらの粘着シートは抜き加工性が劣ることがわかる。 From Table 1, the adhesive sheets prepared in Examples 1 to 25 were excellent in adhesive strength and punching processability.
On the other hand, as shown in Table 2, all of the pressure-sensitive adhesive sheets produced in Comparative Examples 1 to 12 resulted in inferior punchability.
FIG. 6 is a photograph when the cut surface of each adhesive sheet after cutting the adhesive sheet with scissors is observed with a digital microscope (manufactured by Keyence Corporation, product name “VHX-2000”). 8 is a photograph of a cut surface of the pressure-sensitive adhesive sheet produced in Comparative Example 11, and FIG. In any of the photographs (a) to (c) in FIG. 6, the right side is an adhesive sheet and the left side is a pedestal, and the cut portion is photographed from the base material.
In the cut surface of the pressure-sensitive adhesive sheet produced in Example 8 of FIG. 6A, the boundary between the base material and the pressure-sensitive adhesive layer is clear, and a state in which a part of the pressure-sensitive adhesive layer oozes out is not seen. It can be seen that the pressure-sensitive adhesive sheet has good punchability.
On the other hand, the cut surfaces of the pressure-sensitive adhesive sheets prepared in Comparative Examples 3 and 11 of FIGS. 6B and 6C are such that part of the pressure-sensitive adhesive layer oozes out to the base material portion, and these pressure-sensitive adhesive sheets Shows that the punching processability is inferior.
　本発明の粘着剤組成物から形成された粘着剤層を有する粘着シートは、優れた粘着力を有すると共に、優れた抜き加工性を有するため、例えば、電子材料部品等の精密性が要求され、抜き加工を必要とする用途において、好適に使用し得る。 The pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has excellent adhesive strength and excellent punching workability. It can be suitably used in applications that require punching.
１ａ、１ｂ、１ｃ、１ｄ　　粘着シート
２　　基材
３、３’　　粘着剤層
４、４’　　剥離シート
１０　　ウレタン系プレポリマー
１２　　ポリマーの主鎖
１４ａ、１４ｂ　　イソシアネート基
２０　　シリル化剤
２２　　活性水素基
２４　　加水分解性シリル基
２６　　分子の主鎖
３０　　シリル基含有ウレタン系ポリマー
３２ａ、３２ｂ　　シリル基含有ウレタン系ポリマーの末端部分 DESCRIPTION OF SYMBOLS 1a, 1b, 1c, 1d Adhesive sheet 2 Base material 3, 3 'Adhesive layer 4, 4' Release sheet 10 Urethane prepolymer 12 Polymer main chain 14a, 14b Isocyanate group 20 Silylating agent 22 Active hydrogen group 24 Water Decomposable silyl group 26 Molecular main chain 30 Silyl group-containing urethane polymer 32a, 32b End portion of silyl group-containing urethane polymer

Claims (16)

  1. 　ウレタン系ポリマー（Ａ）及びフィラー（Ｂ）を含む粘着剤組成物であって、前記粘着剤組成物中のフィラー（Ｂ）の平均アスペクト比が５～３５０である、粘着剤組成物。 A pressure-sensitive adhesive composition comprising a urethane polymer (A) and a filler (B), wherein the average aspect ratio of the filler (B) in the pressure-sensitive adhesive composition is 5 to 350.
  2. 　前記粘着剤組成物中の（Ｂ）成分の長辺の長さの平均が、０．０５～２０００μｍである、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the average of the lengths of the long sides of the component (B) in the pressure-sensitive adhesive composition is 0.05 to 2000 μm.
  3. 　（Ｂ）成分の形状が、柱状、筒状、錘状、繊維状、及び扁球状からなる群より選ばれる１種以上の形状を含む、請求項１又は２に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the shape of the component (B) includes at least one shape selected from the group consisting of a columnar shape, a cylindrical shape, a weight shape, a fiber shape, and an oblate shape.
  4. 　（Ｂ）成分が、カーボンナノ材料、ベーマイト、水酸化アルミニウム、及びダイアスポアからなる群から選ばれる１種以上の成分を含む、請求項１～３のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the component (B) comprises one or more components selected from the group consisting of carbon nanomaterials, boehmite, aluminum hydroxide, and diaspore.
  5. 　（Ｂ）成分の含有量が、前記粘着剤組成物中の有効成分の全量に対して、０．２～７０．０質量％である、請求項１～４のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the content of the component (B) is 0.2 to 70.0 mass% with respect to the total amount of the active ingredients in the pressure-sensitive adhesive composition. Agent composition.
  6. 　（Ａ）成分が、ポリオキシアルキレン構造を有するウレタン系ポリマーを含む、請求項１～５のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the component (A) comprises a urethane-based polymer having a polyoxyalkylene structure.
  7. 　（Ａ）成分が、シリル基含有ウレタン系ポリマーを含む、請求項１～６のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the component (A) comprises a silyl group-containing urethane polymer.
  8. 　さらに粘着付与樹脂（Ｃ）を含む、請求項１～７のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 7, further comprising a tackifier resin (C).
  9. 　（Ｃ）成分が、水素化テルペンフェノール系樹脂を含む、請求項８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 8, wherein the component (C) comprises a hydrogenated terpene phenol resin.
  10. 　（Ｃ）成分の含有量が、（Ａ）成分１００質量部に対して、３０～１８０質量部である、請求項８又は９に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 8 or 9, wherein the content of the component (C) is 30 to 180 parts by mass with respect to 100 parts by mass of the component (A).
  11. 　前記粘着剤組成物中に含まれる樹脂成分の全量に対する（Ａ）成分の含有量が４０～１００質量％である、請求項１～１０のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 10, wherein the content of the component (A) is 40 to 100% by mass relative to the total amount of the resin components contained in the pressure-sensitive adhesive composition.
  12. 　請求項１～１１のいずれか１項に記載の粘着剤組成物から形成された粘着剤層を有する、粘着シート。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 11.
  13. 　２枚の剥離シートにより前記粘着剤層が挟持された構造を有する、請求項１２に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 12, which has a structure in which the pressure-sensitive adhesive layer is sandwiched between two release sheets.
  14. 　基材の少なくとも片面に、前記粘着剤層を有する、請求項１２に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 12, which has the pressure-sensitive adhesive layer on at least one side of a substrate.
  15. 　基材の両面に、前記粘着剤層を有する、請求項１２に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 12, comprising the pressure-sensitive adhesive layer on both surfaces of the substrate.
  16. 　請求項１２～１５のいずれか１項に記載の粘着シートを、所定の大きさに抜き加工する工程を有する、粘着シートの加工方法。
          A method for processing an adhesive sheet, comprising a step of punching out the adhesive sheet according to any one of claims 12 to 15 to a predetermined size.
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