Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/062—Copolymers with monomers not covered by C09J133/06
  • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • 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
  • C08G18/80—Masked polyisocyanates
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
  • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
  • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
  • C08G18/8029—Masked aromatic polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • 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
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/385—Acrylic polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/718—Weight, e.g. weight per square meter
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/748—Releasability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
• • 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
• • 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
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

• the present invention relates to a pressure-sensitive adhesive composition, and more specifically, it can be easily re-applied, does not cause floating or peeling, and does not cause adhesive residue even when peeled after being placed in a high-temperature environment.
• the present invention relates to an adhesive composition and an adhesive film using the same.
• Electronic boards and wiring boards used in various electronic devices are manufactured through various processes such as mounting of electronic components on the board, lead frame fabrication, soldering, and heat treatment.
• a protective film that can be peeled off from the surface of the board to protect the mounted electrical components or prevent paint or solder from adhering to locations other than the desired location during lead frame processing or soldering.
• the protective film is peeled off after work.
• Such a protective film has a layer structure in which a pressure-sensitive adhesive layer is provided on one surface of a film substrate, and the protective film is bonded to an electronic substrate or the like that is an adherend. Bonded to the adherend.
• Such a protective film requires that the substrate and the protective film are in close contact with each other in which the electronic substrate and the wiring substrate are manufactured without causing floating or peeling, but if the adhesive force is too high.
• Some electronic substrates are extremely thin, and when a protective film having a strong adhesive force is bonded to an electronic substrate having low self-supporting property, there is a problem that the electronic substrate itself is damaged at the time of peeling.
• the adhesive strength between the adhesive and the adherend increases after a heat treatment or the like, and the protective film is attached to the substrate. When peeled off, a part of the pressure-sensitive adhesive remains on the substrate and contaminates the substrate, so-called adhesive residue may occur.
• the pressure-sensitive adhesive used for the protective film one containing an acrylic resin as a main ingredient and a crosslinking agent capable of crosslinking with the acrylic resin is generally used.
• a crosslinking agent capable of crosslinking with the acrylic resin.
• various properties such as adhesive strength, cohesiveness, and adhesive residue can be controlled.
• a pressure-sensitive adhesive composition having such characteristics.
• JP-A-2005-307134 discloses an ultraviolet curable resin composition containing three types of urethane acrylate oligomers in a heat-resistant temporary fixing pressure-sensitive adhesive tape used for mounting electronic components on a substrate. It is taught that this adhesive does not change its adhesiveness at room temperature even after being used in a solder reflow furnace (200 to 300 tens of degrees Celsius).
• JP 2002-348543 A and JP 2009-35717 A disclose pressure sensitive adhesives using a specific acrylic resin as a main agent and an ultraviolet curable resin as a crosslinking agent thereof, It is taught that this adhesive can improve the cohesive strength without reducing the adhesive strength.
• an acrylic pressure-sensitive adhesive that is, an adhesive containing an acrylic resin and a cross-linking agent that cross-links the acrylic resin.
• the object of the present invention is low initial adhesive force, so even a thin film-like adherend having no self-supporting property can be easily reattached, and after bonding to the adherend There is no lifting or peeling, and even when placed in a high temperature environment, the adhesive strength does not change and it has excellent peelability, thus reducing contamination of the adherend due to adhesive residue, etc. It is providing the adhesive composition which can be performed, and an adhesive sheet using the same.
• the pressure-sensitive adhesive composition according to the present invention includes an acrylic resin, a crosslinking agent for crosslinking the acrylic resin, a photocurable resin, and a photocuring agent for curing the photocurable resin. It is characterized by comprising.
• the acrylic resin is mainly composed of (meth) acrylic acid ester and has a glass transition temperature of 30 ° C. or lower.
• the acrylic resin has a mass average molecular weight of 5 to 1,000,000.
• the crosslinking agent is preferably a thermosetting epoxy compound or a thermosetting isocyanate compound.
• the photocurable resin is at least one selected from the group consisting of urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, polyethylene acrylate, silicone acrylate, and polyol acrylate. It is preferable.
• the photocurable resin is contained in a range of 5 to 60% by mass with respect to the acrylic resin.
• the cross-linking agent is contained in the range of 0.5 to 20% by mass with respect to the acrylic resin.
• the pressure-sensitive adhesive sheet according to another embodiment of the present invention is a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer provided on one surface of the base material, wherein the pressure-sensitive adhesive layer is as described above. It comprises a pressure-sensitive adhesive composition according to any one of the embodiments, wherein the acrylic resin in the pressure-sensitive adhesive composition is crosslinked, and the photocurable resin is cured. .
• a release sheet is provided on the surface of the pressure-sensitive adhesive layer on the side opposite to the substrate side.
• a method for producing a pressure-sensitive adhesive sheet according to another embodiment of the present invention is a method for producing a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer provided on one surface of the base material, Applying the pressure-sensitive adhesive composition according to any one of claims 1 to 7 to one surface of the substrate, The pressure-sensitive adhesive composition is heated to crosslink the acrylic resin, and the pressure-sensitive adhesive composition is irradiated with light to cure the photocurable resin, thereby forming a pressure-sensitive adhesive layer. It is characterized by comprising.
• the pressure-sensitive adhesive composition is dried and then dried before the heating and / or light irradiation. It is preferable that a release sheet is provided on the surface to form a laminate.
• an acrylic pressure-sensitive adhesive that is, a pressure-sensitive adhesive containing an acrylic resin and a cross-linking agent that crosslinks the acrylic resin
• the initial adhesive strength is low, so even a thin film-like adherend having no self-supporting property can be easily reattached.
• the adhesive strength does not change, and it has excellent releasability. It is also possible to reduce the contamination of the adherend due to.
• the adhesive composition by this invention does not contain a silicone adhesive and is silicone free, it can be utilized as an adhesive sheet (masking sheet) for various electronic equipment uses.
• the pressure-sensitive adhesive composition according to the present invention includes, as essential components, an acrylic resin, a crosslinking agent for crosslinking the acrylic resin, a photocurable resin, and a photocuring agent for curing the photocurable resin. Including.
• each component which comprises an adhesive composition is demonstrated.
• the acrylic resin which comprises the adhesive composition by this invention can use suitably the acrylic resin which has (meth) acrylic acid ester as a main component.
• (meth) acrylic acid shall mean acrylic acid and / or methacrylic acid.
• (meth) acrylic acid esters examples include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, isopentyl ester, hexyl ester, heptyl ester, Octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, isononyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, octadecyl ester, eicosyl (Meth) acrylic acid alkyl esters such as esters having 1 to 30 carbon atoms, particularly linear or branched alkyl esters
• the functional group-containing (meth) acrylate copolymerizable with the above (meth) acrylic acid ester acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid , Carboxyl group-containing monomers such as fumaric acid and crotonic acid, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ( 4-hydroxymethylcyclohexyl) me Hydroxyl group-containing monomers such as ru (meth)
• monomers containing nitrogen atoms such as cyano group-containing monomers such as acrylonitrile, amide group-containing monomers such as acrylamide, amino group-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate, and isocyanate group-containing monomers may be used. It may be used as a polymerization component.
• the acrylic resin (copolymer) used in the present invention can be obtained by polymerizing the above monomers by a method such as ordinary solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization.
• the acrylic resin is preferably produced by solution polymerization in which the resin is obtained as a solution. By obtaining the acrylic resin as a solution, it can be used as it is for producing the pressure-sensitive adhesive composition of the present invention.
• Examples of the solvent used for the solution polymerization include organic solvents such as ethyl acetate, toluene, n-hexane, acetone, and methyl ethyl ketone.
• Examples of the polymerization initiator used in the polymerization include peroxides such as benzoyl peroxide and lauryl peroxide, azobis compounds such as azobisisobutyronitrile and azobisvaleronitrile, and polymer azo polymerization initiators. These can be used alone or in combination.
• polymerization in order to adjust the molecular weight of acrylic resin, a conventionally well-known chain transfer agent can be used.
• the mass average molecular weight of the acrylic copolymer is preferably in the range of 50,000 to 1,000,000, more preferably in the range of 100,000 to 800,000. When the mass average molecular weight is less than 100,000, the tackiness of the pressure-sensitive adhesive composition may be inferior. On the other hand, when the mass average molecular weight exceeds 1,000,000, the coating property of the pressure-sensitive adhesive composition is deteriorated.
• the mass average molecular weight can be measured by GPC (gel permeation chromatography) using a polystyrene standard sample.
• the glass transition temperature of the acrylic resin is preferably 30 ° C. or less.
• an acrylic resin having a glass transition temperature of 30 ° C. or lower as the main component of the pressure-sensitive adhesive, the compatibility between the acrylic resin and other components can be improved while maintaining the cohesive strength of the pressure-sensitive adhesive.
• a more preferable glass transition temperature of the acrylic resin is ⁇ 15 to 20 ° C.
• the glass transition temperature of the acrylic resin can be appropriately adjusted by changing the type of monomer units to be used, the ratio of monomer units to be combined, and the like.
• Acrylic resins may be monomer units in which the glass transition temperature is in the above range even when polymerized alone (homopolymer), but the glass transition temperature of the homopolymer is not in the above range.
• the glass transition temperature of a polymer obtained by copolymerizing various monomer units may be in the above range.
• a glass transition temperature of a polymer (homopolymer) obtained by polymerizing n-butyl (meth) acrylate alone is ⁇ 54 ° C.
• a glass transition temperature of a polymer (homopolymer) obtained by polymerizing methyl acrylate alone is 6 ° C. ° C.
• the glass transition temperature of polyacrylonitrile is 101 ° C. Therefore, an acrylic resin having a glass transition temperature of 30 ° C. or lower can be obtained by appropriately combining these monomer units.
• the glass transition temperature of the polymer means a value measured by a method (DMA method) based on the peak top value of loss tangent (tan ⁇ ).
• the loss tangent is determined by the value of loss elastic modulus / storage elastic modulus.
• the pressure-sensitive adhesive composition according to the present invention includes a cross-linking agent for cross-linking the above acrylic resin.
• a crosslinking agent for cross-linking the above acrylic resin.
• stickiness can be improved while maintaining the adhesive strength.
• crosslinking agent conventionally known crosslinking agents can be used as long as they are thermosetting crosslinking agents, and examples thereof include polyfunctional epoxy compounds and isocyanate compounds.
• Polyfunctional epoxy-based compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, Examples include 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutadiene diglycidyl ether.
• an isocyanate compound a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polyisocyanate compound and a polyol compound, and 3 amounts of the urethane prepolymer Examples include the body.
• polyisocyanate compound examples include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3 -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like.
• crosslinking agents may be used alone or in combination of two or more.
• the crosslinking agent is preferably contained in the range of 0.1 to 20% by mass with respect to the acrylic resin.
• the addition amount of the crosslinking agent is preferably contained in the range of 0.1 to 20% by mass with respect to the acrylic resin.
• the cohesiveness can be enhanced while suppressing the initial adhesive force of the adhesive, and as a result, it can be easily reattached and applied to the adherend. It can be set as the adhesive which does not float and peel after bonding.
• a preferable addition amount of the crosslinking agent is 0.5 to 10% by mass.
• the pressure-sensitive adhesive composition according to the present invention contains a photocurable resin in addition to the acrylic resin and the crosslinking agent described above.
• the photocurable resin means a precursor or a composition before being irradiated with actinic rays, and an actinic ray curable resin is obtained by irradiating actinic rays and curing the actinic ray curable resin.
• the actinic ray means radiation that chemically acts on the actinic ray curable resin to promote polymerization. Specifically, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ It means a line, a gamma ray and the like.
• the acrylic resin and the crosslinking agent described above in addition to the acrylic resin and the crosslinking agent described above, by including a photocurable resin and a photoinitiator, it can be easily reattached, and after being bonded to an adherend. There is no lifting or peeling, and even when placed in a high temperature environment, the adhesive strength does not change and it has excellent peelability, thus reducing contamination of the adherend due to adhesive residue, etc. it can. The reason is not clear, but it is thought as follows. That is, since the conventional acrylic pressure-sensitive adhesive has crosslinked the acrylic resin by heat, when the pressure-sensitive adhesive is placed in a high temperature environment, the crosslinking reaction has progressed, and adhesive residue has become a problem.
• the photocurable resin in the pressure sensitive adhesive composition is cured by light irradiation separately from heat to become a photocurable resin. Even when the reaction proceeds, it is considered that the pressure-sensitive adhesive has excellent peelability with no adhesive residue.
• any radically polymerizable compound that can be polymerized by irradiation with ionizing radiation can be used without particular limitation.
• acrylate group, vinyl group, allyl group, isopropenyl group can be used.
• the monomer, oligomer, prepolymer etc. which have radically polymerizable unsaturated groups, such as these, can be used.
• urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, polyethylene acrylate, silicone acrylate, polyol acrylate and the like can be preferably used.
• acrylate-based photocurable compounds examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, Tetrahydrofurfuryloxyhexanolide acrylate, acrylate of ⁇ -caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates with methacrylate, itaconate, crotonate, Methacrylic acid instead of maleate, itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol Acrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate,
• acrylic resins for example, bisphenol A / epichlorohydrin / (meth) acrylic acid, ethoxylated bisphenol A diacrylate, phenol novolac / epichlorohydrin / (meth) acrylic acid, etc.
• Epoxy acrylates in which (meth) acrylic acid is introduced into epoxy resin such as ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethyl Phthalyl methacrylate, xylene diisocyanate, 1,2-polybutadiene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, trimethylol group
• epoxy resin such as ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethyl Phthalyl methacrylate, xylene diisocyanate, 1,2-polybutadiene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, trimethylol group
• the photocurable resin is preferably contained in the range of 5 to 60% by mass with respect to the acrylic resin.
• the photocurable resin in the above range, it is possible to balance the initial adhesive force, the cohesive force, and the change in the adhesive force when placed in a high temperature environment at an even higher level.
• a preferable content of the photocurable resin is 5 to 40% by mass.
• the pressure-sensitive adhesive composition according to the present invention includes a photoinitiator for curing the above-described photocurable resin.
• a photoinitiator for curing the above-described photocurable resin.
• Any photoinitiator can be used without particular limitation as long as it exhibits the ability to initiate living radical polymerization upon light irradiation.
• examples include 2-2dimethoxy-1,2-diphenylethane-1-one, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl.
• Ether benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Thanong -1, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, 2,4,6-trimethylbenzoyl - phenyl - may be a known photoinitiator such as phosphine oxide.
• the photocurable resin when performing light irradiation on the pressure-sensitive adhesive composition, the photocurable resin can be reliably cured even if light irradiation is performed through a substrate or a release sheet as described later, and heat resistance Bisacylphosphine-based initiators such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide having the following are preferably used.
• the pressure-sensitive adhesive composition according to the present invention can be applied to, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, and flame retardancy as necessary.
• processability heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, and flame retardancy as necessary.
• lubricants plasticizers, fillers, fillers, antistatic agents, antiblocking agents, crosslinking agents, light stabilizers, dyes
• a colorant such as a pigment, and the like may be added.
• a coupling agent such as silane, titanium, and aluminum can be further included.
• the pressure-sensitive adhesive composition according to the present invention can be prepared by mixing the above-described components and kneading and dispersing as necessary.
• the mixing or dispersing method is not particularly limited, and a usual kneading and dispersing machine such as a two-roll mill, a three-roll mill, a pebble mill, a tron mill, a Szegvari attritor, a high-speed impeller disperser, a high-speed stone mill, A high speed impact mill, a desper, a high speed mixer, a ribbon blender, a kneader, an intensive mixer, a tumbler, a blender, a desperser, a homogenizer, an ultrasonic disperser, and the like can be applied.
• a diluent solvent may be added to mix each component.
• the pressure-sensitive adhesive sheet according to the present invention may be one in which the above-mentioned pressure-sensitive adhesive composition is used as a pressure-sensitive adhesive layer and both surfaces thereof are sandwiched between release sheets, and is provided on one surface of the base material and the base material. And a pressure-sensitive adhesive layer. Moreover, when an adhesive layer is provided on one surface of the substrate, a release sheet may be provided on the other surface of the adhesive layer.
• the pressure-sensitive adhesive layer one obtained by curing the photocurable resin in the above-described pressure-sensitive adhesive composition is used.
• the base material various forms such as a film, a sheet, or a tape can be used according to the intended use.
• the material for the substrate can be appropriately selected depending on the intended use, and is not particularly limited.
• low density polyethylene linear low density polyethylene, high density polyethylene, ethylene-propylene copolymer, polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene-vinyl acetate copolymer
• Polyolefin resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6,6 and nylon 1,12, polyimide, ethylene- (meth) acrylic acid copolymer, ethylene- ( Acrylic copolymers such as methyl (meth) acrylate copolymer and ethylene-ethyl (meth) acrylate copolymer, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, ethylene-vinyl chloride-
• the thickness of the base material is not particularly limited, and when the adhesive sheet is used as a protective sheet for an electronic circuit board or the like, it may have a thickness required according to the application, for example, a thickness of 5 to 500 ⁇ m. Can be used.
• the surface of the base material to which the pressure-sensitive adhesive composition is applied may be subjected to corona treatment or primer treatment.
• the pressure-sensitive adhesive sheet according to the present invention is obtained by forming the pressure-sensitive adhesive layer by applying the above-mentioned pressure-sensitive adhesive composition to one surface of a substrate and curing the pressure-sensitive adhesive composition by heating or light irradiation. Can do.
• the method for applying the pressure-sensitive adhesive composition to the substrate is not particularly limited. For example, roll coating, reverse roll coating, transfer roll coating, gravure coating, gravure reverse coating, comma coating, rod coating, blade coating Bar coat, wire bar coat, die coat, lip coat, dip coat, etc. can be applied.
• the acrylic resin in an adhesive composition is bridge
• the heating temperature at the time of crosslinking (curing) of the acrylic resin is about 50 to 150 ° C., preferably 90 to 120 ° C.
• the heating time is 1 to 240 minutes, preferably several minutes to 60 minutes.
• the light irradiation can be performed by irradiation with ionizing radiation.
• a monomer of a photocurable resin can be polymerized by irradiation with ultraviolet rays using a conventionally known apparatus.
• a release sheet may be provided on the surface of the pressure-sensitive adhesive layer on the side opposite to the base material side in consideration of its handleability.
• the release sheet When providing the release sheet, apply the adhesive composition to one side of the substrate and dry it, and provide the release sheet on the surface of the adhesive composition (the side opposite to the side with the substrate) After that, the pressure-sensitive adhesive composition may be heated or irradiated with light to form a pressure-sensitive adhesive layer.
• the release sheet conventionally known ones such as a release film, a separate paper, a separate film, a separate paper, a release film, and a release paper can be suitably used. Moreover, you may use what formed the release layer in the single side
• the release layer is not particularly limited as long as it is a material having releasability.
• the release sheet is formed by applying a coating liquid in which a release layer component is dispersed and / or dissolved to one side of a release paper base film, followed by heating and drying and / or curing.
• a coating method of the coating liquid a known and arbitrary coating method can be applied, for example, roll coating, gravure coating, spray coating and the like.
• the pressure-sensitive adhesive sheet having a release sheet is attached by peeling the release sheet from the pressure-sensitive adhesive sheet and bonding the release surface of the pressure-sensitive adhesive sheet to the adherend before bonding the pressure-sensitive adhesive sheet to the adherend.
• An adhesive sheet can be applied to the surface of the body. Therefore, the pressure-sensitive adhesive sheet according to the present invention can be used as a masking sheet for an electronic circuit board, etc., and can be easily reapplied even if the circuit board is extremely thin. After joining, there is no floating or peeling, and even when placed in a high temperature environment, the adhesive strength does not change and it has excellent peelability, so circuit boards etc. due to adhesive residue etc. Contamination can also be reduced.
• Example 1 Preparation of pressure-sensitive adhesive composition> Acrylic copolymer resin (mass average molecular weight) containing, as monomer units, methyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and 2-hydroxyethyl acrylate in a weight ratio of 50: 40: 0.5: 9.5, respectively. 200,000, glass transition temperature 6 ° C.).
• a pressure-sensitive adhesive sheet 1 was obtained by laminating a polyimide film substrate (trade name: Kapton 100H, manufactured by Toray DuPont) with a thickness of 25 ⁇ m on the surface of the formed pressure-sensitive adhesive layer.
• Example 2 A pressure-sensitive adhesive sheet 2 was obtained in the same manner as in Example 1 except that 7 parts by mass of bifunctional urethane acrylate (trade name: Beam Set 502H, manufactured by Arakawa Chemical Co., Ltd.) was further added as a photocurable resin.
• bifunctional urethane acrylate trade name: Beam Set 502H, manufactured by Arakawa Chemical Co., Ltd.
• Example 3 instead of the acrylic copolymer resin used in Example 1, an acrylic copolymer resin obtained by copolymerizing acrylonitrile and (meth) acrylic acid ester (trade name: Teisan Resin SG-700AS, manufactured by Nagase ChemteX Corporation) The pressure-sensitive adhesive sheet 3 was obtained in the same manner as in Example 1 except that.
• Example 4 A pressure-sensitive adhesive sheet 4 was obtained in the same manner as in Example 1 except that the photo-curable resin used in Example 1 was changed to U-200PA (manufactured by Shin-Nakamura Chemical), which is a polyester-based curable resin.
• U-200PA manufactured by Shin-Nakamura Chemical
• Example 5 A pressure-sensitive adhesive sheet 5 was obtained in the same manner as in Example 1 except that the photocurable resin used in Example 1 was changed to A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.), which is an epoxy-based curable resin.
• Comparative Example 1 Preparation of pressure-sensitive adhesive composition> As the pressure-sensitive adhesive composition, one prepared in the same manner as in Example 1 was used except that the photocurable resin and the photocurable agent were not blended.
• a pressure-sensitive adhesive sheet 4 was obtained by laminating a polyimide film substrate (trade name: Kapton 100H, manufactured by Toray DuPont) with a thickness of 25 ⁇ m on the surface of the formed pressure-sensitive adhesive layer.
• the obtained pressure-sensitive adhesive sheet is cut into a size of 25 mm ⁇ 150 mm, the polyester film subjected to the easy peeling treatment is peeled from the pressure-sensitive adhesive sheet to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is made of copper foil (product). Name: RCF-T58, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.), pressure-bonded using a 2 kg roller, and allowed to stand in a normal temperature and normal pressure (about 23 ° C., about 60% RH) environment for 20 minutes.

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• Chemical & Material Sciences (AREA)
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• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)
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• Application Of Or Painting With Fluid Materials (AREA)

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• 2014
  • 2014-02-05 JP JP2014020236A patent/JP5858347B2/ja active Active
• 2015
  • 2015-01-29 WO PCT/JP2015/052562 patent/WO2015119042A1/ja active Application Filing
  • 2015-01-29 KR KR1020167019773A patent/KR20160118239A/ko not_active Application Discontinuation
  • 2015-01-29 CN CN201580004040.6A patent/CN105899633A/zh active Pending
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