WO2011068117A1 - 光硬化型粘接着剤組成物、光硬化型粘接着剤層、および光硬化型粘接着シート - Google Patents
光硬化型粘接着剤組成物、光硬化型粘接着剤層、および光硬化型粘接着シート Download PDFInfo
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- WO2011068117A1 WO2011068117A1 PCT/JP2010/071475 JP2010071475W WO2011068117A1 WO 2011068117 A1 WO2011068117 A1 WO 2011068117A1 JP 2010071475 W JP2010071475 W JP 2010071475W WO 2011068117 A1 WO2011068117 A1 WO 2011068117A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—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
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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
- 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
- C09J2451/00—Presence of graft polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Definitions
- the present invention relates to a photocurable adhesive composition in which such a photocurable adhesive layer is formed on at least one surface of a photocurable adhesive composition, a photocurable adhesive layer, and a support.
- the present invention relates to an adhesive sheet.
- an acrylic pressure-sensitive adhesive is widely used because it is excellent in heat resistance and light resistance.
- the acrylic pressure-sensitive adhesive cannot exhibit a high peeling resistance like an adhesive.
- thermosetting type that is cured by heat treatment has been proposed for bonding applications such as electronic components.
- a thermosetting adhesive is excellent in adhesive strength and heat resistance, but is not tacky at room temperature bonding and is difficult to temporarily bond.
- the adhesive component is a low molecular weight component, which causes problems such as sticking out of the adhesive during adhesion. Therefore, an adhesive sheet that exhibits moderate tackiness as a pressure-sensitive adhesive at the initial stage of adhesion to an adherend and exhibits high adhesion and high heat resistance equivalent to the adhesive after bonding is desired.
- Patent Document 1 a curable thermal adhesive sheet including a resin having an acrylic polymer and an epoxy group, a photoinitiator, and a tackifying resin has been proposed (Patent Document 1).
- Patent Document 1 since it contains a low molecular weight epoxy resin or the like, it is difficult to prevent the paste from protruding during temporary bonding.
- the present invention is excellent in heat resistance, has no adhesive sticking out at normal temperature and normal pressure, has sufficient initial adhesive strength by drying and crosslinking, is easily cured by light irradiation, and has high peeling resistance. It aims at providing the photocurable adhesive composition which can form an adhesive layer.
- Another object of the present invention is to provide a photocurable adhesive layer and a photocurable adhesive sheet formed from the photocurable adhesive composition.
- the present invention provides a graft polymer obtained by graft-polymerizing a chain containing a cyclic ether group-containing monomer to a (meth) acrylic polymer containing 0.2 to 10% by weight of a hydroxyalkyl (meth) acrylamide monomer as a monomer unit; And a photocurable adhesive composition characterized by containing a photocationic polymerization initiator.
- the graft polymer is preferably obtained by graft polymerization of a chain having the cyclic ether group-containing monomer and other monomers on a (meth) acrylic polymer.
- the photocurable adhesive composition it is preferable to further contain a crosslinking agent.
- the cyclic ether group-containing monomer is preferably one or both of an epoxy group-containing monomer and an oxetane group-containing monomer.
- the glass transition temperature of the (meth) acrylic polymer is preferably 250 K or less.
- the graft polymer may contain 2 to 50 parts by weight of the cyclic ether group-containing monomer and 5 to 50 parts by weight of the other monomer to 100 parts by weight of the (meth) acrylic polymer. It is preferably obtained by graft polymerization in the presence of 0.02 to 5 parts by weight of peroxide.
- the photocationic polymerization initiator is composed of allylsulfonium hexafluorophosphate salt, sulfonium hexafluorophosphate salt, and bis (alkylphenyl) iodonium hexafluorophosphate. It is preferably at least one selected from the group.
- the present invention also relates to a photocurable pressure-sensitive adhesive layer obtained by crosslinking the photocurable pressure-sensitive adhesive composition described above.
- the present invention also relates to a photocurable pressure-sensitive adhesive sheet, characterized in that the above-mentioned pressure-sensitive adhesive layer for optical members is formed on at least one side of a support.
- the present invention is also a method for producing the photocurable adhesive composition according to any one of the above, wherein after the preparation of the (meth) acrylic polymer, the (meth) acrylic polymer contains a cyclic ether group. And a step of graft-polymerizing a monomer and optionally other monomers to prepare a graft polymer; and a step of mixing a photocationic polymerization initiator into the graft polymer.
- the present invention relates to a method for producing a composition.
- the step of preparing the graft polymer it is preferable to graft polymerize a cyclic ether group-containing monomer and other monomers to the (meth) acrylic polymer after the preparation of the (meth) acrylic polymer.
- the photocurable adhesive composition of the present invention can provide a photocurable adhesive layer and a photocurable adhesive sheet excellent in heat resistance, and there is no paste protruding at room temperature and normal pressure. It is possible to form an adhesive layer that has a sufficient initial adhesive force by drying and crosslinking, is easily cured by light irradiation, and has a high peeling resistance.
- the photo-curable adhesive composition of the present invention has a fluidity in the production process of the graft polymer contained therein, is easy to handle, and as a result has excellent workability and final adhesiveness. It becomes a thing.
- the photocurable adhesive composition of the present invention is a chain containing a cyclic ether group-containing monomer in a (meth) acrylic polymer containing 0.2 to 10% by weight of a hydroxyalkyl (meth) acrylamide monomer as a monomer unit.
- any (meth) acrylate can be used and is not particularly limited.
- an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms is contained in an amount of 50% by weight or more of the entire (meth) acrylic polymer.
- alkyl (meth) acrylate simply refers to (meth) acrylate having a linear or branched alkyl group.
- the alkyl group has 4 or more carbon atoms, preferably 4 to 9 carbon atoms.
- (Meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.
- alkyl (meth) acrylates include n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl ( (Meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth)
- the alkyl (meth) acrylate is 50% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more based on the total monomer components of the (meth) acrylic polymer.
- the alkyl (meth) acrylate is preferably 99.8% by weight or less, and may be 98% by weight or less or 97% by weight or less.
- the (meth) acrylic polymer of the present invention contains a hydroxyl group-containing monomer containing at least one hydroxyl group in the alkyl group. That is, this monomer is a hydroxyalkyl (meth) acrylamide monomer containing a hydroxyalkyl group having one or more hydroxyl groups.
- the hydroxyl group is preferably present at the terminal of the alkyl group.
- the number of carbon atoms of the alkyl group is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.
- the position at which hydrogen abstraction occurs during graft polymerization and the compatibility between the graft polymer and the homopolymer of the cyclic ether group-containing monomer produced during graft polymerization are achieved. It has a positive effect and is believed to help prepare a graft polymer with good heat resistance.
- hydroxyalkyl (meth) acrylamide having a polymerizable functional group having an unsaturated double bond of a (meth) acryloyl group and having a hydroxyl group can be used without particular limitation.
- hydroxyalkyl (meth) acrylamides such as octyl (meth) acrylamide and 10-hydroxydecyl (meth) acrylamide.
- Hydroxyalkyl (meth) acrylamide is 0.2% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more based on the total amount of monomer components forming the (meth) acrylic polymer. Yes, up to 10% by weight. Preferably, it is 1 to 10% by weight.
- the monomer component for forming the (meth) acrylic polymer other copolymers may be used alone or in combination as long as the object of the present invention is not impaired.
- an unsaturated carboxylic acid-containing monomer can be used in addition to the monomer.
- a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation.
- the unsaturated carboxylic acid-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These can be used alone or in combination. Among these, it is preferable to use (meth) acrylic acid, particularly acrylic acid.
- the unsaturated carboxylic acid-containing monomer is preferably used in a proportion of 0.01 to 2% by weight, more preferably 0.05 to 2% by weight, based on the total amount of monomer components forming the (meth) acrylic polymer. %, More preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1% by weight.
- comonomer examples include, for example, an aromatic group having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an aromatic ring. Ring-containing monomers.
- aromatic ring-containing monomer examples include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, 2-naphthoethyl (meth) acrylate, 2- (4-methoxy-1- And naphthoxy) ethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and polystyryl (meth) acrylate.
- acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrene sulfonic acid and allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) Sulfonic acid group-containing monomers such as acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; methoxyethyl (meth) acrylate, ( And (meth) acrylic acid alkoxyalkyl monomers such as ethoxyethyl (meth) acrylate.
- acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone a
- vinyl monomers such as vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N-vinylcaprolactam; glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) Epoxy group-containing monomers such as acrylate; glycol-based acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate Amide group-containing monomers, amino group-containing monomers, imide group-containing monomer, N- acryloyl
- the weight average molecular weight of the (meth) acrylic polymer of the present invention is preferably 600,000 or more, more preferably 700,000 to 3 million.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
- Such a (meth) acrylic polymer can be produced by appropriately selecting a known production method such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. Further, the (meth) acrylic polymer obtained may be either a random copolymer or a block copolymer.
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out under an inert gas stream such as nitrogen and a polymerization initiator is added, usually at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), persulfates such as potassium persulfate and ammonium persulfate , Di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl Peroxydicarbonate, t
- the polymerization initiator may be used singly or as a mixture of two or more, but the total content is 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer. Is preferably about 0.02 to 0.5 parts by weight.
- the amount of the polymerization initiator used is a monomer.
- the amount is preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight with respect to 100 parts by weight of the total amount of the components.
- chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
- emulsifier used in emulsion polymerization examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer are listed. These emulsifiers may be used alone or in combination of two or more.
- reactive emulsifiers emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10N (manufactured by ADEKA), and the like.
- Reactive emulsifiers are preferred because they are incorporated into the polymer chain after polymerization and thus have improved water resistance.
- the amount of the emulsifier used is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
- the glass transition temperature (Tg) of the (meth) acrylic polymer is 250K or less, preferably 240K or less.
- the glass transition temperature is also preferably 200K or higher.
- the adhesive composition has good heat resistance and excellent internal cohesive strength.
- Such a (meth) acrylic polymer can be adjusted by appropriately changing the monomer component and composition ratio to be used.
- Such a glass transition temperature is obtained by, for example, solution polymerization using 0.06 to 0.2 part of a polymerization initiator such as azobisisovityronitrile or benzoyl peroxide and using a polymerization solvent such as ethyl acetate. Then, it is obtained by reacting at 50 to 70 ° C.
- the glass transition temperature (Tg) of a single polymer is Polymer. Obtained from Handbook (4th edition, John Wiley & Sons. Inc.).
- Graft polymerization is carried out by reacting a (meth) acrylic polymer with a cyclic ether group-containing monomer and optionally a cyclic ether group-containing monomer and other monomers.
- the cyclic ether group-containing monomer is not particularly limited, but is preferably an epoxy group-containing monomer, an oxetane group-containing monomer, or a combination of both.
- epoxy group-containing monomer examples include 4-hydroxybutyl glycidyl acrylate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, or 4-hydroxybutyl acrylate glycidyl ether. These can be used alone or in combination.
- oxetane group-containing monomers examples include 3-oxetanylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, and 3-butyl-3-oxetanylmethyl. Examples thereof include (meth) acrylate and 3-hexyl-3-oxetanylmethyl (meth) acrylate, and these can be used alone or in combination.
- the amount of the cyclic ether group-containing monomer is preferably 2 parts by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic polymer.
- the upper limit is not particularly limited, but is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less.
- the amount of the cyclic ether group-containing monomer is 2 parts by weight or more, the function of the composition as a pressure-sensitive adhesive is sufficiently exhibited.
- the amount is 50 parts by weight or more, tackiness is reduced and initial adhesion is difficult. There is.
- Such a monomer is not particularly limited as long as it does not contain a cyclic ether group, and examples thereof include alkyl (meth) acrylates having 1 to 9 carbon atoms.
- alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl acrylate and the like.
- alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate can also be used. These can be used alone or in combination.
- the irradiation amount at the time of light irradiation for effecting the adhesive can be lowered. This is presumably because the mobility of the graft chain is increased, or because the compatibility between the graft chain and the by-product ungrafted chain and the backbone polymer is improved.
- Such other monomers are also preferably selected from the same monomers as the main chain (trunk), that is, the components of the (meth) acrylic polymer.
- the amount of other monomers other than the cyclic ether group-containing monomer is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. If the content of other monomers is small, the effect of reducing the light irradiation amount for curing may not be sufficient, and if it is large, the peeling resistance after light irradiation may increase.
- Graft polymerization conditions are not particularly limited, and can be carried out by methods known to those skilled in the art.
- a peroxide it is preferable to use as a polymerization initiator.
- the amount of such a polymerization initiator is 0.02 to 5 parts by weight with respect to 100 parts by weight of the meth) acrylic polymer.
- the amount of this polymerization initiator is small, it takes too much time for the graft polymerization reaction, and when it is large, many homopolymers of cyclic ether group-containing monomers are formed, which is not preferable.
- a cyclic ether group-containing monomer and a viscosity-adjustable solvent are added to the acrylic copolymer solution, followed by nitrogen substitution, and then a peroxide system such as dibenzoyl peroxide.
- the polymerization initiator may be added by 0.02 to 5 parts by weight and heated at 50 to 80 ° C. for 4 to 15 hours, but is not limited thereto.
- the state of the obtained graft polymer (molecular weight, branch polymer branch size, etc.) can be appropriately selected depending on the reaction conditions.
- the adhesive composition of the present invention contains the graft polymer thus obtained and a photocationic polymerization initiator.
- any photocationic polymerization initiator known to those skilled in the art can be preferably used. More specifically, at least one selected from the group consisting of allylsulfonium hexafluorophosphate salt, sulfonium hexafluorophosphate salt, and bis (alkylphenyl) iodonium hexafluorophosphate can be used. .
- Such a cationic photopolymerization initiator may be used alone or in combination of two or more, but the total content is 100 weight of the (meth) acrylic polymer.
- the amount is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight.
- a crosslinking agent is added to the photocurable pressure-sensitive adhesive composition of the present invention as necessary.
- a crosslinking agent Isocyanate which is a compound which has two or more isocyanate groups (including the isocyanate reproduction
- a system crosslinking agent is illustrated.
- isocyanate-based crosslinking agent examples include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), tri Methylolpropane / hexamethylene diisocyanate trimer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene dii Isocyan
- the isocyanate-based crosslinking agent may be used alone or in combination of two or more, but the total content is 100 parts by weight of the (meth) acrylic polymer.
- the isocyanate compound crosslinking agent is preferably contained in an amount of 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and 0.05 to 1.5 parts by weight. More preferably. It can be appropriately contained in consideration of cohesive force and prevention of peeling in a durability test.
- an organic crosslinking agent or a polyfunctional metal chelate may be used in combination.
- the organic crosslinking agent include epoxy crosslinking agents (referring to compounds having two or more epoxy groups in one molecule).
- examples of the epoxy-based crosslinking agent include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, terephthalic acid diglycidyl ester acrylate, spiroglycol diglycidyl ether, and the like. These may be used alone or in combination of two or more.
- the multifunctional metal chelate is a polyvalent metal having a covalent bond or a coordinate bond with an organic compound.
- polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. can give.
- the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
- oxazoline-based crosslinking agent those having an oxazoline group in the molecule can be used without particular limitation.
- the oxazoline group may be any of 2-oxazoline group, 3-oxazoline group, and 4-oxazoline group.
- a polymer obtained by copolymerizing an unsaturated monomer with an addition-polymerizable oxazoline is preferable, and a compound using 2-isopropenyl-2-oxazoline as the addition-polymerizable oxazoline is particularly preferable.
- the peroxide can be used as appropriate as long as it generates radical active species by heating and proceeds with crosslinking of the base polymer of the adhesive composition, but in consideration of workability and stability, It is preferable to use a peroxide having a 1 minute half-life temperature of 80 ° C. to 160 ° C., and more preferable to use a peroxide having a 90 ° C. to 140 ° C.
- peroxides examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl
- di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.)
- dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C)
- dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C) and the like are preferably used.
- the peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half.
- the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".
- the peroxide may be used alone or as a mixture of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer.
- the peroxide is 0.01 to 2 parts by weight, preferably 0.04 to 1.5 parts by weight, more preferably 0.05 to 1 part by weight. In order to adjust processability, reworkability, cross-linking stability, peelability, and the like, it is appropriately selected within this range.
- the peroxide decomposition amount remaining after the reaction treatment for example, it can be measured by HPLC (High Performance Liquid Chromatography).
- the adhesive layer is formed by the crosslinking agent
- the addition amount of the entire crosslinking agent is adjusted, and the influence of the crosslinking treatment temperature and the crosslinking treatment time is sufficiently considered. There is a need.
- the photocurable adhesive composition of the present invention may further contain an epoxy resin or an oxetane resin in order to further improve the adhesive strength and heat resistance.
- epoxy resin examples include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolak type, cresol novolak type.
- epoxy resins include bifunctional epoxy resins such as trishydroxyphenylmethane type and tetraphenylolethane type and polyfunctional epoxy resins, and glycidylamine types such as hydantoin type and trisglycidyl isocyanurate type. These epoxy resins can be used alone or in combination of two or more.
- epoxy resins are not limited, but commercially available epoxy resins can be used.
- commercially available epoxy resins include, but are not limited to, for example, bisphenol type epoxy resins such as Japan Epoxy Resin Co., Ltd. jER828, jER806, etc .; alicyclic epoxy resins such as Japan Epoxy Resin Co., Ltd. YX8000, YX8034, etc. ADEKA Co., Ltd. EP4000, EP4005, etc .; polyglycidyl ethers of polyalcohol include known epoxy resins such as Nagase ChemteX Corporation Denacol EX-313, EX-512, EX-614B, EX-810, etc. .
- oxetane resins include xylylene oxetane such as 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and 3-ethyl-3- ⁇ [3-ethyloxetane-3-yl] methoxy. ⁇ Methyl ⁇ oxetane, 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl-3-hydroxymethyloxetane, and other known oxetane resins can be used. These oxetane resins can be used singly or in combination of two or more.
- the oxetane resin is not limited, but a commercially available resin can be used.
- Examples of such commercially available oxetane resins include Aron Oxetane OXT-121, OXT221, OXT101, and OXT212 manufactured by Toa Gosei Co., Ltd., but are not limited thereto.
- Such an epoxy resin and an oxetane resin can be used in the photocurable adhesive composition of the present invention by either one or a combination of both.
- an epoxy resin and / or an oxetane resin and other tackifiers can be blended.
- the total amount is contained with respect to 100 parts by weight of the graft polymer, It is 10 parts by weight or more, more preferably 20 parts by weight or more, preferably 100 parts by weight or less, more preferably 80 parts by weight or less.
- the photocurable adhesive composition of the present invention may contain other known additives such as powders such as colorants and pigments, dyes, surfactants, plasticizers, and adhesives.
- Property imparting agent, surface lubricant, leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, UV absorber, polymerization inhibitor, inorganic or organic filler, metal powder, particulate, foil Or the like can be added as appropriate according to the use for which the material is used.
- the photo-curing adhesive layer of the present invention is preferably formed on at least one side of the support.
- a photocurable adhesive agent layer can be formed by apply
- a photocurable adhesive layer or a photocurable adhesive sheet can also be obtained by transferring a photocurable adhesive layer formed on a separator (release film) to one or both sides of a support substrate. Can be formed. Furthermore, it can also be used as a double-sided adhesive sheet
- the photo-curing adhesive sheets are used in the form of a sheet or tape.
- the supporting substrate in the adhesive sheet examples include a porous substrate made of paper, cloth, nonwoven fabric, etc., a plastic film or sheet such as polyethylene, polypropylene, polyethylene terephthalate, and polyester film, a net, a foam, a metal foil, and Appropriate thin leaves such as these laminates can be mentioned.
- These support base materials are appropriately selected according to the use for which the adhesive sheet is used.
- the thickness of the supporting substrate is not particularly limited, and is appropriately determined depending on the application.
- the method for forming the photocurable adhesive layer is, for example, applying the adhesive composition to a release-treated separator, drying and removing the polymerization solvent, etc.
- one or more solvents other than the polymerization solvent may be added as appropriate.
- a silicone release liner is preferably used as the release-treated separator.
- a method of drying the adhesive according to the purpose, Appropriate methods can be employed.
- a method of heating and drying the coating film is used.
- the heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C.
- the drying time an appropriate time can be adopted as appropriate.
- the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
- an adhesive layer can be formed after an anchor layer is formed on the surface of the support or after various easy adhesion treatments such as corona treatment and plasma treatment. Moreover, you may perform an easily bonding process on the surface of an adhesive agent layer.
- Various methods are used as a method for forming the adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
- the thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 ⁇ m.
- the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 35 ⁇ m.
- the adhesive layer When the adhesive layer is exposed, the adhesive layer may be protected with a peeled sheet (separator) until practical use.
- plastic films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous materials such as paper, cloth, nonwoven fabric, nets, foamed sheets, metal foils, and these
- a plastic film is preferably used from the viewpoint of excellent surface smoothness.
- the plastic film is not particularly limited as long as it can protect the adhesive layer, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, chloride film.
- the adhesive layer for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, chloride film.
- examples thereof include a vinyl copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.
- a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment, the peelability from the adhesive layer can be further enhanced.
- the sheet subjected to the above-described peeling treatment can be used as it is as a separator for a photo-curing adhesive sheet, and the process can be simplified.
- the photocurable adhesive composition, the photocurable adhesive layer, and the photocurable adhesive sheet of the present invention are cured by irradiating specific light. Therefore, the photocurable pressure-sensitive adhesive sheet of the present invention can be easily cured by irradiating light immediately before or after bonding to the adherend.
- the photo-curing adhesive sheet interposed between the adherend and the member is preferably used in a form such as a double-sided adhesive tape, and is cured by irradiating light any time after bonding. You can also. By such a curing reaction, adhesion to the adherend or adhesion between the adherend and the member is ensured.
- the light for irradiation is active energy rays, such as an ultraviolet-ray, visible light, and an electron beam.
- the crosslinking treatment by ultraviolet irradiation can be performed using an appropriate ultraviolet ray source such as a high pressure mercury lamp, a low pressure mercury lamp, an excimer laser, or a metal halide lamp.
- the irradiation amount of the ultraviolet ray can be appropriately selected according to the required degree of crosslinking, but it is usually preferable to select the ultraviolet ray within a range of 0.2 to 10 J / cm 2.
- the temperature at the time of irradiation is not specifically limited, Considering the heat resistance of a support body, about 140 degreeC is preferable.
- the use of the photocurable adhesive composition, the photocurable adhesive layer, and the photocurable adhesive sheet of the present invention is not particularly limited, for example, an adhesive application for an optical member, a semiconductor Applications include bonding elements to organic substrates and lead frames, bonding of automobile parts, and architectural applications.
- the weight average molecular weight of the obtained (meth) acrylic polymer was measured by GPC (gel permeation chromatography).
- the sample was prepared by dissolving the sample in dimethylformamide to give a 0.1% by weight solution, which was allowed to stand overnight and then filtered through a 0.45 ⁇ m membrane filter.
- the pressure-sensitive adhesive film after photocuring was subjected to TMA (thermomechanical analysis) measurement under the following conditions to measure the heat resistance level.
- Thermophysical properties were measured at 20 ° C. to 300 ° C. at a temperature increase rate of 10 ° C./min with a cross-sectional area of 0.6 mm 2 , a sample length of 10 mm, and a load of 19.6 mN using TMA / SS6100 manufactured by SII Nano Technology. .
- the inflection point temperature was adopted as the heat resistant temperature.
- Example 1 (Preparation of acrylic polymer) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 97 parts by weight of n-butyl acrylate, 3 parts by weight of hydroxyethyl acrylamide (Kojin HEAA), and 2,2 ′ as a polymerization initiator -Charge 0.1 parts by weight of azobisisobutyronitrile together with 140 parts by weight of ethyl acetate and 60 parts by weight of toluene, introduce nitrogen gas with gentle stirring, and replace with nitrogen for 1 hour. A polymerization reaction was carried out for 10 hours while maintaining the temperature at around 55 ° C. to prepare an acrylic polymer solution having a weight average molecular weight of 900,000. The glass transition temperature of the obtained acrylic polymer was 225K.
- Adhesive strength measurement sample 1A Next, 0.3 parts by weight of trimethylolpropane adduct of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., Coronate HL), 100 parts by weight of the solid content of the graft polymer solution thus obtained, allylsulfonium hexafluoro An adhesive solution was prepared by blending 1 part by weight of phosphate (manufactured by LAMBERTI, ESACURE 1064).
- the adhesive solution was applied to one side of a 25 ⁇ m polyethylene terephthalate (PET) film (“S-10” manufactured by Toray Industries Inc.) so that the thickness of the adhesive layer after drying was 20 ⁇ m.
- PET polyethylene terephthalate
- a test sample was prepared by drying at 120 ° C. for 3 minutes, and bonded to a 38 ⁇ m PET separator (MRF-38, manufactured by Mitsubishi Plastics, Inc.) subjected to silicone treatment.
- Sample for gel fraction measurement 1A Further, the gel fraction is measured without irradiating light to the test sample 1A thus obtained, and this is set as the gel fraction not irradiated with light.
- test sample 2A is irradiated with 1 J / cm 2 light with a meta-harara UV lamp, and then subjected to dark reaction treatment (50 ° C., 48 hours).
- the gel fraction is measured with this sample to obtain the gel fraction at the time of light irradiation.
- Example 2 (Preparation of acrylic polymer) In the same manner as in Example 1, an acrylic polymer solution was prepared.
- a diluted solution (I) The obtained acrylic polymer solution was diluted with ethyl acetate so that the solid content was 25% to prepare a diluted solution (I).
- a diluted solution (I) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 10 parts of 4-hydroxybutyl acrylate glycidyl ether and 10 parts of isobornyl acrylate with respect to 400 parts by weight of the diluted solution (I) And 0.1 part of benzoyl peroxide were added, nitrogen gas was introduced with gentle stirring, and the atmosphere was purged with nitrogen for 1 hour. The liquid temperature in the flask was kept at around 60 ° C. for 4 hours, and then at 70 ° C. for 4 hours. A polymerization reaction was performed to obtain a graft polymer solution.
- the adhesive solution was applied to one side of a 25 ⁇ m polyethylene terephthalate (PET) film (“S-10” manufactured by Toray Industries Inc.) so that the thickness of the adhesive layer after drying was 20 ⁇ m.
- PET polyethylene terephthalate
- a test sample was prepared by drying at 120 ° C. for 3 minutes, and bonded to a 38 ⁇ m PET separator (MRF-38, manufactured by Mitsubishi Plastics, Inc.) subjected to silicone treatment.
- Sample for gel fraction measurement 2A Further, the gel fraction is measured without irradiating light to the test sample 2A thus obtained, and this is set as the gel fraction not irradiated with light.
- test sample 2A is irradiated with 1 J / cm 2 light with a meta-harara UV lamp, and then subjected to dark reaction treatment (50 ° C., 48 hours).
- the gel fraction is measured with this sample to obtain the gel fraction at the time of light irradiation.
- Comparative Example 1 (Preparation of acrylic polymer) In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, and condenser, 97 parts by weight of n-butyl acrylate, 3 parts by weight of 4-hydroxybutyl acrylate, and 2,2′-azobis as a polymerization initiator After charging 0.1 parts by weight of isobutyronitrile together with 140 parts by weight of ethyl acetate and 60 parts by weight of toluene, nitrogen gas was introduced with gentle stirring and the atmosphere was purged with nitrogen for 1 hour. And an acrylic polymer solution having a weight average molecular weight of 880,000 was prepared. The glass transition temperature of the obtained polymer was 223K.
- the adhesive solution was applied to one side of a 25 ⁇ m polyethylene terephthalate (PET) film (“S-10” manufactured by Toray Industries Inc.) so that the thickness of the adhesive layer after drying was 20 ⁇ m.
- PET polyethylene terephthalate
- a test sample was prepared by drying at 120 ° C. for 3 minutes, and bonded to a 38 ⁇ m PET separator (MRF-38, manufactured by Mitsubishi Plastics, Inc.) subjected to silicone treatment.
- Sample for gel fraction measurement 3A Moreover, the gel fraction is measured without irradiating light to the test sample 3A thus obtained, and this is set as the gel fraction not irradiated with light.
- test sample 3A is irradiated with 1 J / cm 2 light with a meta-harara UV lamp, and then subjected to dark reaction treatment (50 ° C., 48 hours).
- the gel fraction is measured with this sample to obtain the gel fraction at the time of light irradiation.
- Comparative Example 2 (Preparation of acrylic polymer) In the same manner as in Comparative Example 1, an acrylic polymer solution was prepared.
- a diluted solution (I) The obtained acrylic polymer solution was diluted with ethyl acetate so that the solid content was 25% to prepare a diluted solution (I).
- a diluted solution (I) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 10 parts of 4-hydroxybutyl acrylate glycidyl ether and 10 parts of isobornyl acrylate with respect to 400 parts by weight of the diluted solution (I) And 0.1 part of benzoyl peroxide were added, nitrogen gas was introduced with gentle stirring, and the atmosphere was purged with nitrogen for 1 hour. The liquid temperature in the flask was kept at around 60 ° C. for 4 hours, and then at 70 ° C. for 4 hours. A polymerization reaction was performed to obtain a graft polymer solution.
- the above adhesive solution was applied to one side of a 25 ⁇ m polyethylene terephthalate (PET) film (“S-10” manufactured by Toray Industries, Inc.) so that the thickness of the adhesive layer after drying was 20 ⁇ m.
- PET polyethylene terephthalate
- a test sample was prepared by drying at 120 ° C. for 3 minutes, and bonded to a 38 ⁇ m PET separator (MRF-38, manufactured by Mitsubishi Plastics, Inc.) subjected to silicone treatment.
- Sample for gel fraction measurement 4A Further, the gel fraction is measured without irradiating light to the test sample 4A thus obtained, and this is set as the gel fraction not irradiated with light.
- test sample 4A is irradiated with 5 J / cm 2 light with a metaharahal UV lamp, and then subjected to dark reaction treatment (50 ° C., 48 hours).
- the gel fraction is measured with this sample to obtain the gel fraction at the time of light irradiation.
- Table 1 shows the evaluation results of the adhesive strength performed on the samples obtained in the above Examples and Comparative Examples.
- Table 2 shows the evaluation results of the gel fraction of the adhesive layer performed on the samples obtained in the above Examples and Comparative Examples.
- Table 3 shows the heat-resistant temperature by TMA of the adhesive layer obtained for the samples obtained in the above Examples and Comparative Examples.
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Abstract
Description
該グラフトポリマーに光カチオン系重合開始剤を混合する工程、を含むことを特徴とする光硬化型粘接着剤組成物の製造方法、に関する。
1/Tg=W1/Tg1+W2/Tg2+W3/Tg3+・・・・
上記Tg1、Tg2、Tg3等は、共重合成分それぞれ単独の重合体1、2、3等のガラス転移温度を絶対温度で表したものであり、W1、W2、W3等は、それぞれの共重合成分の重量分率である。なお、単独の重合体のガラス転移温度(Tg)は、Polymer
Handbook (4th edition, John Wiley & Sons. Inc.)から得た。
得られた(メタ)アクリル系ポリマーの重量平均分子量は、GPC(ゲル・パーミエー
ション・クロマトグラフィー)により測定した。サンプルは、試料をジメチルホルムアミドに溶解して0.1重量%の溶液とし、これを一晩静置した後、0.45μmのメンブレンフィルターで濾過した濾液を用いた。
・分析装置:東ソー社製、HLC-8120GPC
・カラム:東ソー社製、G7000HXL+GMHXL+GMHXL
・カラムサイズ;各7.8mmφ×30cm 計90cm
・溶離液:テトラヒドロフラン(濃度0.1重量%)
・流量:0.8ml/min
・検出器:示差屈折計(RI)
・カラム温度:40℃
・ 注入量:100μl
・ 標準試料:ポリスチレン
乾燥・架橋処理した粘着剤(最初の重量W1)を、酢酸エチル溶液に浸漬して、室温で1週間放置した後、不溶分を取り出し、乾燥させた重量(W2)を測定し、下記のように求めた。
ゲル分率=(W2/W1)×100
光硬化させた後の粘着接着フィルムについて、以下のような条件で、TMA(熱機械分析)測定を行い、耐熱性のレベルを測定した。熱物性は、SIIナノテクノロジー社製TMA/SS6100にて、断面積0.6mm2、サンプル長10mm、19.6mNの荷重で10℃/minの昇温速度で、20℃~300℃で測定した。耐熱温度としては、屈曲点温度を採用した。
(アクリル系ポリマーの調製)
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、n-ブチルアクリレート97重量部、ヒドロキシエチルアクリルアミド(興人HEAA)3重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1重量部を酢酸エチル140重量部およびトルエン60重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を55℃付近に保って10時間重合反応を行い、重量平均分子量90万のアクリル系ポリマー溶液を調製した。得られたアクリル系ポリマーのガラス転移温度は225Kであった。
得られたアクリル系ポリマー溶液を、酢酸エチルにて固形分が25%になるように希釈して、希釈溶液(I)を調製した。攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、希釈溶液(I)400重量部に対して、4-ヒドロキシブチルアクリレートグリシジルエーテル10部、2-エチルヘキシルアクリレート10部とベンゾイルパーオキサイド0.1部を加え、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を60℃付近に保って4時間、次いで70℃で4時間重合反応を行い、グラフトポリマー溶液を得た。
次いで、このようにして得られたグラフトポリマー溶液の固形分100重量部に対して、ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体(日本ポリウレタン社製、コロネートHL)0.3重量部、アリルスルホニウムヘキサフルオロフォスフェート(LAMBERTI社製、ESACURE1064)1重量部を配合して粘接着剤溶液を調製した。
また、このようにして得られた試験サンプル1Aに光を照射せずにゲル分率の測定を行い、これを光未照射のゲル分率とする。
ついで、試験サンプルから20mm×100mmのサンプル片を切り出し、厚さ 2mmのアクリル板(三菱レイヨン社製「アクリライト」)および厚さ0.4mmのBA板(SUS430鋼板表面仕上げBA鋼板)に2kgのロール1往復で貼り付けた。このときの180°ピール接着力(剥離速度300mm/分)を測定し、光未照射時の接着力とする。これに、メタハラUVランプで、1J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルの180°ピール接着力を測定し、光照射時の接着力とする。
試験サンプル2Aに、メタハラUVランプで、1J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルでゲル分率を測定し、光照射時のゲル分率とする。
(アクリル系ポリマーの調製)
実施例1と同様にして、アクリル系ポリマー溶液を調製した。
得られたアクリル系ポリマー溶液を、酢酸エチルにて固形分が25%になるように希釈して、希釈溶液(I)を調製した。攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、希釈溶液(I)400重量部に対して、4-ヒドロキシブチルアクリレートグリシジルエーテル10部、イソボルニルアクリレート10部とベンゾイルパーオキサイド0.1部を加え、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を60℃付近に保って4時間、次いで70℃で4時間重合反応を行い、グラフトポリマー溶液を得た。
次いで、このようにして得られたグラフトポリマー溶液の固形分100重量部に対して、ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体(日本ポリウレタン社製、コロネートHL)0.3重量部、アリルスルホニウムヘキサフルオロフォスフェート(LAMBERTI社製、ESACURE1064)1重量部を配合して粘接着剤溶液を調製した。
また、このようにして得られた試験サンプル2Aに光を照射せずにゲル分率の測定を行い、これを光未照射のゲル分率とする。
ついで、試験サンプル2Aから20mm×100mmのサンプル片を切り出し、厚さ 2mmのアクリル板(三菱レイヨン社製「アクリライト」)および厚さ0.4mmのBA板(SUS430鋼板表面仕上げBA鋼板)に2kgのロール1往復で貼り付けた。このときの180°ピール接着力(剥離速度300mm/分)を測定し、光未照射時の接着力とする。これに、メタハラUVランプで、1J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルの180°ピール接着力を測定し、光照射時の接着力とする。
試験サンプル2Aに、メタハラUVランプで、1J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルでゲル分率を測定し、光照射時のゲル分率とする。
(アクリル系ポリマーの調製)
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、n-ブチルアクリレート97重量部、4-ヒドロキシブチルアクリレート3重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1重量部を酢酸エチル140重量部およびトルエン60重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を55℃付近に保って10時間重合反応を行い、重量平均分子量88万のアクリル系ポリマー溶液を調製した。得られたポリマーのガラス転移温度は、223Kであった。
得られたアクリル系ポリマー溶液を、酢酸エチルにて固形分が25%になるように希釈して、希釈溶液(I)を調製した。攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、希釈溶液(I)400重量部に対して、4-ヒドロキシブチルアクリレートグリシジルエーテル10部、2-エチルエキシルアクリレート10部とベンゾイルパーオキサイド0.1部を加え、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を60℃付近に保って4時間、次いで70℃で4時間重合反応を行い、グラフトポリマー溶液を得た。
次いで、このようにして得られたグラフトポリマー溶液の固形分100重量部に対して、ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体(日本ポリウレタン社製、コロネートHL)0.3重量部、アリルスルホニウムヘキサフルオロフォスフェート(LAMBERTI社製、ESACURE1064)1重量部を配合して粘接着剤溶液を調製した。
また、このようにして得られた試験サンプル3Aに光を照射せずにゲル分率の測定を行い、これを光未照射のゲル分率とする。
ついで、試験サンプル3Aから20mm×100mmのサンプル片を切り出し、厚さ 2mmのアクリル板(三菱レイヨン社製「アクリライト」)および厚さ0.4mmのBA板(SUS430鋼板表面仕上げBA鋼板)に2kgのロール1往復で貼り付けた。このときの180°ピール接着力(剥離速度300mm/分)を測定し、光未照射時の接着力とする。これに、メタハラUVランプで、1J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルの180°ピール接着力を測定し、光照射時の接着力とする。
試験サンプル3Aに、メタハラUVランプで、1J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルでゲル分率を測定し、光照射時のゲル分率とする。
(アクリル系ポリマーの調製)
比較例1と同様にして、アクリル系ポリマー溶液を調製した。
得られたアクリル系ポリマー溶液を、酢酸エチルにて固形分が25%になるように希釈して、希釈溶液(I)を調製した。攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、希釈溶液(I)400重量部に対して、4-ヒドロキシブチルアクリレートグリシジルエーテル10部、イソボルニルアクリレート10部とベンゾイルパーオキサイド0.1部を加え、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を60℃付近に保って4時間、次いで70℃で4時間重合反応を行い、グラフトポリマー溶液を得た。
次いで、このようにして得られたグラフトポリマー溶液の固形分100重量部に対して、ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体(日本ポリウレタン社製、コロネートHL)0.3重量部、アリルスルホニウムヘキサフルオロフォスフェート(LAMBERTI社製、ESACURE1064)1重量部を配合して粘接着剤溶液を調製した。
また、このようにして得られた試験サンプル4Aに光を照射せずにゲル分率の測定を行い、これを光未照射のゲル分率とする。
ついで、試験サンプルから20mm×100mmのサンプル片を切り出し、厚さ 2mmのアクリル板(三菱レイヨン社製「アクリライト」)および厚さ0.4mmのBA板(SUS430鋼板表面仕上げBA鋼板)に2kgのロール1往復で貼り付けた。このときの180°ピール接着力(剥離速度300mm/分)を測定し、光未照射時の接着力とする。これに、メタハラUVランプで、5J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルの180°ピール接着力を測定し、光照射時の接着力とする。
試験サンプル4Aに、メタハラUVランプで、5J/cm2光照射を行った後、暗反応処理(50℃、48時間)を行う。このサンプルでゲル分率を測定し、光照射時のゲル分率とする。
Claims (11)
- モノマー単位としてヒドロキシアルキル(メタ)アクリルアミドモノマーを0.2~10重量%含有する(メタ)アクリル系ポリマーに、環状エーテル基含有モノマーを含む鎖がグラフト重合されてなるグラフトポリマー;および光カチオン系重合開始剤を含有してなることを特徴とする光硬化型粘接着剤組成物。
- 前記グラフトポリマーが、前記(メタ)アクリル系ポリマーに、前記環状エーテル基含有モノマーおよびその他のモノマーを有する鎖がグラフト重合されてなることを特徴とする請求項1記載の光硬化型粘接着剤組成物。
- さらに、架橋剤を含有することを特徴とする請求項1または2に記載の光硬化型粘接着剤組成物。
- 前記環状エーテル基含有モノマーが、エポキシ基含有モノマーおよびオキセタン基含有モノマーのいずれか1つあるいはその両方であることを特徴とする請求項1から3までのいずれか1項に記載の光硬化型粘接着剤組成物。
- 前記(メタ)アクリル系ポリマーのガラス転移温度が、250K以下であることを特徴とする請求項1から4までのいずれか1項に記載の光硬化型粘接着剤組成物。
- 前記グラフトポリマーが、前記(メタ)アクリル系ポリマー100重量部に、前記環状エーテル基含有モノマー2~50重量部およびその他のモノマー5~50重量部を、過酸化物0.02~5重量部の存在下にてグラフト重合させることにより得られることを特徴とする請求項1から5までのいずれかに記載の光硬化型粘接着剤組成物。
- 光カチオン系重合開始剤が、アリルスルホニウムヘキサフルオロフォスフェート塩、スルホニウムヘキサフルオロフォスフェート塩類、およびビス(アルキルフェニル)イオドニウムヘキサフルオロフォスフェートからなる群より選択される少なくとも1種であることを特徴とする請求項1から6までのいずれかに記載の光硬化型粘接着剤組成物。
- 請求項1から7までのいずれかに記載の光硬化型粘接着剤組成物を架橋してなることを特徴とする光硬化型粘接着剤層。
- 支持体の少なくとも片側に、請求項8に記載の光硬化型粘接着剤層が形成されていることを特徴とする光硬化型粘接着シート。
- 請求項1から7までのいずれかに記載の光硬化型粘接着剤組成物を製造する方法であって、
(メタ)アクリル系ポリマーの調製後に、該(メタ)アクリル系ポリマーに環状エーテル基含有モノマーおよび任意にその他のモノマーをグラフト重合させて、グラフトポリマーを調製する工程;および
該グラフトポリマーに光カチオン系重合開始剤を混合する工程、
を含むことを特徴とする光硬化型粘接着剤組成物の製造方法。 - 前記グラフトポリマーを調製する工程において、(メタ)アクリル系ポリマーの調製後に、該(メタ)アクリル系ポリマーに環状エーテル基含有モノマーおよびその他のモノマーをグラフト重合させることを特徴とする、請求項10に記載の光硬化型粘接着剤組成物の製造方法。
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US13/513,437 US20120244349A1 (en) | 2009-12-03 | 2010-12-01 | Photocurable pressure-sensitive adhesive composition, photocurable pressure-sensitive adhesive layer, and photocurable pressure-sensitive adhesive sheet |
EP10834567.9A EP2508583B1 (en) | 2009-12-03 | 2010-12-01 | Photocurable pressure-sensitive adhesive composition, photocurable pressure-sensitive adhesive layer, and photocurable pressure-sensitive adhesive sheet |
CN201080054663.1A CN102648261B (zh) | 2009-12-03 | 2010-12-01 | 光固化型粘合粘接剂组合物、光固化型粘合粘接剂层、和光固化型粘合粘接片 |
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JP2021155752A (ja) * | 2019-08-07 | 2021-10-07 | Kjケミカルズ株式会社 | ヒドロキシアルキル(メタ)アクリルアミドを用いた重合性組成物、その重合物及びそれらからなる成形品 |
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JP5424720B2 (ja) | 2008-06-06 | 2014-02-26 | 日東電工株式会社 | 光硬化型粘接着剤組成物、光硬化型粘接着剤層、および光硬化型粘接着シート |
JP5791235B2 (ja) * | 2010-04-30 | 2015-10-07 | 日東電工株式会社 | 光硬化型粘接着剤組成物、光硬化型粘接着剤層、および光硬化型粘接着シート |
JP6566324B2 (ja) * | 2017-09-29 | 2019-08-28 | サイデン化学株式会社 | 粘着シート |
CN115960561A (zh) * | 2023-01-04 | 2023-04-14 | 宁波力合博汇光敏材料有限公司 | 一种阳离子光固化压敏胶及其制备方法和应用 |
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CN102648261B (zh) | 2014-05-14 |
KR20120101099A (ko) | 2012-09-12 |
EP2508583A4 (en) | 2015-03-11 |
JP5379658B2 (ja) | 2013-12-25 |
US20120244349A1 (en) | 2012-09-27 |
JP2011116863A (ja) | 2011-06-16 |
EP2508583B1 (en) | 2016-08-31 |
EP2508583A1 (en) | 2012-10-10 |
CN102648261A (zh) | 2012-08-22 |
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