WO2016092970A1 - Ultraviolet-curable adhesive agent composition and adhesive sheet - Google Patents

Ultraviolet-curable adhesive agent composition and adhesive sheet Download PDF

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Publication number
WO2016092970A1
WO2016092970A1 PCT/JP2015/080554 JP2015080554W WO2016092970A1 WO 2016092970 A1 WO2016092970 A1 WO 2016092970A1 JP 2015080554 W JP2015080554 W JP 2015080554W WO 2016092970 A1 WO2016092970 A1 WO 2016092970A1
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Prior art keywords
ultraviolet
urethane resin
meth
polyol
mass
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PCT/JP2015/080554
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French (fr)
Japanese (ja)
Inventor
まり子 綱島
昌幸 岩窪
大地　尉夫
綱島　啓次
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Dic株式会社
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Priority to JP2016519896A priority Critical patent/JP5967461B1/en
Publication of WO2016092970A1 publication Critical patent/WO2016092970A1/en

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    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an ultraviolet curable pressure-sensitive adhesive composition that is excellent in adhesion to a highly polar adherend and moisture and heat whitening resistance.
  • ⁇ Adhesive products continue to expand applications mainly in the industrial field due to their good workability, and are expected to grow in the future.
  • ultraviolet curable adhesives do not require aging time, which is an essential process for thermosetting adhesives, and thus high productivity can be expected, and demand is expected to increase.
  • Examples of the ultraviolet curable pressure-sensitive adhesive include a pressure-sensitive adhesive obtained using a solventless pressure-sensitive adhesive composition containing a urethane acrylate having a (meth) acryloyl group at the terminal, an acrylic monomer, and a photopolymerization initiator. Is known (see, for example, Patent Document 1).
  • the pressure-sensitive adhesive has a problem that it has poor adhesion to a highly polar adherend such as a metal plate or a glass plate, and has poor heat and heat whitening resistance.
  • the problem to be solved by the present invention is to provide an ultraviolet curable pressure-sensitive adhesive composition that is excellent in adhesion to a highly polar adherend such as a metal plate or a glass plate and in resistance to moist heat whitening.
  • the present invention is a reaction product of a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having two or more hydroxyl groups, a urethane resin (A) having a hydroxyl group at the terminal, and light.
  • An ultraviolet curable pressure-sensitive adhesive composition comprising a polymerization initiator (B), and a pressure-sensitive adhesive sheet comprising a cured product layer of the ultraviolet curable pressure-sensitive adhesive composition are provided. .
  • the ultraviolet curable pressure-sensitive adhesive composition of the present invention is excellent in adhesion to a highly polar adherend such as a metal plate or a glass plate and resistance to moist heat whitening.
  • the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive sheet in various fields such as medical use, stationery use, and optical member use.
  • the ultraviolet curable pressure-sensitive adhesive composition of the present invention is a reaction product of a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having two or more hydroxyl groups, and a urethane having a hydroxyl group at the terminal.
  • Resin (A) and a photoinitiator (B) are contained.
  • the urethane resin (A) Since the urethane resin (A) has a highly polar hydroxyl group at the end, it can exhibit excellent adhesion to a highly polar adherend. In particular, the molecular terminals are considered to have high flexibility and contribute greatly to adhesion.
  • the urethane resin (A) since the urethane resin (A) has two or more hydroxyl groups in the (a3) react with the polyisocyanate (a2) and is taken into the molecular chain during its production, the urethane resin (A) has an intramolecular structure. (Meth) acryloyl group will be present. Therefore, since this (meth) acryloyl group crosslinks between the urethane resins (A) at the time of ultraviolet irradiation, it is possible to express excellent moisture and heat whitening resistance by improving the crosslink density.
  • polyether polyol for example, polyether polyol, polycarbonate polyol, polyester polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacryl polyol, dimer diol, polyisoprene polyol and the like can be used.
  • These polyols may be used alone or in combination of two or more.
  • polyether polyol examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxyethylene polyoxytetramethylene polyol, polyoxypropylene polyoxytetramethylene polyol. Etc. can be used. These polyether polyols may be used alone or in combination of two or more. Among these, at least one polyether polyol selected from the group consisting of polyoxyethylene polyol, polyoxypropylene polyol, and polyoxytetramethylene polyol is used because it can further improve the resistance to moist heat and whitening and flexibility. It is preferable to use it.
  • polycarbonate polyol for example, those obtained by reacting a carbonate ester and / or phosgene with a compound having two or more hydroxyl groups can be used.
  • carbonate ester for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used. These carbonates may be used alone or in combination of two or more.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and tripropylene glycol.
  • An alicyclic polyol such as 1,2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanedimethanol, cycloheptanediol, cyclooctanediol, hydroxypropylcyclohexanol; bisphenol A, Aromatic polyols such as bisphenol F and 4,4′-biphenol can be used. These compounds may be used alone or in combination of two or more.
  • an aliphatic polyol and / or an alicyclic polyol from the viewpoint that the cutting property (no adhesive residue at the time of cutting) can be further improved, and 1,4-butanediol, 1,5-pentane is preferable. It is more preferable to use one or more compounds selected from the group consisting of diol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol.
  • the number average molecular weight of the polyol (a1) is preferably in the range of 500 to 7,000, more preferably in the range of 700 to 4,000, from the viewpoints of heat and heat whitening resistance, flexibility, and mechanical strength.
  • the range of 800 to 3,000 is more preferable.
  • the number average molecular weight of the said polyol (a1) shows the value measured on condition of the following by gel permeation chromatography (GPC) method.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • a chain extender having a hydroxyl group and having a number average molecular weight in the range of 50 to 400 may be used in combination.
  • the chain extender having a hydroxyl group the same compounds as the compound having two or more hydroxyl groups can be used.
  • 1,4-butanediol, 1,5-pentanediol, 1,6 can be introduced from the point that a hard segment having an appropriate chain length can be introduced into the urethane resin (A), and excellent moisture and heat whitening resistance can be obtained.
  • one or more compounds selected from the group consisting of hexanediol and 1,4-cyclohexanedimethanol are used.
  • polyisocyanate (a2) examples include aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4 Aliphatic or alicyclic polyisocyanates such as' -dicyclohexylmethane diisocyanate, diisocyanate methylcyclohexane, and tetramethylxylylene diisocyanate can be used.
  • aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate
  • polyisocyanates may be used alone or in combination of two or more.
  • alicyclic polyisocyanates are preferably used from the viewpoint of further improving mechanical strength, adhesive properties and transparency, and 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate and diisocyanate. It is more preferable to use one or more polyisocyanates selected from the group consisting of methylcyclohexane.
  • the (meth) acrylic compound (a3) having two or more hydroxyl groups is used for the purpose of introducing a (meth) acryloyl group into the molecule of the urethane resin (A).
  • a method of introducing a (meth) acryloyl group into a urethane resin there is a method of using a (meth) acrylic compound having one hydroxyl group or one isocyanate, and in this case, only the end of the urethane resin (A) is (meth). Since an acryloyl group cannot be introduced, the crosslink density cannot be increased any further, and the desired moisture and heat whitening resistance cannot be obtained.
  • the (meth) acrylic compound (a3) is used as in the present invention, the crosslink density between the urethane resins (A) can be increased. Sex is obtained.
  • Examples of the (meth) acrylic compound (a3) include glycerin mono (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate or the like can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use a (meth) acryl compound having two hydroxyl groups and one (meth) acryloyl group from the viewpoint of having good ultraviolet curability and obtaining excellent moisture and heat whitening resistance. It is more preferable to use glycerin mono (meth) acrylate and / or 3,4-dihydroxybutyl (meth) acrylate.
  • the amount of the (meth) acrylic compound (a3) used is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyol (a1) from the viewpoints of ultraviolet curability and wet heat whitening resistance. It is preferable that the range is 0.5 to 10 parts by mass.
  • the urethane resin (A) for example, the polyol (a1) and the (meth) acrylic compound (a3) are charged in the absence of a solvent, and then the polyisocyanate (a2) is supplied and mixed.
  • the method of manufacturing by making it react can be used.
  • the reaction is preferably performed, for example, at 20 to 120 ° C. for 30 minutes to 24 hours.
  • the urethane resin (A) preferably has two or more hydroxyl groups at the end in order to obtain excellent adhesion to a highly polar adherend.
  • the molecular weight of the urethane resin (A) can be controlled, and the adhesion to a highly polar adherend can be further improved, and the range of 1.1 to 2 is more preferable.
  • urethane resin (A) When producing the urethane resin (A), a polymerization inhibitor, a urethanization catalyst or the like may be used as necessary.
  • polymerization inhibitor examples include 3,5-bistertiary butyl-4-hydroxytoluene, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether (methoquinone), para tertiary butyl catechol methoxyphenol, and 2,6-ditertiary butyl cresol. Phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene and the like can be used. These polymerization inhibitors may be used alone or in combination of two or more.
  • the urethanization catalyst examples include nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; metal salts such as potassium acetate, zinc stearate, and tin octylate; dibutyltin laurate, zirconium tetraacetylacetonate, and the like. These organometallic compounds can be used. These urethanization catalysts may be used alone or in combination of two or more.
  • the content of the (meth) acryloyl group in the urethane resin (A) is preferably in the range of 0.01 to 2 mol / kg from the viewpoint of obtaining excellent heat and heat whitening resistance by good ultraviolet curing.
  • the range of 0.03 to 0.5 mol / kg is more preferable.
  • the mass ratio of the urethane bond in the urethane resin (A) is 4 to 20% by mass in the total amount of the urethane resin (A) from the viewpoint that good cutting properties, adhesive physical properties, and heat and heat whitening resistance can be obtained by hydrogen bonding.
  • the range is preferably 5 to 15% by mass.
  • the urethane bond amount of the said urethane resin (A) shows the mass ratio of the urethane bond structure which occupies in the said raw material with respect to the total mass of the raw material of the said urethane resin (A).
  • the weight average molecular weight of the urethane resin (A) is in the range of 5,000 to 100,000 from the viewpoint of further improving cutting properties, adhesive physical properties, and adhesion to a highly polar adherend. The range of 15,000 to 50,000 is more preferable. In addition, the weight average molecular weight of the said urethane resin (A) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a1).
  • the photopolymerization initiator (B) generates radicals by light irradiation, heating, or the like, and initiates radical polymerization of the urethane resin (A).
  • Examples of the photopolymerization initiator (B) include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-isopropylphenyl) -2.
  • photopolymerization initiator (B) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy is preferable because it can further improve the adhesive properties, ultraviolet curability, and resistance to moist heat whitening. It is preferable to use at least one photopolymerization initiator selected from the group consisting of cyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferable.
  • the amount of the photopolymerization initiator (B) used is from 0.01 to 100 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of further improving the physical properties of adhesive, UV curable property and wet heat whitening resistance.
  • the range is preferably 20 parts by mass, and more preferably in the range of 0.1 to 15 parts by mass.
  • the ultraviolet curable adhesive composition of the present invention may contain other additives as necessary.
  • the other additives include organic solvents, silane coupling agents, antioxidants, light stabilizers, rust inhibitors, thixotropic agents, sensitizers, polymerization inhibitors, leveling agents, tackifiers, An antistatic agent, a flame retardant, etc. can be used. These additives may be used alone or in combination of two or more. Among these, it is preferable to contain the organic solvent from the point of the coating property to a to-be-adhered body, and workability
  • organic solvent examples include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, propionitrile, isobutyronitrile, valeronitrile, dimethyl sulfoxide, dimethylformamide, and the like. be able to.
  • organic solvents may be used alone or in combination of two or more.
  • the amount used in the case of using the organic solvent is preferably 60% by mass or less in the ultraviolet curable pressure-sensitive adhesive composition from the viewpoint that the drying property and coating property can be further improved. A range is more preferred.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
  • Silane coupling agents having an epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) propylmethyldimethoxy Syrah Silane coupling agents having an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) propyltriethoxysilane and 2- (3,4-epoxycyclohexyl) propylmethyldiethoxysilane; vinyltrichlorosilane,
  • silane coupling agents may be used alone or in combination of two or more.
  • a silane coupling agent having an epoxy group and / or a silane coupling agent having an alicyclic epoxy group from the viewpoint that the adhesive strength after heat and humidity resistance can be further improved.
  • the amount used in the case of using the silane coupling agent is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) because the adhesive strength after heat and moisture resistance can be further improved.
  • the range of 0.05 to 5 parts by mass is more preferable, and the range of 0.05 to 1 part by mass is even more preferable.
  • antioxidants examples include hindered phenol compounds (primary antioxidants) that capture radicals generated by thermal degradation, phosphorus compounds that decompose peroxides generated by thermal degradation, and sulfur compounds (secondary antioxidants). Agent) and the like.
  • hindered phenol compound examples include triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-).
  • sulfur compound examples include didodecyl-3,3′-thiopropionate, dilauryl-3,3′-thiodipropionate, lauryl thiodithionate, ditridecyl-3,3′-thiodipropionate, Dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, tetrakis-methylene-3-laurylthiopropionate methane, distearyl-3,3′-methyl-3, 3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, ⁇ - Laurylthiopropionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzoy Imidazole, can be used dioct
  • one or more antioxidants selected from the group consisting of phosphite and tris (2,4-di-tert-butylphenyl) phosphite, and triphenylphosphine, bis (2,4-diphenyl).
  • the amount used in the case of using the antioxidant is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of further improving wet heat yellowing resistance. Is preferred.
  • the light stabilizer captures radicals generated by photodegradation.
  • a radical scavenger such as a thiol compound, a thioether compound, or a hindered amine compound
  • an ultraviolet absorber such as a benzophenone compound or a benzoate compound
  • These light stabilizers may be used alone or in combination of two or more. Among these, it is preferable to use a hindered amine compound from the viewpoint that the heat and heat yellowing resistance can be further improved.
  • hindered amine compound examples include a reaction product of cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro 1,3,5-triazine.
  • the amount used in the case of using the light stabilizer is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint that the heat and heat yellowing resistance can be further improved. Is preferred.
  • the viscosity of the ultraviolet curable pressure-sensitive adhesive composition of the present invention is preferably in the range of 500 to 30,000 mPa ⁇ s, and preferably 1,000 to 20,000 mPa ⁇ s from the viewpoint of coating properties and workability. A range is more preferred.
  • the said viscosity shows the value measured with the B-type viscometer at 25 degreeC.
  • Examples of the method for producing the pressure-sensitive adhesive sheet of the present invention include a method in which the ultraviolet curable pressure-sensitive adhesive composition is applied to an adherend, dried as necessary, and then UV-cured.
  • Examples of the adherend include a plastic substrate, a flexible printed substrate, a substrate obtained by subjecting these substrates to a release treatment, and a substrate obtained by vapor deposition of ITO (indium tin oxide); glass plate, steel plate, zinc A highly polar base material such as a steel plate, a tin plate, or an aluminum plate can be used.
  • the same base material may be used for both surfaces of the adhesion layer, or different base materials may be used.
  • plastic substrate examples include acrylic resin, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE (polyphenylene ether), PET (polyethylene terephthalate), COP (cycloolefin polymer),
  • TAC triacetylcellulose
  • an antireflection film, an antifouling film, a transparent conductive film constituting a touch panel, or the like can be used.
  • Examples of a method of applying the ultraviolet curable pressure-sensitive adhesive composition to the substrate include a method of applying using an applicator, a roll coater, a knife coater, a gravure coater and the like. After the coating, when drying is performed, the obtained laminate is put in a dryer or the like, and dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes, for example.
  • an adhesive sheet is obtained by irradiating with ultraviolet rays.
  • the method of irradiating with ultraviolet rays include known ultraviolet light irradiation devices such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, and a low pressure mercury lamp. The method using is mentioned.
  • the irradiation dose of the ultraviolet preferably be 0.05 ⁇ 5J / cm 2, more preferably 0.1 ⁇ 3J / cm 2, particularly preferably in the range of 0.3 ⁇ 1.5J / cm 2 Good.
  • the irradiation amount of ultraviolet rays is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker “UVR-N1” manufactured by GS Yuasa Corporation.
  • the thickness of the pressure-sensitive adhesive sheet obtained by the above method is appropriately determined according to the intended use, but is, for example, in the range of 10 to 500 ⁇ m.
  • the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be used in combination with thermal crosslinking and ultraviolet curing, and can adhere to a highly polar adherend such as a metal plate or a glass plate and can be resistant to heat and heat whitening. It is excellent.
  • the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used in various fields such as medical use, stationery use, and optical member use.
  • IPDI isophorone diisocyanate
  • 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain urethane resin (A-1).
  • the obtained urethane resin (A-1) had a weight average molecular weight of 40,400 and an acryloyl group content of 0.1 mol / kg.
  • urethane resin (A-2) After raising the temperature in the reaction vessel to 40 ° C., 110 parts by mass of IPDI was added. Therefore, 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain a urethane resin (A-2).
  • the obtained urethane resin (A-2) had a weight average molecular weight of 56,000 and an acryloyl group content of 0.1 mol / kg.
  • urethane resin (A-3) had a weight average molecular weight of 39,500 and an acryloyl group content of 0.05 mol / kg.
  • urethane resin (A-4) had a weight average molecular weight of 42,000 and an acryloyl group content of 0.25 mol / kg.
  • Example 1 ⁇ Preparation of UV-curable adhesive composition>
  • a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer 100 parts by mass of the urethane resin (A-1), 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide (hereinafter referred to as “(B-1)”) 0.5 parts by weight of decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 0.5 parts by weight of triphenylphosphine 0.5 parts by mass were sequentially added and stirred until uniform. Thereafter, the mixture was filtered through a 200 mesh wire net to obtain an ultraviolet curable pressure-sensitive adhesive composition.
  • Example 2 to 4 An ultraviolet curable pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the type of the urethane resin (A) used was changed as shown in Table 1.
  • urethane resin (A′-1) had a weight average molecular weight of 29,000 and an acryloyl group content of 0.03 mol / kg.
  • UV curable pressure-sensitive adhesives obtained in Examples and Comparative Examples so that the film thickness after drying the organic solvent is 100 ⁇ m on the surface of a 50 ⁇ m-thick polyethylene terephthalate film (release PET 50) having a release treatment on the surface.
  • the fat composition was applied, dried in an 80 ° C. dryer for 3 minutes, and then a 100 ⁇ m thick PET film was bonded.
  • the release PET is peeled off and bonded to the adherend glass plate and steel plate by 2 kg roller ⁇ 2 reciprocation, and the integrated light quantity of the wavelength in the UV-A region after passing through the PET film is 1 J / cm 2. Were irradiated with ultraviolet rays to obtain test pieces.
  • test specimens were evaluated for adhesion to various adherends according to the following criteria by the cross-cut method (JISK5600-5-6-1999).
  • a polyester adhesive tape (“N0.31B” manufactured by Nitto Denko Corporation) was used.
  • T 100 squares of the pressure-sensitive adhesive layer remained on the adherend.
  • F The number of grids of the pressure-sensitive adhesive layer remaining on the adherend was 99 or less.
  • UV curable pressure-sensitive adhesives obtained in Examples and Comparative Examples so that the film thickness after drying the organic solvent is 100 ⁇ m on the surface of a 50 ⁇ m-thick polyethylene terephthalate film (release PET 50) having a release treatment on the surface.
  • the fat composition was applied and dried in an 80 ° C. dryer for 3 minutes, and then release PET was bonded. This was cut into 50 mm length and 40 mm width. Thereafter, ultraviolet rays were irradiated so that the integrated light quantity of the wavelength in the UV-A region after passing through the glass plate was 1 J / cm 2 to obtain a laminate having an adhesive sheet, which was used as a test piece.
  • the haze (%) of the test piece was measured with a turbidimeter “NDH5000” (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7361-1-1997.
  • NH5000 turbidimeter
  • the obtained test piece was allowed to stand for 100 hours under the conditions of 85 ° C. and 85% RH (hereinafter abbreviated as “after wet heat resistance test”), and then taken out in an atmosphere of 23 ° C. and 50% RH. .
  • the haze (%) was measured with a turbidimeter “NDH5000” (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7361-1-1997. Evaluated.
  • T The difference in haze (%) value before and after the wet heat resistance test is less than 1%.
  • F The difference in haze (%) values before and after the wet heat resistance test is 1% or more.
  • Examples 1 to 5 which are the ultraviolet curable pressure-sensitive adhesive compositions of the present invention, are excellent in heat and heat whitening resistance and adhesion to glass plates and steel plates which are highly polar adherends.
  • Comparative Example 1 is an embodiment that uses HEA instead of the (meth) acrylic compound (a3) and a urethane resin into which an acryloyl group is introduced at the terminal, but has poor moisture and heat whitening resistance. Also, the adhesion to glass plates and steel plates was poor.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The present invention addresses the problem of providing an ultraviolet-curable adhesive agent composition which has excellent adhesion to a high-polarity adherend, such as a metal plate or a glass plate, and excellent resistance to whitening under heat and humidity. Provided are: an ultraviolet-curable adhesive agent composition characterised by being a product of reacting a polyol (a1), a polyisocyanate (a2), and a (meth)acrylic compound (a3) that has two or more hydroxyl groups and by containing a urethane resin (A) that has a hydroxyl group at a terminal thereof and further containing a photopolymerisation initiator (B); and an adhesive sheet characterised by having a cured product layer of the ultraviolet-curable adhesive agent composition. This ultraviolet-curable adhesive agent composition can use both thermal crosslinking and ultraviolet curing and has excellent adhesion to a high-polarity adherend, such as a metal plate or a glass plate, and excellent resistance to whitening under heat and humidity.

Description

紫外線硬化型粘着剤組成物、及び、粘着シートUV curable adhesive composition and adhesive sheet
　本発明は、高極性な被着体への密着性及び耐湿熱白化性に優れる紫外線硬化型粘着剤組成物に関する。 The present invention relates to an ultraviolet curable pressure-sensitive adhesive composition that is excellent in adhesion to a highly polar adherend and moisture and heat whitening resistance.
　粘着剤製品は、作業性の良さから、主に工業分野での用途拡大を続けており、今後も伸長が期待されている。特に、紫外線硬化型粘着剤は、熱硬化型粘着剤では必須工程であるエージング時間が不要であることから、高生産性が期待でき、需要拡大が確実視されている。 ¡Adhesive products continue to expand applications mainly in the industrial field due to their good workability, and are expected to grow in the future. In particular, ultraviolet curable adhesives do not require aging time, which is an essential process for thermosetting adhesives, and thus high productivity can be expected, and demand is expected to increase.
　前記紫外線硬化型粘着剤としては、例えば、末端に（メタ）アクリロイル基を有するウレタンアクリレート、アクリル単量体及び光重合開始剤を含有する無溶剤型粘着剤組成物を用いて得られた粘着剤が知られている（例えば、特許文献１を参照。）。 Examples of the ultraviolet curable pressure-sensitive adhesive include a pressure-sensitive adhesive obtained using a solventless pressure-sensitive adhesive composition containing a urethane acrylate having a (meth) acryloyl group at the terminal, an acrylic monomer, and a photopolymerization initiator. Is known (see, for example, Patent Document 1).
　しかしながら、前記粘着剤では金属板やガラス板等の高極性の被着体への密着性が不良であることや、耐湿熱白化性が不良であるとの問題点があった。 However, the pressure-sensitive adhesive has a problem that it has poor adhesion to a highly polar adherend such as a metal plate or a glass plate, and has poor heat and heat whitening resistance.
特開２００６－１０４２９６号公報JP 2006-104296 A
　本発明が解決しようとする課題は、金属板やガラス板等の高極性な被着体への密着性及び耐湿熱白化性に優れる紫外線硬化型粘着剤組成物を提供することである。 The problem to be solved by the present invention is to provide an ultraviolet curable pressure-sensitive adhesive composition that is excellent in adhesion to a highly polar adherend such as a metal plate or a glass plate and in resistance to moist heat whitening.
　本発明は、ポリオール（ａ１）とポリイソシアネート（ａ２）と水酸基を２個以上有する（メタ）アクリル化合物（ａ３）との反応物であり、末端に水酸基を有するウレタン樹脂（Ａ）、及び、光重合開始剤（Ｂ）を含有することを特徴とする紫外線硬化型粘着剤組成物、及び前記紫外線硬化型粘着剤組成物の硬化物層を有することを特徴とする粘着シートを提供するものである。 The present invention is a reaction product of a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having two or more hydroxyl groups, a urethane resin (A) having a hydroxyl group at the terminal, and light. An ultraviolet curable pressure-sensitive adhesive composition comprising a polymerization initiator (B), and a pressure-sensitive adhesive sheet comprising a cured product layer of the ultraviolet curable pressure-sensitive adhesive composition are provided. .
　本発明の紫外線硬化型粘着剤組成物は、金属板やガラス板等の高極性な被着体への密着性及び耐湿熱白化性に優れるものである。本発明の紫外線硬化型粘着剤組成物は、医療用、文具用、光学部材用等の様々な分野の粘着シートとして好適に使用することができる。 The ultraviolet curable pressure-sensitive adhesive composition of the present invention is excellent in adhesion to a highly polar adherend such as a metal plate or a glass plate and resistance to moist heat whitening. The ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive sheet in various fields such as medical use, stationery use, and optical member use.
　本発明の紫外線硬化型粘着剤組成物は、ポリオール（ａ１）とポリイソシアネート（ａ２）と水酸基を２個以上有する（メタ）アクリル化合物（ａ３）との反応物であり、末端に水酸基を有するウレタン樹脂（Ａ）、及び、光重合開始剤（Ｂ）を含有するものである。 The ultraviolet curable pressure-sensitive adhesive composition of the present invention is a reaction product of a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having two or more hydroxyl groups, and a urethane having a hydroxyl group at the terminal. Resin (A) and a photoinitiator (B) are contained.
　前記ウレタン樹脂（Ａ）は、末端に高極性な水酸基を有するため、高極性な被着体への優れた密着性を発現することができる。特に、分子末端はフレキシビリティが高く、密着性への寄与が大きいと考えられる。また、前記ウレタン樹脂（Ａ）は、その製造中に前記（ａ３）が有する２個以上の水酸基がポリイソシアネート（ａ２）と反応し分子鎖中に取り込まれるため、ウレタン樹脂（Ａ）の分子内に（メタ）アクリロイル基が存在することとなる。よって、この（メタ）アクリロイル基は紫外線照時にウレタン樹脂（Ａ）間で架橋するため、架橋密度の向上により優れた耐湿熱白化性を発現することができる。 Since the urethane resin (A) has a highly polar hydroxyl group at the end, it can exhibit excellent adhesion to a highly polar adherend. In particular, the molecular terminals are considered to have high flexibility and contribute greatly to adhesion. In addition, since the urethane resin (A) has two or more hydroxyl groups in the (a3) react with the polyisocyanate (a2) and is taken into the molecular chain during its production, the urethane resin (A) has an intramolecular structure. (Meth) acryloyl group will be present. Therefore, since this (meth) acryloyl group crosslinks between the urethane resins (A) at the time of ultraviolet irradiation, it is possible to express excellent moisture and heat whitening resistance by improving the crosslink density.
　前記ポリオール（ａ１）としては、例えば、ポリエーテルポリオール、ポリカーボネートポリオール、ポリエステルポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリアクリルポリオール、ダイマージオール、ポリイソプレンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。これらの中でも、その骨格により非常に優れた耐湿熱白化性が得られる点から、ポリエーテルポリオール及び／又はポリカーボネートポリオールを含有することが好ましい。 As the polyol (a1), for example, polyether polyol, polycarbonate polyol, polyester polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacryl polyol, dimer diol, polyisoprene polyol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to contain a polyether polyol and / or a polycarbonate polyol from the viewpoint that the heat and whitening resistance which is very excellent by the skeleton is obtained.
　前記ポリエーテルポリオールとしては、例えば、ポリオキシエチレンポリオール、ポリオキシプロピレンポリオール、ポリオキシテトラメチレンポリオール、ポリオキシエチレンポリオキシプロピレンポリオール、ポリオキシエチレンポリオキシテトラメチレンポリオール、ポリオキシプロピレンポリオキシテトラメチレンポリオール等を用いることができる。これらのポリエーテルポリオールは単独で用いても２種以上を併用してもよい。これらの中でも、耐湿熱白化性、及び、柔軟性をより一層向上できる点から、ポリオキシエチレンポリオール、ポリオキシプロピレンポリオール及びポリオキシテトラメチレンポリオールからなる群より選ばれる１種以上のポリエーテルポリオールを用いることが好ましい。 Examples of the polyether polyol include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxyethylene polyoxytetramethylene polyol, polyoxypropylene polyoxytetramethylene polyol. Etc. can be used. These polyether polyols may be used alone or in combination of two or more. Among these, at least one polyether polyol selected from the group consisting of polyoxyethylene polyol, polyoxypropylene polyol, and polyoxytetramethylene polyol is used because it can further improve the resistance to moist heat and whitening and flexibility. It is preferable to use it.
　前記ポリカーボネートポリオールとしては、例えば、炭酸エステル及び／又はホスゲンと、２個以上の水酸基を有する化合物とを反応させて得られるものを用いることができる。 As the polycarbonate polyol, for example, those obtained by reacting a carbonate ester and / or phosgene with a compound having two or more hydroxyl groups can be used.
　前記炭酸エステルとしては、例えば、メチルカーボネート、ジメチルカーボネート、エチルカーボネート、ジエチルカーボネート、シクロカーボネート、ジフェニルカーボネート等を用いることができる。これらの炭酸エステルは単独で用いても２種以上を併用してもよい。 As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used. These carbonates may be used alone or in combination of two or more.
　また、前記２個以上の水酸基を有する化合物としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、１，５－ペンタンジオール、１，５－ヘキサンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１１－ウンデカンジオール、１，１２－ドデカンジオール、２－メチル－１，３－プロパンジオール、ネオペンチルグリコール、２－ブチル－２－エチル－１，３－プロパンジオール、３－メチル－１，５－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２－メチル－１，８－オクタンジオール等の脂肪族ポリオール；１，２－シクロブタンジオール、１，３－シクロペンタンジオール、１，４－シクロヘキサンジメタノール、シクロヘプタンジオール、シクロオクタンジオール、ヒドロキシプロピルシクロヘキサノール等の脂環式ポリオール；ビスフェノールＡ、ビスフェノールＦ、４，４’－ビフェノール等の芳香族ポリオールなどを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、カッティング性（裁断時に糊残りがない）をより一層向上できる点から、脂肪族ポリオール及び／又は脂環式ポリオールを用いることが好ましく、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，４－シクロヘキサンジメタノールからなる群より選ばれる１種以上の化合物を用いることがより好ましい。 Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and tripropylene glycol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2 -Methyl-1,3-propanediol, neopentyl Coal, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, etc. An alicyclic polyol such as 1,2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanedimethanol, cycloheptanediol, cyclooctanediol, hydroxypropylcyclohexanol; bisphenol A, Aromatic polyols such as bisphenol F and 4,4′-biphenol can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polyol and / or an alicyclic polyol from the viewpoint that the cutting property (no adhesive residue at the time of cutting) can be further improved, and 1,4-butanediol, 1,5-pentane is preferable. It is more preferable to use one or more compounds selected from the group consisting of diol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol.
　前記ポリオール（ａ１）の数平均分子量としては、耐湿熱白化性、柔軟性及び、機械的強度の点から、５００～７，０００の範囲であることが好ましく、７００～４，０００の範囲がより好ましく、８００～３，０００の範囲が更に好ましい。なお、前記ポリオール（ａ１）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記条件で測定した値を示す。 The number average molecular weight of the polyol (a1) is preferably in the range of 500 to 7,000, more preferably in the range of 700 to 4,000, from the viewpoints of heat and heat whitening resistance, flexibility, and mechanical strength. The range of 800 to 3,000 is more preferable. In addition, the number average molecular weight of the said polyol (a1) shows the value measured on condition of the following by gel permeation chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
　前記ポリオール（ａ１）には、必要に応じて水酸基を有する数平均分子量５０～４００の範囲の鎖伸長剤を併用してもよい。 In the polyol (a1), a chain extender having a hydroxyl group and having a number average molecular weight in the range of 50 to 400 may be used in combination.
　前記水酸基を有する鎖伸長剤としては、前記２個以上の水酸基を有する化合物と同様のものを用いることができる。中でも、適度な鎖長のハードセグメントをウレタン樹脂（Ａ）に導入でき、非常に優れた耐湿熱白化性が得られる点から、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、及び１，４－シクロヘキサンジメタノールからなる群より選ばれる１種以上の化合物を用いることがより好ましい。 As the chain extender having a hydroxyl group, the same compounds as the compound having two or more hydroxyl groups can be used. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6 can be introduced from the point that a hard segment having an appropriate chain length can be introduced into the urethane resin (A), and excellent moisture and heat whitening resistance can be obtained. More preferably, one or more compounds selected from the group consisting of hexanediol and 1,4-cyclohexanedimethanol are used.
　前記ポリイソシアネート（ａ２）としては、例えば、キシリレンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、ジイソシアナートメチルシクロヘキサン、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環式ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。これらの中でも、機械的強度、粘着物性及び透明性をより一層向上できる点から、脂環式ポリイソシアネートを用いることが好ましく、４，４’－ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、シクロヘキサンジイソシアネート及びジイソシアナートメチルシクロヘキサンからなる群より選ばれる１種以上のポリイソシアネートを用いることがより好ましい。 Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4 Aliphatic or alicyclic polyisocyanates such as' -dicyclohexylmethane diisocyanate, diisocyanate methylcyclohexane, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, alicyclic polyisocyanates are preferably used from the viewpoint of further improving mechanical strength, adhesive properties and transparency, and 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate and diisocyanate. It is more preferable to use one or more polyisocyanates selected from the group consisting of methylcyclohexane.
　前記水酸基を２個以上有する（メタ）アクリル化合物（ａ３）は、ウレタン樹脂（Ａ）の分子内に（メタ）アクリロイル基を導入する目的で用いるものである。ウレタン樹脂に（メタ）アクリロイル基を導入する方法としては、水酸基又はイソシアネートを１個有する（メタ）アクリル化合物を用いる方法があるが、この場合にはウレタン樹脂（Ａ）の末端にしか（メタ）アクリロイル基を導入することができないため、架橋密度をそれ以上増加させることができず、所望の耐湿熱白化性が得られない。一方、本発明のように前記（メタ）アクリル化合物（ａ３）を用いた場合には、ウレタン樹脂（Ａ）間の架橋密度を増加させることができるため、水分の侵入を防ぎ優れた耐湿熱白化性が得られる。 The (meth) acrylic compound (a3) having two or more hydroxyl groups is used for the purpose of introducing a (meth) acryloyl group into the molecule of the urethane resin (A). As a method of introducing a (meth) acryloyl group into a urethane resin, there is a method of using a (meth) acrylic compound having one hydroxyl group or one isocyanate, and in this case, only the end of the urethane resin (A) is (meth). Since an acryloyl group cannot be introduced, the crosslink density cannot be increased any further, and the desired moisture and heat whitening resistance cannot be obtained. On the other hand, when the (meth) acrylic compound (a3) is used as in the present invention, the crosslink density between the urethane resins (A) can be increased. Sex is obtained.
　前記（メタ）アクリル化合物（ａ３）としては、例えば、グリセリンモノ（メタ）アクリレート、３，４－ジヒドロキシブチル（メタ）アクリレート、トリメチロールプロパンモノ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、良好な紫外線硬化性を有し、優れた耐湿熱白化性が得られる点から、水酸基を２個及び（メタ）アクリロイル基を１個有する（メタ）アクリル化合物を用いることが好ましく、グリセリンモノ（メタ）アクリレート及び／又は３，４－ジヒドロキシブチル（メタ）アクリレートを用いることがより好ましい。 Examples of the (meth) acrylic compound (a3) include glycerin mono (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate or the like can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use a (meth) acryl compound having two hydroxyl groups and one (meth) acryloyl group from the viewpoint of having good ultraviolet curability and obtaining excellent moisture and heat whitening resistance. It is more preferable to use glycerin mono (meth) acrylate and / or 3,4-dihydroxybutyl (meth) acrylate.
　前記（メタ）アクリル化合物（ａ３）の使用量としては、紫外線硬化性、及び耐湿熱白化性の点から、前記ポリオール（ａ１）１００質量部に対して、０．１～３０質量部の範囲であることが好ましく、０．５～１０質量部の範囲がより好ましい。 The amount of the (meth) acrylic compound (a3) used is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyol (a1) from the viewpoints of ultraviolet curability and wet heat whitening resistance. It is preferable that the range is 0.5 to 10 parts by mass.
　前記ウレタン樹脂（Ａ）の製造方法としては、例えば、無溶剤下で、前記ポリオール（ａ１）と前記（メタ）アクリル化合物（ａ３）とを仕込み、次いで前記ポリイソシアネート（ａ２）を供給し、混合、反応させることによって製造する方法等を用いることができる。前記反応は、例えば２０～１２０℃の条件下で３０分～２４時間行うことが好ましい。 As a method for producing the urethane resin (A), for example, the polyol (a1) and the (meth) acrylic compound (a3) are charged in the absence of a solvent, and then the polyisocyanate (a2) is supplied and mixed. The method of manufacturing by making it react can be used. The reaction is preferably performed, for example, at 20 to 120 ° C. for 30 minutes to 24 hours.
　前記ウレタン樹脂（Ａ）は優れた高極性な被着体への密着性を得るうえで、末端に好ましくは２個以上の水酸基を有するものである。前記ウレタン樹脂（Ａ）を製造する際の、前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）と前記（メタ）アクリル化合物（ａ３）との反応は、前記ポリオール（ａ１）が有する水酸基及び前記（メタ）アクリル化合物（ａ３）が有する水酸基の合計量と、ポリイソシアネート（ａ２）の有するイソシアネート基とのモル比［水酸基の合計量／イソシアネート基］＝１．０１～３の範囲で行うことが、ウレタン樹脂（Ａ）の分子量と制御でき、かつ高極性な被着体への密着性をより一層向上できることから好ましく、１．１～２の範囲であることがより好ましい。 The urethane resin (A) preferably has two or more hydroxyl groups at the end in order to obtain excellent adhesion to a highly polar adherend. The reaction of the polyol (a1), the polyisocyanate (a2), and the (meth) acrylic compound (a3) when producing the urethane resin (A) is carried out by reacting the hydroxyl group of the polyol (a1) and the ( The molar ratio of the total amount of hydroxyl groups of the (meth) acrylic compound (a3) and the isocyanate group of the polyisocyanate (a2) [total amount of hydroxyl groups / isocyanate group] = 1. The molecular weight of the urethane resin (A) can be controlled, and the adhesion to a highly polar adherend can be further improved, and the range of 1.1 to 2 is more preferable.
　ウレタン樹脂（Ａ）を製造する際には、必要に応じて重合禁止剤、ウレタン化触媒等を用いてもよい。 When producing the urethane resin (A), a polymerization inhibitor, a urethanization catalyst or the like may be used as necessary.
　前記重合禁止剤としては、例えば、３，５－ビスターシャリーブチル－４－ヒドロキシトルエン、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル（メトキノン）、パラターシャリーブチルカテコールメトキシフェノール、２，６－ジターシャリーブチルクレゾール、フェノチアジン、テトラメチルチウラムジスルフィド、ジフェニルアミン、ジニトロベンゼン等を用いることができる。これらの重合禁止剤は単独で用いても２種以上を併用してもよい。 Examples of the polymerization inhibitor include 3,5-bistertiary butyl-4-hydroxytoluene, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether (methoquinone), para tertiary butyl catechol methoxyphenol, and 2,6-ditertiary butyl cresol. Phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene and the like can be used. These polymerization inhibitors may be used alone or in combination of two or more.
　前記ウレタン化触媒としては、例えば、トリエチルアミン、トリエチレンジアミン、Ｎ－メチルモルホリン等の含窒素化合物；酢酸カリウム、ステアリン酸亜鉛、オクチル酸錫等の金属塩；ジブチルチンラウレート、ジルコニウムテトラアセチルアセトネート等の有機金属化合物などを用いることができる。これらのウレタン化触媒は単独で用いても２種以上を併用してもよい。 Examples of the urethanization catalyst include nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; metal salts such as potassium acetate, zinc stearate, and tin octylate; dibutyltin laurate, zirconium tetraacetylacetonate, and the like. These organometallic compounds can be used. These urethanization catalysts may be used alone or in combination of two or more.
　前記ウレタン樹脂（Ａ）中における（メタ）アクリロイル基の含有量としては、良好な紫外線硬化による優れた耐湿熱白化性が得られ点から、０．０１～２ｍｏｌ／ｋｇの範囲であることが好ましく、０．０３～０．５ｍｏｌ／ｋｇの範囲であることがより好ましい。 The content of the (meth) acryloyl group in the urethane resin (A) is preferably in the range of 0.01 to 2 mol / kg from the viewpoint of obtaining excellent heat and heat whitening resistance by good ultraviolet curing. The range of 0.03 to 0.5 mol / kg is more preferable.
　前記ウレタン樹脂（Ａ）中のウレタン結合の質量割合としては、水素結合により良好なカッティング性、粘着物性及び耐湿熱白化性が得られる点から、ウレタン樹脂（Ａ）の全量中４～２０質量％の範囲であることが好ましく、５～１５質量％の範囲であることがより好ましい。なお、前記ウレタン樹脂（Ａ）のウレタン結合量は、前記ウレタン樹脂（Ａ）の原料の合計質量に対する、前記原料中に占めるウレタン結合構造の質量割合を示す。 The mass ratio of the urethane bond in the urethane resin (A) is 4 to 20% by mass in the total amount of the urethane resin (A) from the viewpoint that good cutting properties, adhesive physical properties, and heat and heat whitening resistance can be obtained by hydrogen bonding. The range is preferably 5 to 15% by mass. In addition, the urethane bond amount of the said urethane resin (A) shows the mass ratio of the urethane bond structure which occupies in the said raw material with respect to the total mass of the raw material of the said urethane resin (A).
　前記ウレタン樹脂（Ａ）の重量平均分子量としては、カッティング性、粘着物性及び高極性な被着体への密着性をより一層向上できる点から、５，０００～１００，０００の範囲であることが好ましく、１５，０００～５０，０００の範囲がより好ましい。なお、前記ウレタン樹脂（Ａ）の重量平均分子量は、前記ポリオール（ａ１）の数平均分子量と同様に測定して得られた値を示す。 The weight average molecular weight of the urethane resin (A) is in the range of 5,000 to 100,000 from the viewpoint of further improving cutting properties, adhesive physical properties, and adhesion to a highly polar adherend. The range of 15,000 to 50,000 is more preferable. In addition, the weight average molecular weight of the said urethane resin (A) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a1).
　前記光重合開始剤（Ｂ）は、光照射や加熱等によってラジカルを発生し、前記ウレタン樹脂（Ａ）のラジカル重合を開始させるものである。 The photopolymerization initiator (B) generates radicals by light irradiation, heating, or the like, and initiates radical polymerization of the urethane resin (A).
　前記光重合開始剤（Ｂ）としては、例えば、４－フェノキシジクロロアセトフェノン、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、４－（２－ヒドロキシエトキシ）－フェニル（２－ヒドロキシ－２－プロピル）ケトン、２－メチル－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、２，２－ジメトキシ－２－フェニルアセトフェノン等のアセトフェノン化合物；ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン化合物；チオキサントン、２－クロロチオキサントン、２，４－ジクロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン化合物；４，４’－ジメチルアミノチオキサントン（別名＝ミネラーズケトン）、４，４’－ジエチルアミノベンゾフェノン、α－アシロキシムエステル、ベンジル、メチルベンゾイルホルメート（「バイアキュア５５」）、２－エチルアンスラキノン等のアンスラキノン化合物；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等のアシルフォスフィンオキサイド化合物；３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルオパーオキシカルボニル）ベンゾフェノン、アクリル化ベンゾフェノン等を用いることができる。これらの光重合開始剤は単独で用いても２種以上を併用してもよい。 Examples of the photopolymerization initiator (B) include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-isopropylphenyl) -2. -Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl- [4- (methylthio) Acetophenone compounds such as phenyl] -2-morpholino-1-propanone and 2,2-dimethoxy-2-phenylacetophenone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether and benzoin isobutyl ether Benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone; thioxanthone, 2 A thioxanthone compound such as chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone; 4,4′-dimethyl Aminothioxanthone (aka Minerals ketone), 4,4'-diethylaminobenzophenone, α-acyloxime ester, benzyl, methylbenzoylformate ( "Biacure 55"), anthraquinone compounds such as 2-ethylanthraquinone; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Compounds; 3,3 ′, 4,4′-tetra (tert-butyloperoxycarbonyl) benzophenone, acrylated benzophenone, and the like can be used. These photopolymerization initiators may be used alone or in combination of two or more.
　前記光重合開始剤（Ｂ）としては、粘着物性、紫外線硬化性及び耐湿熱白化性をより一層向上できる点から、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド及びビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイドからなる群より選ばれる１種以上の光重合開始剤を用いることが好ましく、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドがより好ましい。 As the photopolymerization initiator (B), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy is preferable because it can further improve the adhesive properties, ultraviolet curability, and resistance to moist heat whitening. It is preferable to use at least one photopolymerization initiator selected from the group consisting of cyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferable.
　前記光重合開始剤（Ｂ）の使用量としては、粘着物性、紫外線硬化性及び耐湿熱白化性をより一層向上できる点から、前記ウレタン樹脂（Ａ）１００質量部に対して、０．０１～２０質量部の範囲であることが好ましく、０．１～１５質量部の範囲がより好ましい。 The amount of the photopolymerization initiator (B) used is from 0.01 to 100 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of further improving the physical properties of adhesive, UV curable property and wet heat whitening resistance. The range is preferably 20 parts by mass, and more preferably in the range of 0.1 to 15 parts by mass.
　本発明の紫外線硬化型粘着剤組成物は、必要に応じてその他の添加剤を含有してもよい。 The ultraviolet curable adhesive composition of the present invention may contain other additives as necessary.
　前記その他の添加剤としては、例えば、有機溶剤、シランカップリング剤、酸化防止剤、光安定剤、防錆剤、チキソ性付与剤、増感剤、重合禁止剤、レベリング剤、粘着付与剤、帯電防止剤、難燃剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。これらの中でも、被着体への塗工性及び作業性の点から有機溶剤を含有することが好ましい。また、本発明の紫外線硬化型粘着剤組成物が耐湿熱後に高い粘着物性を要求される用途に使用される場合には、シランカップリング剤を含有することが好ましい。また、本発明の紫外線硬化型粘着剤組成物が高い耐湿熱黄変性を要求される用途に使用される場合には、酸化防止剤及び光安定剤を含有することが好ましい。 Examples of the other additives include organic solvents, silane coupling agents, antioxidants, light stabilizers, rust inhibitors, thixotropic agents, sensitizers, polymerization inhibitors, leveling agents, tackifiers, An antistatic agent, a flame retardant, etc. can be used. These additives may be used alone or in combination of two or more. Among these, it is preferable to contain the organic solvent from the point of the coating property to a to-be-adhered body, and workability | operativity. Moreover, when the ultraviolet curable adhesive composition of this invention is used for the use by which high adhesive physical property is required after heat-and-moisture resistance, it is preferable to contain a silane coupling agent. In addition, when the ultraviolet curable pressure-sensitive adhesive composition of the present invention is used for applications requiring high heat and heat yellowing resistance, it preferably contains an antioxidant and a light stabilizer.
　前記有機溶剤としては、例えば、トルエン、酢酸エチル、酢酸ブチル、メチルエチルケトン、ヘキサン、アセトン、シクロヘキサノン、３－ペンタノン、アセトニトリル、プロピオニトリル、イソブチロニトリル、バレロニトリル、ジメチルスルホキシド、ジメチルホルムアミド等を用いることができる。これらの有機溶剤は単独で用いても２種以上を併用してもよい。 Examples of the organic solvent include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, propionitrile, isobutyronitrile, valeronitrile, dimethyl sulfoxide, dimethylformamide, and the like. be able to. These organic solvents may be used alone or in combination of two or more.
　前記有機溶剤を用いる場合の使用量としては、乾燥性及び塗工性をより一層向上できる点から、紫外線硬化型粘着剤組成物中６０質量％以下であることが好ましく、５～５０質量％の範囲がより好ましい。 The amount used in the case of using the organic solvent is preferably 60% by mass or less in the ultraviolet curable pressure-sensitive adhesive composition from the viewpoint that the drying property and coating property can be further improved. A range is more preferred.
　前記シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン等のエポキシ基を有するシランカップリング剤；２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）プロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）プロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）プロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）プロピルメチルジエトキシシラン等の脂環エポキシ基を有するシランカップリング剤；ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、シリコーンアルコキシオリゴマーなどを用いることができる。これらのシランカップリング剤は単独で用いても２種以上を併用してもよい。これらの中でも、耐湿熱後の粘着力をより一層向上できる点から、エポキシ基を有するシランカップリング剤及び／又は脂環エポキシ基を有するシランカップリング剤を用いることが好ましく、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン及び３－グリシドキシプロピルトリエトキシシランからなる群より選ばれる１種以上のシランカップリング剤を用いることがより好ましい。 Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Silane coupling agents having an epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) propylmethyldimethoxy Syrah Silane coupling agents having an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) propyltriethoxysilane and 2- (3,4-epoxycyclohexyl) propylmethyldiethoxysilane; vinyltrichlorosilane, vinyltri Methoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, silicone alkoxy oligomer, etc. may be used. Kill. These silane coupling agents may be used alone or in combination of two or more. Among these, it is preferable to use a silane coupling agent having an epoxy group and / or a silane coupling agent having an alicyclic epoxy group from the viewpoint that the adhesive strength after heat and humidity resistance can be further improved. Selected from the group consisting of 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane It is more preferable to use one or more silane coupling agents.
　前記シランカップリング剤を用いる場合の使用量としては、耐湿熱後の粘着力をより一層向上できる点から、前記ウレタン樹脂（Ａ）１００質量部に対して、０．０１～１０質量部の範囲であることが好ましく、０．０５～５質量部の範囲がより好ましく、０．０５～１質量部の範囲が更に好ましい。 The amount used in the case of using the silane coupling agent is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) because the adhesive strength after heat and moisture resistance can be further improved. The range of 0.05 to 5 parts by mass is more preferable, and the range of 0.05 to 1 part by mass is even more preferable.
　前記酸化防止剤としては、熱劣化で発生するラジカルの捕捉するヒンダードフェノール化合物（一次酸化防止剤）、及び、熱劣化で発生する過酸化物を分解するリン化合物、イオウ化合物（二次酸化防止剤）等を用いることができる。 Examples of the antioxidant include hindered phenol compounds (primary antioxidants) that capture radicals generated by thermal degradation, phosphorus compounds that decompose peroxides generated by thermal degradation, and sulfur compounds (secondary antioxidants). Agent) and the like.
　前記ヒンダードフェノール化合物としては、例えば、トリエチレングリコール－ビス－［３－（３－ｔ－ブチル－５－メチル－４ヒドロキシフェニル）プロピオネート］、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、オクタデシル［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ベンゼンプロパン酸－３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシ－Ｃ7－Ｃ9側鎖アルキルエステル、４，６－ビス（ドデシルチオメチル）－ｏ－クレゾール、Ｎ－フェニルベンゼンアミンと２，４，４－トリメチルペンテンとの反応生成物、２－ｔ－ブチル－６－（３－ｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート、３，９－ビス［２－〔３－（ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル］２，４，８，１０－テトラオキサスピロ〔５・５〕ウンデカン、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，５－ジ－ｔｅｒｔ－アミルハイドロキノン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the hindered phenol compound include triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate, octadecyl [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxy-C 7 -C 9 side chain alkyl ester, 4,6-bis (dodecylthiomethyl) -O-cresol, N-phenylbenzenamine and 2,4,4-trimethylpente Product of 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 3,9-bis [2- [3- (t -Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5 · 5] undecane, 2,6-di-tert-butyl -4-Methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,5-di-tert-amylhydroquinone and the like can be used. These compounds may be used alone or in combination of two or more.
　前記リン化合物としては、例えば、トリフェニルホスフィン、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）＝エチル＝ホスフィット、トリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２，４－ジブチルフェニル）ホスファイト、トリス（２，４－ジブチル－５－メチルフェニル）ホスファイト、トリス〔２－第三ブチル－４－（３－ブチル－４－ヒドロキシ－５－メチルフェニルチオ）－５－メチルフェニル〕ホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６－トリブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）－４，４’－ｎ－ブチリデンビス（２－ブチル－５－メチルフェノール）ジホスファイト、ヘキサ（トリデシル）－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ブチルフェニル）ブタントリホスファイト、テトラキス（２，４－ジブチルフェニル）ビフェニレンジホスホナイト、９，１０－ジハイドロ－９－オキサ－１０－ホスファフェナンスレン－１０－オキサイド、２，２’－メチレンビス（４，６－ブチルフェニル）－２－エチルヘキシルホスファイト、２，２’－メチレンビス（４，６－ブチルフェニル）－オクタデシルホスファイト、２，２’－エチリデンビス（４，６－ジブチルフェニル）フルオロホスファイト、トリス（２－〔（２，４，８，１０－テトラキスブチルジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン－６－イル）オキシ〕エチル）アミン、２－エチル－２－ブチルプロピレングリコールと２，４，６－トリブチルフェノールのホスファイト等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the phosphorus compound include triphenylphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) = ethyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (2, 4-dibutylphenyl) phosphite, tris (2,4-dibutyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-butyl-4-hydroxy-5-methylphenylthio)- 5-methylphenyl] phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol di Phosphite, di (nonylphenyl) pentaerythrito Rudiphosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite, bis (2,6-dibutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tributylphenyl) penta Erythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-butyl) -5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-butylphenyl) butanetriphosphite, tetrakis (2,4-dibutylphenyl) biphenylene diphospho Knight, 9,10- Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-dibutylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakisbutyldibenzo [d, f] [ 1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tributylphenol phosphite, and the like can be used. These compounds may be used alone or in combination of two or more.
　前記イオウ化合物としては、例えば、ジドデシル－３，３’－チオプロピオネート、ジラウリル－３，３’－チオジプロピオネート、ラウジリルチオジチオネート、ジトリデシル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート、テトラキス－メチレン－３－ラウリルチオプロピオネートメタン、ジステアリル－３，３’－メチル－３，３’－チオジプロピオネート、ラウリルステアリル－３，３’－チオジプロピオネート、ビス［２－メチル－４－（３－ｎ－アルキルチオプロピオニルオキシ）－５－ｔ－ブチルフェニル］スルフィド、β－ラウリルチオプロピオネート、２－メルカプトベンゾイミダゾール、２－メルカプト－５－メチルベンゾイミダゾール、ジオクタデシル－３，３’－チオジプロチオネート等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the sulfur compound include didodecyl-3,3′-thiopropionate, dilauryl-3,3′-thiodipropionate, lauryl thiodithionate, ditridecyl-3,3′-thiodipropionate, Dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, tetrakis-methylene-3-laurylthiopropionate methane, distearyl-3,3′-methyl-3, 3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, β- Laurylthiopropionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzoy Imidazole, can be used dioctadecyl 3,3'-thio dipropionate isethionate, and the like. These compounds may be used alone or in combination of two or more.
　これらの中でも、粘着力及び耐湿熱黄変性をより一層向上できる点から、リン化合物を用いることが好ましく、トリフェニルホスフィン、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）＝エチル＝ホスフィット及びトリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイトからなる群より選ばれる１種以上の酸化防止剤を用いることがより好ましく、トリフェニルホスフィン、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）＝エチル＝ホスフィットを用いることがより好ましい。 Among these, it is preferable to use a phosphorus compound from the viewpoint that the adhesive strength and heat-and-humidity yellowing resistance can be further improved. Triphenylphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) = ethyl It is more preferable to use one or more antioxidants selected from the group consisting of phosphite and tris (2,4-di-tert-butylphenyl) phosphite, and triphenylphosphine, bis (2,4-diphenyl). It is more preferred to use -tert-butyl-6-methylphenyl) = ethyl = phosphite.
　前記酸化防止剤を用いる場合の使用量としては、耐湿熱黄変性をより一層向上できる点から、前記ウレタン樹脂（Ａ）１００質量部に対して、０．０１～１０質量部の範囲であることが好ましい。 The amount used in the case of using the antioxidant is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of further improving wet heat yellowing resistance. Is preferred.
　前記光安定剤は、光劣化で発生するラジカルを捕捉するものであり、例えば、チオール化合物、チオエーテル化合物、ヒンダードアミン化合物等のラジカル捕捉剤；ベンゾフェノン化合物、ベンゾエート化合物等の紫外線吸収剤などを用いることができる。これらの光安定剤は単独で用いても２種以上を併用してもよい。これらの中でも、耐湿熱黄変性をより一層向上できる点から、ヒンダードアミン化合物を用いることが好ましい。 The light stabilizer captures radicals generated by photodegradation. For example, a radical scavenger such as a thiol compound, a thioether compound, or a hindered amine compound; an ultraviolet absorber such as a benzophenone compound or a benzoate compound may be used. it can. These light stabilizers may be used alone or in combination of two or more. Among these, it is preferable to use a hindered amine compound from the viewpoint that the heat and heat yellowing resistance can be further improved.
　前記ヒンダードアミン化合物としては、例えば、シクロヘキサンと過酸化Ｎ－ブチル２，２，６，６－テトラメチル－４－ピペリジンアミン－２，４，６－トリクロロ１，３，５－トリアジンとの反応生成物と２－アミノエタノールとの反応生成物、デカン二酸ビス（２，２，６，６－テトラメチル－１－（オクチルオキシ）－４－ピペリジニル）エステル、１，１－ジメチルエチルヒドロペルオキシドとオクタンの反応生成物等のアミノエーテル基を有するヒンダードアミン化合物；Ｎ－アセチル－３－ドデシル－１－（２，２，６，６－テトラメチル－４－ピペリジニル）ピロリジン－２，５－ジオン等のＮ－アセチル系ヒンダードアミン化合物；ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）＝デカンジオアート、ビス（１，２，２，６，６，－ペンタメチル－４－ピペリジル）｛［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル｝ブチルマロネート、コハク酸ジメチル・１－（２－ヒドロキシエチル）－４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン重縮合物、プロバンジオイックアシッド［｛４－メトキシフェニル｝メチレン］－ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）エステルのＮ－アルキルヒンダードアミン化合物等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the hindered amine compound include a reaction product of cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro 1,3,5-triazine. , 2-aminoethanol reaction product, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane A hindered amine compound having an amino ether group such as a reaction product of N; N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione and the like N -Acetyl-based hindered amine compounds; bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decanedioate, bi (1,2,2,6,6, -pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate, dimethyl succinate -(2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, Provandioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) ester N-alkyl hindered amine compounds and the like can be used. These compounds may be used alone or in combination of two or more.
　前記光安定剤を用いる場合の使用量としては、耐湿熱黄変性をより一層向上できる点から、前記ウレタン樹脂（Ａ）１００質量部に対して、０．０１～１０質量部の範囲であることが好ましい。 The amount used in the case of using the light stabilizer is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint that the heat and heat yellowing resistance can be further improved. Is preferred.
　本発明の紫外線硬化型粘着剤組成物の粘度としては、塗工性及び作業性の点から、５００～３０，０００ｍＰａ・ｓの範囲であることが好ましく、１，０００～２０，０００ｍＰａ・ｓの範囲がより好ましい。なお、前記粘度は、２５℃でＢ型粘度計にて測定した値を示す。 The viscosity of the ultraviolet curable pressure-sensitive adhesive composition of the present invention is preferably in the range of 500 to 30,000 mPa · s, and preferably 1,000 to 20,000 mPa · s from the viewpoint of coating properties and workability. A range is more preferred. In addition, the said viscosity shows the value measured with the B-type viscometer at 25 degreeC.
　本発明の粘着シートの製造方法としては、例えば、前記紫外線硬化型粘着剤組成物を被着体に塗工し、必要に応じて乾燥し、その後紫外線硬化することにより製造する方法が挙げられる。 Examples of the method for producing the pressure-sensitive adhesive sheet of the present invention include a method in which the ultraviolet curable pressure-sensitive adhesive composition is applied to an adherend, dried as necessary, and then UV-cured.
　前記被着体としては、例えば、プラスチック基材、フレキシブルプリント基材、これらの基材に離型処理を施した基材やＩＴＯ（酸化インジウム錫）を蒸着した基材；ガラス板、鋼板、亜鉛鋼板、ブリキ板、アルミニウム板等の高極性な基材を用いることができる。なお、粘着層の両面にはそれぞれ同一の基材を用いても別々の基材を用いてもよい。 Examples of the adherend include a plastic substrate, a flexible printed substrate, a substrate obtained by subjecting these substrates to a release treatment, and a substrate obtained by vapor deposition of ITO (indium tin oxide); glass plate, steel plate, zinc A highly polar base material such as a steel plate, a tin plate, or an aluminum plate can be used. In addition, the same base material may be used for both surfaces of the adhesion layer, or different base materials may be used.
　前記プラスチック基材としては、例えば、アクリル樹脂、ＰＣ（ポリカーボネート）、ＰＢＴ（ポリブチレンテレフタレート）、ＰＰＳ（ポリフェニレンサルファイド）、変性ＰＰＥ（ポリフェニレンエーテル）、ＰＥＴ（ポリエチレンテレフタレート）、ＣＯＰ（シクロオレフィンポリマー）、ＴＡＣ（トリアセチルセルロース）等を原料として得られるプラスチックフィルム、反射防止フィルム、防汚フィルム、タッチパネルを構成する透明導電膜のフィルム等を用いることができる。 Examples of the plastic substrate include acrylic resin, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE (polyphenylene ether), PET (polyethylene terephthalate), COP (cycloolefin polymer), A plastic film obtained by using TAC (triacetylcellulose) or the like as a raw material, an antireflection film, an antifouling film, a transparent conductive film constituting a touch panel, or the like can be used.
　前記紫外線硬化型粘着剤組成物を前記基材に塗工する方法としては、例えば、アプリケーター、ロールコーター、ナイフコーター、グラビアコーター等を使用して塗布する方法が挙げられる。前記塗工後は、乾燥を行う場合は得られた積層体を乾燥機等に入れ、例えば温度５０～１３０℃の範囲で、１～３０分乾燥させる方法が挙げられる。 Examples of a method of applying the ultraviolet curable pressure-sensitive adhesive composition to the substrate include a method of applying using an applicator, a roll coater, a knife coater, a gravure coater and the like. After the coating, when drying is performed, the obtained laminate is put in a dryer or the like, and dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes, for example.
　その後、紫外線照射することにより粘着シートが得られるが、前記紫外線照射する方法としては、例えば、キセノンランプ、キセノン－水銀ランプ、メタルハライドランプ、高圧水銀ランプ、低圧水銀ランプ等の公知の紫外線光照射装置を用いる方法が挙げられる。 Thereafter, an adhesive sheet is obtained by irradiating with ultraviolet rays. Examples of the method of irradiating with ultraviolet rays include known ultraviolet light irradiation devices such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, and a low pressure mercury lamp. The method using is mentioned.
　前記紫外線の照射量としては、好ましくは０．０５～５Ｊ／ｃｍ２、より好ましくは０．１～３Ｊ／ｃｍ２、特に好ましくは０．３～１．５Ｊ／ｃｍ２の範囲であることがよい。なお、紫外線の照射量は、ＧＳユアサ株式会社製ＵＶチェッカー「ＵＶＲ－Ｎ１」を用いて３００～３９０ｎｍの波長域において測定した値を基準とする。 The irradiation dose of the ultraviolet, preferably be 0.05 ~ 5J / cm 2, more preferably 0.1 ~ 3J / cm 2, particularly preferably in the range of 0.3 ~ 1.5J / cm 2 Good. The irradiation amount of ultraviolet rays is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker “UVR-N1” manufactured by GS Yuasa Corporation.
　以上の方法にして得られる粘着シートの厚さとしては、使用される用途に応じて適宜決定されるが、例えば１０～５００μｍの範囲である。 The thickness of the pressure-sensitive adhesive sheet obtained by the above method is appropriately determined according to the intended use, but is, for example, in the range of 10 to 500 μm.
　以上、本発明の紫外線硬化型粘着剤組成物は、熱架橋及び紫外線硬化を併用し得るものであり、金属板やガラス板等の高極性な被着体への密着性及び耐湿熱白化性に優れるものである。 As described above, the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be used in combination with thermal crosslinking and ultraviolet curing, and can adhere to a highly polar adherend such as a metal plate or a glass plate and can be resistant to heat and heat whitening. It is excellent.
　従って、本発明の紫外線硬化型粘着剤組成物は、医療用、文具用、光学部材用等の様々分野で好適に使用することができる。 Therefore, the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used in various fields such as medical use, stationery use, and optical member use.
　以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
［合成例１］
＜ウレタン樹脂（Ａ－１）の合成＞
　攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ポリプロピレングリコール（数平均分子量；１，０００、以下「ＰＰＧ」と略記する。）を１９４質量部、１，４－シクロヘキサンジメタノール（以下「ＣＨＤＭ」と略記する。）を３９．４質量部、グリセリンモノメタクリレート（日油株式会社「ブレンマーＧＬＭ」、以下「ＧＬＭ」と略記する。）を５．５質量部、２，６－ジ－ターシャリーブチル－クレゾールを１質量部、ｐ－メトキシフェノールを０．５質量部添加した。反応容器内温度が４０℃になるまで昇温した後、イソホロンジイソシアネート（以下「ＩＰＤＩ」と略記する。）を１０９質量部添加した。そこで、ジオクチルスズジネオデカネート０．１質量部添加し、１時間かけて８０℃まで昇温した。その後、８０℃で１２時間ホールドし、全てのイソシアネート基が消失していることを確認後、冷却しウレタン樹脂（Ａ－１）を得た。得られたウレタン樹脂（Ａ－１）は、重量平均分子量が４０，４００、アクリロイル基の含有量が０．１ｍｏｌ／ｋｇであった。 [Synthesis Example 1]
<Synthesis of urethane resin (A-1)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 194 parts by weight of polypropylene glycol (number average molecular weight; 1,000, hereinafter abbreviated as “PPG”), 1,4-cyclohexanedi 39.4 parts by mass of methanol (hereinafter abbreviated as “CHDM”), 5.5 parts by mass of glycerin monomethacrylate (“Nippon Corporation“ Blenmer GLM ”, hereinafter abbreviated as“ GLM ”), 2, 6 -1 part by weight of di-tertiary butyl-cresol and 0.5 part by weight of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 ° C., 109 parts by mass of isophorone diisocyanate (hereinafter abbreviated as “IPDI”) was added. Therefore, 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain urethane resin (A-1). The obtained urethane resin (A-1) had a weight average molecular weight of 40,400 and an acryloyl group content of 0.1 mol / kg.
［合成例２］
＜ウレタン樹脂（Ａ－２）の合成＞
　撹拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ポリオキシテトラメチレングリコール（数平均分子量；１，０００、以下「ＰＴＭＧ」と略記する。）を２５９質量部、１，４－ブタンジオール（以下、「１，４ＢＧ」と略記する。）を１９質量部、ＧＬＭを６．２質量部、２，６－ジ－ターシャリーブチル－クレゾールを１質量部、ｐ－メトキシフェノールを０．５質量部添加した。反応容器内温度が４０℃になるまで昇温した後、ＩＰＤＩを１１０質量部添加した。そこで、ジオクチルスズジネオデカネート０．１質量部添加し、１時間かけて８０℃まで昇温した。その後、８０℃で１２時間ホールドし、全てのイソシアネート基が消失していることを確認後、冷却しウレタン樹脂（Ａ－２）を得た。得られたウレタン樹脂（Ａ－２）は、重量平均分子量が５６，０００、アクリロイル基の含有量が０．１ｍｏｌ／ｋｇであった。 [Synthesis Example 2]
<Synthesis of urethane resin (A-2)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 259 parts by mass of polyoxytetramethylene glycol (number average molecular weight; 1,000, hereinafter abbreviated as “PTMG”), 19 parts by weight of 4-butanediol (hereinafter abbreviated as “1,4BG”), 6.2 parts by weight of GLM, 1 part by weight of 2,6-ditertiarybutyl-cresol, p-methoxyphenol Was added in an amount of 0.5 parts by mass. After raising the temperature in the reaction vessel to 40 ° C., 110 parts by mass of IPDI was added. Therefore, 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain a urethane resin (A-2). The obtained urethane resin (A-2) had a weight average molecular weight of 56,000 and an acryloyl group content of 0.1 mol / kg.
［合成例３］
＜ウレタン樹脂（Ａ－３）の合成＞
　撹拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ポリカーボネートポリオール（旭化成ケミカルズ株式会社製「デュラネートＴ５６５１」、数平均分子量；１，０００、以下「ＰＣ」と略記する。）を２５６質量部、ＣＨＤＭを３３質量部、ＧＬＭを３．２質量部、２，６－ジ－ターシャリーブチル－クレゾールを１質量部、ｐ－メトキシフェノールを０．５質量部添加した。反応容器内温度が４０℃になるまで昇温した後、ＩＰＤＩを１０９質量部添加した。そこで、ジオクチルスズジネオデカネート０．１質量部添加し、１時間かけて８０℃まで昇温した。その後、８０℃で１２時間ホールドし、全てのイソシアネート基が消失していることを確認後、冷却しウレタン樹脂（Ａ－３）を得た。得られたウレタン樹脂（Ａ－３）は、重量平均分子量が３９，５００、アクリロイル基の含有量が０．０５ｍｏｌ／ｋｇであった。 [Synthesis Example 3]
<Synthesis of urethane resin (A-3)>
Polycarbonate polyol (“Duranate T5651” manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight; 1,000, hereinafter abbreviated as “PC”) in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer. , 256 parts by mass of CHDM, 3.2 parts by mass of GLM, 3.2 parts by mass of 2,6-di-tert-butyl-cresol, and 0.5 parts by mass of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 ° C., 109 parts by mass of IPDI was added. Therefore, 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain urethane resin (A-3). The obtained urethane resin (A-3) had a weight average molecular weight of 39,500 and an acryloyl group content of 0.05 mol / kg.
［合成例５］
＜ウレタン樹脂（Ａ－４）の合成＞
　撹拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ＰＰＧを２１７質量部、ＣＨＤＭを２７．５質量部、ＧＬＭを１５．３質量部、２，６－ジ－ターシャリーブチル－クレゾールを１質量部、ｐ－メトキシフェノールを０．５質量部添加した。反応容器内温度が４０℃になるまで昇温した後、ＩＰＤＩを１１０質量部添加した。そこで、ジオクチルスズジネオデカネート０．１質量部添加し、１時間かけて８０℃まで昇温した。その後、８０℃で１２時間ホールドし、全てのイソシアネート基が消失していることを確認後、冷却しウレタン樹脂（Ａ－４）を得た。得られたウレタン樹脂（Ａ－４）は、重量平均分子量が４２，０００、アクリロイル基の含有量が０．２５ｍｏｌ／ｋｇであった。 [Synthesis Example 5]
<Synthesis of urethane resin (A-4)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, PPG is 217 parts by mass, CHDM is 27.5 parts by mass, GLM is 15.3 parts by mass, and 2,6-ditertiary. 1 part by mass of butyl-cresol and 0.5 part by mass of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 ° C., 110 parts by mass of IPDI was added. Therefore, 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain urethane resin (A-4). The obtained urethane resin (A-4) had a weight average molecular weight of 42,000 and an acryloyl group content of 0.25 mol / kg.
［実施例１］
＜紫外線硬化型粘着剤組成物の調製＞
　攪拌機、還流冷却管、温度計を備えた反応容器に、前記ウレタン樹脂（Ａ－１）１００質量部、２，４，６－トリメチルベンゾイルジフェニル－フォスフィンオキサイド（以下「（Ｂ－１）」と略記する。）を０．５質量部、デカン二酸ビス（２，２，６，６－テトラメチル－１－（オクチルオキシ）－４－ピペリジニル）エステルを０．５質量部、トリフェニルフォスフィン０．５質量部を順次添加し、均一になるまで撹拌した。その後、２００メッシュ金網で濾過し、紫外線硬化型粘着剤組成物を得た。 [Example 1]
<Preparation of UV-curable adhesive composition>
In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 100 parts by mass of the urethane resin (A-1), 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide (hereinafter referred to as “(B-1)”) 0.5 parts by weight of decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 0.5 parts by weight of triphenylphosphine 0.5 parts by mass were sequentially added and stirred until uniform. Thereafter, the mixture was filtered through a 200 mesh wire net to obtain an ultraviolet curable pressure-sensitive adhesive composition.
［実施例２～４］
　用いるウレタン樹脂（Ａ）の種類を表１に示す通りに変更した以外は実施例１と同様にして紫外線硬化型粘着剤組成物を得た。 [Examples 2 to 4]
An ultraviolet curable pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the type of the urethane resin (A) used was changed as shown in Table 1.
［比較合成例１］
＜ウレタン樹脂（Ａ’－１）の合成＞
　攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ＰＰＧを２０５質量部、ＣＨＤＭを４２質量部、２－ヒドロキシエチルアクリレート（以下「ＨＥＡ」と略記する。）１．３質量部、２，６－ジ－ターシャリーブチル－クレゾールを０．５質量部、ｐ－メトキシフェノール０．１質量部を添加した。反応容器内温度が４０℃になるまで昇温した後、ＩＰＤＩを１１０質量部添加した。そこで、ジオクチルスズジネオデカネート０．１質量部添加し、１時間かけて８０℃まで昇温した。その後、８０℃で１２時間ホールドし、全てのイソシアネート基が消失していることを確認後、冷却しウレタン樹脂（Ａ’－１）を得た。得られたウレタン樹脂（Ａ’－１）は、重量平均分子量が２９，０００、アクリロイル基の含有量が０．０３ｍｏｌ／ｋｇであった。 [Comparative Synthesis Example 1]
<Synthesis of urethane resin (A'-1)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 205 parts by mass of PPG, 42 parts by mass of CHDM, and 1.3 parts by mass of 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”). Part, 0.5 parts by weight of 2,6-ditertiarybutyl-cresol and 0.1 parts by weight of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 ° C., 110 parts by mass of IPDI was added. Therefore, 0.1 part by mass of dioctyltin dineodecanate was added, and the temperature was raised to 80 ° C. over 1 hour. Thereafter, it was held at 80 ° C. for 12 hours, and after confirming that all isocyanate groups had disappeared, it was cooled to obtain a urethane resin (A′-1). The obtained urethane resin (A′-1) had a weight average molecular weight of 29,000 and an acryloyl group content of 0.03 mol / kg.
［比較例１］
　ウレタン樹脂（Ａ－１）の代わりに、比較合成例１で得られたウレタン樹脂（Ａ’－１）を用いた以外は、実施例１と同様にして紫外線硬化型組成物を得た。 [Comparative Example 1]
An ultraviolet curable composition was obtained in the same manner as in Example 1, except that the urethane resin (A′-1) obtained in Comparative Synthesis Example 1 was used instead of the urethane resin (A-1).
［各種被着体への密着性の評価方法］
　表面に離型処理された厚さ５０μｍのポリエチレンテレフタレートフィルム（離型ＰＥＴ５０）の表面に、有機溶剤乾燥後の膜厚が１００μｍとなるように実施例及び比較例で得られた紫外線硬化型粘着剤脂組成物を塗布し、８０℃乾燥機中で３分間乾燥させた後に厚さ１００μｍのＰＥＴフィルムを貼り合せた。次いで、離型ＰＥＴを剥離し、被着体であるガラス板及び鋼板に２ｋｇローラー×２往復で貼り合せ、ＰＥＴフィルム透過後のＵＶ－Ａ領域の波長の積算光量が１Ｊ／ｃｍ２となるように紫外線照射し、試験片を得た。次いで、得られた試験片をクロスカット法（ＪＩＳＫ５６００－５－６－１９９９）により、各種被着体に対する密着性を以下の基準で評価した。なお、前記クロスカット試験では、ポリエステル粘着テープ（日東電工株式会社製「Ｎ０．３１Ｂ」）を使用した。
　「Ｔ」；被着体上に残存した粘着剤層のマス目が１００個であった。
　「Ｆ」；被着体上に残存した粘着剤層のマス目が９９個以下であった。 [Method for evaluating adhesion to various adherends]
UV curable pressure-sensitive adhesives obtained in Examples and Comparative Examples so that the film thickness after drying the organic solvent is 100 μm on the surface of a 50 μm-thick polyethylene terephthalate film (release PET 50) having a release treatment on the surface. The fat composition was applied, dried in an 80 ° C. dryer for 3 minutes, and then a 100 μm thick PET film was bonded. Next, the release PET is peeled off and bonded to the adherend glass plate and steel plate by 2 kg roller × 2 reciprocation, and the integrated light quantity of the wavelength in the UV-A region after passing through the PET film is 1 J / cm 2. Were irradiated with ultraviolet rays to obtain test pieces. Next, the obtained test specimens were evaluated for adhesion to various adherends according to the following criteria by the cross-cut method (JISK5600-5-6-1999). In the cross-cut test, a polyester adhesive tape (“N0.31B” manufactured by Nitto Denko Corporation) was used.
“T”: 100 squares of the pressure-sensitive adhesive layer remained on the adherend.
“F”: The number of grids of the pressure-sensitive adhesive layer remaining on the adherend was 99 or less.
［耐湿熱白化性の評価方法］
　表面に離型処理された厚さ５０μｍのポリエチレンテレフタレートフィルム（離型ＰＥＴ５０）の表面に、有機溶剤乾燥後の膜厚が１００μｍとなるように実施例及び比較例で得られた紫外線硬化型粘着剤脂組成物を塗布し、８０℃乾燥機中で３分間乾燥させた後に離型ＰＥＴを貼り合せた。これを縦５０ｍｍ、横４０ｍｍに裁断した。その後、ガラス板透過後のＵＶ－Ａ領域の波長の積算光量が１Ｊ／ｃｍ２となるように紫外線照射し、粘着シートを有する積層体を得、試験片とした。該試験片のヘイズ（％）を濁度計「ＮＤＨ５０００」（日本電色工業（株）製）にて、ＪＩＳＫ７３６１－１－１９９７に準じて測定した。次いで、得られた試験片を８５℃、８５％ＲＨの条件下で１００時間放置した後（以下、「耐湿熱試験後」と略記する。）、２３℃、５０％ＲＨの雰囲気下で取り出した。取り出し後、１０分以内にヘイズ（％）を濁度計「ＮＤＨ５０００」（日本電色工業（株）製）にて、ＪＩＳＫ７３６１－１－１９９７に準じて測定し、耐湿熱白化性を以下のように評価した。
　「Ｔ」：耐湿熱試験前後のヘイズ（％）値の差が１％未満である。
　「Ｆ」：耐湿熱試験前後のヘイズ（％）値の差が１％以上である。 [Evaluation method for resistance to moist heat whitening]
UV curable pressure-sensitive adhesives obtained in Examples and Comparative Examples so that the film thickness after drying the organic solvent is 100 μm on the surface of a 50 μm-thick polyethylene terephthalate film (release PET 50) having a release treatment on the surface. The fat composition was applied and dried in an 80 ° C. dryer for 3 minutes, and then release PET was bonded. This was cut into 50 mm length and 40 mm width. Thereafter, ultraviolet rays were irradiated so that the integrated light quantity of the wavelength in the UV-A region after passing through the glass plate was 1 J / cm 2 to obtain a laminate having an adhesive sheet, which was used as a test piece. The haze (%) of the test piece was measured with a turbidimeter “NDH5000” (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7361-1-1997. Next, the obtained test piece was allowed to stand for 100 hours under the conditions of 85 ° C. and 85% RH (hereinafter abbreviated as “after wet heat resistance test”), and then taken out in an atmosphere of 23 ° C. and 50% RH. . Within 10 minutes after removal, the haze (%) was measured with a turbidimeter “NDH5000” (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7361-1-1997. Evaluated.
“T”: The difference in haze (%) value before and after the wet heat resistance test is less than 1%.
“F”: The difference in haze (%) values before and after the wet heat resistance test is 1% or more.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明の紫外線硬化型粘着剤組成物である実施例１～５は、耐湿熱白化性、並びに、高極性な被着体であるガラス板及び鋼板に対する密着性に優れることが分かった。 It was found that Examples 1 to 5, which are the ultraviolet curable pressure-sensitive adhesive compositions of the present invention, are excellent in heat and heat whitening resistance and adhesion to glass plates and steel plates which are highly polar adherends.
　一方、比較例１は、（メタ）アクリル化合物（ａ３）の代わりにＨＥＡを用いて、末端にアクリロイル基を導入したウレタン樹脂を用いた態様であるが、耐湿熱白化性が不良であり、また、ガラス板及び鋼板に対する密着性も不良であった。 On the other hand, Comparative Example 1 is an embodiment that uses HEA instead of the (meth) acrylic compound (a3) and a urethane resin into which an acryloyl group is introduced at the terminal, but has poor moisture and heat whitening resistance. Also, the adhesion to glass plates and steel plates was poor.

Claims (5)

  1. ポリオール（ａ１）とポリイソシアネート（ａ２）と水酸基を２個以上有する（メタ）アクリル化合物（ａ３）との反応物であり、末端に水酸基を有するウレタン樹脂（Ａ）、及び、光重合開始剤（Ｂ）を含有することを特徴とする紫外線硬化型粘着剤組成物。 It is a reaction product of a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having two or more hydroxyl groups, a urethane resin (A) having a hydroxyl group at the terminal, and a photopolymerization initiator ( An ultraviolet curable pressure-sensitive adhesive composition comprising B).
  2. 前記ポリオール（ａ１）が、ポリエーテルポリオール及び／又はポリカーボネートポリオールを含有するものである請求項１記載の紫外線硬化型粘着剤組成物。 The ultraviolet curable pressure-sensitive adhesive composition according to claim 1, wherein the polyol (a1) contains a polyether polyol and / or a polycarbonate polyol.
  3. 前記（メタ）アクリル化合物（ａ３）が、グリセリンモノ（メタ）アクリレート及び／又は３，４－ジヒドロキシブチル（メタ）アクリレートである請求項１記載の紫外線硬化型粘着剤組成物。 The ultraviolet curable pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylic compound (a3) is glycerin mono (meth) acrylate and / or 3,4-dihydroxybutyl (meth) acrylate.
  4. 前記ウレタン樹脂（Ａ）中における（メタ）アクリロイル基の含有量が、０．０１～２ｍｏｌ／ｋｇの範囲である請求項１記載の紫外線硬化型粘着剤組成物。 The ultraviolet curable pressure-sensitive adhesive composition according to claim 1, wherein the content of the (meth) acryloyl group in the urethane resin (A) is in the range of 0.01 to 2 mol / kg.
  5. 請求項１～４のいずれか１項記載の紫外線硬化型粘着剤組成物の硬化物層を有することを特徴とする粘着シート。
    v     An adhesive sheet comprising a cured product layer of the ultraviolet curable adhesive composition according to any one of claims 1 to 4.
    v
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