Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
• • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2310/00—Treatment by energy or chemical effects
  • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
  • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
  • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation

Definitions

• the present invention relates to an ultraviolet curable pressure-sensitive adhesive composition that can be suitably used for production of IT-related products.
• a touch panel is installed in a mobile terminal such as a smartphone or a tablet.
• the touch panel includes a cover glass, an electrode glass / film, and a liquid crystal panel laminate.
• OCA Optical Clear Adhesive
• a smartphone a decorative layer is provided on the cover glass, and a step of about 20 ⁇ m is formed. Therefore, the OCA needs to adhere to the cover glass while following the step (without involving bubbles or the like). is there.
• the design of smartphones has increased and the decorative layer has become thicker, approximately 60 ⁇ m. Further, since the tablet has a large screen, the distortion is large, and the OCA is required to be capable of following a thicker step or distortion. In particular, from the viewpoint of design, it is necessary to follow a large step without increasing the thickness of the OCA.
• UV curable pressure-sensitive adhesive composition examples include a pressure-sensitive adhesive obtained by using a solventless pressure-sensitive adhesive composition containing urethane acrylate, an acrylic monomer, and a photopolymerization initiator. (For example, see Patent Document 1).
• the step followability is good, but if the pressure-sensitive adhesive is too soft, it flows during heating and entrains bubbles. And sticking out of the adhesive and non-uniform film thickness. Thus, it has been difficult to achieve both the contradictory performance between the step following property and the shape retaining property.
• the problem to be solved by the present invention is to obtain an ultraviolet curable pressure-sensitive adhesive sheet excellent in step followability and shape retention, and excellent in a cured product layer obtained by irradiating the ultraviolet curable pressure-sensitive adhesive sheet with ultraviolet rays.
• Another object of the present invention is to provide an ultraviolet curable pressure-sensitive adhesive composition capable of imparting heat and heat resistance to whitening.
• the present invention relates to a urethane resin (A) having a hydroxyl group and a (meth) acryloyl group, a polyisocyanate crosslinking agent (B), a (meth) acrylic compound (C) having two or more (meth) acryloyl groups, an organic solvent (
• the present invention provides an ultraviolet curable pressure-sensitive adhesive composition comprising D) and a photopolymerization initiator (E).
• this invention provides the manufacturing method of the ultraviolet curable adhesive sheet characterized by being obtained by drying the organic solvent (D), after apply
• the present invention provides a method for producing a laminate, which is obtained by bonding at least two adherends with the ultraviolet curable adhesive sheet and then irradiating with ultraviolet rays.
• the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be used in combination with thermal crosslinking and ultraviolet curing, and an ultraviolet curable pressure-sensitive adhesive sheet excellent in step followability and shape retention can be obtained. Moreover, the hardened
• the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used as an ultraviolet curable pressure-sensitive adhesive composition used for an optical member, and in particular, a touch panel, a liquid crystal display, a plasma display, an organic EL, a personal computer. It can be suitably used for manufacturing IT-related products such as mobile phones.
• the ultraviolet curable pressure-sensitive adhesive composition of the present invention includes a urethane resin (A) having a hydroxyl group and a (meth) acryloyl group, a polyisocyanate crosslinking agent (B), and a (meth) acryl having two or more (meth) acryloyl groups.
• a compound (C), an organic solvent (D), and a photoinitiator (E) are contained.
• the urethane resin (A) has a hydroxyl group and a (meth) acryloyl group, and when the organic solvent (D) is dried, the hydroxyl group is thermally crosslinked with a polyisocyanate crosslinking agent (B) described later, and has excellent shape retention.
• a polyisocyanate crosslinking agent (B) described later since it has an appropriate flexibility before UV curing, even if it is bonded to a substrate having a step, it can follow well without entraining bubbles or the like.
• the (meth) acryloyl group crosslinks with the (meth) acrylic compound (C) described later by ultraviolet irradiation, and the crosslink density is increased, whereby excellent moisture and heat whitening resistance can be exhibited.
• urethane resin (A) for example, a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having a hydroxyl group or an isocyanate group can be reacted under conditions where the hydroxyl group becomes excessive. Can be used.
• 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, one or more polyether polyols selected from the group consisting of polyoxyethylene polyols, polyoxypropylene polyols and polyoxytetramethylene polyols are used from the viewpoint of further improving the resistance to moist heat whitening and flexibility. It is preferable.
• 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) it is possible to further improve the heat and whitening resistance, flexibility, and mechanical strength, and further improve the balance between the step following ability and the shape retention.
• the range is preferably from 500 to 7,000, more preferably from 700 to 4,000, and still more preferably from 800 to 3,000.
• 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 of 50 to 400 may be used in combination.
• chain extender for example, a compound similar to a compound having two or more hydroxyl groups used as a raw material for the polycarbonate polyol can be used.
• 1,4-butanediol and 1,5-pentane are preferred because a hard segment having an appropriate chain length can be introduced into the urethane resin (A), and excellent shape retention and moisture and heat whitening resistance can be obtained.
• the chain extender is preferably in the range of 3 to 50% by mass in the polyol (a1), and more preferably in the range of 5 to 20% by mass.
• 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 a hydroxyl group or an isocyanate group is used for the purpose of introducing a (meth) acryloyl group into the urethane resin (A).
• (meth) acryl means acryl and / or methacryl
• (meth) acrylate means acrylate and / or methacrylate
• (meth) acryloyl means acryloyl. And / or methacryloyl.
• Examples of the (meth) acrylic compound having a hydroxyl group that can be used as the compound (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylic acid alkyl ester having a hydroxyl group such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyethylacrylamide; trimethylolpropane di (meth) Polyfunctional (meth) acrylate having a hydroxyl group such as acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate; polyethylene glycol monoacrylate, And the like can be used polypropylene glycol monoacrylate.
• These compounds may be used alone or in combination of two or more.
• an acrylic acid (meth) alkyl ester having a hydroxyl group from the viewpoint of easy availability of raw materials, UV curable properties and adhesive properties, and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are used. It is more preferable.
• Examples of the (meth) acrylic compound having an isocyanate group that can be used as the compound (a3) include 2- (meth) acryloyloxyethyl isocyanate and 2- (2- (meth) acryloyloxyethyloxy) ethyl.
• Isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, and the like can be used. These compounds may be used alone or in combination of two or more.
• 2- (meth) acryloyloxyethyl isocyanate is preferably used from the viewpoint of easy availability of raw materials, and 2-acryloyloxyethyl isocyanate is more preferably used from the viewpoint of ultraviolet curability.
• the said urethane resin (A) As a manufacturing method of the said urethane resin (A) in the case of using the (meth) acrylic compound which has a hydroxyl group as said compound (a3), the said polyol (a1) and the said (meth) acrylic compound ( After preparing a3) in the reaction system, the above-mentioned polyisocyanate (a2) is supplied, mixed, and reacted to produce a method.
• the reaction is preferably performed, for example, at 20 to 120 ° C. for 30 minutes to 24 hours.
• the urethane resin (A) when using a (meth) acrylic compound having an isocyanate group as the compound (a3) for example, in the absence of a solvent, the polyol (a1), the polyisocyanate (a2), A urethane prepolymer having a hydroxyl group can be obtained by charging and reacting, and then the (meth) acrylic compound (a3) having an isocyanate group is supplied, mixed, and reacted to be used. .
• the reaction is preferably performed, for example, at 20 to 120 ° C. for 30 minutes to 24 hours.
• the urethane resin (A) may be produced in the presence of an organic solvent (D) described later.
• the reaction may be carried out when the equivalent ratio exceeds 1, but in that case, 1,2-propylene glycol, 1,3-propylene glycol, or 1,3-propylene glycol is used for the purpose of deactivating the isocyanate group of the urethane resin (A).
• a bifunctional alcohol composed of primary and secondary hydroxyl groups such as butylene glycol.
• the total amount of the hydroxyl group of the polyol (a1), the hydroxyl group of the (meth) acrylic compound (a3) and the hydroxyl group of the alcohol, and the equivalent ratio of the polyisocyanate group [isocyanate group / hydroxyl group It is preferable to adjust so that [total amount] is within the above range.
• an alcohol that can be used for the purpose of deactivating the isocyanate group of the urethane resin (A) for example, a monofunctional alcohol such as methanol, ethanol, propanol, or butanol may be used in combination.
• 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 hydroxyl group in the urethane resin (A) is from 0.01 to 0.00 because it is possible to obtain good shape retention and step following property by thermal crosslinking and to maintain a high level of moisture and heat whitening resistance.
• the range is preferably 5 mol / kg, more preferably 0.02 to 0.2 mol / kg.
• the content of the (meth) acryloyl group in the urethane resin (A) is 0. from the viewpoint that good heat and heat whitening resistance by ultraviolet curing can be obtained, and the shape retention and step following ability can be maintained at a high level. It is preferably in the range of 005 to 0.5 mol / kg, more preferably in the range of 0.01 to 0.2 mol / kg.
• the mass ratio of the urethane bond in the urethane resin (A) is in the range of 4 to 20% by mass in the urethane resin (A) from the viewpoint that good cutting property, adhesive physical property and wet heat whitening resistance can be obtained by hydrogen bonding. Preferably, it is in the range of 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 preferably in the range of 5,000 to 200,000, and preferably 15,000 to 100,000, from the viewpoints of adhesive properties, shape retention, and step following ability. A range is more preferred.
• the weight average molecular weight of the said urethane (meth) acrylate (A) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a1).
• the polyisocyanate cross-linking agent (B) is an essential component for obtaining an ultraviolet curable pressure-sensitive adhesive sheet that is thermally cross-linked with the hydroxyl group of the urethane resin (A) and has excellent shape retention, such as toluene diisocyanate, Polyisocyanates such as chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate; these trimethylolpropane adducts; these isocyanurate bodies; Can be used.
• Polyisocyanates such as chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphen
• the polyisocyanate is preferably one selected from the group consisting of toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate because it has an appropriate chain length. Is more preferable.
• the amount of the polyisocyanate crosslinking agent (B) used is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of crosslinkability with the urethane resin (A).
• the range of 0.2 to 5 parts by mass is more preferable.
• the (meth) acrylic compound (C) having two or more (meth) acryloyl groups is an essential component for obtaining excellent moisture and heat whitening resistance, such as ethylene glycol di (meth) acrylate and propylene glycol diene.
• (meth) acrylic compounds may be used alone or in combination of two or more. Among these, from the point that good ultraviolet curability can be obtained, moist heat whitening resistance, and since the appropriate hardness can be imparted, the balance between the step following ability and the shape retention can be further improved.
• a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylate having an isocyanurate skeleton is preferably used.
• 1,6-hexanediol di (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tris
• one or more (meth) acrylic compounds selected from the group consisting of (meth) acrylate, pentaerythritol tetra (meth) acrylate, and tris (2- (meth) acryloyloxyethyl) isocyanurate.
• the amount of the (meth) acrylic compound (C) used is 100 parts by mass of the urethane resin (A) from the viewpoint of further improving the balance between moisture and heat whitening resistance, and step balance and shape retention.
• the range is preferably 1 to 50 parts by mass, and more preferably 3 to 40 parts by mass.
• organic solvent (D) examples include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, propionitrile, isobutyronitrile, valeronitrile, dimethyl sulfoxide, dimethylformamide. Etc. can be used. These organic solvents may be used alone or in combination of two or more.
• the amount of the organic solvent (D) used is preferably 80% 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.
• the photopolymerization initiator (E) generates radicals by light irradiation, heating, or the like, and initiates radical polymerization between the (meth) acrylic compounds (A).
• Examples of the photopolymerization initiator (E) include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-isopropylphenyl) -2.
• photopolymerization initiator (E) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4,6-trimethylbenzoyldiphenylphosphine oxide and one or more photopolymerization initiators selected from the group consisting of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferably used. 6-trimethylbenzoyldiphenylphosphine oxide is more preferred.
• the amount of the photopolymerization initiator (E) used is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic compound (C) because the curability can be further improved.
• the range is 0.05 to 5 parts by mass, and more preferably 0.05 to 1 part by mass.
• the ultraviolet curable adhesive composition of the present invention may contain other additives as necessary.
• the other additives include a silane coupling agent, an antioxidant, a light stabilizer, a rust inhibitor, a thixotropic agent, a sensitizer, a polymerization inhibitor, a leveling agent, a tackifier, and an antistatic agent.
• a flame retardant or the like can be used.
• These additives may be used alone or in combination of two or more.
• a silane coupling agent when the ultraviolet curable pressure-sensitive adhesive composition of the present invention is used for applications requiring high pressure-sensitive adhesive properties after heat and humidity resistance, it is preferable to contain a silane coupling agent.
• the ultraviolet curable pressure-sensitive adhesive composition of the present invention when used for applications requiring high heat and heat yellowing resistance, it preferably contains an antioxidant and a light stabilizer.
• 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 0.01 to 10% by mass with respect to 100 parts by mass of the urethane (meth) acrylate (A) because the adhesive strength after heat and moisture resistance can be further improved.
• the range is preferably from 5 to 5 parts by weight, more preferably from 0.05 to 5 parts by weight, and still more preferably from 0.05 to 1 part by weight.
• 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.
• the ultraviolet curable pressure-sensitive adhesive sheet is obtained by applying the ultraviolet curable pressure-sensitive adhesive composition to a substrate, drying the organic solvent (D), and then aging as necessary.
• the urethane resin (A) and the polyisocyanate crosslinking agent (B) are thermally crosslinked, so that an ultraviolet curable pressure-sensitive adhesive sheet having excellent shape retention is obtained. It is done.
• the said (meth) acrylic compound (C) contains a hydroxyl group, it crosslinks with the said urethane resin (A) through the said polyisocyanate crosslinking agent (B).
• the curing proceeds more efficiently when irradiated with ultraviolet rays to be described later, so that an ultraviolet curable pressure-sensitive adhesive sheet having excellent moisture and heat whitening resistance can be obtained.
• Examples of the method of applying the ultraviolet curable pressure-sensitive adhesive composition to a substrate include a method of applying using an applicator, a roll coater, a knife coater, a gravure coater and the like.
• the base material for example, a plastic base material, a flexible print base material, a glass base material, a base material obtained by subjecting these base materials to a mold release treatment, a base material obtained by vapor deposition of ITO (indium tin oxide), or the like is used. Can do.
• 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 the drying of the organic solvent (D) include a method of carrying out at a temperature of 60 to 120 ° C. for 1 minute to 1 hour.
• Aging may be performed at a temperature of 10 to 40 ° C. for 1 to 7 days.
• the thickness of the ultraviolet curable pressure-sensitive adhesive sheet is appropriately determined depending on the intended use, and is, for example, in the range of 10 to 500 ⁇ m.
• the laminate is obtained by laminating at least two adherends with the ultraviolet curable adhesive sheet and then irradiating with ultraviolet rays.
• the adherend in addition to the above-described base material, in particular, when the laminate of the present invention is used for manufacturing IT-related products, for example, a touch panel, a liquid crystal module, a cover glass, a cover glass-touch panel A body panel (OGS) or the like can be used.
• a touch panel for example, a liquid crystal module, a cover glass, a cover glass-touch panel A body panel (OGS) or the like can be used.
• OGS cover glass-touch panel
• the said adherend may have a level
• the ultraviolet curable adhesive sheet of this invention since the ultraviolet curable adhesive sheet of this invention has the outstanding level
• liquid crystal module / cured material layer of UV curable pressure sensitive adhesive sheet / touch panel liquid crystal module / cured material layer of UV curable pressure sensitive adhesive sheet / Touch panel / cured material layer of UV curable adhesive sheet / cover glass, liquid crystal module / cured material layer of UV curable adhesive sheet / OGS, and the like.
• Examples of the ultraviolet irradiation method include a method using a known ultraviolet light irradiation device such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, or a low pressure mercury lamp.
• a known ultraviolet light irradiation device such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, or a low pressure mercury lamp.
• 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 urethane resin (A) and the (meth) acrylic compound (C) are completely cured and the crosslink density is improved, so that excellent moisture and heat whitening resistance is exhibited.
• the storage elastic modulus at 30 ° C. is 1 ⁇ 10 4 Pa or more when measured at a frequency of 1 Hz, from the point that the moisture and heat whitening resistance can be further improved. preferable.
• the measuring method of the storage elastic modulus of the said adhesive sheet is described in an Example.
• the storage elastic modulus in 80 degreeC and 100 degreeC is 1 * 10 ⁇ 4 > Pa or more when measured at a frequency of 1 Hz from the point which can improve moisture-heat whitening resistance further.
• the measuring method of the storage elastic modulus of the said adhesive sheet is described in an Example.
• the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be used in combination with thermal crosslinking and ultraviolet curing, and an ultraviolet curable pressure-sensitive adhesive sheet excellent in step followability, shape retention and cutting properties can be obtained. Moreover, the hardened
• the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used as an ultraviolet curable pressure-sensitive adhesive composition used for an optical member, and in particular, a touch panel, a liquid crystal display, a plasma display, an organic EL, a personal computer. It can be suitably used for manufacturing IT-related products such as mobile phones.
• IPDI isophorone diisocyanate
• 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) and 10 parts by mass of trimethylolpropane triacrylate (“Aronix M-309” manufactured by Toagosei Co., Ltd.)
• Aronix M-309 trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd.
• the mixture was stirred until uniform. Thereafter, the mixture was cooled to room temperature, and 1-hydroxy-cyclohexyl-phenyl-ketone (hereinafter abbreviated as “(E-1)”) in an amount of 0.5 parts by mass and bis (2,2,6) decanedioate under stirring.
• (E-1) 1-hydroxy-cyclohexyl-phenyl-ketone
• Examples 2 to 8 Implemented except that the type of urethane resin (A) used and the type and / or amount of the polyisocyanate crosslinking agent (B) and (meth) acrylic compound (C) were changed as shown in Tables 1-2. In the same manner as in Example 1, an ultraviolet curable pressure-sensitive adhesive composition was obtained.
• Example 2 An ultraviolet curable pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 10 parts by mass of trimethylolpropane triacrylate was changed to 0 parts by mass.
• 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 to obtain an ultraviolet curable pressure-sensitive adhesive sheet.
• the ultraviolet curable pressure-sensitive adhesive sheet was bonded to a polyethylene terephthalate film (PET100) having a thickness of 100 ⁇ m to produce a laminate in which PET100 was bonded. This was cut into 50 mm length and 40 mm width. Thereafter, ultraviolet rays were irradiated from the glass plate side 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.
• PET100 polyethylene terephthalate film
• 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.
• ⁇ The difference in haze (%) values before and after the wet heat resistance test is less than 0.3%.
• ⁇ The difference in haze (%) value before and after the wet heat resistance test is 0.3% or more and less than 1.0%.
• X The difference in haze (%) values before and after the wet heat resistance test is 1% or more.
• ⁇ The area magnification of the adhesive sheet after being left is less than 103%.
• ⁇ The area magnification of the pressure-sensitive adhesive sheet after being left is 103% or more and less than 105%.
• X The area magnification of the adhesive sheet after being left is 105% or more.
• the ultraviolet curable pressure-sensitive adhesive sheet was bonded to a 100 ⁇ m-thick polyethylene terephthalate film (PET100), and a laminate in which PET100 was bonded to one side was produced. What cut
• PET100 polyethylene terephthalate film
• Examples 1 to 8 which are the ultraviolet curable pressure-sensitive adhesive composition of the present invention, were excellent in heat-and-moisture whitening resistance, level difference followability and shape retention.
• Comparative Example 1 was an embodiment in which the polyisocyanate crosslinking agent (B) was not used, but the shape retention was poor.
• Comparative Example 2 was an embodiment in which the (meth) acrylic compound (C) was not used, but the moisture and heat whitening resistance was poor and the step following ability was insufficient.

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• 2015
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