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
• • 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
• • 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
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

• the present invention relates to an adhesive sheet, an article to which the adhesive sheet is attached, and a method for manufacturing the article.
• a hard coat layer or matte layer is directly applied to the surface of a resin molded product used for the exterior of home appliances, the exterior of mobile terminals, the interior and exterior of automobiles, etc. for the purpose of preventing scratches and improving slipperiness.
• Laminated members are laminated by a method of laminating a laminated member on the surface of which a hard coat layer or a mat layer is laminated on the surface of these molded products. For this reason, a method of bonding the bonding member to the surface of these molded articles is often used (for example, Patent Document 1).
• a vacuum molding machine or the like is used as a method of bonding the bonding member to the molded product.
• the bonding member is heated at about 100 to 170 ° C. for about 1 to 300 seconds. For example, a method is used in which the product is pressed while the base material is stretched and bonded.
• a method of bonding a bonding member to a molded product there is a method in which the bonding member is heated to a temperature at which tackiness occurs or more to a semi-solid state and bonded to the surface of the molded product. Since the surface layer is softened and the appearance tends to be poor, a method of laminating an adhesive layer having tackiness at room temperature on the back surface of the bonding member and bonding the laminated layer to a molded product is often used.
• the adhesive layer it is conceivable to use a liquid adhesive that undergoes a curing reaction by heat or moisture, but in this case, the curing is performed for about 24 hours after the laminating member is laminated to the molded product. Since time is required, there are problems that the bonding member floats and peels during curing, the liquid adhesive flows and protrudes, and the layer thickness is easily changed.
• thermoplastic pressure-sensitive adhesive tape or a hot-melt adhesive it is conceivable to use a thermoplastic pressure-sensitive adhesive tape or a hot-melt adhesive, but since these do not change while their elastic modulus remains low, they are used for evaluating the reliability of molded products.
• swelling or floating occurs due to gas generation from the bonding member or molded product, or swelling or floating occurs due to residual stress or distortion when the bonding member is stretched and bonded. There was a problem that it easily occurred.
• a step of preliminarily heating these members to release the gas is required, resulting in poor production efficiency (for example, Patent Document 2). .
• an ultraviolet-curable adhesive or an adhesive sheet (for example, Patent Document 3) can be used as the adhesive layer.
• the problem to be solved by the present invention is to suppress the formation of bubbles by gas that can be generated from the surface of the adherend even in a moist heat environment, and to prevent two or more adherends including the adherend from protruding from the end face. Suppresses lifting and peeling that can occur due to factors such as residual stress and distortion when bonding the body, and UV absorbers and light stabilizers are kneaded inside, and UV absorbers and light stabilizers are It is an object of the present invention to provide an adhesive sheet that can be cured and bonded by irradiation with active energy rays, and that can also achieve excellent transparency and adhesion after curing, even when the member is a laminated member having a coated coat layer. .
• an adhesive sheet having an adhesive layer having various tensile elasticities That is, according to the present invention, the tensile elasticity ( E'A25 ) measured at a temperature of 25 ° C. and a frequency of 1 Hz is 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa, and the tensile elasticity measured at a temperature of 100 ° C. and a frequency of 1 Hz.
• the tensile storage elastic modulus (E ′ A′100 ) measured at a temperature of 100 ° C. and a frequency of 1 Hz is 2 ⁇ 10 5 to 1 ⁇ 10 9 Pa
• the adhesive (A) has an absorption wavelength in a wavelength region of 380 nm or more.
• Is used for bonding at least two adherends (B1) and (B2), and at least one of the adherends (B1) and (B2) has a temperature of 85 Under the environment of °C and humidity 85% RH
• an active energy ray-curable polyurethane adhesive sheet characterized in that if it is left for 4 hours as an adherend capable of generating gas.
• the adhesive sheet of the present invention suppresses the floating or peeling of the bonding member generated due to the formation of bubbles due to gas that can be generated from the surface of the molded product or the bonding member surface or the residual stress of the bonding member. Even if the bonding member has a UV absorber or light stabilizer kneaded inside or a coating layer with a UV absorber or light stabilizer on the surface, it can be cured and bonded by irradiation with active energy rays. And can also achieve excellent transparency and adhesiveness, greatly contributing to the manufacture of resin molded products used for exteriors of home appliances, exteriors of mobile terminals, interior and exterior of automobiles, etc. be able to.
• the adhesive sheet of the present invention has a tensile modulus ( E'A25 ) of 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa measured at a temperature of 25 ° C. and a frequency of 1 Hz, and was measured at a temperature of 100 ° C. and a frequency of 1 Hz.
• the adherend (B1) and B2) is an active energy ray-curable polyurethane adhesive sheet characterized in that at least one of them is an adherend capable of generating gas when left for 24 hours in an environment of a temperature of 85 ° C and a humidity of 85% RH. is there.
• the adhesive layer and the adhesive sheet include the concept of a so-called pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) and a pressure-sensitive adhesive sheet (pressure-sensitive adhesive sheet).
• the adhesive sheet With the adhesive sheet, it is possible to adhere even to a bonding member that has been treated with an ultraviolet absorber or a light stabilizer while maintaining excellent transparency.
• good adhesion and cohesion can be achieved at the same time with respect to the adherends (B1) and (B2), and the gas can be generated from at least one of the adherends (B1) and (B2). It is possible to suppress the formation and formation of air bubbles, and the floating and peeling caused by residual stress and distortion when the adherends (B1) and (B2) are bonded to each other.
• a single layer of the adhesive layer (A) or a sheet composed of two or more layers can be used.
• Adhesive layer (A) As the adhesive layer (A), one having a tensile elastic modulus (E ′ A25 ) of 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa measured at a temperature of 25 ° C. and a frequency of 1 Hz is used. is preferably 4 ⁇ 5 ⁇ 10 5 Pa, more preferably 5 ⁇ 10 4 ⁇ 5 ⁇ 10 5 Pa.
• E'A25 By setting E'A25 within the above range, pressure-sensitive bonding can be performed to the adherend (B1) or (B2) without heating, and until the adhesive layer (A) is cured by irradiating active energy rays. In addition to suppressing floating and peeling caused by residual stress and distortion when the adherends (B1) and (B2) are bonded to each other, during storage and storage of the adhesive sheet, only from the end face Discharge and crushing can be suppressed.
• E ′ A100 tensile storage elastic modulus
• the pressure is preferably 5 ⁇ 10 3 to 8 ⁇ 10 4 Pa, and more preferably 1 ⁇ 10 4 to 7 ⁇ 10 4 Pa.
• the adhesive layer (A) forms a layer (A ′) (hereinafter, a cured layer (A ′)) in which the adhesive layer (A) is cured by irradiation with active energy rays.
• the cured storage layer (A ′) has a tensile storage elastic modulus (E ′ A′100 ) of 2 ⁇ 10 5 to 1 ⁇ 10 9 Pa, but more preferably 3 ⁇ 10 5 to 1 ⁇ 10 7 Pa. .
• E'A'100 By setting E'A'100 within the above range, more excellent cohesive force can be imparted, and the formation of bubbles caused by gas generated from at least one of the adherends (B1) and (B2), It is possible to suppress the floating and peeling that occur due to residual stress and distortion when the bodies (B1) and (B2) are bonded.
• the tensile storage modulus at 25 ° C. (E ′ A25 ) and the tensile storage modulus at 100 ° C. (E ′ A100 ) and (E ′ A′100 ) are measured by a viscoelasticity tester ( TA Instruments). -Using a product name: RSA III (manufactured by Japan Co., Ltd.), in a tensile mode, at a vibration frequency of 1 Hz and a heating rate of 3 ° C./min, in a temperature range of ⁇ 40 to 150 ° C., a tensile storage elastic modulus ( E ′) is measured.
• the adhesive layer (A) was cut to 50 to 100 ⁇ m, the width was 5 mm, the length of the measuring part was 20 mm, and the length of the handle at each end was 20 mm. Use a rectangular one.
• the cured layer (A ′) formed by irradiation with the active energy ray has a 180 ° peel adhesion to a polycarbonate substrate having a smooth surface in a 25 ° C. atmosphere in a range of 5 to 50 N / 20 mm. And more preferably in the range of 7 to 30 N / 20 mm.
• the cured layer (A ′) formed by irradiation with the active energy ray may have a peeling adhesive strength to a polycarbonate substrate having a smooth surface in a 90 ° C. atmosphere in a range of 5 to 50 N / 20 mm. More preferably, it is in the range of 7 to 30 N / 20 mm.
• the peeling adhesive strength was measured after removing the release liner on one side of the adhesive sheet of the present invention in which the release liner was laminated on both sides and bonding a 50 ⁇ m-thick polyester film under a 25 ° C. atmosphere. For 30 seconds, affixed to a polycarbonate substrate having a smooth surface with a thickness of about 1 to 3 mm in an atmosphere of 25 ° C., and subjected to one reciprocating pressure with a 2 kg roller, and then a thickness of 0.05 to 5 mm to be described later.
• the surface of the polyester film was covered with a transparent resin sheet and cured with an active energy ray to be described later as a sample, and the polyester film was subjected to 180 ° C under a 25 ° C and 90 ° C atmosphere using a Tensilon-type tensile tester equipped with a thermostat. It can be obtained by measuring the peeling resistance when pulled at a speed of 50 mm / min in the ° direction.
• the gel fraction of the adhesive layer (A) before irradiation with the active energy ray is preferably 0 to 10% by mass, more preferably 0 to 5% by mass.
• pressure-sensitive adhesion to the adherend (B1) or (B2) can be performed without heating.
• the adhesive layer after heating is applied.
• the gel fraction of (A) is preferably from 0 to 10% by mass, more preferably from 0 to 5% by mass.
• the gel fraction of the cured layer (A ′) formed by irradiating the active energy ray is preferably 75 to 95% by mass, more preferably 80 to 90% by mass.
• the adhesive layer (A) has excellent pressure-sensitive adhesiveness
• the cured layer (A ′) has excellent cohesive force
• the adherend (B1) and (B2) At least one of the gas generated from the gas generated from at least one of (B2), the residual stress and the distortion generated when the adherend (B1) and (B2) are bonded to each other, and the like. Peeling can be suppressed.
• the gel fraction is obtained by the following equation.
• Gel fraction (% by mass) [(weight of cured layer (A ′) after immersion in toluene) / (weight of cured layer (A ′) before immersion in toluene)] ⁇ 100
• the adhesive layer (A) can be manufactured by, for example, applying an adhesive composition to a surface of a release liner or the like and drying the surface.
• an adhesive composition containing a urethane resin (a) having a hydroxyl group and a (meth) acryloyl group can be used.
• 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 are reacted under the condition that the hydroxyl group becomes excessive. Those obtained 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.
• 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.
• methyl carbonate 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.
• Aliphatic polyols such as 1,2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanedimethanol, cycloheptanediol, cyclooctanediol and 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.
• 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, and still more preferably in the range of 800 to 3,000.
• the adhesive layer (A) has pressure-sensitive adhesiveness, does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, and suppresses protruding and crushing only from the end face.
• the number average molecular weight of the polyol (a1) is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "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 Book “TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (sample concentration: 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene.
• a chain extender having a hydroxyl group may be used in combination, if necessary.
• chain extender having a hydroxyl group for example, the same compounds as the compounds having two or more hydroxyl groups can be 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, and 4,4.
• aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate
• hexamethylene diisocyanate lysine diisocyanate
• cyclohexane diisocyanate isophorone diisocyanate
• An aliphatic or alicyclic polyisocyanate such as' -dicy
• the adhesive layer (A) has a pressure-sensitive adhesive property, does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, prevents the adhesive sheet from coming out or crushed only from the end face, and the adhesive layer (A) And an excellent cohesive force can be imparted to the cured layer (A ′), the formation of air bubbles resulting from gas that can be generated from at least one of the adherends (B1) and (B2), and the formation of the adherends (B1) and ( It is preferable to use an alicyclic polyisocyanate in order to obtain an adhesive sheet capable of suppressing floating and peeling that occur due to residual stress, distortion, and the like at the time of laminating B2) with 4,4 ′.
• polyisocyanates selected from the group consisting of dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate and diisocyanatomethylcyclohexane. Ri preferred.
• the (meth) acrylic compound (a3) having a hydroxyl group or an isocyanate group is used for introducing a (meth) acryloyl group into the urethane resin (a).
• (meth) acryl refers to acryl and / or methacryl
• (meth) acrylate refers to acrylate and / or methacrylate
• (meth) acryloyl refers to acryloyl And / or methacryloyl.
• Examples of the (meth) acrylic compound having a hydroxyl group that can be used as the compound (a3) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Alkyl (meth) acrylate having a hydroxyl group such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and hydroxyethylacrylamide; trimethylolpropanedi (meth) Polyfunctional (meth) acrylates 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.
• acrylic acid (meth) alkyl esters having a hydroxyl group are preferably used, and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are used from the viewpoint of easy availability of raw materials, photocurability and adhesive properties. Is more preferable.
• Examples of the (meth) acrylic compound having an isocyanate group that can be used as the compound (a3) include, for example, 2- (meth) acryloyloxyethyl isocyanate, 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 from the viewpoint of easy availability of raw materials, and it is more preferable to use 2-acryloyloxyethyl isocyanate from the viewpoint of photocurability.
• the compound (a3) As a method for producing the urethane resin (a), for example, the polyol (a1) and the (meth) acrylic compound ( a3) is charged into a reaction system, and then the above-mentioned polyisocyanate (a2) is supplied, mixed, and reacted to produce a product.
• the reaction is preferably carried out, for example, at 20 to 120 ° C. for 30 minutes to 24 hours.
• a (meth) acrylic compound having an isocyanate group is used as the compound (a3), as a method for producing the urethane resin (A), for example, in the absence of a solvent, the polyol (a1) and the polyisocyanate (a2) And then reacting to obtain a urethane prepolymer having a hydroxyl group, and then supplying, mixing, and reacting the (meth) acrylic compound (a3) having an isocyanate group. .
• the reaction is preferably carried out, for example, at 20 to 120 ° C. for 30 minutes to 24 hours.
• the production of the urethane resin (a) may be performed in the presence of an organic solvent.
• organic solvent examples include ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone, methyl ethyl ketone, methyl butyl ketone, ketone solvents such as cyclohexanone, and ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
• ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate
• acetone methyl ethyl ketone
• ketone solvents such as cyclohexanone
• ether esters such as methyl cellosolve acetate and butyl cellosolve acetate.
• a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, and an amide solvent such as dimethylformamide and dimethylacetamide can be used alone or in combination of two or
• the reaction may be carried out when the equivalent ratio exceeds 1, but in that case, for the purpose of deactivating the isocyanate group of the urethane resin (a), 1,2-propylene glycol or 1,3-propylene glycol is used. It is preferable to use a bifunctional alcohol having primary and secondary hydroxyl groups such as butylene glycol. In that case, 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 Total amount] is preferably within the above range.
• Alcohols that can be used to deactivate the isocyanate group of the urethane resin (a) include, for example, monofunctional alcohols such as methanol, ethanol, propanol, and butanol.
• 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-bister-butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methquinone), para-tert-butyl catechol methoxyphenol, and 2,6-di-tert-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.
• urethanization catalyst examples include nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; metal salts such as bismuth carboxylate, potassium acetate, zinc stearate, and tin octylate; dibutyltin laurate, dioctyltin Organic metal compounds such as dineodecat and zirconium tetraacetylacetonate; metal complexes such as zirconium complexes and aluminum complexes can be used. These urethanization catalysts may be used alone or in combination of two or more.
• the urethane resin (a) has a (meth) acryloyl group that causes radical polymerization to proceed by light irradiation or heating.
• the adhesive layer (A) has a pressure-sensitive adhesive property and does not become too soft during storage and storage of the adhesive sheet or when heat-bonded.
• the adhesive layer (A) and the cured layer (A ') have a cohesion of 1,000 to 200,000 g / eq. 3,000 to 100,000 g / eq.
• the (meth) acryloyl group equivalent is a value obtained by dividing the total mass of the raw materials of the urethane resin (a) by the equivalent of the (meth) acryl group present in the urethane resin (a).
• the mass ratio of urethane bonds in the urethane resin (a) an excellent cohesive force can be imparted, and the formation of bubbles due to a gas that can be generated from at least one of the adherends (B1) and (B2);
• the total amount of the urethane resin (a) is used to obtain an adhesive sheet capable of suppressing floating and peeling that occur due to residual stress and distortion when the adherends (B1) and (B2) are bonded.
• the content is preferably in the range of 4 to 20% by mass, more preferably in the range of 5 to 15% by mass.
• the urethane bond amount of the urethane resin (a) indicates a mass ratio of the urethane bond structure in the raw material to the total mass of the raw material of the urethane resin (a).
• the weight-average molecular weight of the urethane resin (a) is such that the adhesive layer (A) has pressure-sensitive adhesive properties and does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, and is only exposed from the end face.
• excellent cohesive force can be imparted to the adhesive layer (A) and the cured layer (A '), and is caused by gas that can be generated from at least one of the adherends (B1) and (B2).
• an adhesive sheet capable of suppressing floating and peeling caused by the formation of air bubbles and residual stress or distortion when the adherends (B1) and (B2) are bonded together It is preferably in the range of 000 to 200,000, more preferably 15,000 to 100,000.
• the weight average molecular weight of the urethane (meth) acrylate (A) indicates a value obtained by measuring the same as the number average molecular weight of the polyol (a1).
• a composition containing a known polyisocyanate crosslinking agent and a polyfunctional (meth) acrylate compound can be used as necessary.
• polyfunctional as used in the present invention means having two or more polymerizable unsaturated double bonds in a molecule.
• polyisocyanate crosslinking agent examples include polyisocyanates such as tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate; and trimethylolpropane.
• Adducts; isocyanurates thereof; burettes thereof; and the like can be used.
• the amount of the polyisocyanate cross-linking agent used is such that the adhesive layer (A) has pressure-sensitive adhesive properties, does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, and is protruded or crushed only from the end face. While providing excellent cohesive force to the adhesive layer (A) and the cured layer (A ′), and the generation of bubbles caused by gas that can be generated from at least one of the adherends (B1) and (B2).
• the urethane resin ( a) It is preferably in the range of 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, per 100 parts by mass.
• polyfunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and hexamethylene glycol.
• (meth) acrylic compounds may be used alone or in combination of two or more.
• a polyolefin having an aliphatic polyfunctional (meth) acrylate and / or isocyanurate skeleton can be used.
• a functional (meth) acrylate trimethylolpropane tri (meth) acrylate, di (trimethylolpropane) tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and it is more preferable to use one or more (meth) acrylic compounds selected from the group consisting of tris (2- (meth) acryloyloxyethyl) isocyanurate.
• the content of the polyfunctional (meth) acrylate compound is preferably from 1 to 30 parts by mass, more preferably from 2 to 20 parts by mass, based on 100 parts by mass of the urethane resin (a). And the range of 4 to 15 parts by mass is more preferable.
• the adhesive layer (A) has excellent pressure-sensitive adhesiveness, does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, and prevents the adhesive sheet from being exposed or crushed only from the end face.
• the adhesive layer (A) and the cured layer (A ′) are provided with excellent cohesive force, and the formation of air bubbles due to gas generated from at least one of the adherends (B1) and (B2) and Thus, it is possible to obtain an adhesive sheet capable of suppressing floating and peeling that occur due to residual stress or distortion when the adherends (B1) and (B2) are bonded.
• the adhesive composition contains a photopolymerization initiator having an absorption wavelength in a wavelength region of 380 nm or more as the photopolymerization initiator.
• one of the adherends (B1) and (B2) is made of a light-transmitting material, and has a layer containing an ultraviolet absorber, thereby absorbing light having a wavelength of 380 nm or less, and Even when it is difficult for the active energy ray to reach the layer (A), it has an absorption wavelength even in a wavelength region exceeding 380 nm, and can initiate photopolymerization.
• Examples of such a photopolymerization initiator include phenylphosphine oxide-based (for example, Omnirad TPO-H, Omnirad-819 manufactured by IGM Resin BV) and ⁇ -aminoalkylphenone-based (for example, IGM Resin BV). Omnirad # 369, 379) is preferred.
• the adherend (B1) or the adhesive layer (A) on which the adhesive layer (A) is laminated by a vacuum molding machine or the like, wherein the adherend (B2) has a convex three-dimensional shape. ) Is heated to 100 to 170 ° C. for about 1 to 300 seconds, and then heated and stretched to be applied to the adherend (B2). It is particularly preferable to use 4,6-trimethylbenzoyl) -phenylphosphine oxide (for example, Omnirad ⁇ TPO ⁇ H) in order to suppress thermal decomposition under these temperature conditions.
• the photopolymerization initiator may be used in combination with an anthracene-based or thioxanthone-based sensitizer, if necessary.
• peroxide usable for the radical polymerization initiator for example, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, cumene hydroperoxide, peroxy
• peroxides such as esters can be used. These may be used alone or in combination of two or more.
• peroxyesters and peroxydicarbonates are preferable, and peroxydicarbonate is particularly preferable.
• peroxy dicarbonate examples include di (4-t-butylcyclohexyl) peroxy dicarbonate, and commercially available products include perloyl TCP (manufactured by NOF CORPORATION). Above all, as the peroxide, it is preferable to use perloyl TCP which can be rapidly cured by irradiating active energy rays such as ultraviolet rays.
• the radical polymerization initiator is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the urethane resin (a). preferable.
• the 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 thixotropy-imparting agent, a sensitizer, a polymerization inhibitor, a leveling agent, a tackifier, and an antistatic agent. , A flame retardant, a coloring dye, a coloring pigment, or the like. These additives may be used alone or in combination of two or more.
• a silane coupling agent when the adhesive sheet of the present invention is used for applications requiring high adhesive properties after moist heat resistance, it is preferable to contain a silane coupling agent.
• an antioxidant and a light stabilizer When the adhesive sheet of the present invention is used for applications requiring high wet heat yellowing resistance.
• 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 Shira 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. Among them, 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 of further improving the adhesive strength after heat and humidity resistance. Selected from the group consisting of 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane More preferably, one or more silane coupling agents are used.
• antioxidant examples include a hindered phenol compound (primary antioxidant) that captures radicals generated by thermal degradation, and a phosphorus compound and a sulfur compound (secondary antioxidant) that decompose peroxides generated by thermal degradation. Agent) can be used.
• primary antioxidant hindered phenol compound
• secondary antioxidant sulfur compound
• hindered phenol compound examples include triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 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-phenylbenzeneamine and 2,4,4-trimethylpente Reaction product with 2-t-butyl-6- (3-t-
• sulfur compound examples include didodecyl-3,3'-thiopropionate, dilauryl-3,3'-thiodipropionate, laudilylthiodithionate, 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, ⁇ - Lauryl thiopropionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzoi Imidazole, can be used dioc
• a phosphorus compound is preferably used in order to further improve the adhesive strength and the resistance to wet heat yellowing
• the antioxidant When used, it is used in an amount 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 the resistance to moist heat yellowing. 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; a benzophenone compound, or an ultraviolet absorber such as a benzoate compound may be used. It can.
• These light stabilizers may be used alone or in combination of two or more. Among them, it is preferable to use a hindered amine compound from the viewpoint of further improving the resistance to wet heat yellowing.
• 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 Product of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) decandioate, 1,1-dimethylethyl hydroperoxide and octane
• the light stabilizer When the light stabilizer is used, it is used in an amount 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 the resistance to wet heat yellowing. Is preferred.
• thermoplastic resin examples include a urethane resin, an acrylic resin, a polyester resin, and an epoxy resin.
• the thermoplastic resin is preferably incorporated into the curing reaction system by introducing an unsaturated bond or the like into the molecule, and is preferable in increasing the tensile storage modulus of the adhesive layer after the curing reaction.
• the thermoplastic resin is preferably semi-solid or solid at 25 ° C., and preferably has a weight average molecular weight in the range of 5,000 to 200,000, and in the range of 15,000 to 100,000. Is more preferred.
• the weight average molecular weight of the thermoplastic resin (meth) acrylate (A) indicates a value obtained by measuring the same as the number average molecular weight of the polyol (a1).
• the amount of the thermoplastic resin to be used is preferably 1 to 50 parts by mass, and more preferably 3 to 20 parts by mass, based on 100 parts by mass of the polymerizable resin, which reduces the cohesive force of the cured layer (A ′). Without performing the above, the formation of air bubbles due to gas that can be generated from at least one of the adherends (B1) and (B2), and residual stress and strain when the adherends (B1) and (B2) are bonded to each other It is particularly preferable for suppressing lifting and peeling caused by factors such as the above.
• the molded part to which the adhesive sheet of the present invention is bonded is used to pass an electromagnetic signal such as a microwave or a millimeter wave such as an emblem of an automobile or a high-frequency electric pulse such as a flexible printed circuit board in the vicinity to transmit an electric signal.
• an electromagnetic signal such as a microwave or a millimeter wave such as an emblem of an automobile or a high-frequency electric pulse such as a flexible printed circuit board in the vicinity to transmit an electric signal.
• a polyolefin resin, an inorganic filler, or the like may be added as long as transparency is not impaired.
• the polyolefin resin is preferably an olefin resin having a relative dielectric constant of about 2 to 3 such as a polyethylene resin or a polypropylene resin, or a rubber resin such as an isoprene-based resin or a butadiene-based resin.
• a part of the side chain may be chlorinated or modified with a carboxylic acid to partially improve the polarity. Further, by introducing an unsaturated bond or the like into the molecule of the polyolefin resin, it is taken into the curing reaction system, which is preferable in increasing the tensile storage modulus of the adhesive layer after the curing reaction.
• an inorganic filler having a dielectric loss tangent of about 10 ⁇ 4 to 10 ⁇ 5 such as boron nitride, forteslite, cordierite, silica, magnesium oxide, and alumina. It is more preferable to use silica which is excellent in compatibility and can enhance the transparency of the adhesive sheet.
• the inorganic filler those having an arbitrary shape such as a spherical shape or a crushed shape can be used.
• a titanate coupling or an aluminate cup is provided on the surface.
• a surface-treated material such as a ring or silane coupling may be used.
• the amount of the polyolefin resin or inorganic filler to be used is preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable resin. It is more preferable from the viewpoint of suppressing the decrease in the adhesion to the surface of the adherend (B1) or the adherend (B2) while reducing the ratio and the dielectric loss tangent.
• the particle size of the inorganic filler it is preferable to use a particle having a 50% particle size of 10 nm to less than 50 ⁇ m, more preferably 10 nm to 20 ⁇ m, and more preferably 1 to 10 ⁇ m. It is particularly preferable to use a material that enhances the transparency of the adhesive sheet and achieves both good dispersibility of the inorganic filler and ease of coating.
• the 50% particle size of the inorganic filler under the integrated sieve distribution is determined by using a numerical value measured using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation and using isopropanol as a dispersion medium. Can be.
• the adhesive sheet of the present invention is obtained, for example, by applying the composition of the adhesive layer (A) in which the composition of the adhesive layer (A) is dissolved in a solvent or the like to the surface of a release liner and drying the composition if necessary. It can be manufactured by forming the adhesive layer (A).
• composition of the adhesive layer (A) on the surface of the release liner for example, a method of applying using a comma coater or a lip coater may be mentioned.
• the drying can be performed using, for example, a dryer set at a temperature of about 60 ° C. to 90 ° C.
• the drying is preferably performed at a temperature of preferably about 40 to less than 100 ° C, more preferably about 50 to 90 ° C. By setting the temperature, the curing reaction due to the thermal decomposition of the polymerization initiator can be suppressed.
• the adhesive layer (A) preferably has a thickness of 25 to 300 ⁇ m, more preferably 50 to 175 ⁇ m.
• a sheet having a thickness in the above range it is preferable to use a sheet having a thickness in the above range.
• two or more adhesive layers (A) may be laminated.
• the polyisocyanate cross-linking agent it is preferable to laminate before the cross-linking is completed.
• the adhesive sheet having a thickness in the above range has excellent pressure-sensitive adhesiveness, and does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, and suppresses protruding and crushing only from the end face,
• the adhesive layer (A) and the cured layer (A ′) can maintain excellent transparency, and can form bubbles due to gas that can be generated from at least one of the adherends (B1) and (B2). It is possible to suppress floating and peeling that occur due to residual stress, distortion, and the like at the time of bonding the body (B1) and (B2).
• a sheet having a thickness of 50 to 300 ⁇ m is preferably used, and a sheet having a thickness of 100 to 250 ⁇ m is more preferably used.
• the adhesive sheet having a thickness in the above range has excellent pressure-sensitive adhesiveness, and does not become too soft during storage and storage of the adhesive sheet or when heat-bonded, and suppresses protruding and crushing only from the end face,
• the adhesive sheet can maintain excellent transparency, and can adhere to the step of the adherend (B1) or (B2) and adhere to the gas, which can be generated from at least one of the adherends (B1) and (B2). It is possible to suppress the formation and generation of bubbles and the floating or peeling caused by residual stress or distortion when the adherends (B1) and (B2) are bonded to each other.
• the said thickness points out the thickness which does not contain a release liner.
• the release liner examples include paper such as kraft paper, glassine paper, and high-quality paper; resin films such as polyethylene, polypropylene (OPP, CPP) and polyethylene terephthalate; and laminated paper obtained by laminating the paper and a resin film. Paper that has been capped with clay or polyvinyl alcohol, etc., and one or both sides of which have been subjected to a release treatment of a silicone resin or the like can be used. It is preferable to use the adhesive sheet in order to enhance the transparency of the adhesive sheet of the present invention.
• the release liner preferably has a thickness of 38 to 150 ⁇ m, and more preferably 50 to 100 ⁇ m.
• the adherend (B2) has a convex three-dimensional shape, and the adherend (B1) or the adhesive layer (A) on which the adhesive layer (A) is laminated by a vacuum molding machine or the like.
• a sticking step in which the release liner on which the adhesive layer (A) is laminated is heated to 100 to 170 ° C. for about 1 to 300 seconds and then stretched while being heated and then attached to the adherend (B2), It is more preferable to use a release liner made of a resin material such as polyethylene or polypropylene (OPP, CPP) having a low softening point and easy to stretch.
• a resin material such as polyethylene or polypropylene (OPP, CPP) having a low softening point and easy to stretch.
• the adhesive sheet of the present invention may be sandwiched by another arbitrary release liner until it is used in the bonding step.
• the adhesive sheet of the present invention may have a configuration in which an adhesive layer (A) is laminated on both surfaces of a substrate, and the substrate has a thickness of about ⁇ or less with respect to the total thickness of the adhesive sheet. It is preferred to use By inserting the base material into the adhesive layer (A), the handleability of the adhesive sheet is improved, and when the adhesive sheet is cut, the protrusion of the adhesive layer (A) and the like are reduced, and the adhesive sheet is excellent. It is preferable for obtaining dimensional stability.
• any film or mesh material such as polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, and polystyrene can be used, and the thickness is 1 to 30 ⁇ m. It is preferable to use one having a thickness of 2 to 15 ⁇ m.
• the adherend (B2) has a convex three-dimensional shape, and the adherend (B1) or the adhesive layer (B1) on which the adhesive layer (A) is laminated by a vacuum molding machine or the like. In the case of the attaching step in which the release liner on which A) is laminated is heated to 100 to 170 ° C.
• adherend (B2) polyethylene terephthalate
• adherend (B2) polyethylene terephthalate
• a resin base material such as polypropylene, polyethylene, and polystyrene which is excellent in colorless transparency, has a low softening point, and is easily stretched by heating.
• the adhesive sheet of the present invention can exhibit the above-mentioned excellent effects even when the adhesive sheet is thin as described above.
• the adhesive sheet in order to maintain the design property and the light-shielding property of the surface of the molded product, it is possible to prevent scratching and reflection.
• it can be suitably used for the production of a molded product in which a transparent or translucent thin sheet having a hard coat layer or a mat layer is laminated on the surface.
• the adhesive sheet of the present invention When the adhesive sheet of the present invention is used for producing the molded article or the like, it is preferable to use an adhesive sheet having a transmittance of light having a wavelength of 380 to 780 nm of 80% or more and a haze of 5.0 or less. It is more preferable to use one having a transmittance of light having a wavelength of 380 to 780 nm of 85% or more and a haze of 2.0 or less. By setting the content in the above range, the design of the bonded article can be enhanced.
• the adhesive sheet of the present invention when used in the production of the molded article, it transmits light having a wavelength of 380 to 780 nm after being left in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH for 500 hours. It is preferable to use one having a transmittance of 80% or more and a haze of 5.0 or less, and one having a transmittance of light having a wavelength of 380 to 780 nm of 85% or more and a haze of 2.0 or less. More preferred. By setting the content in the above range, the design of the bonded article can be enhanced.
• the adhesive sheet of the present invention is used for bonding the adherends (B1) and (B2), at least one of which can generate gas when left in an environment of a temperature of 85 ° C. and a humidity of 85% RH for 48 hours. .
• Examples of the adherend (B1) to be bonded to the adhesive sheet of the present invention include a transparent member made of plastic.
• Examples of the transparent member constituting the adherend (B1) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, Resin base materials such as polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, nylon, acrylic resin, etc. Can be used.
• polycarbonate and acrylic resin are preferable as the resin substrate in order to achieve both high transparency and surface hardness.
• a resin base material such as polycarbonate easily generates gas at about 80 ° C., which forms bubbles and causes peeling.
• the adhesive sheet of the present invention even when polycarbonate or the like is used, it is difficult to form bubbles due to gas, so that it does not cause peeling, and also has excellent transparency and hardness due to polycarbonate and the like. it can.
• the adherend (B1) preferably has a thickness of 0.05 to 5 mm, more preferably has a thickness of 0.2 to 3 mm, and more preferably has a thickness of 0.2 to 1 mm. It is more preferable to use one having a thickness. By setting the thickness as described above, durability for protecting the surface of the light-irradiated molded article can be imparted.
• the adherend (B1) may be coated on the surface of the adherend (B1) with an arbitrary hard coat layer or the like by direct application or coextrusion for the purpose of preventing scratches on the surface and improving slipperiness.
• a mat layer or the like may be laminated.
• the adherend (B1) When the adherend (B1) is used for an article used outdoors such as an exterior part of a vehicle, the adherend (B1), the cured layer (A ′) of the adhesive sheet, and the adherend.
• a coating agent or the like containing an arbitrary ultraviolet absorbent or the like is applied to the surface of the adherend (B1), or the adherend (B1)
• a layer that absorbs a wavelength of 325 to 380 nm corresponding to an ultraviolet region by kneading and dispersing an arbitrary ultraviolet absorber into the inside of the substrate may be provided on the entire surface or a part of the adherend (B1). Further, it may be applied by being added to the hard coat layer, the mat layer and the like.
• the adherend (B1) preferably has a transmittance of light having a wavelength of 325 to 380 nm of 0 to 20%, and more preferably 0 to 10% for imparting outdoor weather resistance.
• the adherend (B1) preferably has a transmittance of 80 to 100% of light having a wavelength of 380 to 780 nm and a haze of 0 to 5.0%, and transmits light having a wavelength of 380 to 780 nm. It is more preferable to use one having a ratio of 85 to 100% and a haze of 0 to 2.0% or less. By setting the content in the above range, the design property of the adherend article can be enhanced.
• the adherend (B1) has the light transmittance
• active energy rays having a wavelength of 325 to 380 nm, which falls in the ultraviolet region are difficult to transmit, and the activation of the photopolymerization initiator is easily inhibited.
• the polymerization initiator having an absorption characteristic in a wavelength range exceeding 380 nm even if the adherend (B1) provided with a layer absorbing ultraviolet rays, an active energy ray having a wavelength exceeding 380 nm is used.
• the curing reaction can be carried out by irradiating the resin.
• Specific examples of the adherend (B2) include molded articles provided with a decorative layer for the purpose of imparting a design property, a light shielding property, and the like.
• adherend (B2) a material having a decorative layer, a plating layer, or the like, for example, and hardly transmitting light can be used.
• adherends (B2) include polycarbonate, polymethyl methacrylate, alloys of polycarbonate and acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, and polystyrene. Any material such as, or bonded to a metal can be used.
• polycarbonate, polymethyl methacrylate, or an alloy of polycarbonate and acrylonitrile-butadiene-styrene copolymer Is preferred.
• the decorative layer or the plating layer is not particularly limited as long as it imparts various design properties, and examples thereof include a character or a figure, or a frame-shaped decorative layer or a plating layer provided in a frame shape. Can be
• the thickness of the decorative layer is preferably in the range of 2 to 50 ⁇ m, more preferably in the range of 5 to 40 ⁇ m, and still more preferably in the range of 10 to 30 ⁇ m.
• the decorative layer becomes clear, a suitable design property can be easily provided, and application unevenness of the decorative layer can be hardly caused.
• a plurality of the adherends (B1) and (B2) may be bonded respectively.
• the same type may be bonded, or another type among the examples described above may be bonded. .
• the adherends (B1) and (B2) are measured at a temperature of 25 ° C. and a frequency of 1 Hz.
• the tensile elastic modulus (E ′ A25 ) is 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa, and the tensile storage elastic modulus (E ′ A100 ) measured at a temperature of 100 ° C.
• a frequency of 1 Hz is 1 ⁇ 10 3 to 1
• the measured tensile storage modulus at 100 ° C. and a frequency 1Hz forming a (E 'A'100) is 2 ⁇ 10 5 ⁇ 1 ⁇ cured layer is 10 9 Pa (a') containing The method and the like.
• the surface of the adherend can be irradiated with active energy rays.
• the method of manufacturing the article goes through one of the following steps.
• the adherend (B2) two or more types of adherends may be simultaneously bonded in the step [2].
• the step [1] is preferably performed in an environment of 0 to 50 ° C., and more preferably performed in an environment of 10 to 40 ° C. in view of the fact that the adhesive sheet of the present invention can be bonded without heating. preferable.
• the adherend (B2) is pressed onto the surface of the adhesive layer of the laminate, and the laminate is adhered while stretching the adherend (b1).
• the adhesive sheet of the present invention is attached to a molding machine while leaving the release liner on one side, and the release liner and the adhesive layer (A) are heated to about 100 to 170 ° C.
• the other adherends two or more types of adherends may be simultaneously bonded in step [4].
• the other adherend is preferably pressed onto the surface of the adhesive layer of the laminate, and the laminate is adhered while stretching the release liner and the adherend (B1).
• the active energy ray is used to cure the adhesive layer (A) constituting the adhesive sheet to form a cured layer (A ′).
• the light irradiation device may perform irradiation in an atmosphere of an inert gas such as nitrogen gas or irradiation in an air atmosphere in order to efficiently perform a curing reaction by light. Further, if necessary, heat may be used in combination as an energy source, and after irradiation with active energy rays, heating may be performed.
• a low-pressure mercury lamp When an ultraviolet ray or a visible ray is used as the active energy ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp (manufactured by Eye Graphics Co., Ltd.), a metal halide lamp B type ( GS Yuasa Corporation), electrodeless lamps (fusion lamps), chemical lamps, black light lamps, mercury-xenon lamps, xenon-flash lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LED lamps, etc. Is mentioned.
• a high-power metal halide lamp or a metal halide lamp B type having a high luminous intensity near 400 nm a high-power metal halide lamp or a metal halide lamp B type having a high luminous intensity near 400 nm.
• the use of an LED lamp having an emission intensity at 385 nm or 405 nm allows the adhesive layer (A) to be efficiently formed while minimizing the heat storage of the adherend (B1) or the adherend (B2). Is preferred because it can be cured.
• a germicidal lamp in addition to the above-mentioned devices, a germicidal lamp, a carbon arc, a scanning type, a curtain type electron beam accelerator and the like can be used.
• the article bonded by the bonding method has a configuration in which the adherend (B1) and the adherend (B2) are laminated via a cured product of the active energy ray-curable polyurethane adhesive sheet.
• the article bonded with the adhesive sheet of the present invention is suitably used for a resin molded product used for an exterior of a home appliance, an exterior of a mobile terminal, an interior and exterior of an automobile, and the like. It is a part formed three-dimensionally by injection molding or extrusion molding, and for the purpose of preventing scratches and improving slipperiness on the surface of these molded products, a bonding member having a hard coat layer or mat layer on the surface, Floating of the bonding member which is bonded by the adhesive sheet of the present invention and which is generated due to formation of air bubbles due to gas that can be generated from the surface of the molded article or the surface of the bonding member or residual stress of the bonding member. It is a molded article having excellent appearance quality, which suppresses peeling and peeling and has both excellent transparency.
• urethane resin (a1) composition In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 94.3 parts by mass of polypropylene glycol (number average molecular weight: 1,000), 0.3 parts by mass of 2-hydroxyethyl acrylate, 1,4-hexane 19.5 parts by mass of dimethanol, 0.5 parts by mass of 2,6-ditert-butylcresol, 0.1 parts by mass of p-methoxyphenol, and 57.4 parts by mass of ethyl acetate were added. After raising the temperature in the reaction vessel to 40 ° C., 50.3 parts by mass of isophorone diisocyanate was added.
• urethane resin (a1) composition was obtained by stirring and cooling until the mixture became uniform for one minute.
• the adhesive composition (b2) was obtained in the same manner as in the preparation of the adhesive composition (b1) except that the composition was changed to (b).
• ⁇ Preparation of adhesive composition (b6)> Based on 100 parts by mass of the solid content of the acrylic resin (a2), 0.18 parts by mass of E-5XM (solid content 5% by mass, manufactured by Soken Chemical Co., Ltd.) as an epoxy-based crosslinking agent, and coronate as an isocyanate-based crosslinking agent. 0.2 parts by mass of L-45E (manufactured by Tosoh Corporation, solid content: 45% by mass) was added, and the mixture was stirred with a stirrer for 20 minutes to obtain an adhesive composition (b6).
• E-5XM solid content 5% by mass, manufactured by Soken Chemical Co., Ltd.
• coronate as an isocyanate-based crosslinking agent
• a tetrafunctional acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester ATM-4PL
• Vernock DN980 manufactured by DIC Corporation, solid content: 75% by mass
• Vernock DN980 manufactured by DIC Corporation, solid content: 75% by mass
• Example 1 The adhesive composition (b1) was coated on a 60 ⁇ m-thick polypropylene film (“60RL-01” manufactured by Oji F-Tex Co., Ltd.) in which one side was peeled off with a silicone compound so that the thickness after drying was 100 ⁇ m. And dried at 85 ° C. for 5 minutes, and a 75 ⁇ m-thick polyethylene terephthalate film (“75E0010BD” manufactured by Fujimori Kogyo Co., Ltd .; hereinafter referred to as “# 75 release liner”), one side of which has been subjected to a release treatment with a silicone compound, is shielded from light. At 23 ° C. for 7 days to prepare an active energy ray-curable polyurethane adhesive sheet (c1).
• 60RL-01 manufactured by Oji F-Tex Co., Ltd.
• Example 2 An adhesive sheet (c2) was obtained in the same manner as in Example 1, except that the adhesive composition (b2) was used instead of the adhesive composition (b1).
• Example 3 An adhesive sheet (c3) was obtained in the same manner as in Example 1, except that the adhesive composition (b3) was used instead of the adhesive composition (b1).
• Example 4 An adhesive sheet (c4) was obtained in the same manner as in Example 1, except that the adhesive composition (b4) was used instead of the adhesive composition (b1).
• Example 5 An adhesive sheet (c5) was obtained in the same manner as in Example 1, except that the thickness of the adhesive composition (b1) after drying was 50 ⁇ m.
• Example 6 An adhesive sheet (c6) was obtained in the same manner as in Example 1, except that the adhesive composition (b5) was used instead of the adhesive composition (b1).
• the light transmittance of the obtained weather-resistant transparent resin sheet (B1 ′) was measured with an ultraviolet-visible-near-infrared spectrophotometer (“V-570” manufactured by JASCO Corporation), the light having a wavelength of 325 to 380 nm was measured.
• the transmittance was 0% at 325 to 370 nm, and the light transmittance increased after exceeding the wavelength of 370 nm, and was 18% at 380 nm.
• the light transmittance of the uncoated transparent resin sheet (B1) at a wavelength of 325 nm is 55%, the light transmittance gradually increases at a wavelength of 325 nm or more, and the light transmittance at a wavelength of 350 to 380 nm is:
• the light transmittance was 80% or more at all wavelengths.
• the # 75 release liner was removed from the adhesive sheets obtained in Examples and Comparative Examples, and the surface of the adhesive sheet was integrated with 1000 mJ / cm 2 using a metal halide lamp B type (“MBL250NL” manufactured by GS Yuasa Co., Ltd.). A cured product was obtained by irradiating the light with the amount of light.
• the tensile storage elastic modulus ( E'A'100 ) of the adhesive layer at 100.degree. C. after irradiation with active energy rays was calculated.
• # 75 release liner was removed from the adhesive sheets produced in Examples and Comparative Examples, and the above-mentioned weather-resistant transparent resin sheet (B1 ') was placed thereon while preventing adhesion to the adhesive layer. , And cured by covering with an ultraviolet absorbing sheet having a wavelength of 325 to 380 nm ( E'A''100 ).
• the # 75 release liner was peeled off and removed from the adhesive sheets prepared in Examples and Comparative Examples, and then bonded to the surface of the transparent resin sheet (B1) at 23 ° C. in an atmosphere of 2 kg with two reciprocating pressure rollers. And cut into 60 mm long and 60 mm wide.
• heating was performed for 30 seconds at 160 ° C. and a pressure of 0.01 MPa using a hot press apparatus, and evaluated according to the following criteria.
• a heat press apparatus a heat press machine “TP-750 air press” manufactured by Tester Sangyo Co., Ltd. was used.
• the # 75 release liner was peeled off from the adhesive sheets prepared in Examples and Comparative Examples, and bonded to the transparent resin sheet (B1) under an atmosphere of 23 ° C., and subjected to two reciprocal pressures with a 2 kg roller. , 60 mm in length and 60 mm in width.
• the mass of the adhesive layer of the adhesive sheet before immersion refers to a value obtained by subtracting the mass of the release liner used for the preparation from the mass of the test piece. Further, the mass of the remaining adhesive layer indicates a value obtained by subtracting the mass of the release liner from the mass of the residue after drying.
• the adhesive sheet obtained in each of Examples and Comparative Examples was heated for 30 seconds at 160 ° C. and a pressure of 0.01 MPa using a hot press apparatus, and then heated in the same manner as described above.
• the gel fraction (D2) of the layer was measured.
• a heat press apparatus a heat press machine “TP-750 air press” manufactured by Tester Sangyo Co., Ltd. was used.
• the transparent resin sheet (B1) was put on the surface of the adhesive sheet obtained in each of Examples and Comparative Examples, and a metal halide lamp B type (“MBL250NL” manufactured by GS Yuasa Co., Ltd.) was applied from the # 75 release liner side of the adhesive sheet.
• a cured product was obtained by irradiating an active energy ray having an integrated light amount of 1000 mJ / cm 2 .
• the gel fraction (D3) of the adhesive layer after curing was measured in the same manner as in the evaluation of the gel fraction of the adhesive layer before irradiation with active energy rays.
• the weather-resistant transparent resin sheet (B1 ′) is used instead of the transparent resin sheet (B1), and cured by covering with an ultraviolet absorbing sheet having a wavelength of 325 to 380 nm in the same manner as described above.
• the gel fraction (D3 ′) of the adhesive layer after curing was measured.
• the # 75 release liner was peeled off from the adhesive sheets prepared in Examples and Comparative Examples, and the surface was affixed to a corona discharge-treated polyethylene terephthalate film having a thickness of 50 ⁇ m and cut to a size of 20 mm in width and 100 mm in length. was used as a test piece.
• heating was performed for 30 seconds at 160 ° C. and a pressure of 0.01 MPa using a hot press device.
• a heat press apparatus a heat press machine “TP-750 air press” manufactured by Tester Sangyo Co., Ltd. was used.
• the release liner on the other side of the test piece was peeled off, and a polycarbonate plate having a width of 70 mm and a length of 150 mm ("Upilon NF-2000UVNS2 Clear” manufactured by Mitsubishi Gas Chemical Company, Inc.) was used as an adherend (B2). 1.5 mm). After leaving it in an environment of 5 atm and 50 ° C.
• the weather-resistant transparent resin sheet (B1 ′) is covered with the surface coated with the ultraviolet absorbing coating agent as the outer surface, and a polyethylene terephthalate film as an adhesive sheet Was applied from the side where is adhered, using a metal halide lamp B type (“MBL250NL” manufactured by GS Yuasa Co., Ltd.) to emit light with an integrated amount of 1000 mJ / cm 2 .
• a metal halide lamp B type (“MBL250NL” manufactured by GS Yuasa Co., Ltd.
• the patch was allowed to stand for 1 hour in an environment at a temperature of 23 ° C. and a relative humidity of 50% RH, and then was subjected to a tensilon-type tensile tester (RTG-1210 manufactured by A & D Corporation) equipped with a thermostat.
• the peeling resistance was measured when the film was pulled in the direction of 180 ° at a pulling speed of 50 mm / min under an atmosphere of 25 ° C. and 90 ° C.
• Total light transmittance Tt and haze The total light transmittance Tt and the haze were determined by removing the # 75 release liner from the adhesive sheets prepared in Examples and Comparative Examples, and applying the ultraviolet light of the weather-resistant transparent resin sheet (B1 ') on the exposed surface of the adhesive layer. The side not coated with the absorbent coating agent was stuck. Next, after leaving it for 20 minutes in an environment of 5 atm and 50 ° C., the accumulated light amount of 1000 mJ / cm 2 was used from the weather-resistant transparent resin sheet side using a metal halide lamp B type (“MBL250NL” manufactured by GS Yuasa Co., Ltd.). To obtain a patch. The release liner on the other side of the patch was peeled off, and the total light transmittance Tt and haze were measured using “HR-100” manufactured by Murakami Color Research Laboratory Co., Ltd.
• the adhesive sheets of Examples 1 to 6 have good foaming resistance by suppressing the adhesive layer from protruding from the end face in the heating step before curing, and have good floating resistance when left in wet heat after curing. It had peelability and was excellent in transparency and adhesiveness. Further, even in the case of a bonding member on which an ultraviolet absorbing coating agent was laminated, curing adhesion by irradiation with active energy rays was possible. On the other hand, in the adhesive sheets of Comparative Examples 1 to 6, the adhesive layer protruded from the end face or bubbles were generated from the end face in the heating step before curing, bubbles were generated when left in wet heat after curing, and floating and peeling occurred. Due to the lamination member on which the ultraviolet absorbing coating agent was laminated, curing and bonding by irradiation with active energy rays could not be performed.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)

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• 2019
  • 2019-06-06 JP JP2020500756A patent/JP6760535B2/ja active Active
  • 2019-06-06 WO PCT/JP2019/022493 patent/WO2019244652A1/ja not_active Ceased
• 2020
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