WO2009139318A1 - 曲げ加工可能なポリカーボネート樹脂積層体および光透過型電磁波シールド積層体並びにそれらの製造方法 - Google Patents
曲げ加工可能なポリカーボネート樹脂積層体および光透過型電磁波シールド積層体並びにそれらの製造方法 Download PDFInfo
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- WO2009139318A1 WO2009139318A1 PCT/JP2009/058630 JP2009058630W WO2009139318A1 WO 2009139318 A1 WO2009139318 A1 WO 2009139318A1 JP 2009058630 W JP2009058630 W JP 2009058630W WO 2009139318 A1 WO2009139318 A1 WO 2009139318A1
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- meth
- acrylate
- laminate
- adhesive
- electromagnetic wave
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- 238000006731 degradation reaction Methods 0.000 description 1
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- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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- 238000007641 inkjet printing Methods 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 150000005309 metal halides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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- 238000007763 reverse roll coating Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- CIFIGXMZHITUAZ-UHFFFAOYSA-M tetraethylazanium;benzoate Chemical compound CC[N+](CC)(CC)CC.[O-]C(=O)C1=CC=CC=C1 CIFIGXMZHITUAZ-UHFFFAOYSA-M 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UUVZTKMMRCCGHN-OUKQBFOZSA-N triethoxy-[(e)-2-phenylethenyl]silane Chemical compound CCO[Si](OCC)(OCC)\C=C\C1=CC=CC=C1 UUVZTKMMRCCGHN-OUKQBFOZSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/28—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled
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Definitions
- a preferred embodiment of the present invention relates to a bendable polycarbonate resin laminate excellent in transparency, adhesive strength, heat resistance, and moisture resistance and a method for producing the same. More specifically, the present invention contains (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer and (C) acrylamide derivative, (D) silane compound and / or (E) organophosphorus compound.
- the step of forming a laminate of two or more layers by laminating a polycarbonate resin substrate using a (meth) acrylate adhesive composition, and controlling the difference in upper and lower surface temperature of the laminate within 20 ° C.
- the present invention relates to a method for producing a polycarbonate resin laminate comprising a step of heating a body to 130 ° C. to 185 ° C. (preferably 150 ° C. to 185 ° C.) and a step of bending the heated laminate into a curved surface having a curvature radius of 10 mm or more.
- the polycarbonate resin laminate of the present invention is a cover and casing for industrial equipment, machinery and electronic equipment, window materials and covers for automobiles, vehicles, ships, aircraft, houses, hospitals and offices, and carports used outdoors. It is useful as a soundproof wall made of resin and a window material for crime prevention.
- a preferred embodiment of the present invention relates to a light transmissive electromagnetic wave shield laminate excellent in bending workability and impact resistance. More specifically, the present invention contains (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer and (C) acrylamide derivative, (D) silane compound and / or (E) organophosphorus compound.
- a step of laminating a polycarbonate substrate (protective layer) on one or both sides of the electromagnetic wave shielding layer using the (meth) acrylate-based adhesive composition to form a laminate of two or more layers, and upper and lower surface temperatures of the laminate The step of controlling the difference within 20 ° C. and heating the laminate to 130 ° C. to 185 ° C.
- the present invention relates to a method for producing a light transmissive electromagnetic wave shield laminate having the following.
- the light-transmitting electromagnetic wave shield laminate of the present invention is useful as a window material or cover for covers, casings, automobiles, vehicles, ships, airplanes, houses, hospitals, offices, etc. for industrial devices, machines and electronic devices.
- Covers and window materials for industrial equipment such as semiconductor manufacturing equipment and flat panel display manufacturing equipment
- covers and window materials for industrial machines such as cranes and excavators, window materials for automobiles, vehicles, ships and aircraft, for housing, hospitals and offices
- glass is used for the window material.
- synthetic resin materials are often used from the viewpoint of economy such as weight reduction and fuel consumption.
- a polycarbonate resin laminate excellent in impact resistance, heat resistance and transparency is preferable.
- the polycarbonate resin laminate is used since the article is used outdoors or in a car under high temperature and high humidity conditions exposed to wind and rain or sunlight. It has problems such as white turbidity and peeling due to deterioration of the body adhesive layer.
- the article is required to have bending workability from the viewpoint of design and safety.
- polycarbonate resin has high heat resistance, it is forced to bend at high temperatures, and warps the polycarbonate resin laminate. , Have problems such as bubbles, whitening and peeling.
- a visible light curable adhesive is described as an adhesive for a polycarbonate resin laminate.
- a normal visible light curable adhesive has insufficient adhesive force, and thus peels off when bending at high temperatures.
- problems such as bubbles and whitening due to deterioration or decomposition of the adhesive layer.
- problems such as white turbidity and peeling under high temperature and high humidity conditions outdoors and in a vehicle.
- the visible light curable adhesive (BENEFIX® PC manufactured by Adel) described in the example of Patent Document 1 was clouded under high temperature and high humidity conditions (65 ° C.-95% RH-24h).
- Patent Document 2 describes a moisture-curable hot melt adhesive, a thermoplastic polyester resin adhesive, and a thermoplastic silane-modified resin adhesive as adhesives for polycarbonate resin laminates.
- the adhesive strength is insufficient, so that not only peeling occurs at the time of bending at high temperature, but also there are problems such as bubbles and whitening due to degradation or decomposition of the adhesive layer.
- it has problems such as white turbidity and peeling under high temperature and high humidity conditions outdoors and in a vehicle.
- Patent Document 3 a polyurethane adhesive film is described as an adhesive for a laminate of a polycarbonate resin and an acrylic resin.
- an adhesive force is obtained, a whitening phenomenon occurs in a bent portion, and the visibility is extremely high. descend.
- it has problems such as white turbidity and peeling under high temperature and high humidity conditions outdoors and in a vehicle.
- electromagnetic waves generated from electronic devices such as personal computers, mobile phones, flat panel displays typified by liquid crystal and plasma, touch panels, car navigation, and portable information terminals, and motors of industrial machinery, have been It causes a malfunction and communication failure, which is a big problem. Furthermore, it has been pointed out that electromagnetic waves may adversely affect the human body, and measures are taken with various electromagnetic shielding materials in order to prevent so-called electromagnetic interference (hereinafter referred to as EMI).
- EMI electromagnetic interference
- a method of laminating the electromagnetic shielding material with various light transmissive resin base materials or glass base materials is used.
- a light-transmitting electromagnetic wave shielding laminate based on polycarbonate resin which is excellent in impact resistance and heat resistance, is preferable, but covers and housings for industrial equipment such as semiconductor manufacturing equipment, industrial machinery, and various electronic equipment.
- bending workability is often required from the viewpoint of design and safety.
- the polycarbonate resin has high heat resistance, it is forced to bend at high temperatures, so it has problems such as warping the light-transmitting electromagnetic wave shield laminate, causing bubbles, whitening, and peeling.
- the bending technique of the electromagnetic wave shield laminate is not disclosed.
- Patent Documents 4 and 5 describe acrylic, rubber-based, silicone-based, polyurethane-based, and polyester-based transparent pressure-sensitive adhesives as adhesives for light-transmitting electromagnetic wave shield laminates. For this reason, there is a problem that not only peeling occurs at the time of bending at high temperature, but also bubbles and whitening occur due to deterioration or decomposition of the adhesive layer.
- Patent Documents 6 and 7 disclose adhesives for light-transmitting electromagnetic wave shield laminates, such as ethylene-vinyl acetate (EVA) copolymer adhesive compositions and copolymers of ethylene, vinyl acetate and / or (meth) acrylate monomers.
- EVA ethylene-vinyl acetate
- problems such as bubbles, whitening, and peeling occur due to deterioration or decomposition of the adhesive layer under bending conditions at high temperatures.
- Patent Document 8 describes a hot-melt adhesive of ethylene-vinyl acetate (EVA) copolymer or ethylene-acrylic ester copolymer as an adhesive for a light transmissive electromagnetic wave shield laminate.
- EVA ethylene-vinyl acetate
- Patent Document 9 describes a urethane-based adhesive as an adhesive for a light-transmitting electromagnetic wave shield laminate, but a urethane-based adhesive can provide an adhesive force, but a whitening phenomenon occurs significantly in a bent portion. Visibility is reduced. Further, this document does not disclose any detailed explanation or examples of the composition content and workability of the adhesive.
- JP-A-8-39746 Japanese Patent No. 3994404 JP-A-9-239936 JP 2006-319251
- An object of the present invention is to provide a polycarbonate resin laminate that solves at least one of the problems of the prior art.
- the present invention does not cause bubbles, whitening, or peeling due to deterioration or decomposition of the adhesive layer even under high temperature bending conditions, and can be used under severe conditions outdoors and in the vehicle.
- Transparency, adhesive strength, heat resistance Another object of the present invention is to provide a polycarbonate resin laminate excellent in moisture resistance and bending workability.
- the present inventors converted two or more polycarbonate resin films and / or sheets into (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer, and (C).
- the step of heating the laminated body to 130 ° C. to 185 ° C. (preferably 150 ° C. to 185 ° C.) by controlling the temperature difference between the upper and lower surfaces within 20 ° C.
- a laminate of two or more layers is formed by laminating a polycarbonate substrate (protective layer) on one or both sides of the electromagnetic shielding layer using a (meth) acrylate adhesive composition containing an organic phosphorus compound A step, a step of heating the laminate to 130 ° C. to 185 ° C. (preferably 150 ° C.
- a method for producing a light-transmitting electromagnetic wave shield laminate having a step of bending a curved surface having a radius of 10 mm or more it is possible to provide a light-transmitting electromagnetic wave shield laminate excellent in bending workability that does not cause bubbles, whitening, peeling or warping of the laminate due to deterioration or decomposition of the adhesive layer.
- the production method of the polycarbonate resin laminate and the production method of the light transmission type electromagnetic wave shield laminate of the present invention, and the polycarbonate resin laminate and the light transmission type electromagnetic wave shield laminate obtained by them include the following aspects.
- a polycarbonate resin film and / or sheet of two or more layers is made from (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer and (C) acrylamide derivative, (D) silane compound and / or ( E) laminating using a (meth) acrylate-based adhesive composition containing an organophosphorus compound to produce a laminate having a thickness of 0.1 mm to 30 mm; Heating the laminate at 130 ° C. to 185 ° C.
- the electromagnetic wave shielding layer is one or more selected from the group consisting of silver, copper, aluminum, nickel, carbon, ITO (indium oxide / tin oxide), ZnO, tin, zinc, titanium, tungsten, and stainless steel.
- the electromagnetic wave shielding layer includes any one selected from the group consisting of a metal thin film mesh, a metal woven mesh, a conductive fiber mesh, and a conductive printing mesh.
- the (B) (meth) acrylate oligomer is at least one selected from the group consisting of a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a polyol (meth) acrylate oligomer.
- the (D) silane compound is selected from the group consisting of amino-functional silane, epoxy-functional silane, vinyl-functional silane, mercapto-functional silane, methacrylate-functional silane, acrylamide-functional silane, and acrylate-functional silane.
- UV ultraviolet light
- EB electron beam
- the polycarbonate resin laminate of the preferred embodiment of the present invention does not cause bubbles, whitening, peeling or warping due to deterioration or decomposition of the adhesive layer even under high temperature bending conditions, and even under severe conditions outdoors or in a car. It can be used, such as covers and window materials for industrial equipment such as semiconductor manufacturing equipment and flat panel display manufacturing equipment, cranes, excavators, etc. that require transparency, adhesive strength, heat resistance, moisture resistance and bending workability.
- covers and windows that require excellent electrotransparency, durability and bending workability at the same time, such as industrial machinery covers and windows, automobiles, vehicles, ships, aircraft windows, houses, hospitals, office windows, etc. Used in the material field.
- the light-transmitting electromagnetic wave shielding laminate according to a preferred embodiment of the present invention has good transparency because it does not cause bubbles, whitening, peeling or warping due to deterioration or decomposition of the adhesive layer even under high temperature bending conditions.
- Excellent electromagnetic shielding performance such as covers and casings for industrial equipment, machinery and electronic equipment, etc., and window materials and covers for automobiles, vehicles, ships, airplanes, houses, hospitals and offices It is used in a wide range of electromagnetic shielding fields that simultaneously require visibility or visibility and bending workability.
- polycarbonate resin laminate and the production method of the light transmission type electromagnetic wave shield laminate of the present invention, and the polycarbonate resin laminate and the light transmission type electromagnetic wave shield laminate obtained by them will be described in detail.
- the method for producing a polycarbonate resin laminate of the present invention two or more polycarbonate resin films and / or sheets are formed from (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer, and (C) acrylamide derivative.
- the manufacturing method of the light transmission type electromagnetic wave shield laminated body of this invention is (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer, (C) acrylamide derivative, (D) Silane compound, and / or.
- a polycarbonate base material (protective layer) is laminated on one side or both sides of the electromagnetic shielding layer using a (meth) acrylate adhesive composition containing an organophosphorus compound, and the thickness of two or more layers is from 0.1 mm to A step of forming a 30 mm laminated body, a step of heating the laminated body to 130 ° C. to 185 ° C. (preferably 150 ° C. to 185 ° C.) by controlling the difference in upper and lower surface temperatures of the laminated body to within 20 ° C., And a step of bending the heated laminated body into a curved surface having a curvature radius of 10 mm or more.
- the polycarbonate resin laminate and the light transmission type electromagnetic wave shield laminate produced by the production method of the present invention preferably have a 180 degree peel strength of 50 N / 25 mm width or more, more preferably 50 to 300 N / 25 mm width. Has a 180 degree peel strength.
- a 180-degree peel strength of 50 N / 25 mm width or more is preferable because it does not peel during bending or drilling.
- the light transmission type electromagnetic wave shield laminate of the present invention has a laminate of two or more layers including an electromagnetic wave shield layer for preventing inflow of electromagnetic waves generated from various electronic devices, machines, motors and the like and a polycarbonate substrate (protective layer). .
- the protective layer is disposed on one or both sides of the electromagnetic shielding layer from the viewpoint of impact resistance, scratch resistance, weather resistance, water resistance, antistatic property, moisture resistance, antifogging property, antireflection property, antifouling property, etc. can do.
- the present invention includes all laminated type light transmissive electromagnetic wave shielding laminates in which a metal thin film mesh, a metal woven mesh, a conductive fiber mesh, or a conductive printing mesh using a conductive compound is used as an electromagnetic wave shielding layer.
- the electromagnetic wave shielding performance of the electromagnetic wave shielding layer is preferably 30 dB or more. If the electromagnetic wave shielding performance is less than 30 decibels, the outflow of electromagnetic waves generated from the electronic device cannot be completely prevented, and malfunctions and communication failures of other machines and electronic devices may occur. Electromagnetic waves entering from the outside cannot be prevented, and there is a possibility of damaging electronic equipment.
- the surface resistivity (sheet resistance value) of the electromagnetic shielding layer is preferably 10 [ ⁇ / ⁇ ] or less. More preferably, it is 1 [ ⁇ / ⁇ ] or less, and still more preferably 0.1 [ ⁇ / ⁇ ] or less.
- the conductive compound constituting the electromagnetic wave shielding layer is not particularly limited as long as it has conductivity.
- iron, gold, silver, copper, aluminum, nickel, carbon, ITO (indium oxide / tin oxide), ZnO (oxidized) A metal compound containing at least one metal component selected from zinc), tin, zinc, titanium, tungsten, and stainless steel can be used. From an economical viewpoint, it is preferable to use a conductive compound containing at least one metal component selected from silver, copper, aluminum, nickel, carbon, ZnO (zinc oxide), tin and stainless steel.
- the electromagnetic wave shielding layer can include, for example, a metal thin film mesh, a metal woven mesh, a conductive fiber mesh, or a conductive printing mesh using a conductive compound.
- the method for producing the metal thin film mesh is not particularly limited.
- a metal such as copper, silver, aluminum, ITO (indium oxide / tin oxide) ⁇ , ZnO (zinc oxide) is formed on the surface of the light transmissive organic polymer material film or sheet.
- electroless plating electroless plating or electroplating is used to form a mesh, rolling a metal plate of copper, silver, aluminum, etc., and punching a metal foil to a predetermined thickness to form a mesh
- These metal thin film meshes are preferably blackened on one side or both sides from the viewpoints of water resistance, moisture resistance, corrosion resistance, rust prevention, and antireflection.
- the metal thin film mesh preferably has a line width of 5 to 200 ⁇ m, a thickness of 0.01 to 100 ⁇ m, and a pitch of 100 to 1000 ⁇ m from the viewpoint of electromagnetic shielding performance and transparency.
- metal foil adhesive for forming the metal thin film mesh
- known adhesives and pressure-sensitive adhesives having good transparency, water resistance, moisture resistance, and adhesive strength can be used.
- the adhesive include known photocurable adhesives, thermosetting adhesives, hot melt adhesives, and the like.
- the pressure-sensitive adhesive examples include pressure-sensitive adhesives such as known acrylic resin compositions, polyurethane-based resin compositions, polyester-based resin compositions, epoxy-based resin compositions, silicone-based resin compositions, and rubber-based resin compositions. I can do it. Among these, the pressure-sensitive adhesive of an acrylic resin composition having excellent transparency, water resistance, moisture resistance and adhesive strength is most preferable.
- hot melt adhesives examples include polyolefin resin compositions such as ethylene- (meth) acrylic acid copolymer resin compositions, ethylene- (meth) acrylic acid ester copolymer resin compositions, and polystyrene resin compositions. , Ethylene vinyl acetate resin composition, vinyl acetate resin composition, acrylic resin composition, polyurethane resin composition, polyester resin composition, epoxy resin composition, polyester resin composition, polyamide resin Examples thereof include a composition, a polyvinyl ether resin composition, a silicone resin composition, and a rubber resin composition. Among these, a hot melt adhesive of an acrylic resin composition having excellent transparency, water resistance, moisture resistance and adhesive strength is most preferable.
- thermosetting adhesive is not particularly limited as long as it is polymerized by heat.
- functional groups such as glycidyl group, acryloyl group, methacryloyl group, hydroxyl group, carboxyl group, isocyanurate group, amino group, amide group, etc.
- epoxy resin composition acrylic resin composition, silicone resin composition, phenol resin composition, thermosetting polyimide resin composition, polyurethane resin composition, polyester resin composition, melamine resin A composition, a urea-type resin composition, etc. are mentioned.
- thermosetting adhesives such as epoxy acrylate resin compositions, urethane acrylate resin compositions, polyether acrylate resin compositions, and polyester acrylate resin compositions are preferred.
- thermosetting adhesives can be used in combination of two or more as required.
- a curing agent in combination with the thermosetting adhesive composition.
- known curing agents can be used, such as isocyanate curing agents, amines such as triethylenetetramine, xylenediamine, N-aminotetramine, diaminodiphenylmethane, phthalic anhydride, maleic anhydride, and dodecyl anhydride.
- Acids such as pyromellitic anhydride and benzophenone tetracarboxylic anhydride, diaminodiphenylsulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These curing agents may be used alone or in combination of two or more.
- photocurable adhesives examples include urethane (meth) acrylate adhesive compositions, polyester (meth) acrylate adhesive compositions, epoxy (meth) acrylate adhesive compositions, and polyol (meth) acrylate adhesives. At least one (meth) acrylate-based adhesive composition selected from the agent composition is preferable. Among these, urethane (from the viewpoint of water resistance, moisture resistance, weather resistance, transparency and adhesive strength) A (meth) acrylate adhesive composition is particularly preferred.
- the photocurable (meth) acrylate adhesive composition having curability by irradiation with active energy rays is particularly preferable from the viewpoints of curing time and safety, and visible light or ultraviolet rays are preferable as the active energy rays.
- the conductive printing mesh can be used by any manufacturing method, and is not particularly limited.
- metal particle compounds such as copper, silver, aluminum, nickel, carbon, etc., epoxy, urethane
- a mesh is formed on the surface of a light-transmitting organic polymer material film or sheet by a method such as screen printing, gravure printing, or offset printing, using an ink or paste mixed with a resin binder such as acrylic, acrylic or EVA.
- a method is mentioned.
- the conductive printing mesh preferably has a line width of 10 to 200 ⁇ m, a thickness of 1 to 100 ⁇ m, and a pitch of 100 to 1000 ⁇ m from the viewpoint of electromagnetic shielding performance and transparency.
- Examples of the light-transmitting organic polymer material used as a metal thin film mesh and conductive printing mesh film or sheet base material include polycarbonate resin, polyethylene terephthalate resin, polyester resin, polyethersulfone resin, polyethylene naphthalate resin, and polystyrene. Resin, polyurethane resin, polyvinyl alcohol resin, polymethyl methacrylate resin, alicyclic polyolefin resin, light-transmitting polyimide resin, polyamide resin, acrylic resin, polyacrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, polypropylene resin, polyethylene Resin etc. are mentioned.
- polycarbonate resin polycarbonate resin
- polyester resin polyethylene terephthalate resin
- polyethylene terephthalate resin are particularly preferable from the viewpoints of transparency, impact resistance and versatility.
- the metal woven mesh can be a metal woven mesh obtained by any manufacturing method, and is not particularly limited. For example, a method of forming a mesh by knitting metal wires such as stainless steel, copper, silver, gold, and iron. Is mentioned. The smaller the mesh size and the thicker the metal wire diameter, the higher the electromagnetic wave shielding performance. On the other hand, the visibility decreases, so the mesh size is preferably 50 to 300 mesh and the metal wire diameter is preferably 10 to 200 ⁇ m. The mesh size indicates a mesh size defined by the Taylor standard sieve.
- any conductive fiber mesh obtained by any manufacturing method can be used, and there is no particular limitation.
- a conductive metal compound such as nickel or copper is added to a surface-treated synthetic fiber such as polyester.
- Examples thereof include a conductive fiber mesh subjected to electroless plating and further blackened.
- the mesh size is preferably 50 to 300 mesh and the fiber diameter is preferably 10 to 100 ⁇ m.
- the light transmissive electromagnetic wave shield laminate of the present invention has impact resistance, scratch resistance, weather resistance, water resistance, antistatic property, moisture resistance, antifogging property, antireflection property, antifouling property and the like.
- a polycarbonate substrate (protective layer) is disposed on one side or both sides of the electromagnetic wave shielding layer.
- the protective layer may be a film or sheet made of a light transmissive organic polymer material or a coating film having various functionalities as long as it is a material that can be visually recognized and transmits light (mainly polycarbonate).
- the polycarbonate resin laminate of the present invention is also a polycarbonate resin from the viewpoint of impact resistance, scratch resistance, weather resistance, water resistance, antistatic property, moisture resistance, antifogging property, antireflection property, antifouling property, etc. It is preferable to arrange a protective layer on one side or both sides of the laminate. As long as the protective layer is visible and allows light to pass through, the protective layer may be a film or sheet material made of a light-transmitting organic polymer material, or may be a film having various functionalities.
- the light-transmitting organic polymer material is not particularly limited, and any organic polymer material that can be visually recognized and transmits light may be used.
- the light transmissive organic polymer material includes various materials such as metal compounds, conductive compounds, organic compounds, and inorganic compounds that have been bonded, vapor-deposited, applied, printed, and processed. Examples of the light transmissive organic polymer material include polycarbonate resin, polyethylene terephthalate resin, polyester resin, polyether sulfone resin, polyethylene naphthalate resin, polystyrene resin, polyurethane resin, polyvinyl alcohol resin, polymethyl methacrylate resin, and alicyclic ring.
- Examples thereof include a polyolefin resin, a light-transmitting polyimide resin, a polyamide resin, an acrylic resin, a polyacrylonitrile resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polypropylene resin, and a polyethylene resin.
- the coating is not particularly limited, but is a silicone resin compound that is excellent in long-term durability and has a relatively high surface hardness, or an acrylic resin that can be processed relatively easily and has a good coating.
- a polyfunctional acrylic resin is preferred.
- the method for curing these coatings depends on the properties of the resin compound used, but in consideration of productivity and simplicity, it is preferable to select a thermosetting or photocurable resin.
- the photocurable resin there may be mentioned a resin composition in which a photopolymerization initiator is added as a curing catalyst to a resin composition composed of one or more monofunctional or polyfunctional acrylate monomers or oligomers.
- the thermosetting resin include polyorganosiloxane and cross-linked acrylic resins.
- Such a resin composition is commercially available as a hard coat agent, and may be appropriately selected in consideration of appropriateness with the coating line.
- these coatings can also contain various stabilizers such as organic solvents and anti-coloring agents, leveling agents, antifoaming agents, thickeners, and antistatic agents.
- a surfactant such as an antifogging agent may be added as appropriate.
- the light-transmitting electromagnetic wave shield laminate of the present invention is preferably provided with an appropriate ground for the purpose of sufficiently exerting its shielding performance and for preventing leakage of electromagnetic waves.
- an appropriate ground for the purpose of sufficiently exerting its shielding performance and for preventing leakage of electromagnetic waves.
- a conductive material in which a metal particle compound such as copper, silver, aluminum, nickel or carbon is mixed with a resin binder such as epoxy, urethane, acrylic or EVA.
- a method of applying a conductive paste to the outer periphery of the end surface of the light transmission type electromagnetic wave shield laminate a method of coating the outer periphery of the end surface of the light transmission type electromagnetic wave shield laminate with a conductive tape, and a method using these in combination. It is preferable to cover 70% or more of the outer periphery of the end surface with a conductive paste or tape.
- the (meth) acrylate-based adhesive composition used in the present invention includes a urethane (meth) acrylate-based adhesive composition, a polyester (meth) acrylate-based adhesive composition, an epoxy (meth) acrylate-based adhesive composition, and It is preferably at least any one (meth) acrylate-based adhesive composition selected from polyol (meth) acrylate-based adhesive compositions, and more preferably a urethane (meth) acrylate-based adhesive composition. .
- the (meth) acrylate-based adhesive composition used in the present invention is preferably a solvent-free (meth) acrylate-based adhesive composition in consideration of environmental properties and handling properties, for example, photocurable (meth) acrylate.
- examples thereof include a thermosetting adhesive composition, a thermosetting (meth) acrylate adhesive composition, and a hot melt (meth) acrylate adhesive composition.
- a photocurable (meth) acrylate adhesive composition having curability by irradiation with active energy rays is particularly preferred from the viewpoint of curing time and safety, and visible light or ultraviolet rays are preferred as the active energy rays.
- the (A) (meth) acrylate polymerizable monomer used in the present invention is not particularly limited, and various (meth) acrylate polymerizable monomers can be used.
- Such (meth) acrylate polymerizable monomers include mono-, di- and poly (meth) acrylate compounds of aliphatic alcohols having 2 to 20 carbon atoms, diols and polyhydric alcohols, glycerin, trimethylolpropane, pentaerythritol.
- a monofunctional (meth) acrylate polymerizable monomer having one (meth) acryloyloxy group in the molecule [hereinafter referred to as a monofunctional (meth) acrylate monomer. ]
- Bifunctional (meth) acrylate polymerizable monomer having two (meth) acryloyloxy groups in the molecule hereinafter referred to as bifunctional (meth) acrylate monomer.
- a polyfunctional (meth) acrylate polymerizable monomer having at least three (meth) acryloyloxy groups in the molecule hereinafter referred to as a polyfunctional (meth) acrylate monomer.
- One or more (meth) acrylate monomers can be used.
- the monofunctional (meth) acrylate monomer examples include tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy- 3-phenoxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate , Isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethyl carbonate
- bitol bito
- Monofunctional (meth) acrylate monomers include vinyl group-containing monomers such as N-vinylpyrrolidone and (meth) acryloylamino group-containing monomers such as 4- (meth) acryloylamino-1-carboxymethylpiperidine. Is done.
- Bifunctional (meth) acrylate monomers include alkylene glycol di (meth) acrylates, polyoxyalkylene glycol di (meth) acrylates, halogen-substituted alkylene glycol di (meth) acrylates, di (meth) acrylates of fatty acid polyols, Typical examples include di (meth) acrylates of bisphenol A or bisphenol F alkylene oxide adducts, epoxy di (meth) acrylates of bisphenol A or bisphenol F, but are not limited thereto. Can be used.
- bifunctional (meth) acrylate monomer examples include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
- Multifunctional (meth) acrylate monomers include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) Poly (meth) of trivalent or higher aliphatic polyols such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.
- Acrylate is typical, and in addition, tri (poly) acrylate of trivalent or higher halogen-substituted polyols, trioxide of alkylene oxide adduct of glycerin.
- the (B) (meth) acrylate oligomer used in the present invention is a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer [hereinafter referred to as a polyfunctional urethane (meth) acrylate oligomer. ] Bifunctional or higher polyfunctional polyester (meth) acrylate oligomer [hereinafter referred to as polyfunctional polyester (meth) acrylate oligomer]. ] Bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer [hereinafter referred to as polyfunctional epoxy (meth) acrylate oligomer].
- Bifunctional or higher polyfunctional polyol (meth) acrylate oligomer [hereinafter referred to as polyfunctional polyol (meth) acrylate oligomer]. And the like.
- polyfunctional polyol (meth) acrylate oligomer One or more (meth) acrylate oligomers can be used.
- polyfunctional urethane (meth) acrylate oligomer an isocyanate compound obtained by reacting polyols with polyisocyanate, and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule;
- the urethanization reaction product of is mentioned.
- urethane (meth) acrylate oligomers urethane (meth) acrylate oligomers containing an alicyclic hydrocarbon compound excellent in water resistance, moisture resistance, weather resistance and adhesive strength are preferred.
- urethane (meth) acrylate oligomers using isophorone diisocyanate or dicyclohexylmethane diisocyanate as a raw material are preferable, and urethane (meth) acrylate oligomers using dicyclohexylmethane diisocyanate as a raw material are particularly preferable.
- Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule used for the urethanization reaction include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate is mentioned.
- Polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates.
- diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate
- di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate
- polyisocyanates obtained by multiplying diisocyanates Is mentioned are preferable, and dicyclohexylmethane diisocyanate is particularly preferable.
- polyols used in the urethanization reaction generally, in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are used.
- aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylol ethane, trimethylol propane, dimethylol heptane, diethylene
- examples include methylol propionic acid, dimethylol butyric acid, glycerin, and hydrogenated bisphenol A.
- the polyester polyol is obtained by a dehydration condensation reaction between the above polyols and a polybasic carboxylic acid (anhydride).
- polybasic carboxylic acids include (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) trimellitic acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, Examples include terephthalic acid.
- the polyether polyol includes a polyoxyalkylene-modified polyol obtained by a reaction of the polyol or phenols with an alkylene oxide.
- urethane (meth) acrylate oligomers are commercially available and can be easily obtained.
- these urethane (meth) acrylate oligomers for example, beam set 575, beam set 551B, beam set 550B, beam set 505A-6, beam set 504H, beam set 510, beam set 502H, beam set 575CB, beam Set 102 (above, trade name of urethane (meth) acrylate oligomer made by Arakawa Chemical Co., Ltd.), Photomer 6008, Photomer 6210 (above, trade name of urethane (meth) acrylate oligomer made by San Nopco), NK Oligo U-4HA, NK Oligo U-108A, NK Oligo U-1084A, NK Oligo U-200AX, NK Oligo U-122A, NK Oligo U-340A, NK Oligo U-324A, NK Oligo UA-100, NK Rigo MA-6 (above, trade name of
- urethane (meta) axle Trade name of related oligomers Ebecryl 254, Ebecryl 264, Ebecryl 265, Ebecryl 1259, Ebecryl 4866, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2283, Ebecryl 2283 ) And the like.
- the polyfunctional polyester (meth) acrylate oligomer can be obtained by a dehydration condensation reaction of (meth) acrylic acid, polybasic carboxylic acid (anhydride) and polyol.
- Polybasic carboxylic acids (anhydrides) used in the dehydration condensation reaction include (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (anhydrous) trimellitic acid, and (anhydrous) pyromellitic. Acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, etc. are mentioned.
- the polyol used in the dehydration condensation reaction is 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylol heptane, dimethylol propionic acid, dimethylol butyrate.
- Examples include phosphonic acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.
- Aronix M-6100, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8530, Aronix M-8050 (above, polyester (meth) acrylate oligomers manufactured by Toagosei Co., Ltd.) Trade names
- Laromer® PE44F, Laromer® LR8907, Laromer® PE55F, LaromerPE46T, Laromar® LR8800 aboveve, product names of polyester (meth) acrylate-based oligomers manufactured by BASF
- Ebecryl80, Ebecryl800e7bEcryl800e, , Ebecryl 584 (above, Daicel UCB Co., Ltd.
- polyester Metal Product Name of the acrylate-based oligomers
- Photomer RCC13-429 Photomer 5018 (or more, San Nopco Co., Ltd.
- polyester (meth) trade name of the oligomer of the acrylate-based polyester (meth) trade name of the oligomer of the acrylate-based
- the polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid.
- the polyfunctional epoxy (meth) acrylate oligomer is not particularly limited, and various epoxy (meth) acrylate oligomers can be used.
- Such an epoxy (meth) acrylate oligomer has a structure in which (meth) acrylic acid is added to an epoxy oligomer, and is a bisphenol A-epichlorohydrin type, a modified bisphenol A type, an amine modified type, a phenol novolak-epichlorohydrin type. , Aliphatic type and alicyclic type.
- polyglycidyl ether includes ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, and the like.
- Laromer® LR8986, Laromer® LR8713, Laromer® EA81 (above, trade names of epoxy (meth) acrylate oligomers manufactured by BASF), NK Oligo EA-6310, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6320, NK Oligo EA-7440, NK Oligo EA-6340 (above, trade name of epoxy (meth) acrylate oligomer manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 3700, Ebecryl 3200, Ebecryl 600 (above, Daicel And a product name of an epoxy (meth) acrylate oligomer manufactured by UCB Co., Ltd.).
- the (meth) acrylate adhesive composition used in the present invention is characterized by containing (C) an acrylamide derivative.
- the (C) acrylamide derivative is not particularly limited, and various acrylamide derivatives can be used.
- alkyl acrylamide and / or alkyl methacrylamide can be mentioned. Specific examples include acrylamide, methacrylamide, diacetone acrylamide, diacetone methacrylamide, alkylene bisacrylamide, dimethyl acrylamide, diethyl acrylamide, isopropyl acrylamide, and 4-acrylomorpholine. More preferred are dimethylacrylamide, isopropylacrylamide, diethylacrylamide and 4-acrylomorpholine. These may be used alone or in combination of two or more.
- the content is usually 1 to 50% by weight, preferably 5 to 30% by weight.
- the (meth) acrylate adhesive composition used in the present invention is characterized by containing (D) a silane compound.
- the (D) silane compound is used as an adhesion promoter for the (meth) acrylate-based adhesive composition, and has an effect of improving not only the adhesive strength but also moisture resistance, water resistance, weather resistance and transparency.
- the (D) silane compound used in the present invention is not particularly limited, and various silane compounds can be used. Examples include amino functional silanes, epoxy functional silanes, vinyl functional silanes, mercapto functional silanes, methacrylate functional silanes, acrylamide functional silanes, and acrylate functional silanes. You may use combining more than a kind.
- amino-functional silane, epoxy-functional silane, vinyl-functional silane, and mercapto-functional silane are particularly preferable.
- (3- (2,3-epoxypropoxy) propyl) trimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycid Epoxy silanes such as xylpropyltriethoxysilane are preferred, and (3- (2,3-epoxypropoxy) propyl) trimethoxysilane is particularly preferred.
- These may be used alone or in combination of two or more. Its content is usually 0.1 to 20% by weight, preferably 1 to 10% by weight.
- the (meth) acrylate-based adhesive composition used in the present invention is characterized by containing (E) an organophosphorus compound.
- the (E) organophosphorus compound is used as an adhesion promoter for a (meth) acrylate adhesive composition to a metal compound, and not only improves adhesion to the metal compound but also improves moisture resistance and water resistance.
- Have The (E) organophosphorus compound used in the present invention is not particularly limited, but phosphoric acid (meth) acrylate is particularly preferred.
- the phosphoric acid (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having a phosphate ester skeleton, such as an ethylene oxide-modified phenoxylated phosphoric acid (meth) acrylate or ethylene oxide.
- a phosphate ester skeleton such as an ethylene oxide-modified phenoxylated phosphoric acid (meth) acrylate or ethylene oxide.
- mono [2- (meth) acryloyloxyethyl] phosphate mono [2- (meth) acryloyloxyethyl] diphenyl phosphate, mono [2- (meth) acryloyloxypropyl] phosphate, bis [2- (meta ) Acryloyloxyethyl] phosphate, bis [2- (meth) acryloyloxypropyl] phosphate, tris [2- (meth) acryloyloxyethyl] phosphate, and the like.
- These may be used alone or in combination of two or more. Its content is usually from 0.1 to 20% by weight, preferably from 1 to 10% by weight.
- the photopolymerization initiator used in the present invention is used for the purpose of polymerizing and curing a (meth) acrylate-based adhesive composition and increasing its curing rate.
- a (meth) acrylate-based adhesive composition and increasing its curing rate.
- those generally known can be used as the photopolymerization initiator that can be used in the present invention.
- 2,2-dimethoxy-1,2-diphenylethane-1-one 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, oligo [2-hydroxy -2-Methyl-1- [4- (1-methylvinyl) phenyl] propanone], bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide 3-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone , Xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin ethyl ether , Benzoinpropyl ether, Michler's ketone,
- 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1-hydroxy-cyclohexyl phenyl ketone are more preferable.
- oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide may be used alone or in combination of two or more. Its content is usually 0.5 to 20% by weight, preferably 1 to 10% by weight.
- Irgacure 184 Irgacure 261, Irgacure 369, Irgacure 379, Irgacure 500, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 2959, Irgacure CGI-403, 1116, Darocur 1173, Darocur 1664, Darocur, 2273 Darocur 4265 (manufactured by Ciba Specialty Chemicals).
- a thermal polymerization initiator can also be used as the polymerization initiator of the (meth) acrylate adhesive composition used in the present invention.
- initiators selected from azo compounds such as 2,2′-azobis (isobutyronitrile), hydroperoxides such as t-butyl hydroperoxide and peroxides such as benzoyl peroxide and cyclohexanone peroxide.
- the thermal polymerization initiator is not limited thereto. These may be used alone or in combination of two or more.
- At least one photosensitizer can be added to the (meth) acrylate-based adhesive composition to control the curing time and the cured state.
- the photosensitizer can be selected from amine compounds, urea compounds, phosphorus compounds, nitrile compounds, benzoin compounds, carbonyl compounds, sulfur compounds, naphthalene compounds, condensed aromatic hydrocarbons, and mixtures thereof.
- amine compounds such as triethylamine, diethylaminoethyl methacrylate, N-methyldiethanolamine, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin octyl.
- Benzoin compounds such as ether, benzyl, diacetyl, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, methylanthraquinone, acetophenone, benzophenone, benzoylformic acid Methyl, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methyl Ruthio) phenyl) -2-morpholino) -propene-1, carbonyl compounds such as 2,2-2-dimethoxy-2-phenylacetophenone, sulfur compounds such as diphenyl disulfide and dithiocarbamate, naphthalene compounds such as ⁇ -chloromethylnaphthalene, Examples thereof include condensed aromatic hydrocarbons such as anthracene and metal salts such as iron chloride.
- the sensitizer described above is preferably one that is excellent in solubility in the (meth) acrylate-based adhesive composition and does not impair ultraviolet light transmittance.
- the (meth) acrylate-based adhesive composition used in the present invention has anti-aging due to hydrolysis and oxidation of the adhesive composition itself, heat resistance and weather resistance under severe conditions exposed to sunlight and wind and rain, etc.
- a light stabilizer and an antioxidant can be added.
- hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1-methyl- 8- (1,2,2,6,6-pentamethyl-4-piperidyl) -sebacate, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl ] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethyl Piperidine, tetrakis (2,2,6,6-t
- nickel-based UV stabilizers include [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel complex-3,5-di-t-butyl-4- Hydroxybenzyl monophosphate, nickel dibutyl dithiocarbamate, etc. can also be used.
- the hindered amine light stabilizer a hindered amine light stabilizer containing only a tertiary amine is preferable.
- bis (1,2,2,6,6-pentamethyl-4-piperidyl) is preferable.
- Sebacate bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malonate, or A condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.
- phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t- Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4 '-Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,3,5-tris (3', 5'-di-t -Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, steary
- the phenolic antioxidant preferably has a molecular weight of 550 or more.
- the thiol antioxidant include distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- ( ⁇ -lauryl-thiopropionate), and the like.
- the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol.
- Diphosphite bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-diphosphonite 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like.
- light stabilizers and antioxidants may be used alone or in combination of two or more.
- a combination of a hindered amine light stabilizer and a hindered phenol antioxidant is preferable, and its content is usually 0.1 to 10% by weight, preferably 0.5 to 3% by weight.
- the light stabilizer and the antioxidant are preferably those that are excellent in solubility in the (meth) acrylate adhesive composition and do not inhibit ultraviolet light transmission.
- the (meth) acrylate adhesive composition used in the present invention can contain an ultraviolet absorber for the purpose of preventing deterioration due to sunlight or ultraviolet rays.
- an ultraviolet absorber examples include benzophenone, benzotriazole, phenyl salicylate, and triazine.
- benzophenone ultraviolet absorber examples include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetra And hydroxy-benzophenone.
- Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole and the like.
- Examples of the phenyl salicylate UV absorber include phenyl saltylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
- Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
- triazine ultraviolet absorbers examples include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-) Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi 2,4-diphenyl-6- (2-hydroxy-4-dodecyl
- the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy. Furthermore, those that exhibit an effect when used in combination with an antioxidant, a colorant, or the like, or a light stabilizer that acts as a light energy conversion agent, called a quencher, can be used in combination.
- a quencher a light stabilizer that acts as a light energy conversion agent
- the amount of the ultraviolet absorber used is 0.1 to 20% by weight, preferably 1 to 15% by weight, and more preferably 3 to 10% by weight. When the amount is more than 20% by weight, the adhesion is deteriorated, and when the amount is less than 0.1% by weight, the weather resistance improving effect is small.
- various additives other than those described above can be further blended.
- antifoaming agents, leveling agents, antistatic agents, surfactants, storage stabilizers, thermal polymerization inhibitors, plasticizers, wettability improvers, adhesion promoters, tackifiers and the like are blended as necessary. I can do it.
- Examples of the method for preparing the (meth) acrylate-based adhesive composition used in the present invention include (meth) acrylate-based polymerizable oligomers, (meth) acrylate-based polymerizable monomers, (A) (meth) acrylate monomers, Each component such as (B) (meth) acrylate oligomer, (C) acrylamide derivative, (D) silane compound, (E) organophosphorus compound, initiator, sensitizer, and other additives is charged at room temperature to 80 ° C. And a method of obtaining a desired adhesive composition by mixing and dissolving the solution and performing filtration with a filter or the like as necessary.
- the adjustment method of an adhesive composition can use a well-known method, and is not limited to the said method.
- the adhesive composition according to the present invention preferably adjusts the mixing ratio of the components so that the viscosity at 25 ° C. is 1 to 5000 mPa.
- the film thickness of the adhesive is preferably 2 ⁇ m or more and 200 ⁇ m or less.
- visible light ultraviolet light
- UV ultraviolet light
- EB electron beam
- examples of the light source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon mercury lamp, xenon lamp, gallium lamp, metal halide lamp, quartz halogen lamp, tungsten lamp, and ultraviolet light.
- a fluorescent lamp, a carbon arc lamp, an electrodeless microwave ultraviolet lamp, etc. are preferably used.
- a predetermined photo-curing adhesive is applied to a polycarbonate resin sheet with a flow coater, and an electromagnetic wave shielding layer using the polycarbonate resin film as a base material.
- a laminator so as not to contain bubbles, and then irradiated with a high-pressure mercury lamp to cure the adhesive to produce a laminate.
- a plurality of layers may be laminated by applying an adhesive to each layer and irradiating light, or after providing an adhesive layer between the layers, The laminate may be manufactured by irradiating light to cure the adhesive layer.
- the thickness of the laminate is preferably in the range of 0.1 to 30 mm, more preferably in the range of 0.1 to 20 mm.
- the bending condition of the light-transmitting electromagnetic wave shield laminate of the present invention is as follows.
- the temperature difference between the upper and lower surfaces of the laminate is controlled within 20 ° C., and the temperature is 130 to 185 ° C. (preferably 150 to 185 ° C.) for 30 seconds to 20
- the shield laminated body heated for a minute is processed into a curved surface having a curvature radius of 10 mm or more (preferably 15 to 2000 mm).
- the bending conditions of the polycarbonate resin laminate of the present invention are as follows.
- the polycarbonate resin laminate is heated to 130 to 185 ° C. (preferably 150 to 185 ° C.) by controlling the temperature difference between the upper and lower surfaces of the laminate within 20 ° C. Is processed into a curved surface having a curvature radius of 10 mm or more (preferably 15 to 2000 mm).
- the heating time is preferably 30 sec to 20 min. According to a preferred embodiment of the present invention, it is possible to obtain a good polycarbonate resin laminate that is free from deterioration, peeling due to decomposition, foaming, and whitening.
- Examples of the bending method for the polycarbonate resin laminate and the light transmission type electromagnetic wave shield laminate of the present invention include bar heater heating, far infrared heater heating, far infrared lamp heating, high frequency heating, dielectric heating, induction heating, and microwave heating.
- a bending method using a wooden mold, a mold or the like that can obtain a predetermined curvature radius, vacuum forming, Press molding or the like is applied.
- the bending method is not limited to the method described above.
- the polycarbonate resin laminate and the light transmission type electromagnetic wave shield laminate of the present invention are resistant to aging due to hydrolysis and oxidation of the light transmission type organic polymer material itself to be laminated, deterioration due to ultraviolet rays, severe exposure to sunlight and wind and rain.
- One or more layers selected from an electromagnetic wave shielding layer, a protective layer, and an adhesive layer constituting a polycarbonate resin laminate or a light-transmitting electromagnetic wave shielding laminate for the purpose of improving heat resistance and weather resistance under conditions It is preferable to contain at least one of ultraviolet absorbers, light stabilizers and antioxidants. It is preferable that all layers constituting the polycarbonate resin laminate or the light transmission type electromagnetic wave shield laminate contain at least one of an ultraviolet absorber, a light stabilizer and an antioxidant.
- Stabilizers and antioxidants are expensive, resulting in high costs and poor economics.
- a film containing at least one of an ultraviolet absorber, a light stabilizer and an antioxidant is formed on one or both sides of a polycarbonate resin laminate or a light transmission type electromagnetic wave shield laminate. It is preferable to form.
- the coating film containing at least one of the ultraviolet absorber, light stabilizer and antioxidant a silicone resin compound or treatment having excellent long-term durability and relatively high surface hardness
- an acrylic resin or a polyfunctional acrylic resin that is relatively simple and can form a good film is preferable.
- the method for curing these coatings depends on the properties of the resin compound used, but in consideration of productivity and simplicity, it is preferable to select a thermosetting or photocurable resin.
- the photocurable resin there may be mentioned a resin composition in which a photopolymerization initiator is added as a curing catalyst to a resin composition composed of one or more monofunctional or polyfunctional acrylate monomers or oligomers.
- thermosetting resin examples include polyorganosiloxane and cross-linked acrylic resins.
- a resin composition is commercially available as a hard coat agent, and may be appropriately selected in consideration of appropriateness with the coating line.
- these coatings include various stabilizers such as organic solvents and anti-coloring agents, leveling agents, antifoaming agents, thickeners, and charging agents as necessary.
- Surfactants such as an inhibitor and an antifogging agent may be added as appropriate.
- the coating film containing at least one of the ultraviolet absorber, the light stabilizer and the antioxidant is formed of a base material for improving the adhesion with the base material of the light transmission type electromagnetic wave shield laminate.
- a film can also be formed on an acrylic resin layer in which acrylic resins are laminated by coextrusion.
- a film comprising a photocurable acrylic resin compound 20 to 80% by weight of another compound copolymerizable with 20 to 80% by weight of 1,9-nonanediol diacrylate or tris (acryloxyethyl) isocyanurate 1 to 10% by weight of a photopolymerization initiator is added to a photopolymerizable compound comprising: an ultraviolet curable resin film composition.
- 1,9-nonanediol diacrylate or tris (acryloxyethyl) isocyanurate is an essential component, and the other copolymerizable compounds are a bifunctional or higher polyfunctional (meth) acrylate monomer and a bifunctional or higher polyfunctional Urethane (meth) acrylate oligomer [hereinafter referred to as polyfunctional urethane (meth) acrylate oligomer. ]
- Bifunctional or higher polyfunctional polyester (meth) acrylate oligomer [hereinafter referred to as polyfunctional polyester (meth) acrylate oligomer].
- Bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer [hereinafter referred to as polyfunctional epoxy (meth) acrylate oligomer]. And the like.
- One or more (meth) acrylate monomers and oligomers can be used.
- Bifunctional (meth) acrylate monomers include alkylene glycol di (meth) acrylates, polyoxyalkylene glycol di (meth) acrylates, halogen-substituted alkylene glycol di (meth) acrylates, di (meth) acrylates of fatty acid polyols, Typical examples include di (meth) acrylates of bisphenol A or bisphenol F alkylene oxide adducts and epoxy di (meth) acrylates of bisphenol A or bisphenol F, but not limited thereto. Can be used.
- bifunctional (meth) acrylate monomer examples include 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol di (meth) acrylate.
- tri- or higher functional (meth) acrylate monomer examples include trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, pentaerythritol tetraacrylate and the like.
- Examples of the polyfunctional urethane (meth) acrylate oligomer include a urethanation reaction product of a polyisocyanate with a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.
- a urethanation reaction product of a polyisocyanate with a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule As the polyfunctional urethane (meth) acrylate oligomer, an isocyanate compound obtained by reacting polyols with polyisocyanate, and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule; The urethanization reaction product of is mentioned.
- Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and hydroxyl group in one molecule used for the urethanization reaction include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate is mentioned.
- Polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates.
- diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate
- di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate
- polyols used for the urethanization reaction generally, in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are used.
- aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylol ethane, trimethylol propane, dimethylol heptane, diethylene
- examples include methylol propionic acid, dimethylol butyric acid, glycerin, and hydrogenated bisphenol A.
- the polyester polyol is obtained by a dehydration condensation reaction between the above polyols and a polybasic carboxylic acid (anhydride).
- polybasic carboxylic acids include (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) trimellitic acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, Examples include terephthalic acid.
- the polyether polyol includes a polyoxyalkylene-modified polyol obtained by a reaction of the polyol or phenols with an alkylene oxide.
- a polyfunctional polyester (meth) acrylate oligomer is obtained by dehydration condensation reaction of (meth) acrylic acid, polybasic carboxylic acid (anhydride) and polyol.
- Polybasic carboxylic acids (anhydrides) used in the dehydration condensation reaction include (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (anhydrous) trimellitic acid, and (anhydrous) pyromellitic. Acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, etc. are mentioned.
- the polyol used in the dehydration condensation reaction is 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylol heptane, dimethylol propionic acid, dimethylol butyrate.
- Examples include phosphonic acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.
- a polyfunctional epoxy (meth) acrylate oligomer is obtained by addition reaction of polyglycidyl ether and (meth) acrylic acid.
- polyglycidyl ether examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.
- photopolymerization initiator used for a film made of a photocurable acrylic resin compound generally known photopolymerization initiators can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, azobisisobutyronitrile, benzoyl peroxide, and the like, but are not limited thereto.
- the film made of a thermosetting silicone resin compound include an organopolysiloxane resin compound containing at least one of an epoxy group-containing silane coupling agent and an amino group-containing silane coupling agent. More specifically, the bifunctional alkoxysilane is 0 to 25% by weight, the trifunctional alkoxysilane is 40 to 80% by weight, and the tetrafunctional alkoxysilane is 10 to 25% with respect to the nonvolatile content (JIS K6833) in the resin compound.
- a cured layer made of an organopolysiloxane resin compound obtained by hydrolysis and partial condensation in the presence can be given.
- Examples of the bifunctional alkoxysilane used for the organopolysiloxane resin compound include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.
- Examples of the trifunctional alkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
- Examples of the tetrafunctional alkoxysilane include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.
- the mixing ratio of the alkoxysilane 0 to 25% by weight of the bifunctional alkoxysilane, 40 to 80% by weight of the trifunctional alkoxysilane, and 10 to 10% of the tetrafunctional alkoxysilane with respect to the nonvolatile content in the paint (JIS K6833). It is preferable to mix at a ratio of ⁇ 25% by weight, and when bifunctional alkoxysilane is added in an amount exceeding 25% by weight or when trifunctional alkoxysilane is added in an amount exceeding 80% by weight, the wear resistance is lowered. If the tetrafunctional alkoxysilane is added in an amount exceeding 30% by weight, the adhesion to the substrate is poor, and if it is less than 10% by weight, the wear resistance is lowered.
- silane coupling agent used for the organopolysiloxane resin compound it is preferable to use at least one of an epoxy group-containing silane coupling agent and an amino group-containing silane coupling agent. It is used in the range of 5 to 10% by weight based on the non-volatile content (JIS K6833). When the silane coupling agent is less than 5% by weight, the film properties and adhesion are deteriorated, and when it exceeds 10% by weight, the wear resistance is lowered.
- Epoxy group-containing silane coupling agents used for organopolysiloxane resin compounds include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri And methoxysilane.
- Examples of amino group-containing silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include triethoxysilane.
- the organopolysilane-based resin compound is produced by adding a lower alcohol and / or water to the mixture of the alkoxysilane and the silane coupling agent in the presence of an acid catalyst to cause hydrolysis and partial condensation.
- a lower alcohol examples include methanol, ethanol, isopropanol, and butanol.
- the above-mentioned organopolysilane resin compound is a vinyl group-containing silane coupling agent such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyl as long as the physical properties thereof are not impaired.
- a methacryloxy group-containing silane coupling agent such as trimethoxysilane can also be used in combination.
- the silane coupling agent-containing organopolysiloxane resin compound is preferably added with a curing catalyst to which a buffer solution is added so that a cured film can be obtained at a temperature of 120 to 140 ° C.
- a curing catalyst examples include dimethylamine, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, sodium propionate, sodium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, and the like.
- the addition amount of this curing catalyst is used in the range of 0.1 to 1% by weight with respect to the nonvolatile content in the resin compound.
- a primer layer may be formed in order to improve the adhesiveness of the coating film containing at least one of the ultraviolet absorber, light stabilizer and antioxidant used in the present invention.
- the compound used for forming the primer layer include an acrylic group-containing organic compound, an acrylic group-containing silane compound condensate, an alkoxysilyl group-containing vinyl compound condensate, and the like.
- the acrylic group-containing compound include alkyl acrylates such as methyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, and ethyl acrylate.
- acrylic group-containing silane compounds include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-acryloxypropyl.
- Trimethoxysilane 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxymethyltrimethoxysilane, 3-methacryloxymethyltriethoxysilane, 3-methacryloxymethylmethyldimethoxysilane, 3-methacryloxymethylmethyldiethoxysilane, 3-acryloxymethyltrimethoxysilane, 3-acryloxymethyltrie Examples include toxisilane, 3-acryloxymethylmethyldimethoxysilane, and 3-acryloxymethylmethyldiethoxysilane.
- 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane are considered from the viewpoint of handling, crosslinking density, reactivity, etc. preferable.
- vinyl monomers containing this alkoxysilyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethylbisbis (2-methoxyethoxy) silane, 3-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane, 3-vinyloxypropylmethyldimethoxysilane, 3-vinyloxypropylmethyldiethoxysilane, styryltrimethoxysilane, Examples include styryltriethoxysilane, styrylmethyldimethoxysilane, and styrylmethyldiethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are considered because of their handling and reactivity. 3-vinyloxypropyl trimethoxy silane are preferred.
- brushes, rolls, dipping, flow coating, spraying, roll coaters, flow coaters, and the like can be applied as a method for applying a film to the polycarbonate resin laminate.
- the thickness of the coating layer cured by heat curing or photocuring is 1 to 20 ⁇ m, preferably 2 to 15 ⁇ m, more preferably 3 to 12 ⁇ m. If the thickness of the coating layer is less than 1 ⁇ m, the effect of improving the weather resistance and the surface hardness tends to be insufficient, and conversely if it exceeds 20 ⁇ m, it is disadvantageous in cost and may cause a reduction in impact resistance.
- the adhesion strength of the sample was measured in accordance with a 180 degree peel adhesion strength test method (JIS K6854-2) or a T-type peel adhesion strength test method (JIS K6854-3). Specifically, a polycarbonate resin sheet or film was bonded with various adhesive compositions to prepare a test piece having a width of 25 mm and a length of 200 mm. The peel adhesion strength [N / 25 mm width] was measured at a peel speed of 10 mm / min with a tensile tester (AGS-100G manufactured by SHIMADZU).
- a polycarbonate resin sheet or film was bonded with various adhesive compositions to prepare a test piece having a width of 50 mm and a length of 200 mm.
- the test piece was heated from above and below with a far-infrared heater, and after the surface temperature of the test piece reached a predetermined temperature, it was bent using a mold having a predetermined curvature radius. The curvature radius and the processing status of the test piece were visually evaluated.
- Table 1 shows components such as (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer, (C) acrylamide derivative, (D) silane compound, (E) organophosphorus compound, and photopolymerization initiator.
- the composition was charged and mixed and heated at 60 ° C. for 1 hour to obtain a desired adhesive composition.
- Each component of the used adhesive composition is as follows.
- HM type adhesive [Hot melt (HM) type adhesive] ⁇ Ethylene vinyl acetate (EVA) HM type adhesive Elphan OH-501 made by Nippon Matai ⁇ Polyamide-based HM adhesive Elfan NT-120 manufactured by Nippon Matai ⁇ Polyurethane-based HM type adhesive Kurashiki Spinning Co., Ltd. Klanger S-1700 ⁇ Polyester type HM type adhesive Kuramabyo G-6 made by Kurashiki Spinning Co., Ltd. ⁇ Polyolefin-based HM type adhesive Cranbetter A-1510 made by Kurashiki Spinning Co., Ltd.
- Example 1 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the “adhesive strength test” was 150 N.
- white turbidity did not occur even after 200 hours of treatment, and good results were shown.
- bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm, the appearance is good and the test piece The curvature radius of was 25 mm.
- Example 2 Urethane (meth) acrylate polymerizable oligomer 30.4% by weight, (meth) acrylate polymerizable monomer 40.6% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, photopolymerization initiator 4 0.0 wt% was prepared, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 70N.
- the moisture resistance test no change was observed after 100 hours of treatment, and it became slightly cloudy after 200 hours of treatment.
- a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, the appearance is good and the curvature radius of the test piece is Was 25 mm.
- Example 3 Urethane (meth) acrylate polymerizable oligomer 32.1 wt%, (meth) acrylate polymerizable monomer 42.9 wt%, acrylamide derivative 20.0 wt%, organophosphorus compound 1.0 wt%, photopolymerization initiator 4.0 wt% was prepared, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 85N.
- the moisture resistance test no white turbidity was observed after 24 treatments, and a slight turbidity was observed after 100 hours of treatment.
- a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, the appearance is good and the curvature radius of the test piece is Was 25 mm.
- Example 4 Urethane (meth) acrylate-based polymerizable oligomer 30.0% by weight, (meth) acrylate-based polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus 1.0 wt% of the compound and 4.0 wt% of the photopolymerization initiator were charged, and an adhesive composition was prepared according to the “adhesive preparation method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a bending workability test with a bending temperature of 130 ° C. (upper part), 130 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, the appearance is good and the curvature radius of the test piece is Was 29 mm.
- Example 5 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a surface temperature difference of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm the appearance is good and the curvature radius of the test piece is Was 25 mm.
- Example 6 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a bending workability test with a bending temperature of 185 ° C. (upper), 185 ° C. (lower), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm, the appearance is good and the curvature radius of the test piece is good.
- a bending workability test with a bending temperature of 185 ° C. (upper), 185 ° C. (lower), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm, the appearance is good and the curvature radius of the test piece is good.
- a bending workability test with a bending temperature of 185 ° C. (upper), 185 ° C. (lower), a surface temperature difference of 0 ° C., and a mold radius of curvature of
- Example 7 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a surface temperature of 160 ° C. (upper part), 140 ° C. (lower part), a surface temperature difference of 20 ° C., and a mold curvature radius of 25 mm the appearance is good and the curvature radius of the test piece is Was 25 mm.
- Example 8 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 10.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a die curvature radius of 50 mm the appearance is good and the curvature radius of the test piece is Was 51 mm.
- Example 9 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 20.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold radius of curvature of 100 mm the appearance is good and the curvature radius of the test piece is Was 105 mm.
- Example 10 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness), the above-mentioned “polycarbonate resin laminate production method using light-transmitting adhesive” A sample was prepared according to the above.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a bending workability test with a surface temperature of 160 ° C. (upper), 160 ° C. (lower), a surface temperature difference of 0 ° C., and a mold curvature radius of 10 mm, the appearance is good and the curvature radius of the test piece is Was 11 mm.
- Example 11 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the polycarbonate resin second layer (PC film 200 ⁇ m thickness), the upper and lower first layers and the third layer (PC sheet 1.5 mm thickness), the “polycarbonate using a light-transmitting adhesive” A sample was prepared according to “Resin laminate preparation method”.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm the appearance is good and the curvature radius of the test piece is Was 26 mm.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- the adhesive layer fluctuates, The curvature radius was 25 mm.
- the adhesive strength of the sample by the adhesive strength test was 150N.
- white turbidity did not occur even after treatment for 200 hours, and good results were shown.
- a surface temperature difference of 170 ° C. (upper part), 140 ° C. (lower part), a surface temperature difference of 30 ° C., and a mold radius of curvature of 25 mm the appearance was warped and the curvature of the test piece The radius was 25 mm.
- Comparative Example 4 The first layer of polycarbonate resin (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness) were formed using the above-mentioned “light-transmitting adhesive” using a visible light curable adhesive (BENEFIX PC manufactured by Adel).
- a sample was prepared according to “Polycarbonate resin laminate production method”. However, the adhesive was cured using a visible light fluorescent lamp as the light source.
- the adhesive strength of the sample by the adhesive strength test was 30 N, and the PC film was broken. In the moisture resistance test, it became cloudy after 24 hours of treatment.
- As a result of evaluation according to a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, the appearance is good and the curvature radius of the test piece is Was 26 mm.
- Comparative Example 5 An ethylene vinyl acetate (EVA) hot melt adhesive is sandwiched between the polycarbonate resin first layer (PC sheet 3.0 mm thickness) and the second layer (PC film 200 ⁇ m thickness).
- a sample was prepared according to “A method for manufacturing a light-transmitting electromagnetic wave shield laminate”. As a result of various evaluations, the adhesive strength of the sample by the adhesive strength test was 7N. In the moisture resistance test, it became cloudy after 24 hours of treatment. Bending conditions were evaluated according to a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm.
- Comparative Example 6 A polyamide-based hot melt adhesive is sandwiched between the first layer of the polycarbonate resin (PC sheet thickness: 3.0 mm) and the second layer (PC film thickness: 200 ⁇ m).
- a sample was prepared according to “Shield laminate manufacturing method”. As a result of various evaluations, the adhesive strength of the sample by the adhesive strength test was 2N. In the moisture resistance test, it became cloudy after 100 hours of treatment. As a result of evaluation according to a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, peeling was performed.
- Comparative Example 7 A polyurethane-based hot melt adhesive is sandwiched between the first layer of the polycarbonate resin (PC sheet thickness: 3.0 mm) and the second layer (PC film thickness: 200 ⁇ m), and the “light-transmitting electromagnetic wave using the hot melt adhesive” is used.
- a sample was prepared according to “Shield laminate manufacturing method”. As a result of various evaluations, the adhesive strength of the sample by the adhesive strength test was 92N. In the moisture resistance test, it became cloudy after 24 hours of treatment. Bending conditions were evaluated according to a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm. .
- Comparative Example 8 A polyester-based hot melt adhesive is sandwiched between the first layer of the polycarbonate resin (PC sheet thickness: 3.0 mm) and the second layer (PC film thickness: 200 ⁇ m), and the above-mentioned “light-transmitting electromagnetic wave using a hot melt adhesive”
- a sample was prepared according to “Shield laminate manufacturing method”.
- the adhesive strength of the sample by the adhesive strength test was 107N. In the moisture resistance test, it became cloudy after 24 hours of treatment.
- a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, foaming was recognized and peeled off.
- Comparative Example 9 A polyolefin-based hot-melt adhesive is sandwiched between the first layer of polycarbonate resin (PC sheet 3.0 mm thickness) and the second layer (PC film thickness 200 ⁇ m), and the above-mentioned “light-transmitting electromagnetic wave using hot-melt adhesive”
- a sample was prepared according to “Shield laminate manufacturing method”.
- the adhesion strength of the sample by the adhesion strength test was 3N. In the moisture resistance test, it became cloudy after 100 hours of treatment.
- a bending workability test with a bending temperature of 160 ° C. (upper), 160 ° C. (lower), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm, peeling occurred.
- Comparative Example 10 An acrylic pressure-sensitive adhesive sheet is sandwiched between the first layer of polycarbonate resin (PC sheet thickness: 3.0 mm) and the second layer (PC film thickness: 200 ⁇ m).
- a sample was prepared according to “Production Method”. As a result of various evaluations, the adhesive strength of the sample by the adhesive strength test was 6N. In the moisture resistance test, it became cloudy after 100 hours of treatment. As a result of evaluation according to a bending workability test with a surface temperature of 160 ° C. (upper part), 160 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, foaming was observed in the adhesive layer, and peeling occurred. did.
- Electromagnetic wave shielding performance test The electromagnetic wave shielding performance in the frequency range of 100 MHz to 1 GHz was measured using an electromagnetic wave shielding performance measuring apparatus (manufactured by Advantest). [Evaluation of electromagnetic shielding performance] Those having an electromagnetic wave shielding performance of frequencies of 100 MHz and 1 GHz of 30 dB or more were evaluated as pass ( ⁇ ), and those less than 30 dB were determined as unacceptable (x).
- the adhesion strength of the sample was measured according to a 180 ° peel adhesion strength test method (JIS K6854-2). Specifically, an electromagnetic wave shielding layer (PC film, PET film) and a protective layer (PC sheet or film) were bonded with various adhesive compositions to prepare a test piece having a width of 25 mm and a length of 200 mm. The peel adhesive strength [N / 25 mm width] was measured with a tensile tester at a peel rate of 10 mm / min. The adhesive strength between the electromagnetic wave shielding layer and the protective layer (front and back surfaces) was measured, and the value with the smaller adhesive strength was described in Examples and Comparative Examples.
- An electromagnetic wave shielding layer (PC film, PET film) and a protective layer (PC sheet or film) were bonded with various adhesive compositions to prepare a test piece having a width of 50 mm and a length of 200 mm.
- the test piece was heated from above and below with a far-infrared heater, and after the surface temperature of the test piece reached a predetermined temperature, it was bent using a mold having a predetermined curvature radius. The curvature radius and the processing status of the test piece were visually evaluated.
- Table 3 to Table 3 show components such as (A) (meth) acrylate monomer, (B) (meth) acrylate oligomer, (C) acrylamide derivative, (D) silane compound, (E) organophosphorus compound, and photopolymerization initiator. 4 was prepared and mixed and heated at 60 ° C. for 1 hour to obtain a desired adhesive composition. Each component of the used adhesive composition is as follows.
- Samples for various evaluations were used as samples after being allowed to stand in a constant temperature and humidity chamber (23 ° C., 50% RH) for 24 hours and then cut into a width of 50 mm and a length of 200 mm.
- [material] Electromagnetic wave shielding layer
- PC film or PET film having a surface resistance value of 1 [ ⁇ / ⁇ ] or less formed as a mesh using various conductive compounds.
- (Conductive compound mesh) ⁇ AgC conductive printing mesh line 100 ⁇ m, pitch 500 ⁇ m, surface resistance 0.5 ⁇ / ⁇ ⁇ Copper compound thin film mesh line 10 ⁇ m, pitch 300 ⁇ m, surface resistance 0.1 ⁇ / ⁇ ⁇ Silver compound thin film mesh line 10 ⁇ m, pitch 180 ⁇ m, surface resistance 0.1 ⁇ / ⁇ (Base material) ⁇ PC film Polycarbonate film (100-200 ⁇ m thickness) manufactured by MGC Phil Sheet ⁇ PET film Easy-to-adhere polyethylene terephthalate (200 ⁇ m thickness) manufactured by Toyobo Co., Ltd. (Protective layer) ⁇ PC sheet Polycarbonate sheet (1.5mm to 20.0mm thickness) manufactured by MGC Phil Sheet ⁇ PC film Polycarbonate film (100 ⁇ m thickness) manufactured by MGC Phil Sheet
- a hot melt adhesive sheet was sandwiched between the electromagnetic shielding layer (PC film 200 ⁇ m thickness) and the protective layer (PC sheet 3.0 mm thickness), and pressed at 135 ° C. for 30 minutes. Samples for various evaluations were used as samples after being allowed to stand in a constant temperature and humidity chamber (23 ° C., 50% RH) for 24 hours and then cut into a width of 50 mm and a length of 200 mm.
- HM type adhesive [Hot melt (HM) type adhesive] ⁇ Ethylene vinyl acetate (EVA) HM type adhesive Elphan OH-501 made by Nippon Matai ⁇ Polyamide-based HM adhesive Elfan NT-120 manufactured by Nippon Matai ⁇ Polyurethane-based HM type adhesive Kurashiki Spinning Co., Ltd. Klanger S-1700 ⁇ Polyester type HM type adhesive Kuramabyo G-6 made by Kurashiki Spinning Co., Ltd. ⁇ Polyolefin-based HM type adhesive Cranbetter A-1510 made by Kurashiki Spinning Co., Ltd.
- Example 12 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- the electromagnetic wave shielding performance of the sample by the “electromagnetic wave shielding performance test” was good.
- the adhesive force of the sample by the “adhesive strength test” was 115 N.
- Example 13 Urethane (meth) acrylate polymerizable oligomer 30.4% by weight, (meth) acrylate polymerizable monomer 40.8% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, photopolymerization initiator 4 0.0 wt% was prepared, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 70N.
- Example 14 Urethane (meth) acrylate polymerizable oligomer 32.1 wt%, (meth) acrylate polymerizable monomer 42.9 wt%, acrylamide derivative 20.0 wt%, organophosphorus compound 1.0 wt%, photopolymerization initiator 4.0 wt% was prepared, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 86N.
- Example 15 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 16 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 17 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- a bending workability test with a bending temperature of 150 ° C. (upper), 150 ° C. (lower), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm, the appearance is good and the curvature radius of the test piece is good.
- Example 18 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 19 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- a bending workability test with a bending temperature of a surface temperature of 180 ° C. (upper part), 180 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, the appearance is good and the curvature radius of the test piece is good.
- Example 20 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 21 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 22 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from an electromagnetic wave shielding layer and a protective layer (PC film 100 ⁇ m thickness) of a copper compound thin film mesh (PC film 100 ⁇ m thickness), “light transmissive electromagnetic wave shielding lamination using a light transmissive adhesive” A sample was prepared according to “Body preparation method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 96N.
- Example 23 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 10.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 110N.
- Example 24 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 20.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 112N.
- Example 25 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), the “light transmissive electromagnetic wave using the light transmissive adhesive” A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 26 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer of the copper compound thin film mesh (PC film thickness of 200 ⁇ m) and the upper and lower protective layers (PC sheet thickness of 1.5 mm), “light transmission type using light transmission type adhesive” A sample was produced according to “Method for producing electromagnetic wave shield laminate”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 100N.
- Example 27 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer and protective layer (PC sheet thickness: 3.0 mm) of the silver compound thin film mesh (PC film thickness: 200 ⁇ m), the “light transmission type electromagnetic wave using the light transmission type adhesive” is used. A sample was prepared according to “Shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 79N.
- Example 28 Urethane (meth) acrylate polymerizable oligomer 30.0% by weight, (meth) acrylate polymerizable monomer 40.0% by weight, acrylamide derivative 20.0% by weight, silane compound 5.0% by weight, organophosphorus compound 0% by weight and 4.0% by weight of a photopolymerization initiator were charged, and an adhesive composition was prepared according to the “Adhesive Preparation Method”. Using the adhesive composition obtained from the electromagnetic wave shielding layer of AgC conductive printing mesh (PC film thickness of 200 ⁇ m) and the protective layer (PC sheet thickness of 3.0 mm), “light transmission type using light transmission type adhesive” A sample was prepared according to “Electromagnetic wave shield laminate manufacturing method”.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 120N.
- the adhesive strength of the sample by the adhesive strength test was 1N.
- a bending workability test with a bending temperature of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, peeling occurred.
- Comparative Example 12 An ethylene vinyl acetate (EVA) hot melt adhesive is sandwiched between the electromagnetic shielding layer of the copper compound thin film mesh (PC film 200 ⁇ m thickness) and the protective layer (PC sheet 3.0 mm thickness).
- EVA ethylene vinyl acetate
- a sample was prepared according to “Method for producing light transmissive electromagnetic wave shield laminate using an agent”. Various evaluations similar to Example 12 were performed. The electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good. The adhesive strength of the sample by the adhesive strength test was 7N. As a result of evaluation according to a bending workability test with a surface temperature difference of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, bubbles were generated in the adhesive layer and separated.
- Comparative Example 13 A polyamide-based hot melt adhesive is sandwiched between the electromagnetic shielding layer and the protective layer (PC sheet thickness: 3.0 mm) of the copper compound thin film mesh (PC film 200 ⁇ m thickness).
- a sample was prepared according to “Transmission type electromagnetic wave shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed. The electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good. The adhesive strength of the sample by the adhesive strength test was 2N. As a result of evaluation according to a bending workability test with a bending temperature of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, peeling occurred.
- Comparative Example 14 A polyurethane-based hot melt adhesive is sandwiched between the electromagnetic shielding layer and the protective layer (PC sheet thickness: 3.0 mm) of the copper compound thin film mesh (PC film 200 ⁇ m thickness), and the “light using the hot melt adhesive” is used.
- a sample was prepared according to “Transmission type electromagnetic wave shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed. The electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good. The adhesive strength of the sample by the adhesive strength test was 92N. Bending conditions were evaluated according to a bending workability test with a surface temperature of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm. .
- Comparative Example 15 A polyester-based hot-melt adhesive is sandwiched between the electromagnetic shielding layer and the protective layer (PC sheet 3.0 mm thickness) of the copper compound thin-film mesh (PC film 200 ⁇ m thickness), and the “light using the hot-melt adhesive” is used.
- a sample was prepared according to “Transmission type electromagnetic wave shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed. The electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good. The adhesive strength of the sample by the adhesive strength test was 107N. As a result of evaluation according to a bending workability test with a surface temperature of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm, foaming was observed in the adhesive layer and peeled.
- Comparative Example 16 A polyolefin-based hot melt adhesive is sandwiched between the electromagnetic shielding layer and the protective layer (PC sheet thickness: 3.0 mm) of the copper compound thin film mesh (PC film 200 ⁇ m thickness).
- a sample was prepared according to “Transmission type electromagnetic wave shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed. The electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good. The adhesive strength of the sample by the adhesive strength test was 3N. As a result of evaluation according to a bending workability test with a bending temperature of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold curvature radius of 25 mm, peeling occurred.
- Comparative Example 17 An acrylic pressure-sensitive adhesive sheet is sandwiched between the electromagnetic wave shielding layer of the copper compound thin film mesh (PC film 200 ⁇ m thickness) and the protective layer (PC sheet 3.0 mm thickness), and “light-transmitting electromagnetic wave using pressure-sensitive adhesive”
- a sample was prepared according to “Shield laminate manufacturing method”. Various evaluations similar to Example 12 were performed. The electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good. The adhesive strength of the sample by the adhesive strength test was 6N. Bending conditions were evaluated according to a bending workability test with a surface temperature of 165 ° C. (upper part), 165 ° C. (lower part), a surface temperature difference of 0 ° C., and a mold radius of curvature of 25 mm. did.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- the curvature radius was 45 mm.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
- Example 12 Various evaluations similar to Example 12 were performed.
- the electromagnetic wave shielding performance of the sample by the electromagnetic wave shielding performance test was good.
- the adhesive strength of the sample by the adhesive strength test was 115N.
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Abstract
Description
本発明のポリカーボネート樹脂積層体の製造方法および光透過型電磁波シールド積層体の製造方法、並びにそれらによって得られるポリカーボネート樹脂積層体および光透過型電磁波シールド積層体は、以下の態様を含むものである。
該積層体を130℃~185℃で、かつ、該積層体の上下表面温度差が20℃以内となるように加熱する工程と、
加熱後の該積層体を曲率半径10mm以上の曲面に曲げ加工する工程と、を有することを特徴とする積層体の製造方法;
(2)前記積層体を加熱する工程が、前記該積層体を150℃~185℃で加熱する工程である、上記(1)に記載の積層体の製造方法;
(3)前記2層以上のポリカーボネート樹脂フィルムおよび/またはシートの一層が、電磁波シールド層であり、更にその少なくとも一層が保護層である、上記(1)または(2)に記載の積層体の製造方法;
(4)前記電磁波シールド層が、銀、銅、アルミ、ニッケル、カーボン、ITO(酸化インジウム/酸化錫)、ZnO、錫、亜鉛、チタン、タングステンおよびステンレスからなる群より選択される1つ以上の金属成分を含有する導電性化合物を含む、上記(3)に記載の積層体の製造方法;
(5)前記電磁波シールド層が、30デシベル以上の電磁波シールド性能を有する、上記(3)または(4)に記載の積層体の製造方法;
(6)前記電磁波シールド層が、金属薄膜メッシュ、金属織物メッシュ、導電性繊維メッシュおよび導電性印刷メッシュからなる群より選択される1種を含む、上記(3)から(5)のいずれかに記載の積層体の製造方法;
(7)前記金属薄膜メッシュおよび導電性印刷メッシュが、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、またはポリエステル樹脂を含有するベース基材を有する、上記(6)に記載の積層体の製造方法;
(8)前記積層体が、50N/25mm幅以上の180度剥離強さを有する、上記(1)から(7)のいずれかに記載の積層体の製造方法;
(9)前記積層体が、65℃、95RH%の条件化で、200時間処理した後も剥離・白濁を生じない、上記(1)から(8)のいずれかに記載の積層体の製造方法;
(10)前記(B)(メタ)アクリレートオリゴマーが、ウレタン(メタ)アクリレートオリゴマー、ポリエステル(メタ)アクリレートオリゴマー、エポキシ(メタ)アクリレートオリゴマーおよびポリオール(メタ)アクリレートオリゴマーからなる群より選ばれた少なくとも1種類以上の(メタ)アクリレートオリゴマーである、上記(1)から(9)のいずれかに記載の積層体の製造方法;
(11)前記ウレタン(メタ)アクリレートオリゴマーが脂環式炭化水素化合物である、上記(10)に記載の積層体の製造方法;
(12)前記ウレタン(メタ)アクリレートオリゴマーの脂環式炭化水素化合物がジシクロヘキシルメタンイソシアネート由来の化合物である、上記(11)に記載の積層体の製造方法;
(13)前記(C)アクリルアミド誘導体が、アルキルアクリルアミドおよび/またはアルキルメタアクリルアミドである、上記(1)から(12)のいずれかに記載の積層体の製造方法;
(14)前記(C)アクリルアミド誘導体が、ジメチルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミド、および4-アクリロモルホリンからなる群より選ばれた少なくとも1種類以上である、上記(1)から(13)のいずれかに記載の積層体の製造方法;
(15)前記(D)シラン化合物が、アミノ官能性シラン、エポキシ官能性シラン、ビニル官能性シラン、メルカプト官能性シラン、メタクリレート官能性シラン、アクリルアミド官能性シラン、およびアクリレート官能性シランからなる群より選ばれた1種類以上である、上記(1)から(14)のいずれかに記載の積層体の製造方法;
(16)前記(D)シラン化合物が、(3-(2,3-エポキシプロポキシ)プロピル)トリメトキシシランである、上記(1)から(15)のいずれかに記載の積層体の製造方法;
(17)前記(E)有機リン化合物が、リン酸アクリレート化合物である、上記(1)から(16)のいずれかに記載の積層体の製造方法;
(18)前記(メタ)アクリレート系接着剤組成物が、無溶剤型(メタ)アクリレート系接着剤組成物である、上記(1)から(17)のいずれかに記載の積層体の製造方法;
(19)前記(メタ)アクリレート系接着剤組成物が、可視光、紫外線(UV)または電子線(EB)を用いて硬化する光硬化型(メタ)アクリレート系接着剤組成物である、上記(1)から(18)のいずれかに記載の積層体の製造方法;
(20)前記積層体の片面または両面に、酸化防止剤、紫外線吸収剤および光安定剤からなる群より選ばれる1種以上を含有する被膜を形成してなる、上記(1)から(19)のいずれかに記載の積層体の製造方法;
(21)前記被膜が熱硬化型樹脂または光硬化型樹脂を含む、上記(20)に記載の積層体の製造方法;
(22)前記被膜がアクリル系樹脂化合物またはシリコーン系樹脂化合物を含む、上記(20)または(21)に記載の積層体の製造方法;
(23)前記ポリカーボネート樹脂を含む層または前記(メタ)アクリレート系接着剤組成物を含む層が、酸化防止剤、紫外線吸収剤および光安定剤からなる群より選ばれる1種以上を含有する、上記(1)から(22)に記載の積層体の製造方法;
(24)上記(1)から(23)のいずれかに記載の方法で製造された積層体;
(25)電子機器カバー、筐体用シールド材料、車両用カバー、半導体製造装置カバー、または窓材用シールド材料に用いられる、上記(24)に記載の積層体;
(26)2層以上のポリカーボネート樹脂フィルムおよび/またはシートを、(A)(メタ)アクリレートモノマー、(B)(メタ)アクリレートオリゴマーおよび(C)アクリルアミド誘導体と、(D)シラン化合物および/または(E)有機リン化合物とを含有する(メタ)アクリレート系接着剤組成物を用いて積層し、厚さ0.1mm~30mmのポリカーボネート樹脂積層体を作製する工程と、
該積層体を130℃~185℃(好ましくは150℃~185℃)で、かつ、該積層体の上下表面温度差が20℃以内となるように加熱する工程と、
加熱後の該積層体を曲率半径10mm以上の曲面に曲げ加工する工程と、を有することを特徴とするポリカーボネート樹脂積層体の製造方法;
(27)電磁波シールド層の片側または両側に、(A)(メタ)アクリレートモノマー、(B)(メタ)アクリレートオリゴマーおよび(C)アクリルアミド誘導体と、(D)シラン化合物および/または(E)有機リン化合物を含有する(メタ)アクリレート系接着剤組成物を用いて、ポリカーボネート基材(保護層)を積層し、厚さ0.1mm~30mmの積層体を作製する工程と、
該積層体を130℃~185℃(好ましくは150℃~185℃)で、かつ、該積層体の上下表面温度差が20℃以内となるように加熱する工程と、
加熱後の該積層体を曲率半径10mm以上の曲面に曲げ加工する工程と、を有することを特徴とする光透過型電磁波シールド積層体の製造方法。
本発明のポリカーボネート樹脂積層体の製造方法は、2層以上のポリカーボネート樹脂フィルムおよび/またはシートを(A)(メタ)アクリレートモノマー、(B)(メタ)アクリレートオリゴマーおよび(C)アクリルアミド誘導体と、(D)シラン化合物および/または(E)有機リン化合物を含有する(メタ)アクリレート系接着剤組成物を用いて積層して0.1mm~30mmのポリカーボネート樹脂積層体を形成する工程と、該積層体の上下表面温度差を20℃以内に制御して前記積層体を130℃~185℃(好ましくは150℃~185℃)に加熱する工程と、加熱後の積層体を曲率半径10mm以上の曲面に曲げ加工する工程とを有することを特徴とする。
活性エネルギー線の照射による硬化性を有する光硬化型(メタ)アクリレート系接着剤組成物は、硬化時間、安全性の面から特に好ましく、活性エネルギー線としては可視光線または紫外線が好ましい。
これらの被膜には紫外線吸収剤、光安定剤、酸化防止剤のほか、必要に応じて、有機溶剤、着色防止剤などの各種安定剤やレベリング剤、消泡剤、増粘剤、帯電防止剤、防曇剤などの界面活性剤等を適宜添加してもよい。
その他ニッケル系紫外線安定剤として、〔2,2’-チオビス(4-t-オクチルフェノレート)〕-2-エチルヘキシルアミンニッケル(II)、ニッケルコンプレックス-3,5-ジ-t-ブチル-4-ヒドロキシベンジル・リン酸モノエチレート、ニッケル・ジブチル-ジチオカーバメート等も使用することが可能である。特にヒンダードアミン系の光安定剤としては、3級のアミンのみを含有するヒンダードアミン系の光安定剤が好ましく、具体的には、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)-セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)-2-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-2-n-ブチルマロネート、または1,2,2,6,6-ペンタメチル-4-ピペリジノール/トリデシルアルコールと1,2,3,4-ブタンテトラカルボン酸との縮合物が好ましい。
チオール系酸化防止剤としては、例えば、ジステアリル-3,3’-チオジプロピオネート、ペンタエリスリトール-テトラキス-(β-ラウリル-チオプロピオネート)等を挙げられる。ホスファイト系酸化防止剤としては、例えば、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジ(2,6-ジ-t-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス-(2,6-ジ-t-ブチル-4-メチルフェニル)-ペンタエリスリトールジホスファイト、テトラキス(2,4-ジ-t-ブチルフェニル)4,4’-ビフェニレン-ジホスホナイト、2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト等が挙げられる。
ベンゾトリアゾール系紫外線吸収剤としては、2ー(2’-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、2ー(2’-ヒドロキシ-3’,5’-ジ-t-ブチルフェニル)ベンゾトリアゾール、2ー(2’-ヒドロキシ-3’-t-ブチル-5’-メチルフェニル)ベンゾトリアゾール等が挙げられる。
サリチル酸フェニル系紫外線吸収剤としては、フェニルサルチレート、2-4-ジ-t-ブチルフェニル-3,5-ジ-t-ブチル-4-ヒドロキシベンゾエート等が挙げられる。ヒンダードアミン系紫外線吸収剤としては、ビス(2,2,6,6-テトラメチルピペリジン-4-イル)セバケート等が挙げられる。
トリアジン系紫外線吸収剤としては、2,4-ジフェニル-6-(2-ヒドロキシ-4-メトキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-6-(2-ヒドロキシ-4-エトキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-(2-ヒドロキシ-4-プロポキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-(2-ヒドロキシ-4-ブトキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-6-(2-ヒドロキシ-4-ブトキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-6-(2-ヒドロキシ-4-ヘキシルオキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-6-(2-ヒドロキシ-4-オクチルオキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-6-(2-ヒドロキシ-4-ドデシルオキシフェニル)-1,3,5-トリアジン、2,4-ジフェニル-6-(2-ヒドロキシ-4-ベンジルオキシフェニル)-1,3,5-トリアジン等が挙げられる。
これらの被膜には前述した紫外線吸収剤、光安定剤、酸化防止剤のほか、必要に応じて、有機溶剤、着色防止剤などの各種安定剤やレベリング剤、消泡剤、増粘剤、帯電防止剤、防曇剤などの界面活性剤等を適宜添加してもよい。
ウレタン化反応に用いられる1分子中に少なくとも1個の(メタ)アクリロイルオキシ基および水酸基を有する(メタ)アクリレートモノマーとしては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、グリセリンジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレートが挙げられる。
ウレタン化反応に用いられるポリイソシアネートとしては、ヘキサメチレンジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、これらジイソシアネートのうち芳香族のイソシアネート類を水素添加して得られるジイソシアネート(例えば水素添加トリレンジイソシアネート、水素添加キシリレンジイソシアネートなどのジイソシアネート)、トリフェニルメタントリイソシアネート、ジメチレントリフェニルトリイソシアネートなどのジまたはトリのポリイソシアネート、あるいはジイソシアネートを多量化させて得られるポリイソシアネートが挙げられる。
ウレタン化反応に用いられるポリオール類としては、一般的に芳香族、脂肪族および脂環式のポリオールのほか、ポリエステルポリオール、ポリエーテルポリオール等が使用される。通常、脂肪族および脂環式のポリオールとしては、1,4-ブタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、エチレングリコール、プロピレングリコール、トリメチロールエタン、トリメチロールプロパン、ジメチロールヘプタン、ジメチロールプロピオン酸、ジメチロールブチリオン酸、グリセリン、水添ビスフェノールAなどが挙げられる。
ポリエステルポリオールとしては、前記のポリオール類と多塩基性カルボン酸(無水物)との脱水縮合反応により得られるものである。多塩基性カルボン酸の具体的な化合物としては(無水)コハク酸、アジピン酸、(無水)マレイン酸、(無水)トリメリット酸、ヘキサヒドロ(無水)フタル酸、(無水)フタル酸、イソフタル酸、テレフタル酸などが挙げられる。また、ポリエーテルポリオールとしてはポリアルキレングリコールのほか、前記ポリオールまたはフェノール類とアルキレンオキサイドとの反応により得られるポリオキシアルキレン変性ポリオールが挙げられる。
多官能エポキシ(メタ)アクリレートオリゴマーは、ポリグリシジルエーテルと(メタ)アクリル酸との付加反応により得られる。ポリグリシジルエーテルとしては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、ビスフェノールAジグリシジルエーテルなどが挙げられる。
アクリル基含有シラン化合物としては、 3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルメチルジメトキシシラン、3-アクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシメチルトリメトキシシラン、3-メタクリロキシメチルトリエトキシシラン、3-メタクリロキシメチルメチルジメトキシシラン、3-メタクリロキシメチルメチルジエトキシシラン、3-アクリロキシメチルトリメトキシシラン、3-アクリロキシメチルトリエトキシシラン、3-アクリロキシメチルメチルジメトキシシラン、3-アクリロキシメチルメチルジエトキシシランなどが例示される。これらの中で取り扱い性、架橋密度、反応性などから3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルメチルジメトキシシランが好ましい。また、このアルコキシシリル基を含有するビニル系単量体としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、ビニルメチルビス(2-メトキシエトキシ)シラン、3-ビニロキシプロピルトリメトキシシラン、3-ビニロキシプロピルトリエトキシシラン、3-ビニロキシプロピルメチルジメトキシシラン、3-ビニロキシプロピルメチルジエトキシシラン、スチリルトリメトキシシラン、スチリルトリエトキシシラン、スチリルメチルジメトキシシラン、スチリルメチルジエトキシシランなどが例示されるが、これらの中で取り扱い性、反応性などからビニルトリメトキシシラン、ビニルトリエトキシシラン、3-ビニロキシプロピルトリメトキシシランが好ましい。
サンプルの接着力は、180度剥離接着強さ試験方法(JIS K6854-2)またはT型剥離接着強さ試験方法(JIS K6854-3)に準拠して測定した。具体的には、ポリカーボネート樹脂シートまたはフィルムを各種接着剤組成物で接着して、幅25mm、長さ200mmの試験片を作製した。引張り試験機(SHIMADZU社製AGS-100G)にて10mm/min剥離速度で剥離接着強さ[N/25mm幅]を測定した。
サンプルを65℃、95%RHの恒温恒湿器に入れ、200h処理後に常温まで冷却し、透明性を目視評価した。
[目視評価]
○:透明性良好、変化なし
△:僅かに白濁、視認性あり
×:白濁、視認性なし
ポリカーボネート樹脂シートまたはフィルムを各種接着剤組成物で接着して、幅50mm、長さ200mmの試験片を作製した。試験片を遠赤外線ヒーターで上下から加熱して、試験片の表面温度が所定温度に達した後、所定の曲率半径の金型を用いて曲げ加工した。試験片の曲率半径と加工状況を目視にて評価した。
[外観評価]
○:外観異常なし
×:剥離、発泡、白化、反り、揺らぎのいずれかが発生
[試験片曲率半径評価]
○:金型の曲率半径に対して誤差10%以内
△:金型の曲率半径に対して誤差20%以内
×:金型の曲率半径に対して誤差20%以上または測定不可
(A)(メタ)アクリレートモノマー、(B)(メタ)アクリレートオリゴマー、(C)アクリルアミド誘導体、(D)シラン化合物、(E)有機リン化合物、光重合開始剤などの各成分を表1に示す組成で仕込み、60℃で1時間混合加熱して、所望の接着剤組成物を得た。使用した接着剤組成物の各成分は以下の通りである。
[接着剤組成物の各成分]
・ウレタン(メタ)アクリレート系重合性オリゴマー
ジシクロヘキシルメタンジイソシアネート由来の脂環式炭化水素化合物含有ウレタン(メタ)アクリレート系オリゴマー
・(メタ)アクリレート系重合性モノマー
イソボニルアクリレート
・アクリルアミド誘導体
ジメチルアクリルアミド
・シラン化合物
(3-(2,3-エポキシプロポキシ)プロピル)トリメトキシシラン
・有機リン化合物
リン酸アクリレート
・光重合開始剤
Irgacure651
バーコーターで各種接着剤組成物を第1層のポリカーボネート樹脂シートまたはフィルムに塗布し、第2層のポリカーボネート樹脂シートまたはフィルムをラミネーターで脱泡しながら重ね合わせた。前記サンプルに高圧水銀ランプ(500W)を用いて90秒間照射し、照射量1J/cm2で十分に硬化させた。また第3層のポリカーボネート樹脂シートまたはフィルムを積層する場合も同様の方法で積層した。
各種評価用サンプルは恒温恒湿室(23℃、50%RH)で24時間静置後、幅50mm、長さ200mmにカットしたものをサンプルとして用いた。
[材料]
・PCシート
MGCフィルシート社製ポリカーボネートシート(1.5mm~20.0mm厚)
・PCフィルム
MGCフィルシート社製ポリカーボネートフィルム(100~200μm厚)
ポリカーボネート樹脂シート第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にホットメルト型接着シートを挟み込み、135℃で30分間プレスした。
各種評価用サンプルは恒温恒湿室(23℃、50%RH)で24時間静置後、幅50mm、長さ200mmにカットしたものをサンプルとして用いた。
[ホットメルト(HM)型接着剤]
・ エチレン酢酸ビニル(EVA)系HM型接着剤
日本マタイ社製エルファンOH-501
・ ポリアミド系HM型接着剤
日本マタイ社製エルファンNT-120
・ ポリウレタン系HM型接着剤
倉敷紡績社製クランジールS-1700
・ ポリエステル系HM型接着剤
倉敷紡績社製クランベターG-6
・ ポリオレフィン系HM型接着剤
倉敷紡績社製クランベターA-1510
ポリカーボネート樹脂シート第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間に感圧型接着シートを挟み込み、5分間プレスした。
各種評価用サンプルは恒温恒湿室(23℃、50%RH)で24時間静置後、幅25mm、長さ200mmにカットしたものをサンプルとして用いた。
[感圧型接着剤]
・ アクリル系感圧型接着シート
日東電工社製CS-9621
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、前記「接着力試験」によるサンプルの接着力は150Nであった。前記「耐湿性試験」において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして前記「曲げ加工性試験」に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.4重量%、(メタ)アクリレート系重合性モノマー40.6重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は70Nであった。耐湿性試験において100h処理後も変化は認められず、200h処理後において僅かに白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー32.1重量%、(メタ)アクリレート系重合性モノマー42.9重量%、アクリルアミド誘導体20.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は85Nであった。耐湿性試験において24処理後に白濁は認められず、100h処理後に僅かに白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度130℃(上部)、130℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は29mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度185℃(上部)、185℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度160℃(上部)、140℃(下部)、表面温度差20℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート10.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径50mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は51mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート20.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径100mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は105mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径10mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は11mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第2層(PCフィルム200μm厚)と上下第1層および第3層(PCシート1.5mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は26mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー41.1重量%、(メタ)アクリレート系重合性モノマー54.9重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は1Nであった。耐湿性試験において24h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、剥離が発生した。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度190℃(上部)、190℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に揺らぎが発生し、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は150Nであった。耐湿性試験において200h処理後も白濁は発生せず、良好な結果を示した。曲げ加工条件を表面温度170℃(上部)、140℃(下部)、表面温度差30℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観に反りが発生し、試験片の曲率半径は25mmであった。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)を可視光硬化型接着剤(アーデル社製BENEFIX PC)を用いて前記「光透過型接着剤を用いたポリカーボネート樹脂積層体作製方法」に従いサンプルを作製した。但し、光源は可視光蛍光ランプを用いて接着剤の硬化を行った。
各種評価を行った結果、接着力試験によるサンプルの接着力は30NでPCフィルムが破断した。耐湿性試験において24h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は26mmであった。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にエチレン酢酸ビニル(EVA)系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は7Nであった。耐湿性試験において24h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に気泡が発生して剥離した。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にポリアミド系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は2Nであった。耐湿性試験において100h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、剥離した。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にポリウレタン系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は92Nであった。耐湿性試験において24h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層が白化して視認性がなくなった。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にポリエステル系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は107Nであった。耐湿性試験において24h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に発泡が認められ、剥離した。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にポリオレフィン系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は3Nであった。耐湿性試験において100h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、剥離が発生した。
ポリカーボネート樹脂第1層(PCシート3.0mm厚)と第2層(PCフィルム200μm厚)の層間にアクリル系感圧型接着シートを挟み込み、「感圧型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、接着力試験によるサンプルの接着力は6Nであった。耐湿性試験において100h処理後に白濁した。曲げ加工条件を表面温度160℃(上部)、160℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に発泡が認められ、剥離が発生した。
電磁波シールド性能測定装置(アドバンテスト社製)を用いて100MHz~1GHzの周波数範囲の電磁波シールド性能を測定した。
[電磁波シールド性能評価]
周波数100MHzと1GHzの電磁波シールド性能が30dB以上を示すものを合格(○)とし、30dB未満のものを不合格(×)とした。
サンプルの接着力は、180度剥離接着強さ試験方法(JIS K6854-2)に準拠して測定した。具体的には、電磁波シールド層(PCフィルム、PETフィルム)と保護層(PCシートまたはフィルム)を各種接着剤組成物で接着して、幅25mm、長さ200mmの試験片を作製した。引張り試験機にて10mm/min剥離速度で剥離接着強さ[N/25mm幅]を測定した。電磁波シールド層と保護層(表裏面)の接着力を測定し、接着力の小さい方の値を実施例および比較例に記載した。
電磁波シールド層(PCフィルム、PETフィルム)と保護層(PCシートまたはフィルム)を各種接着剤組成物で接着して、幅50mm、長さ200mmの試験片を作製した。試験片を遠赤外線ヒーターで上下から加熱して、試験片の表面温度が所定温度に達した後、所定の曲率半径の金型を用いて曲げ加工した。試験片の曲率半径と加工状況を目視にて評価した。
[外観評価]
○:外観異常なし
×:剥離、発泡、白化、反り、揺らぎのいずれかが発生
[試験片曲率半径評価]
○:金型の曲率半径に対して誤差10%以内
△:金型の曲率半径に対して誤差20%以内
×:金型の曲率半径に対して誤差20%以上または測定不可
(A)(メタ)アクリレートモノマー、(B)(メタ)アクリレートオリゴマー、(C)アクリルアミド誘導体、(D)シラン化合物、(E)有機リン化合物、光重合開始剤などの各成分を表3~表4に示す組成で仕込み、60℃で1時間混合加熱して、所望の接着剤組成物を得た。使用した接着剤組成物の各成分は以下の通りである。
[接着剤組成物の各成分]
・ウレタン(メタ)アクリレート系重合性オリゴマー
ジシクロヘキシルメタンジイソシアネート由来の脂環式炭化水素化合物含有ウレタン(メタ)アクリレート系オリゴマー
・(メタ)アクリレート系重合性モノマー
イソボニルアクリレート
・アクリルアミド誘導体
ジメチルアクリルアミド
・シラン化合物
(3-(2,3-エポキシプロポキシ)プロピル)トリメトキシシラン
・有機リン化合物
リン酸アクリレート
・光重合開始剤
Irgacure651
バーコーターで各種接着剤組成物を保護層(PCシートまたはフィルム)に塗布し、ラミネーターで電磁波シールド層(PCフィルム、PETフィルム)を脱泡しながら重ね合わせた。前記サンプルに高圧水銀ランプ(500W)を用いて90秒間照射し、照射量1J/cm2で十分に硬化させた。また電磁波シールド層の両面に保護層を積層する場合も同様の方法で積層した。
各種評価用サンプルは恒温恒湿室(23℃、50%RH)で24時間静置後、幅50mm、長さ200mmにカットしたものをサンプルとして用いた。
[材料]
(電磁波シールド層)
各種導電性化合物を用いてメッシュ形成した表面抵抗値1[Ω/□]以下のPCフィルムまたはPETフィルム。
(導電性化合物メッシュ)
・AgC導電性印刷メッシュ
ライン100μm、ピッチ500μm、表面抵抗0.5Ω/□
・ 銅化合物薄膜メッシュ
ライン10μm、ピッチ300μm、表面抵抗0.1Ω/□
・ 銀化合物薄膜メッシュ
ライン10μm、ピッチ180μm、表面抵抗0.1Ω/□
(ベース基材)
・PCフィルム
MGCフィルシート社製ポリカーボネートフィルム(100~200μm厚)
・PETフィルム
東洋紡社製易接着ポリエチレンテレフタレート(200μm厚)
(保護層)
・PCシート
MGCフィルシート社製ポリカーボネートシート(1.5mm~20.0mm厚)
・PCフィルム
MGCフィルシート社製ポリカーボネートフィルム(100μm厚)
電磁波シールド層(PCフィルム200μm厚)と保護層(PCシート3.0mm厚)の各層間にホットメルト型接着シートを挟み込み、135℃で30分間プレスした。
各種評価用サンプルは恒温恒湿室(23℃、50%RH)で24時間静置後、幅50mm、長さ200mmにカットしたものをサンプルとして用いた。
[ホットメルト(HM)型接着剤]
・ エチレン酢酸ビニル(EVA)系HM型接着剤
日本マタイ社製エルファンOH-501
・ ポリアミド系HM型接着剤
日本マタイ社製エルファンNT-120
・ ポリウレタン系HM型接着剤
倉敷紡績社製クランジールS-1700
・ ポリエステル系HM型接着剤
倉敷紡績社製クランベターG-6
・ ポリオレフィン系HM型接着剤
倉敷紡績社製クランベターA-1510
電磁波シールド層(PCフィルム200μm厚)と保護層(PCシート3.0mm厚)の各層間に感圧型接着シートを挟み込み、5分間プレスした。
各種評価用サンプルは恒温恒湿室(23℃、50%RH)で24時間静置後、幅25mm、長さ200mmにカットしたものをサンプルとして用いた。
[感圧型接着剤]
・ アクリル系感圧型接着シート
日東電工社製CS-9621
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
各種評価を行った結果、前記「電磁波シールド性能試験」によるサンプルの電磁波シールド性能は良好であった。前記「接着力試験」によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして前記「曲げ加工性試験」に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.4重量%、(メタ)アクリレート系重合性モノマー40.8重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は70Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー32.1重量%、(メタ)アクリレート系重合性モノマー42.9重量%、アクリルアミド誘導体20.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は86Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度130℃(上部)、130℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は29mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度135℃(上部)、135℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は27mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度150℃(上部)、150℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度180℃(上部)、180℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度180℃(上部)、160℃(下部)、表面温度差20℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度170℃(上部)、160℃(下部)、表面温度差10℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム100μm厚)の電磁波シールド層と保護層(PCフィルム100μm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は96Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート10.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は110Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径50mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は51mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート20.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は112Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径100mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は105mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径10mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は11mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と上下保護層(PCシート1.5mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は100Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は26mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銀化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は79Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。AgC導電性印刷メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は120Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であり、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー41.1重量%、(メタ)アクリレート系重合性モノマー54.9重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は1Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、剥離が発生した。
銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)の各層間にエチレン酢酸ビニル(EVA)系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は7Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に気泡が発生して剥離した。
銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)の各層間にポリアミド系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は2Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、剥離が発生した。
銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)の各層間にポリウレタン系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は92Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層が白化して視認性がなくなった。
銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)の各層間にポリエステル系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は107Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に発泡が認められ、剥離した。
銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)の各層間にポリオレフィン系ホットメルト型接着剤を挟み込み、前記「ホットメルト型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は3Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、剥離が発生した。
銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)の各層間にアクリル系感圧型接着シートを挟み込み、「感圧型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は6Nであった。曲げ加工条件を表面温度165℃(上部)、165℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に発泡が認められ、剥離が発生した。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度125℃(上部)、125℃(下部)、表面温度差0℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は良好であったが、試験片の曲率半径は45mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度190℃(上部)、190℃(下部)、表面温度差25℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、接着層に揺らぎが発生し、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度165℃(上部)、140℃(下部)、表面温度差25℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観に反りが発生し、試験片の曲率半径は25mmであった。
ウレタン(メタ)アクリレート系重合性オリゴマー30.0重量%、(メタ)アクリレート系重合性モノマー40.0重量%、アクリルアミド誘導体20.0重量%、シラン化合物5.0重量%、有機リン化合物1.0重量%、光重合開始剤4.0重量%を仕込み、前記「接着剤調製方法」に従い接着剤組成物を調製した。銅化合物薄膜メッシュ(PCフィルム200μm厚)の電磁波シールド層と保護層(PCシート3.0mm厚)を得られた接着剤組成物を用いて前記「光透過型接着剤を用いた光透過型電磁波シールド積層体作製方法」に従いサンプルを作製した。
実施例12と同様の各種評価を行った。電磁波シールド性能試験によるサンプルの電磁波シールド性能は良好であった。接着力試験によるサンプルの接着力は115Nであった。曲げ加工条件を表面温度165℃(上部)、130℃(下部)、表面温度差35℃、金型曲率半径25mmとして曲げ加工性試験に従い評価した結果、外観は反りと剥離が発生した。
Claims (25)
- 2層以上のポリカーボネート樹脂フィルムおよび/またはシートを、(A)(メタ)アクリレートモノマー、(B)(メタ)アクリレートオリゴマーおよび(C)アクリルアミド誘導体と、(D)シラン化合物および/または(E)有機リン化合物とを含有する(メタ)アクリレート系接着剤組成物を用いて積層し、厚さ0.1mm~30mmの積層体を作製する工程と、
該積層体を130℃~185℃で、かつ、該積層体の上下表面温度差が20℃以内となるように加熱する工程と、
加熱後の該積層体を曲率半径10mm以上の曲面に曲げ加工する工程と、を有することを特徴とする積層体の製造方法。 - 前記積層体を加熱する工程が、前記該積層体を150℃~185℃で加熱する工程である、請求項1に記載の積層体の製造方法。
- 前記2層以上のポリカーボネート樹脂フィルムおよび/またはシートの一層が、電磁波シールド層であり、更にその少なくとも一層が保護層である、請求項1または2に記載の積層体の製造方法。
- 前記電磁波シールド層が、銀、銅、アルミ、ニッケル、カーボン、ITO(酸化インジウム/酸化錫)、ZnO、錫、亜鉛、チタン、タングステンおよびステンレスからなる群より選択される1つ以上の金属成分を含有する導電性化合物を含む、請求項3に記載の積層体の製造方法。
- 前記電磁波シールド層が、30デシベル以上の電磁波シールド性能を有する、請求項3または4に記載の積層体の製造方法。
- 前記電磁波シールド層が、金属薄膜メッシュ、金属織物メッシュ、導電性繊維メッシュおよび導電性印刷メッシュからなる群より選択される1種を含む、請求項3から5のいずれかに記載の積層体の製造方法。
- 前記金属薄膜メッシュおよび導電性印刷メッシュが、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、またはポリエステル樹脂を含有するベース基材を有する、請求項6に記載の積層体の製造方法。
- 前記積層体が、50N/25mm幅以上の180度剥離強さを有する、請求項1から7のいずれかに記載の積層体の製造方法。
- 前記積層体が、65℃、95RH%の条件化で、200時間処理した後も剥離・白濁を生じない、請求項1から8のいずれかに記載の積層体の製造方法。
- 前記(B)(メタ)アクリレートオリゴマーが、ウレタン(メタ)アクリレートオリゴマー、ポリエステル(メタ)アクリレートオリゴマー、エポキシ(メタ)アクリレートオリゴマーおよびポリオール(メタ)アクリレートオリゴマーからなる群より選ばれた少なくとも1種類以上の(メタ)アクリレートオリゴマーである、請求項1から9のいずれかに記載の積層体の製造方法。
- 前記ウレタン(メタ)アクリレートオリゴマーが脂環式炭化水素化合物である、請求項10に記載の積層体の製造方法。
- 前記ウレタン(メタ)アクリレートオリゴマーの脂環式炭化水素化合物がジシクロヘキシルメタンイソシアネート由来の化合物である、請求項11に記載の積層体の製造方法。
- 前記(C)アクリルアミド誘導体が、アルキルアクリルアミドおよび/またはアルキルメタアクリルアミドである、請求項1から12のいずれかに記載の積層体の製造方法。
- 前記(C)アクリルアミド誘導体が、ジメチルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミド、および4-アクリロモルホリンからなる群より選ばれた少なくとも1種類以上である、請求項1から13のいずれかに記載の積層体の製造方法。
- 前記(D)シラン化合物が、アミノ官能性シラン、エポキシ官能性シラン、ビニル官能性シラン、メルカプト官能性シラン、メタクリレート官能性シラン、アクリルアミド官能性シラン、およびアクリレート官能性シランからなる群より選ばれた1種類以上である、請求項1から14のいずれかに記載の積層体の製造方法。
- 前記(D)シラン化合物が、(3-(2,3-エポキシプロポキシ)プロピル)トリメトキシシランである、請求項1から15のいずれかに記載の積層体の製造方法。
- 前記(E)有機リン化合物が、リン酸アクリレート化合物である、請求項1から16のいずれかに記載の積層体の製造方法。
- 前記(メタ)アクリレート系接着剤組成物が、無溶剤型(メタ)アクリレート系接着剤組成物である、請求項1から17のいずれかに記載の積層体の製造方法。
- 前記(メタ)アクリレート系接着剤組成物が、可視光、紫外線(UV)または電子線(EB)を用いて硬化する光硬化型(メタ)アクリレート系接着剤組成物である、請求項1から18のいずれかに記載の積層体の製造方法。
- 前記積層体の片面または両面に、酸化防止剤、紫外線吸収剤および光安定剤からなる群より選ばれる1種以上を含有する被膜を形成してなる、請求項1から19のいずれかに記載の積層体の製造方法。
- 前記被膜が熱硬化型樹脂または光硬化型樹脂を含む、請求項20に記載の積層体の製造方法。
- 前記被膜がアクリル系樹脂化合物またはシリコーン系樹脂化合物を含む、請求項20または21に記載の積層体の製造方法。
- 前記ポリカーボネート樹脂を含む層または前記(メタ)アクリレート系接着剤組成物を含む層が、酸化防止剤、紫外線吸収剤および光安定剤からなる群より選ばれる1種以上を含有する、請求項1から22に記載の積層体の製造方法。
- 請求項1から23のいずれかに記載の方法で製造された積層体。
- 電子機器カバー、筐体用シールド材料、車両用カバー、半導体製造装置カバー、または窓材用シールド材料に用いられる、請求項24に記載の積層体。
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EP09746525.6A EP2305451B1 (en) | 2008-05-13 | 2009-05-07 | Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof |
US12/736,818 US8585860B2 (en) | 2008-05-13 | 2009-05-07 | Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof |
CN2009801174046A CN102026795B (zh) | 2008-05-13 | 2009-05-07 | 可弯曲加工的聚碳酸酯树脂层压体和透光型电磁波屏蔽层压体以及它们的制造方法 |
US14/055,013 US8815373B2 (en) | 2008-05-13 | 2013-10-16 | Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof |
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JP2008125730A JP5312839B2 (ja) | 2008-05-13 | 2008-05-13 | 曲げ加工可能な光透過型電磁波シールド積層体およびその製造方法 |
JP2008-125730 | 2008-05-13 | ||
JP2008125726A JP5551854B2 (ja) | 2008-05-13 | 2008-05-13 | 曲げ加工可能な高耐久性ポリカーボネート樹脂積層体の製造方法 |
JP2008-125726 | 2008-05-13 |
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US12/736,818 A-371-Of-International US8585860B2 (en) | 2008-05-13 | 2009-05-07 | Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof |
US14/055,013 Division US8815373B2 (en) | 2008-05-13 | 2013-10-16 | Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof |
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EP (1) | EP2305451B1 (ja) |
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Publication number | Publication date |
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CN102026795B (zh) | 2013-08-07 |
TW201005013A (en) | 2010-02-01 |
EP2305451A4 (en) | 2012-10-03 |
TWI454509B (zh) | 2014-10-01 |
CN102026795A (zh) | 2011-04-20 |
US20140044927A1 (en) | 2014-02-13 |
EP2305451A1 (en) | 2011-04-06 |
KR101563764B1 (ko) | 2015-10-27 |
EP2305451B1 (en) | 2013-11-20 |
KR20110011670A (ko) | 2011-02-08 |
US20110070448A1 (en) | 2011-03-24 |
US8815373B2 (en) | 2014-08-26 |
US8585860B2 (en) | 2013-11-19 |
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