TW200928468A - Film-shaped optical waveguide - Google Patents

Abstract

Disclosed is a film-shaped optical waveguide having excellent bending durability and transparency. Specifically disclosed is a film-shaped optical waveguide (1) comprising a lower cladding layer (15), a core portion (22), an intermediate cladding layer (36) and an upper cladding layer (33). The lower cladding layer (15) and the upper cladding layer (33) are made of a cured product of a photocurable resin composition which contains, when the solid content of the photocurable resin composition is taken as 100% by mass, 30-80% by mass of a urethane (meth)acrylate oligomer (A), 15-69% by mass of a reactive diluted monomer (B) and 0.1-10% by mass of a photopolymerization initiator (C). The intermediate cladding layer (36) is made of a cured product of a photocurable resin composition which contains, when the solid content of the photocurable resin composition is taken as 100% by mass, 5-80% by mass of a urethane (meth)acrylate oligomer (a), 1-40% by mass of a reactive diluted monomer (b), 0.1-10% by mass of a photopolymerization initiator (c) and 15-75% by mass of a vinyl polymer (d) having an ethylenically unsaturated group.

Description

200928468 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a film-shaped optical waveguide. [Prior Art] In the era of multimedia, optical waveguides, which are optical transmission media, have attracted attention due to the demand for large-capacity and high-speed data processing in optical communication systems and computers. The optical waveguides of the past are represented by quartz-based optical waveguides.

D However, the quartz-based optical waveguide has a long processing time at a high temperature due to the deposition of the quartz film during manufacture, and the patterning time of the optical waveguide includes the step of using the photoresist and the etching using a high-risk gas. The steps, and because of the need for special devices, etc. in these steps, there are many complicated steps and special devices, and low yields. In order to improve these problems, in order to reduce the number of steps of the optical waveguide, shorten the manufacturing time, and increase the productivity of the lift, it has been proposed in recent years that Φ has a liquid hardening composition as a core portion and a coating. The polymer of the layer material is an optical waveguide. As an example thereof, a polyimine-based optical waveguide is proposed, which is characterized in that the polyimine is obtained from a polyiminoimine obtained from a tetracarboxylic dianhydride and a diamine as a constituent element. It is a polyfluorinated diamine represented by a specific structural formula or a polyimine containing such a diamine, or a mixture thereof (Patent Document 1). The poly-fee-type optical waveguide has excellent transfer characteristics (low waveguide loss) and excellent heat resistance. Further, as another example, a photosensitive resin composition for an optical waveguide comprising (A) a structure having a side chain portion containing a radical polymerizable reactive group bonded via a urethane bond has been proposed. The unit and the polymer containing the structural unit having no polymerizable side chain '(B) have more than one ethylenically unsaturated group in the molecule, the molecular weight is less than I,000, and the boiling point at 130 ° C is 0.1 ° The above compound, and (C) photoradical polymerization initiator (Patent Document 2). i When the photosensitive resin is used, an optical waveguide having high shape accuracy and suppressing deterioration in transmission characteristics under high temperature and high humidity can be formed. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the state of the object (film-shaped optical waveguide) is repeatedly bent, cracking or cracking occurs, and the problem of good transmission characteristics cannot be maintained. On the other hand, when other members such as a light-emitting element are fixed on the lower surface of the film-like optical waveguide, it is desirable to have high transparency since the alignment of the film-shaped optical waveguide is required to be aligned from above. Accordingly, an object of the present invention is to provide a film-shaped optical waveguide excellent in bending durability and transparency. [Means for Solving the Problems] -6 - 200928468 The inventors of the present invention have found that the lower cladding layer, the core portion, the intermediate cladding layer, and the cladding layer are contained, and the lower cladding layer is provided. The film-shaped optical waveguide composed of a cured product of a curable resin composition having a specific composition and the above-mentioned coating layer can achieve the above object of the invention, and the present invention has been completed. That is, the present invention provides the following [1] to [4]: [1] A film-like optical waveguide comprising a lower cladding layer, a core portion, an intermediate cladding layer, and an upper cladding layer, The lower cladding layer and the upper cladding layer are composed of a cured product of a photocurable resin composition containing the following components (A) to (C): (A) 30 to 80% by mass of (meth)acrylic acid amine a methacrylate oligomer, (B) 15 to 69% by mass of a reactive diluent monomer, (C) 0 · 1 to 10% by mass of a photopolymerization initiator, (wherein, a photocurable resin is composed The total amount of the solid content of the material is 1% by mass. The intermediate coating layer is composed of a cured product of a photocurable resin composition containing the following components (a) to (d): (a) 5~ 80% by mass of (meth)acrylic acid urethane oligomer, (b) 1 to 40% by mass of a reactive diluent monomer, (c) 0.1 to 10% by mass of a photopolymerization initiator, (d) 15 to 75 mass% of an ethyl fluorene-based polymer having an ethylenically unsaturated group (wherein the total solid content of the photocurable resin composition is 100% by mass). [2] The film-shaped optical waveguide according to the above [1], wherein the component (A) comprises (A-1) a polyol compound, (A-2) a polyisocyanate compound, and (A-3) a hydroxyl group-containing (methyl group). a (meth)acrylic acid urethane oligomer of the reaction product of an acrylate. [3] The film-shaped optical waveguide according to [2] above, wherein the (A-1) polyol compound is selected from the group consisting of aliphatic polyether polyols, aromatic polyether polyols, polyester polyols, and polycarbonate polyols. More than one group. [4] The film-shaped optical waveguide according to any one of [1] to [3] wherein the photocurable resin composition forming the lower cladding layer and the upper cladding layer does not contain an ethylene-based unsaturated group. When the total amount of the solid content of the polymer of the photocurable resin composition is 100% by mass, the ethylene-based polymer having an ethylenically unsaturated group is contained in an amount of 10% by mass or less. [Effect of the Invention] The film-shaped optical waveguide of the present invention includes a lower cladding layer, an intermediate cladding layer, and an upper cladding layer, which are composed of a photocurable resin composition having a specific component group φ. The film-like optical waveguide of the present invention has high transparency because of the coating layer composed of the photocurable resin composition having a specific composition, and the film is not broken or cracked, and the film has a high transparency. When the film-shaped optical waveguide is fixed to another member such as a light-emitting element, the film-shaped optical waveguide can be seen through, and the alignment can be easily and accurately performed. [Embodiment] -8 - 200928468 The film-shaped optical waveguide of the present invention comprises a lower cladding layer, a core portion, an intermediate cladding layer and an upper cladding layer, and the lower cladding layer and the upper cladding layer are composed of specific components. a cured product of a photocurable resin composition (also referred to as a photocurable resin composition for a coating layer), and the intermediate coating layer is different from the photocurable resin composition for the coating layer A cured product of a photocurable resin composition (also referred to as a photocurable resin composition for an intermediate layer) having a specific component composition. First, the photocurable resin composition for a coating layer will be described.光 The photocurable resin composition for the coating layer contains the components (A) to (C) and other components to be blended as needed. Hereinafter, various components will be described in detail. [Component (A)] Component (A) is a (meth)acrylic acid urethane oligomer. The (meth)acrylic acid urethane oligomer used as the component (A) can be, for example, a (A-1) polyol compound, (A-2) polyisocyanate compound φ, and (A-3) It is produced by reacting a hydroxyl group-containing (meth) acrylate. Specifically, it is produced by any of the following methods 1 to 4. Process 1 · A method in which a polyol compound, a polyisocyanate compound, and a (meth) acrylate containing a thiol group are fed in one time. Process 2: A method of reacting a polyol compound and a polyisocyanate compound, followed by reacting a hydroxyl group-containing (meth) acrylate. Process 3: A method of reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate vinegar followed by a reaction of a polyol compound. Process 4: A method in which a polyisocyanate compound and a hydroxyl group-containing (meth)propene 200928468 enoate are reacted, followed by reacting a polyol compound, and finally reacting a (meth) acrylate compound. Hereinafter, the (A-1) polyol compound used in the (meth)acrylic acid urethane oligomer, (A-2) polyisocyanate (A-3) hydroxyl group-containing (meth) acrylate will be described in detail. . [(A-1) Polyol Compound] (A-1) The polyol compound is exemplified by an aliphatic polyether polyol family polyether polyol, an aromatic polyether polyol, a polyester polyol, an ester polyol, and a polycap. Lactone polyols and the like. The aliphatic polyether polyol is exemplified by, for example, being selected from the group consisting of epoxy propylene oxide, butylene oxide, tetrahydrofuran, 2-methyltetrahydrofuranyltetrahydrofuran, substituted tetrahydrofuran, oxetane, and oxygen heterocycle. At least one compound (co)polymerization of butane, tetrahydropyran and oxaheptane is obtained. Specific examples thereof include polyethylene glycol, propylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, 12-poly, polyisobutylene glycol, copolymer of propylene oxide and tetrahydrofuran, and polyoxyethylene B. Copolymer of alkane and tetrahydrofuran, polyol of ethylene oxide and ring, polyol of tetrahydrofuran and 3-methyltetrahydrofuran, copolymer of ethylene oxide and 1,2-butylene oxide The alcohol or the like as the alicyclic polyether polyol is exemplified by, for example, hydrogenated bisphenol oxyethylene addition diol, hydrogenated bisphenol A propylene oxide addition, hydrogenated diacid A butylene oxide addition diol 'Hydrogenated bisphenol oxyethylene addition diol, hydrogenated bisphenol F propylene oxide addition hydroxy-containing compound, alicyclic polyethylene carbonate, 3-methyl substituted ring opening 1, 2-polybutanediol, propylene oxide polymer, ring diol of diol F of poly(A) ring, -10- 200928468 hydrogenated bisphenol F, butylene oxide addition diol, dicyclopentane Alkene dimethylol compound, tricyclodecane dimethanol, and the like. Commercial products of the above aliphatic polyether polyols and alicyclic polyether polyols are listed as Unisafe DC1100, Unisafe DC 1 800, Unisafe DCB1 100, Unisafe DCB 1 8 00 (above manufactured by Nippon Oil & Fats Co., Ltd.), PPTG4000, PPTG2000, PPTG 1 000, PTG2000, PTG3 000 Ο

, PTG65 0, PTGL2000, Ρ GL GL 1 0 0 0 (above is manufactured by Hodogaya Chemical Co., Ltd.); EXINOL4020, EXENOL3 020, EXENOL2020, EXENOL1020 (above is manufactured by Asahi Glass Co., Ltd.); PBG3000, PBG2000, PBG 1 000, Z300 1 ( The above is manufactured by First Industrial Pharmaceutical Co., Ltd.); ACCLAIM 2200, 3201, 4200, 6300, 8200 (above is manufactured by Sumit Chemical Bayer Amino Acid Company); NPML-2002, 3002, 4002, 8002 (above is manufactured by Asahi Glass Co., Ltd.) )Wait. The aromatic polyether polyol is exemplified by, for example, an ethylene oxide addition diol of bisphenol A, a propylene oxide addition diol of bisphenol A, a butylene oxide addition diol of bisphenol A, and a bisphenol. Ethylene oxide addition diol of F, propylene oxide addition diol of bisphenol F, butylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, naphthoquinone An alkylene oxide addition diol or the like. Commercially available products of the aromatic polyether polyols are listed as Unio1 DA400, DA700, and DA1000 (the above are manufactured by Sakamoto Oil & Fats Co., Ltd.). The polyester polyol is exemplified by, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, a polyvalent alcohol such as 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol or 2-methyl-1,8-octanediol, and Orthophthalic acid 200928468 A polyester polyol obtained by reacting a polybasic acid such as acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid or sebacic acid. Commercial products are listed as Curapol P-2030, P-1030, P-2010, P-5010, P-2050, F-2010, P-201 1, PMIPA, PKA-A, PKA-A2, PNA-2000 ( The above is manufactured by Kuraray Co., Ltd.). The polycarbonate polyol is exemplified by a copolymerized polycarbonate diol such as 1,6-hexanediol polycarbonate, 1,6-hexanediol and 1,5-pentanediol, 3-methyl- 0 1 a copolymerized polycarbonate diol of 5-pentanediol and 1,6-hexanediol, a copolymerized polycarbonate diol of 1,3-propanediol and 1,4-butanediol, and the like. Commercially available products are listed as PCDL T5652, G3452, G3450J (manufactured by Asahi Kasei Corporation); DN-980, 981, 982, 983 (above manufactured by Japan Polyurethane Co., Ltd.); Kuraraypolyol C-590, C1050, C- 1090, C-2050, C-2090, C-3090, C-5090, C-1065N, C-2065N, C-1015N, C-2015N (above is manufactured by Kuraray); PLACCEL-CD20 5, CD-983, CD220 (above is manufactured by Dicel Chemical Industries, Inc.); PC-φ 8000 (manufactured by PPG, USA). The polycaprolactone polyol is exemplified by ε-caprolactone with ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene A polycaprolactone obtained by reacting a diol such as a diol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol or 1,4-butanediol. Commercial products 歹U are PLACCEL205, 205AL, 212, 212AL, 220, 220AL (the above is manufactured by Dicel Chemical Industry Co., Ltd.). Other polyol compounds used in the present invention are exemplified by ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol-12-200928468, 1,4-cyclohexanedimethanol, poly-β-methyl-δ-valerolactone, hydroxyl terminated polybutadiene, hydroxyl terminated hydrogenated polybutadiene, and oil-modified polyol, polydimethylene a terminal diol compound of a oxyalkylene oxide, a polyhydric alcohol modified with a polydimethyl methoxy carbitol, and the like. Among them, aliphatic polyether polyols, aromatic polyether polyols, polyester polyols, and polycarbonate polyols are preferred, and polyester polyols and polycarbonate polyols are more preferred. (Α-1) The polyol compound may be used singly or in combination of two or more. (Α-2) The polyol compound is preferably one or more selected from the group consisting of aliphatic polyether polyols, aromatic polyether polyols, polyester polyols, and polycarbonate polyols, more preferably polyester. Polyol and/or polycarbonate polyol. (Α-1) The number average molecular weight of the polyol compound is preferably from 1 〇〇 to 15 , 〇〇〇, more preferably from 1, 〇〇〇 to 14,000, most preferably from 1,500 to 12,000 ° (Α-1). When the number average molecular weight of the polyol compound is less than 1 Å, the Young's modulus of the coating layer (the lower cladding layer and the upper cladding layer) obtained by hardening the composition φ is increased at normal temperature and low temperature, and is not obtained. A film-like optical waveguide having sufficient bending resistance. On the other hand, when the number average molecular weight exceeds 15,000, the viscosity of the composition increases, which may cause a problem that the coatability is deteriorated. [(Α-2) Polyisocyanate Compound] (Α-2) Polyisocyanate Compound is exemplified by 2,4-toluene diisocyanate, 2,6-toluene diisocyanate '13-xylene diisocyanate, ι,4-dimethylbenzene Isocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate-13- 200928468, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl Isocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-stranded diisocyanate, 1,6-hexane diisocyanate, different Fulcone diisocyanate, 2,4-toluene diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene Diisocyanate, bis(2-isocyanateethyl)fumarate, 6-isopropyl-1,3-phenyldiisocyanate, 4_diphenylpropane diisocyanate, diazonic acid diisocyanate, hydrogenated diphenyl A polyisocyanate compound such as methane diisocyanate, hydrogenated xylylene diisocyanate or tetramethyl xylylene diisocyanate. Among them, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or the like is preferred. (A-2) The polyisocyanate compound may be used singly or in combination of two or more. [(A-3) (meth) acrylate having a hydroxyl group] (A-3) A (meth) acrylate compound having a hydroxyl group may, for example, be 2-hydroxyethyl (meth) acrylate or (meth) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-Methyl hydroxyalkyl methacrylate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylic acid, neopentyl glycol mono(meth)acrylic acid Ester, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. Further, an addition reaction of a glycidyl group-containing compound such as an alkyl glycidyl ether, an allyl condensed water-14-200928468 glyceryl ether or a glycidyl (meth) acrylate with (meth)acrylic acid is exemplified. The compound obtained. Among them, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are suitable. (A-3) The (meth) acrylate containing a hydroxyl group may be used singly or in combination of two or more. (A) The compounding ratio of each raw material constituting the (meth)acrylic acid urethane oligomer is (M-1) (m-1) with respect to (A-3) hydroxyl group-containing (meth) acrylate (A-1) The polyol is 0.5 to 2 mol, and the (A-2) polyisocyanate compound is 1 to 2.5 mol%. Further, as the component (A), a (meth)acrylic acid urethane oligomer having a reaction product of a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate can be used. In this case, examples of the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate are the same as those of the above (A-2) polyisocyanate compound and (A-3) hydroxyl group-containing (meth) acrylate. As the component (A), a single one or a combination of two or more kinds of (meth)acrylic acid urethane oligomers may be used. From the viewpoint of bending durability, the component (A) preferably contains a reaction product of (A-1) a polyol compound and (A-2) a polyisocyanate compound and (A-3) a hydroxyl group-containing (meth) acrylate. (Meth)acrylic acid urethane oligomer. (meth)propionate amine group A of the reaction product of '(A-1) polyol compound and (A_2) polyisocyanate compound and (A-3) hydroxyl group-containing (meth) acrylate in component (A) The ratio of the acid ester oligomer is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the component (A) of 1〇〇-15 to 200928468% by mass. The number average molecular weight of the component (A) is preferably from 1 〇〇 to 15 , 〇〇〇, more preferably from 3 00 to 1 2,000. When the enthalpy is less than 100, the viscosity of the composition is too small, and there is a problem that the coating property is deteriorated. On the other hand, when the enthalpy exceeds 1 5,000, the viscosity is too high, so it is difficult to handle. In the photocurable resin composition for a coating layer, the blending ratio of the component (A) is preferably 100% when the total solid content of the photocurable resin composition for the coating layer is 100% by mass. 80% by mass, more preferably 3 5 to 7.5 % by mass, most preferably 40 to 70% by mass. When the blending ratio is less than 30% by mass, the Young's modulus of the coating layer (the lower cladding layer and the upper cladding layer) which is cured by the composition is increased, and it becomes difficult to form a film having sufficient bending durability. Optical waveguide. On the other hand, when the above compounding ratio exceeds 80% by mass, the viscosity of the composition becomes large, and it is difficult to form a coating layer having a uniform thickness. [Component B] Component (B) is a reactive diluent monomer. The reactive diluent system in this specification acts as a diluent (low viscosity) monomer for other photopolymerizable reactive components. The reactive diluent monomer is exemplified by a monomer having one ethylenically unsaturated group in the molecule (hereinafter referred to as a monofunctional monomer) and a monomer having two or more ethylenically unsaturated groups in the molecule (hereinafter referred to as a polyfunctional group). Base monomer). The ethylenically unsaturated group is exemplified by a (meth) acrylonitrile group, a vinyl group or the like, but more preferably a (meth) acrylonitrile group. The above monofunctional monomer may, for example, be acryloylmorpholine, dimethyl-16-200928468-based acrylamide, diethyl acrylamide, diisopropylacrylamide, isobornyl (meth)acrylate , dicyclopentenyl acrylate, dicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate 'dicyclopentenyloxyethyl (meth) acrylate , methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, tricyclodecyl (meth) acrylate, diacetone Acrylamide, isobutoxymethyl (meth) acrylamide, N-vinyl pyrrolidone, _ N-vinyl caprolactam, 3-hydroxycyclohexyl (meth)acrylate, 2_ Propylene decyl cyclohexyl citrate, phenoxyethyl (meth) acrylate, tribromophenol ethoxylate (meth) acrylate, alcohol (meth) acrylate of ethylene oxide adduct of phenol, Alcohol (meth) acrylate of ethylene oxide adduct of p-cumylphenol, 4-(b) 1-(phenylethyl)phenoxyethyl ester, an alcoholic (meth) acrylate of an ethylene oxide adduct of nonylphenol, o-phenylphenol glycidyl ether (meth) acrylate, Hydroxyethylated o-phenylphenol acrylate, 2-methacryloxyethyl phthalic acid, methoxypolyethylene diol (meth) acrylate, and the like. Among them, preferred are N-vinyl compounds such as acryloyl morpholine, dimethyl methacrylate, N-vinyl pyrrolidone and N-vinyl caprolactone and having a carbon number of 10 The monofunctional (meth) acrylate of the above aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 10 or more carbon atoms may contain any of a linear chain, a branched chain and an alicyclic ring. Preferred examples of the monofunctional (meth) acrylate having an aliphatic hydrocarbon group having 10 or more carbon atoms are exemplified by isobornyl (meth)acrylate, isodecyl (meth)acrylate, and (meth)acrylic acid Alkyl ester. Commercial products of monofunctional monomers are listed as ACMO, DMMA (above -17-200928468 manufactured by Xingren Co., Ltd.); Unifrontier IBA (manufactured by First Industrial Pharmaceutical Co., Ltd.); IBXA, IBXMA, ADMA (manufactured by Osaka Organic Chemical Co., Ltd.) ; FA511A, FA512A, FA513A (above is manufactured by Hitachi Chemical Co., Ltd.); Lightester Μ, E, BH, IB-X, H0-MS, H0-HH, L, P0, S, TD, Lightacrylate LA, SA, EC-A , MTG-A, 130Α, PO-A, P-200A, NP-4EA, THF-A, IB-XA, HOA-MS, HOA-MPL, HOA-MPE (above is manufactured by Kyoeisha Chemical Co., Ltd.); Aronix Ml 50 ' Ml 56 ' M5300, TO 1 3 1 5 ' T01316 (above is 东亚 East Asia Synthetic Company); FA544A, 512M, 512MT, 513M (above is manufactured by Hitachi Chemical Co., Ltd.), NK Ester A-CMP-1E, A -LEN- 10, M-450G, S, S-1 800M, S-1800A, PHE-1G, NPA-8E, NPA-5P 'NPA-10G, M-90G, LMA, LA, IB, CB-26 , CB-23 'CB-1, AMP-60G, AM-30G, A-SA, A-IB, 702A (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Among the above polyfunctional monomers, a monomer having two ethylenically unsaturated π groups in the molecule (2-functional monomer) is exemplified by, for example, ethylene glycol bis(meth)acrylate and di(meth)acrylic acid. Tetraethylene glycol ester, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, ι,6· hexanediol di(meth)acrylate, 1,9-nonanediol methyl methacrylate, neopentyl glycol di(meth)acrylate, 2,2-bis-4-(2-hydroxy-3-propenyloxypropyl phenyl) propane , ginseng (2-hydroxyethyl) isocyanurate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, ethylene oxide addition bisphenol A type II (Meth) acrylate, ethylene oxide addition tetrabromobisphenol A type di(meth) acrylate, propylene oxide addition bisphenol A type di(meth) acrylate, propylene oxide plus -18- 200928468 Bisphenol A type epoxy 2 obtained by ring-opening reaction of tetrabromobisphenol A type di(meth)acrylate, bisphenol a diglycidyl ether and (meth)acrylic acid (meth) acrylate, tetrabromo double Tetrabromobisphenol A type epoxy di(meth)acrylate, bisphenol F diglycidyl ether and (meth)acrylic acid obtained by ring-opening reaction of A diglycidyl ether with (meth)acrylic acid epoxy group The epoxy group ring-opening reaction to obtain the bisphenol F-type epoxy di(meth) acrylate, tetrabromobisphenol F diglycidyl ether and (meth)acrylic acid epoxy ring opening anti- Bromobisphenol F type epoxy di(meth) acrylate or the like. Wherein '1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,2-bis-4(2-hydroxy-3-propene oxide) Propyl phenyl)propane, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, ethylene oxide addition bisphenol A type di(meth)acrylate Bisphenol A type epoxy obtained by ring opening reaction of ethylene oxide addition tetrabromobisphenol A type di(meth)acrylate, bisphenol A diglycidyl ether and (meth)acrylic acid Commercial products of a bifunctional monomer such as di(meth)acrylate or tetrabromobisphenol A epoxy di(meth)acrylate are exemplified by, for example, Biscoat #700, #540 (above is Osaka Organic Chemical Industry Co., Ltd.) Manufactured; Aronix M-208, M210 (above manufactured by East Asia Synthetic Company); NK Ester BPE-100, BPE-200, BPE-500, A-BPE-4, A-BPEF (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) ;Lightacrylate 1,6-HX-A, Lightester BP-4E A, BP-4PA, Epoxyester 3 002M, 3 002 A, 3 000M, 3000A (above is manufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD R-55 1, R -712 (The above is a Japanese chemical Division Manufacturing); BPE-4, BPE-1 0, BR- -19- 200928468 42M (above the first industrial pharmaceutical company); Lypoxy VR-77, VR-60, VR-90, SP-1 506 'SP - 1 5 07, SP-1 509, SP-1 5 63 (The above is manufactured by Showa Polymer Co., Ltd.); Neopol V779, Neopol V779MA (manufactured by Sakamoto Upica Co., Ltd.). Further, among the above polyfunctional monomers, a monomer having three or more ethylenically unsaturated groups (a monomer having three or more functional groups) is exemplified by, for example, stilbene (2-hydroxyethyl) isocyanurate III (A) Acrylate, caprolactone modified ginseng (2-^hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tris(meth)acrylate, epoxy B Alkane (hereinafter referred to as "EO") modified trimethylolpropane tri(meth)acrylate, propylene oxide (hereinafter referred to as "PO") modified trimethylolpropane tri(meth)acrylic acid Ester, bis(trimethylol)propane tetra(meth) acrylate, pentaerythritol tri(meth) acrylate, 2,2,2-cis (meth) propylene decyloxymethyl ethyl phthalate , 2,2,2-paraxyl (meth) propylene methoxymethyl ethyl succinic acid, EO modified tris(propylene decyloxy) isocyanurate, caprolactone modified ginseng - (2 - propylene oxiranyl ethyl) φ isocyanurate, propylene (propylene oxy) isocyanurate, pentaerythritol tetrakis (meth) acrylate, PO modified pentaerythritol IV Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, EO modified dipentaerythritol hexa (meth) acrylate, PO modified dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, bis (trihydroxyl) Methyl) propane tetra(meth)acrylate, propylene propylene oxide ethyl phosphate, and the like. Among them, preferred is EO modified trimethylolpropane tris(methyl)propan-20- 200928468 enoate, ginseng (propylene oxy) isocyanurate, dipentaerythritol hexa(meth)acrylic acid ester. Commercial products of the trifunctional monomer are exemplified by, for example, Aronix M-315, M-3 2 5, M-32 7, TO-75 6 , TO-1 3 82 (manufactured by Toagosei Co., Ltd.), NK Ester TM-4EL, CBX-0, CBX-1N, A-DPH-6H, Α-9300, A-DPH, A-93 00-1 CL, TMPT, TMPT-9EO, ATM-4P, ATM-4E, ATM-35E, AD- TMP, A-TMPT, A-TMPT-3EO, A-TMPT-3PO, A-TMMT, A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Lightester TMP, Lightacrylate TMP-A, TMP-6EO-3A , PE-3A, PE-4A, DPE-6A > BA-134 'TMP-3EO-A (manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 295, 360, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD PET -30, DPHA (manufactured by Nippon Kayaku Co., Ltd.), etc. The component (B) may be used singly or in combination with any of the above monofunctional monomer and the above polyfunctional monomer. Preferably, component (B) contains a plurality of φ functional monomer. In the photocurable resin composition for a coating layer, the compounding ratio of the component (B) is preferably from 100 to 69% by mass based on the total amount of the solid content of the photocurable composition for the coating layer, and is preferably from 15 to 69% by mass. It is 20 to 66% by mass, more preferably 25 to 60% by mass. When the blending ratio is less than 15% by mass, the heat resistance of the cured product is lowered, and when a film-shaped optical waveguide is used in a high-temperature and high-humidity atmosphere, it is difficult to maintain good transfer characteristics and bending durability. On the other hand, when the blending ratio exceeds 69% by mass, the photocurability of the composition is lowered, and it is difficult to form a cured product having a sufficient mechanical property (lower cladding layer, upper cladding layer) - 21 - 200928468 [Ingredient (C )] The component (c) is a photopolymerization initiator which can generate an active species (free radical) which can polymerize the component (A) and the component (B) by light. Light here means infrared, visible, ultraviolet and X-ray, electron beam, alpha ray, beta ray, gamma ray ionizing radiation. The photopolymerization initiator is exemplified by, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, Anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4 , 4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropyl Phenyl)-2- keto-2-methylpropan-1-indole, 2-cyano-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl thioxanthene Ketone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-propan-1-one, 2, 4,6-paraxylmethylbenzhydryldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphorus oxide, and the like. Among them, 1-hydroxycyclohexyl phenyl ketone or the like is preferable from the viewpoint of polymerization rate and solution stability. Commercial products of component (C) are listed, for example, as Irgacure 184, 369, 379, 65 1 , 500, 819, 907, 784, 2959, CGI-1 700, CGI-1750' CGI-1850, CG24-61, Darocur 1116. , 1173 (above is made by Steam Batt Chemical Company); Lucirin ΤΡΟ, LR8 893, LR8970 (above is manufactured by BASF); Yubecryl P36 (manufactured by UCB Corporation-22-200928468). The photoradical polymerization initiator may be used singly or in combination of two or more. In the present invention, a photosensitizer may be used together with the photopolymerization initiator. Examples of the photosensitizer are, for example, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylamine benzoic acid, methyl 4-dimethylaminebenzoate, 4-dimethylamine benzene. Ethyl formate, isoamyl 4-dimethylaminobenzoate, and the like. Commercially available products of the photosensitizer are, for example, Yubecryl P102, 103, 104, and 105 (manufactured by UCB Corporation). ❹ In the photocurable composition for the coating layer, the compounding ratio of the component (C) is 0.1% by mass based on the total solid content of the photocurable composition for the coating layer, and is 0.1 to 10% by mass. Preferably, it is 0.2 to 7 mass%, more preferably 0.5 to 5 mass%. If the above-mentioned blending ratio is less than 0.1% by mass, the hardening may be incomplete, and it is difficult to form a cured product (lower cladding layer, upper cladding layer) having sufficient mechanical properties. Further, when the above compounding ratio exceeds 1% by mass, the photopolymerization initiator may have an adverse effect on the long-term characteristics of the film-shaped optical waveguide. [Optional component] The photocurable resin composition for the coating layer may be formulated with an organic solvent (ingredient (D)) as needed. By formulating an organic solvent, a suitable viscosity can be imparted to form a coating layer having a uniform thickness. The kind of the organic solvent can be appropriately selected within the range not impairing the object and effect of the present invention, but it is preferably a crucible at a pressure of 50 to 200 ° C at atmospheric pressure, and the constituent components can be made uniform. Soluble. -23- 200928468 Preferred examples of the organic solvent are alcohols, ethers, esters and ketones. Preferred compound names for organic solvents are selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethylene glycol dimethyl ether, methyl isobutyl ketone, methyl amyl ketone. At least one solvent of the group consisting of toluene, xylene and methanol. The amount of the organic solvent is preferably from 5 to 500 parts by mass, more preferably from 10 to 300 parts by mass, even more preferably from 20 to 200 parts by mass per 100 parts by mass of the total solid content of the photocurable resin composition for a coating layer. Parts by mass. If the amount is less than 5 parts by mass, the viscosity of the photocurable resin composition may be difficult to adjust. When the amount is more than 500 parts by mass, there is a problem that it is difficult to form a cured product having a sufficient thickness (lower cladding layer, upper cladding layer). Further, the photocurable resin composition for a coating layer preferably contains substantially no ethylene-based polymer (component (E)) having an ethylenically unsaturated group. Moreover, component (E) is a high polymer (polymer) rather than a low polymer (oligomer). In the photocurable resin composition for a coating layer, the blending ratio of the vinyl polymer having an ethylenically unsaturated group is preferably 100% by mass based on the total solid content of the photocurable resin composition for a coating layer. 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, and most preferably 0% by mass. When the amount of the above compounding exceeds 1% by mass, the bending durability may be lowered. Further, the ethylene-based polymer having an ethylenically unsaturated group is a structural unit containing a monomer derived from a vinyl group-containing monomer and/or a (meth)acryl fluorenyl group, and has one or more ethylenic groups in the molecule. Saturated base. Ethylene -24-200928468 The unsaturated group is exemplified by a vinyl group, a (meth) acryl fluorenyl group or the like, but is preferably a (meth) acrylonitrile group. Specific examples of the ethylene-based polymers include 2-hydroxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, methyl (meth)acrylate, and n-butyl (meth)acrylate. After radical polymerization of an ester, styrene, or α-methylstyrene in a solvent in the presence of a catalyst for radical polymerization, the hydroxyl group of the side chain of the obtained copolymer is added to 2-methyl isocyanate. Acrylate methyl ester-derived.

In addition to the above-mentioned components, the photocurable resin composition for the coating layer may be polymerized other than the components (Α) to (D), as long as the properties of the resin composition of the present invention are not impaired. Reactive group compound, or polymer resin (for example, epoxy resin, acrylic resin, polyamide resin, polyamidamine resin, polyurethane resin, polybutadiene tree, polychlorinated Butadiene resin, polyether resin, polyester resin, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, fiber φ resin, fluorine polymer, oxime polymer) Wait. Further, the photocurable resin composition for the coating layer may be formulated with various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a sand compound coupling agent, a coating surface modifier, a thermal polymerization inhibiting agent, and a leveling agent. , surfactant, colorant, storage stabilizer, plasticizer, slip agent, chelating agent, inorganic particles, anti-aging agent, wettability improver, antistatic agent, and the like. The photocurable resin composition for the coating layer can be mixed and stirred in accordance with a usual method. Next, a photocurable resin composition for an intermediate layer will be described. -25- 200928468 The photocurable resin composition for an intermediate layer comprises (a) a (meth)acrylic acid urethane oligomer, (b) a reactive diluent monomer, and (c) a photopolymerization initiator; e) a vinyl-based polymer having an ethylenically unsaturated group, and other optional components formulated as needed. Each component will be described below. .

[Component (a)] I Component (a) is a (meth)acrylic acid urethane oligomer. The above (meth)acrylic acid urethane oligomer is exemplified by the same component (A) as the photocurable composition for the coating layer. Further, as the (meth)acrylic acid urethane oligomer of the component (a), it is preferable to use the same (meth)acrylic acid urethane oligomer as the component (A) in terms of economy and manufacturing management. Polymer. In the photocurable resin composition for an intermediate layer, the compounding ratio of the component (a) is 1 〇〇 φ% by mass, preferably 5 to 80% by mass based on the total solid content of the photocurable resin composition for the intermediate layer. More preferably, it is 10 to 75% by mass, and preferably 10 to 70% by mass. When the blending ratio is less than 5% by mass, the Young's modulus of the intermediate coating layer obtained by curing the composition is increased, and it is difficult to form a film-shaped optical waveguide having sufficient bending durability. On the other hand, when the compounding ratio exceeds 80% by mass, the viscosity of the composition becomes small, so that it is difficult to form a cured product (intermediate coating layer) having a uniform thickness. [Component (b)] Component (b) is a reactive diluent monomer. -26- 200928468 The reactive diluent monomer may be the same as the component (B) of the photocurable composition for a coating layer. Further, as the reactive diluent monomer of the component (b), it is preferable to use the same reactive diluent monomer as the component (B) economically and administratively. In the photocurable resin composition for an intermediate layer, the blending ratio of the component (b) is 100% by mass, preferably 1 to 40% by mass, based on the total amount of the solid content of the photocurable resin composition for the intermediate layer. 〇' is preferably 3 to 30% by mass 'and preferably 5 to 25% by mass. By setting the blending ratio of the component (b) within the above range, it is possible to further improve the bending durability. When the blending ratio of the component (b) exceeds 40% by mass, the viscosity of the composition becomes small, so that it is difficult to form a cured product (intermediate coating layer) having a uniform thickness. [Component (c)] Component (C) is a photopolymerization initiator. The photopolymerization initiator is the same as the component (C) of the photocurable group φ for the coating layer. In the photocurable resin composition for an intermediate layer, the compounding ratio of the component (C) is preferably 100% by mass, preferably 0% by mass, based on the total solid content of the photocurable resin composition for the intermediate layer. The mass% is more preferably 0.2 to 5% by mass. When the above-mentioned blending ratio is less than 0.1% by mass, the hardening cannot be sufficiently performed, and there is a problem in the transmission characteristics of the optical waveguide. On the other hand, when the above compounding ratio exceeds 1% by mass, the photopolymerization initiator has a possibility of adversely affecting long-term transport characteristics. -27- 200928468 [Component (e)] Component (e) is a vinyl polymer having an ethylenically unsaturated group. The component (e) (ethylene-based polymer having an ethylenically unsaturated group) can be polymerized with the above component (a) or component (b), and the component (e) can be blended to impart photocurability to the intermediate layer. The resin composition has a moderate viscosity and good coatability. In addition, component (e) is a high polymer (polymer) rather than a low polymer (oligomer). The ethylene-based polymer having an ethylenically unsaturated group (hereinafter referred to as an ethylene-based polymer) contains a structural unit derived from a vinyl-containing monomer and/or a (meth)acryl-containing monomer, and is intramolecular. A person having more than one ethylenically unsaturated group. The ethylenically unsaturated group is exemplified by a vinyl group, a (meth) acryl fluorenyl group or the like, but is preferably a (meth) acrylonitrile group. Specific examples of the above-mentioned ethylene-based polymer include a polymer (for example, a random copolymer) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2). R1 CH2—C—— (1) 200928468 (wherein '...and R2 are each independently a hydrogen atom or a methyl group, and R3 is a (meth)propene' X is a divalent organic group' Y is not polymerizable Organic base). A preferred example of the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (3).

[Chemical 2] R1

W (3) Ο

I c=o N——Η Z——R3 (wherein R1 is a hydrogen atom or a methyl group, R3 is a (meth)acryloyl group, W and ζ each ·· stomach ^舄 single bond or divalent organic group ). In the above, the W (divalent organic group) in the formula (3) is exemplified by the structure shown in the following (4) or the phenyl group. [化3]

I c = o I (4) 〇 (wherein R 4 is a methylene group or a C 2 to 8 alkyl group). -29- 200928468 An example of Z (divalent organic group) in the formula (3) is exemplified by _(cH2)n-〇- (wherein η is an integer of 1 to 8). Examples of the oxime in the formula (2) are a structure represented by the following formula (5), a phenyl group, a cyclic guanamine group, a pyridyl group or the like. 【化4】

I c = o (wherein R 5 is a group having a linear, branched or cyclic carbon chain having 1 to 20 carbon atoms). The weight average molecular weight of the above vinyl polymer in terms of polystyrene is preferably from 5,000 to 100, more preferably from 8,000 to 70,000, most preferably from 10,000 to 5,000. If the enthalpy does not reach 5,000, the viscosity of the composition becomes small φ 'There is a disadvantage that an appropriate film thickness cannot be obtained, and when the enthalpy exceeds 100,000, the viscosity of the composition is too large, and there is a disadvantage that the coating property is poor. . The method for producing the vinyl polymer is, for example, a (e-Ι) radical polymerizable compound having a hydroxyl group and a component (e-2) (corresponding to the radical polymerizable compound of the formula (2)) in a solvent. After radical polymerization, a method of adding (e-3) (meth)acrylonitrile-based isocyanate to the hydroxyl group of the side chain of the obtained copolymer is added. The compounds (e-Ι) to (e-3) used in the method are explained. The compound (e-fluorene) (radical polymerizable compound having a hydroxyl group) is used in -30-200928468 to react a hydroxyl group in the compound with an isocyanate group (-N = C = 0) in the compound (e-3), A constituent unit having a side bond moiety containing a urethane bond (-NH-COO-) and a (meth)propidyl group derived from the compound (e-3) is introduced into the component (e). Examples of the compound (e-oxime) are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxyl group (meth)acrylate. Ester, 4-hydroxycyclohexyl (meth)acrylate, and the like. _ The compound (e-Ι) may be used alone or in combination of two or more.

The content of the structural unit derived from the compound (e-1) in the ethylene-based polymer is preferably from 3 to 80% by mass, more preferably from 7 to 60% by mass, and most preferably from 10 to 40% by mass. When the content rate is less than 3% by mass, the hardening is incompletely deteriorated. When the content ratio exceeds 80% by mass, the refractive index adjustment may be difficult. The compound (e-2) (corresponding to the compound of the structure of the formula (2)) is mainly used for moderately controlling the mechanical properties and refractive index of the (meth)acrylic polymer containing an unsaturated group. Examples of the compound (e-2) are methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. (meth)acrylic acid alkyl esters such as dibutyl ester and (butyl) (meth)acrylate; (meth)acrylic acid (di) pentene ester (meth)acrylate, (meth)acrylic acid such as cyclohexyl (meth)acrylate Esters with cyclic hydrocarbon compounds; phenyl (meth) acrylate, benzyl (meth) acrylate, o-phenyl phenol glycidyl ether (meth) acrylate, 4-(1-methyl-1- Phenylethyl)phenoxyethyl acrylate, p-cumylphenoxyethylene glycol (meth) acrylate, etc. (methyl) propyl-31 - 200928468 aryl aryl esters; tribromophenol Ethoxy (meth) acrylate, 2,2,2-trifluoromethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H (meth) acrylate , 1H, 5H-octafluoropentyl ester; halogenated (meth) acrylates such as perfluorooctyl ethyl (meth)acrylate; styrene, α-methylstyrene, m-methylphenyl a conjugated diene such as a olefin, p-methyl styrene, vinyl toluene or p-methoxy styrene; 1,3-butadiene, isoprene, 1,4-dimethylbutane a conjugated diene such as an olefin; a polymerizable compound containing a nitrile group such as acrylonitrile or methacrylonitrile; a polymerizable compound containing a guanamine bond such as acrylamide or methacrylamide; or a fatty acid such as vinyl acetate. Vinyl esters, etc. Among them, dicyclopentenyl (meth)acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 4-(1-methyl-1-phenylethyl acrylate) Phenoxyethyl ester, α-methylstyrene and the like are suitable. The compound (e-2) may be used alone or in combination of two or more. The content of the structural unit derived from the compound ❹ (e-2) in the (meth)acrylic polymer containing an unsaturated group is preferably from 15 to 9 2% by mass, more preferably from 2 5 to 84% by mass, most preferably Good is 35~78% by mass. When the content is less than 15% by mass, the refractive index adjustment may become difficult. When the content is more than 92% by mass, it is easy to be insufficiently hardened. Examples of the compound (e-3) (isocyanate having a (meth) acrylonitrile group) are exemplified by 2-methacryloxyethyl isocyanate, N-methylpropenyl isocyanate, and methacryloxymethyl group. Isocyanate, 2-propylene methoxyethyl isocyanate, N-propylene decyl isocyanate, propylene methoxymethyl isocyanate, and the like. -32- 200928468 The content of the structural unit derived from the compound (e-3) in the vinyl polymer is preferably from 5 to 8 % by mass, more preferably from 9 to 60 % by mass. /. It is preferably I2 to 45% by mass. When the content is less than 5% by mass, it tends to become insufficiently hardened. When the content is more than 80% by mass, the refractive index adjustment may be difficult. The vinyl polymer may contain constituent units other than the constituent units represented by the general formulae (1) and (2). Examples of the compound for introducing such a constituent unit (hereinafter referred to as the compound (e-4) are dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate. a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene chloride. The content of the structural unit derived from the compound (e-4) in the vinyl polymer is preferably from 0 to 20% by mass, more preferably from 0 to 10% by mass. In the production process of the ethylene-based polymer, various additives such as a thermal polymerization inhibitor, a storage stabilizer, and a curing catalyst may be added during the addition reaction of the compound (e-2). The thermal polymerization inhibitor is for suppressing heat. Formulated by polymerization. Examples of thermal polymerization inhibitors are, for example, pyrogallol, benzoquinone, hydroquinone, methyl blue, tert-butylcatechol, monobenzyl ether, methoxyphenol, pentyl hydrazine. , pentamidine oxyhydroquinone, n-butyl phenol, phenol, hydroquinone monopropyl ether, etc. Examples of storage stabilizers are listed as 2,6-di-t-butyl-p-cresol, benzoquinone, p- Cresol, p-xylenol, phenyl-α-naphthylamine, etc. Examples of hardening catalysts are dibutyltin dilaurate and dilaurin Dioctyltin, dibutyltin dioleate, dibutyltin diacetate, titanium tetramethoxide, titanium tetraethoxide, etc. -33- 200928468 Total amount of these various additives relative to compounds (el) to (e -3) The total amount is 1 part by mass, usually 10 parts by mass or less, preferably 5 parts by mass or less. In the production of a vinyl polymer, it can be used for the compound (e-oxime) and a compound which is used as needed. The solvent in the radical polymerization of (e-2) and the compound (e-4) is, for example, an alcohol such as methanol, ethanol, ethylene glycol, diethylene glycol or propylene glycol; or a cyclic ether such as tetrahydrofuran or dioxane. ; ethylene glycol monomethyl ether _ 'ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Alkyl ethers of polyvalent alcohols such as ether, diethylene glycol dimethyl _, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether ; ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetic acid _, propylene glycol monomethyl ether acetate, etc. Alkyl ether acetates of valent alcohols; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone and diacetone; ethyl acetate, butyl acetate, ethyl lactate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 Ethyl methacrylate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate An ester such as ester, ethyl 3-ethoxypropionate, or methyl 3-ethoxypropionate. Among them, cyclic ethers, alkyl ethers of polyvalent alcohols, alkyl ether acetates of polyvalent alcohols Esters, ketones, esters, etc. are preferred. The glass transition temperature of the vinyl polymer is preferably from 20 ° C to 150 ° C & At this time, the glass transition temperature is usually defined as the enthalpy measured using the differential scanning calorie -34-200928468 (DSC). When the temperature is less than 20 °C, it is difficult to form a cured product (intermediate coating layer), or there is a disadvantage that adhesion occurs to deteriorate the workability when laminating a dry film. On the other hand, when the temperature exceeds 150 °C, the hard (intermediate coating) becomes hard, and embrittlement and bending durability are lowered. In the photocurable resin composition for an intermediate layer, the compounding ratio of the component (e) is from 100% by mass to 15% by mass, preferably from 20% to 75% by mass, based on the solid content of the photocurable resin composition for the intermediate layer. 70% by mass, preferably 30 to 70% by mass. When the above-mentioned blending ratio is less than 15% by mass, the viscosity of the composition becomes small, and the coatability may deteriorate. On the other hand, when the above-mentioned blending ratio exceeds 75 mass%, the cured product (intermediate coating layer) is too hard, which causes embrittlement and a decrease in bending durability. [Optional component] The organic solvent (component (d)) can be formulated as needed in the intermediate layer photocurable resin composition. By formulating an organic solvent, an appropriate viscosity can be imparted to form an intermediate coating layer having a uniform thickness. The organic solvent is the same as the component (D) of the photocurable composition for the coating layer. The amount of the organic solvent to be added is preferably from 5 to 500 parts by mass, more preferably from 10 to 30,000 parts by mass, even more preferably from 20 parts by mass to the solid content of the photocurable resin composition for the intermediate layer. 200 parts by mass. When the amount of the above-mentioned compounding amount is less than 5 parts by mass, the viscosity adjustment of the photocurable resin composition becomes difficult. If the amount of the above compounding exceeds 500 parts by mass, there is a problem that it is difficult to form an intermediate coating layer having a sufficient thickness. -35- 200928468 In addition to the above component (d) (organic solvent), the intermediate layer photocurable resin composition may be polymerized in addition to the above components (a), (b), and (d). A compound of a reactive group, a polymer resin, various additives, and the like. Specific examples of the polymer resin and the additive are the same as those exemplified as the optional components of the photocurable resin composition for a coating layer. The photocurable resin composition for preparing the intermediate layer can be mixed and stirred in accordance with a usual method. Next, a photocurable resin composition for forming a core portion of a film-shaped optical waveguide of the present invention (hereinafter referred to as a photocurable resin composition for a core) will be described as an example of a suitable photocurable resin composition for a core. (1) an ethylene-based polymer having an ethylenically unsaturated group, (2) a (meth)acrylic acid urethane oligomer, (3) a reactive diluent monomer, and (4) a photopolymerization A photohardenable composition of the initiator. [Component (1)] Component (1) is a vinyl polymer having an ethylenically unsaturated group. The ethylene-based polymer having an ethylenically unsaturated group is the same as the component (e) of the photocurable resin composition for an intermediate layer. [Component (2)] The component (2) is a (meth)acrylic acid urethane oligomer. The (meth)acrylic acid urethane oligomer is the same as the component (A) of the photocurable resin composition for coating of the above-mentioned package -36-200928468. In the photocurable resin composition for a core, the compounding amount of the component (2) is preferably from 10 to 100 parts by mass, more preferably from 20 to 80 parts by mass, more preferably from 35 to 80 parts by mass, based on 100 parts by mass of the component (?). 70 parts by mass. When the amount of the above-mentioned compounding is less than 10 parts by mass, the cured product (core portion) of the photocurable composition layer cannot obtain sufficient bending resistance. On the other hand, when the above compounding amount exceeds 1 part by mass, the compatibility with the component (1) is deteriorated, and film roughness occurs on the surface of the core portion, and sufficient transparency cannot be obtained. [Component (3)] Component (3) is a reactive diluent monomer. The reactive diluent monomer is the same as the component (B) of the photocurable composition for the coating layer. In the photocurable resin composition for a core, the amount of the component (3) is preferably 5 to 100 parts by mass, more preferably 1 to 7 〇 φ by mass, per part by mass of the component (1). It is preferably 20 to 50 parts by mass. When the amount of the above-mentioned compounding is less than 5 parts by mass, the shape of the waveguide may be deteriorated when the film-shaped optical waveguide is formed. On the other hand, when the amount is more than 100 parts by mass, the compatibility with the component (1) is deteriorated, and a rough film is formed on the surface of the cured product (core portion) of the photocurable resin composition. [Component (4)] Component (4) is a photopolymerization initiator. The photopolymerization initiator is the same as the component (C) of the above-mentioned coating layer photocurable group -37-200928468. In the photocurable resin composition for a core, the compounding ratio of the component (4) is 100 parts by mass or less, preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, based on the total amount of the photocurable resin composition for the core. 5 parts by mass. When the above compounding ratio is less than 0.1 part by mass, the hardening cannot be sufficiently performed, and there is a problem that the transfer characteristics of the film-shaped optical waveguide are problematic. On the other hand, when the above compounding ratio exceeds 10% by mass, there is a possibility that the long-term transport characteristics of the photopolymerization initiator are adversely affected. [Optional component] The photocurable resin composition for a core may contain an organic solvent (ingredient (5)) as needed. The proper viscosity can be imparted by formulating an organic solvent. The organic solvent is the same as the component (D) of the photocurable composition for the coating layer. In the photocurable resin composition for a core layer, the ratio of φ of the component (5) (organic solvent) is 100% by mass, preferably 5 to 80% by mass, based on the total amount of the photocurable resin composition for the core. More preferably, it is 10 to 60% by mass, preferably 15 to 55% by mass. When the blending ratio is less than 5% by mass, the viscosity of the photocurable resin composition is difficult to adjust. On the other hand, if the above-mentioned compounding ratio exceeds 80% by mass, there is a problem that it is difficult to form a film-shaped optical waveguide having a sufficient thickness. In addition, the photocurable resin composition for a core may contain various additives as needed, such as an antioxidant, an ultraviolet absorber, a light stabilizer, a decane coupling agent, a coating surface modifier, a thermal polymerization inhibitor, a leveling agent, and an interfacial activity-38. - 200928468 Agents, colorants, storage stabilizers, plasticizers, slip agents, chelating agents, inorganic particles, anti-aging agents, wettability improvers, antistatic agents, etc. The photocurable resin composition for blending the core can be mixed and stirred in accordance with a usual method. Next, an example of a film-shaped optical waveguide of the present invention and a method of manufacturing the same will be described with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an example of a film-shaped optical waveguide of the present invention.

Fig. 4 is a flow chart showing an example of a method of manufacturing the film-shaped optical waveguide of the present invention. [Structure of Film-Shaped Optical Waveguide] In FIG. 1, the film-shaped optical waveguide 1 includes a lower cladding layer 15, a core portion 22 formed on the lower cladding layer 15, and a lower cladding layer 15 on the core portion. The side of the 22 is formed as an intermediate φ cladding layer 36 having substantially the same thickness as the core portion 22, the optical waveguide body formed by forming the upper cladding layer 33 on the core portion 22 and the intermediate cladding layer 36, and The support films 2, 3 above and below the optical waveguide body. The optical waveguide body has a lower layer composed of a lower cladding layer 15, an intermediate layer composed of a core portion 22 and an intermediate cladding layer 36, and a three-layer structure in which an upper cladding layer 33 constitutes an upper layer. The lower cladding layer 15 is laminated and formed on the support film 2, and a core portion 22 having a specific width and an intermediate cladding layer 36 are formed on the lower cladding layer 15. The core portion 22 and the intermediate cladding layer 36 are laminated on top of each other and form an upper portion - 39 - 200928468 cladding layer 33, and a support film 3 is disposed on the upper cladding layer 33. Further, the core portion 22 is embedded in the lower cladding layer 15, the intermediate cladding layer 36, and the upper cladding layer 33 which form the outer surface of the optical waveguide body. The intermediate cladding layer 36 is layered and formed on the lower cladding layer 15 (except for the region in which the core portion 22 is formed) and has almost the same height as the core portion 22. The thickness of the lower cladding layer 15, the core portion 22, the intermediate cladding layer 36, and the upper cladding layer 33 in the film-shaped optical waveguide is not particularly limited, but may be set such that, for example, the thickness of the lower cladding layer 15 is 1~ 2 00 μηη, the core portion 22 has a thickness of 3 to 2 0 0 μιη, the intermediate cladding layer has a thickness of 3 to 200 μm, and the upper cladding layer 33 has a thickness of 00 μm. The width of the core portion is not particularly limited, but may be, for example, 1 to 200 μm. The lower cladding layer 15 and the upper cladding layer 33 are composed of a cured product of the coating layer with a photohardenable resin composition. The intermediate coating layer 36 is composed of a cured product of the above-mentioned intermediate layer photocurable resin composition. The core portion 22 is preferably composed of a cured product of the above-mentioned core photocurable resin composition. Further, at least one of the lower cladding layer 15, the core portion 22, the intermediate cladding layer 36, and the upper cladding layer 33 is formed using a dry film described later. That is, at least one of the portions is formed by hardening a layer formed of an uncured photocurable resin composition in the dry film. Preferably, at least the intermediate coating layer 36 is formed using a dry film. The refractive index of the core portion 22 must be greater than the refractive index of either of the lower cladding layer 15, the intermediate cladding layer 36, and the upper cladding layer 33. For example, the refractive index of the core portion 22 is 1.420 to 1.650 with respect to the wavelength of 400 to 1, 600 nm, and the refractive index of the lower cladding layer 15, the intermediate cladding layer 36, and the upper cladding layer 33-40-200928468 is 1.400 to 1.648, and the refractive index of the core portion 22 is preferably at least 0.1% greater than the refractive index of any of the three layers of the cladding layers 14, 33, and 36. The refractive index difference Δ between the portions of the lower cladding layer 15, the intermediate cladding layer 36, and the upper cladding layer 33 and the core portion 22 is preferably at least 1%. The specific refractive index difference Δ is expressed by the following equation: Δ = (n1 - n2) / n1 ❹ where η1 is the refractive index of the core portion 22, and η2 is the cladding layer (the lower cladding layer 15 and the intermediate cladding layer 3 6 The refractive index of the upper cladding layer 3 3 ). Thus, since light can be confined inside the core portion 22, a good optical waveguide can be formed. The cladding layer (the lower cladding layer 15, the intermediate cladding layer 36, and the upper cladding layer 33) has high transparency. Specifically, when the coating layer has a thickness of ΙΟμπι, it has a transmittance of φ of 80% or more, preferably 90% or more, for light having a wavelength of 405 nm. By providing the cladding layer with high transparency, a light-emitting element such as a surface-emitting laser or a light-receiving element such as a light-emitting diode is bonded to the lower surface of the thin film optical waveguide to form an interface for electrical/optical signal conversion. The top view of the thin film optical waveguide is correctly aligned with the position of the light-emitting element or the light-receiving element and the position of the core portion in the film-shaped optical waveguide. In addition, by making the cladding layer have high transparency, it can exhibit high transmittance for light in the wavelength region used in the optical signal, and light loss when the optical signal from the light-emitting element passes through the cladding layer to reach the core portion. Minimal 'and -41 - 200928468 minimizes the loss of light when the optical signal from the core passes through the cladding to the light-receiving element. [Dry Film] Next, a dry film used in the film-shaped optical waveguide of the present invention will be described. In the present specification, the term "dry film" is defined as a layer (not a liquid material; for example, a dried product) composed of an uncured photocurable resin composition, and a support for the photocurable resin. The base film of the layer of matter. That is, the dry film may be composed of (i) a base film and a photocurable resin composition as long as it has a layer composed of an uncured photocurable resin composition and a base film for supporting the layer. a laminate of a layer (unhardened layer) or a layer composed of a base film and a cured product of a photocurable resin composition (hardened layer) and a layer composed of a photocurable resin composition (not a laminate of hardened layers). Specific examples of the above dry film are shown below. Examples of the dry film of the above (i) are (a) a laminate of a layer (unhardened layer) composed of a base film and a photocurable resin composition for a lower cladding layer, and (b) a base film and a core. A laminate of a layer (unhardened layer) composed of a photocurable resin composition, and (c) a laminate of a layer (unhardened layer) composed of a base film and a photocurable resin composition for an intermediate coating layer. (d) A laminate of a layer (unhardened layer) composed of a base film and a photocurable resin composition for the upper cladding layer. Examples of the dry film of the above (Π) are, for example, (e) a base film and a lower coating layer (a layer composed of a cured product of a photocurable resin composition for a lower cladding layer) and an intermediate coating layer. Photocurable resin-42- 200928468 A laminate of a layer (unhardened layer) composed of a composition, (a base film and a lower cover layer (hardened by a photocurable resin composition for a lower cladding layer) a layer of a layer (unhardened layer) composed of a photocurable resin composition for a core, (g) a base film and an upper cladding layer (photocurable resin composition for the upper cladding layer) A laminate of a layer of a cured material and a layer of an optically curable resin for an intermediate coating layer (unhardened layer). Alternatively, the dry film may be used (h) in the above (a) to (a) In any of the laminates of g), a laminate obtained by laminating a cover film on a layer composed of an uncured photocurable resin composition. In the method for producing a film-shaped optical waveguide of the present invention, as described above, preferably At least the intermediate cladding layer 36 is formed using a dry film The intermediate coating layer may be formed by using the above-described laminate (the laminate of the above (g) is preferably formed. [Method for Producing Film-Shaped Optical Waveguide] The method for producing the film-shaped optical waveguide 1 includes preparing to use the intermediate coating. The step of forming the dry film 30 for the layer 36 and the upper cladding layer 33; the step of forming the lower cladding layer 15; and the step of forming the core portion 22; and forming the intermediate cladding layer 36 and the upper package using the dry film 30 The step of coating the layer 3 3. Further, the composition for forming the lower cladding layer 15, the core portion 22, the intermediate cladding layer 36, and the upper cladding layer 33 of the film-shaped optical waveguide is convenient for See, respectively, the composition for the upper and lower layers, the composition for the core, the composition for the intermediate layer, and the composition for the upper layer. -43- 200928468 (1) Preparation of the composition for the underlayer, composition for the core, intermediate layer The composition of the composition and the composition of the upper layer are set so that the refractive index relationship of each of the lower cladding layer 15, the core portion 22, the intermediate cladding layer 36, and the upper cladding layer 33 satisfies the film-shaped optical waveguide. Requirements. Specifically, the allocation is folded. The difference in rate is three or four photocurable compositions of an appropriate size, wherein the photocurable composition of the cured film imparting the highest refractive index is used as the core group, and the other photocurable composition is used as the lower layer. The composition for the composition, the composition for the intermediate layer, and the composition for the upper layer. Further, the composition for the lower layer and the composition for the upper layer are preferably the same photocurable composition (light for the cladding layer) in terms of economy and management. (2) Step of preparing a dry film for forming an intermediate coating layer and an upper cladding layer. Preparation of a base film 31 and an upper cladding layer 33 (a layer composed of a cured product of the composition for an upper layer) And the step of forming the dry film 30 of the laminate of the layer 34 of φ from the composition of the uncured intermediate layer. The dry film 31 is preferably flexible and used for curing the photocurable resin composition. The light has a high permeability. The base film is exemplified by a polyethylene terephthalate film or a polyethylene naphthalate film. The thickness of the base film is not particularly limited and may be, for example, 10 to 200 μm. By using such a base film, in the step (5) to be described later, the light from the side of the base film 31 can be irradiated to harden the layer 34 composed of the uncured intermediate layer composition, and the base film 31 can be cured. Further, it is directly used as the support film 3 of the film-shaped optical waveguide. Further, in the dry film 30, a cover film 35 may be provided on the layer 34 made of the composition for the intermediate layer as needed. The cover film is exemplified by a polyethylene film, a polypropylene film, a polyethylene terephthalate film or the like. The thickness of the cover film is not particularly limited, but may be, for example, 5 to 100 μm. The dry film 30 is obtained, for example, as follows. First, the composition for the upper layer is applied onto the base film 31, and dried or pre-baked as necessary to form the film 32 for the upper layer ((a) in Fig. 3). Next, the upper layer film 3 2 is irradiated with light to harden it to form a hardening layer.

The upper cladding layer 33 of the D body ((b) in Fig. 3). Next, a composition for the intermediate layer is applied on the upper cladding layer 33, and the solvent is volatilized by drying or prebaking, thereby forming a layer 34 composed of the composition of the uncured intermediate layer (in FIG. 3 ( c)). The dry film 30 ((d) in Fig. 3) is obtained by providing the cover film 35 on the layer 34 composed of the composition of the uncured intermediate layer, as the case may be. The method of applying the photocurable resin composition (the composition for the upper layer and the composition for the intermediate layer) is a spin coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a curtain coating method, and a gravure method. Printing method, screen printing method or inkjet method.

The temperature at which the composition for drying the upper layer is dried or pre-baked is, for example, 50 to 200 ° C. The amount of light irradiation when the coating layer is formed is not particularly limited, but preferably has a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW/cm 2 . The light is irradiated and exposed to an exposure amount of 10 to 5,000 mJ/cm 2 . As the type of the irradiation light, visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, or γ-ray can be used, but ultraviolet light is preferable. Photographs -45- 200928468 The shooting device is preferably used such as high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, excimer laser lamps, and the like. Further, in the formation of the upper cladding layer, it is preferred to illuminate the entire surface of the upper layer film 32 to harden the whole. Further, after the exposure, the entire upper cladding layer 33 is sufficiently cured, and then it is preferably subjected to heat treatment (post-baking). The heating condition varies depending on the composition of the photocurable resin composition, the type of the additive, etc., but usually the heating temperature is 30 to 300 ° C, preferably 50 to 200 ° C, and the heating time is 5 minutes to 72. hour. The intermediate layer composition is dried or pre-baked for the purpose of volatilizing the organic solvent. The temperature condition at this time is preferably from 30 to 15 ° C, more preferably from 5 0 to 140. (:: The amount of the organic solvent remaining in the layer 34 composed of the composition for the intermediate layer after drying, and the photocurable resin composition after volatilization with the organic solvent is 100% by mass, preferably 20% by mass or less. The thickness of the layer 34 composed of the composition for hardening the intermediate layer is usually φ 1 to 200 μ*». Further, the thickness of the layer 34 composed of the composition of the uncured intermediate layer is relatively good with respect to the sound of the core portion 22. The thickness of the layer 34 composed of the composition for the uncured intermediate layer is 1 to 1.2 times the height of the core portion 22, and the dryness can be improved in the step (5) to be described later. The workability when the film 3 is formed into the intermediate cladding layer 36 can further improve the shape accuracy, transfer characteristics, and the like of the finally obtained film-shaped optical waveguide. (3) The lower cladding layer is formed on the support film 2 The step of forming the lower cladding layer 15. -46- 200928468 Specifically, 'coating the composition for the lower layer on the surface of the support film 2' and drying or pre-baking as needed to form the film 14 for the lower layer (Fig. 4 (a)). Next, the film for the lower layer is irradiated with light 1 4 to harden it to form a lower cladding layer 15 of the hardened body ((b) in Fig. 4). Further, it is preferable to irradiate the entire surface of the coating film with light to make it harden in its entirety in the formation of the lower cladding layer 15. Further, after the exposure, it is preferably further subjected to heat treatment (post-baking) to sufficiently cure the coating film. _ As for the support film 2, it is preferably flexible and used for curing of the photocurable resin composition. The light having high permeability is exemplified by a polyethylene terephthalate film, a polyethylene naphthalate film, etc. The thickness of the support film is not particularly limited, but may be, for example, 10 ~200μιη ° In the step of forming the lower cladding layer, the coating method of the composition, the amount of light irradiation, the type, and the irradiation device of light (ultraviolet rays), the conditions of prebaking or postbaking, etc. are the same as the above steps ( 2) The upper cladding layer is formed in the same strip ρ. Alternatively, the lower cladding layer 15 may be formed using a dry film. In this case, a dry film 10 prepared in advance (from the base film 11 and the uncured lower layer) is used. a laminate of layers 13 composed of a composition Referring to FIG. 2(b))', the lower cladding layer 15 is formed by irradiating the layer 13 composed of the composition of the uncured lower layer with light to form a lower cladding layer 15. The base film 11 can directly become a film-shaped optical waveguide. The support film 2. The dry film 1 is, for example, coated on the underlying film crucible with the composition 12 for the lower layer ((a) in Fig. 2), and dried or prebaked to volatilize the organic solvent by -47- 200928468 is formed by forming a layer 13 composed of a composition of an uncured lower layer ((b) in Fig. 2). The dry film 10 can be disposed on the layer 13 composed of the composition of the uncured lower layer as needed. The cover film (not shown in the figure as the base film or the cover film may be the same as the base film or the cover film in the dry film 30 of the above step (2). The coating method, drying or prebaking conditions of the lower layer composition are the same as those of the intermediate layer composition in the above step (2). The layer 13 composed of the composition for the uncured lower layer is the same as the film 14 for the lower layer, and may be dried or pre-baked as needed, post-baked after exposure, or the like. (4) Step of forming the core portion A step of forming the core portion 22 on the surface of the lower cladding layer 15. Specifically, as shown in (c) of Fig. 4, a core composition is coated on the surface of the lower cladding layer 15, and dried or pre-baked as necessary to form a film 21 for the core. Subsequently, as shown in (d) of Fig. 4, for the upper surface of the core film 21, the light 5 is irradiated (exposed) according to a predetermined pattern, for example, through a mask 4 having a predetermined straight line pattern. According to this, in the core film 21, since only the portion to be irradiated is hardened, the unhardened portion other than the portion can be removed by the developing process, thereby coating the lower portion as shown in (e) of FIG. A core portion 22 composed of a patterned cured film is formed on the layer 15. The method of illuminating by a predetermined pattern in this step is not limited to the method of using the photomask 4 composed of the light transmitting portion and the opaque portion, and any of the methods a to c shown below may be employed. -48- 200928468 a_ A method of forming a reticle image of a light-transmitting region and an opaque region by electro-optical means by a predetermined pattern using the same principle as that of a liquid crystal display device. b. A method of illuminating a light guiding member that bundles a plurality of optical fibers with respect to an optical fiber corresponding to a predetermined pattern in the light guiding member. c. A method of scanning a photosensitive resin composition by laser light or by condensing light obtained by a concentrating optical system such as a lens or a mirror. The details of the development processing in this step are as follows.

The D development process is subjected to pattern exposure by a predetermined pattern, and for the selectively hardened film, the difference in solubility between the hardened portion and the uncured portion is utilized, and the developer is used to remove only the uncured portion. That is, after the pattern is exposed, the unhardened portion is removed, and the hardened portion is left, resulting in the formation of the core portion. As the developing liquid, a general organic solvent used in the developing treatment or a dilute alkaline aqueous solution can be used. When the photocurable resin composition for forming a core is used as the composition for a core, it is possible to perform development processing by a dilute alkaline aqueous solution which is excellent in environmental safety. Examples of the basic compound for preparing a dilute alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and di-n-butyl. Propylamine, triethylamine, methyldiethylamine, N-methylpyrrolidone, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-decane, and the like. Among them, tetramethylammonium hydroxide (TMAH), sodium hydroxide and the like are suitable. -49- 200928468 The concentration of the basic compound in the alkaline aqueous solution varies depending on the type of the basic compound to be used, but when it is an organic base, it is preferably 0.05 to 10% by mass. /. , preferably 0.1 to 7 mass%. For example, when tetramethylammonium hydroxide (TMAH) is used, the concentration is preferably from 5% to 2.5% by mass. Further, it is also preferred to appropriately add a water-soluble organic solvent such as methanol or ethanol or a surfactant as the developer liquid to the dilute alkaline aqueous solution. Further, the development time is usually 30 to 600 seconds, and as a development method, a conventional method such as a liquid overflow method, a dipping method, or a leaching development method can be used. Subsequently, 〇

The running water is washed, for example, for 30 to 90 seconds, and air-dried by compressed air or compressed nitrogen gas to remove moisture on the surface, thereby forming a patterned hardened body. Then, a heating means such as a plate or an oven may be heated, and post-baking treatment is performed at a temperature of, for example, 30 to 300 ° C for 5 to 600 minutes, and the composition in the forming step of forming the core portion of the core portion 22 is sufficiently hardened. Conditions such as the coating method, the amount of irradiation of light, the type, and the irradiation device of light (ultraviolet rays) are the same as those of the upper cladding layer of φ in the above step (2). Also, the core portion 22 can be formed using a dry film. In this case, a dry film prepared in advance (including a base film, a layer formed of an uncured core composition, and a dry film of a cover film as needed) is used on the lower cladding layer 15 so as to be The hardened core is laminated to peel off the dry film of the cover film in a manner opposite to the layer formed by the composition. Next, the layer formed of the core composition is subjected to light irradiation by a predetermined pattern, and the uncured portion is subjected to development processing and removed, whereby a patterned cured film is formed on the lower cladding layer 15. The core portion 22 is formed. -50- 200928468 The base film or the cover film may be the same as the base film or the cover film in the dry film 30 in the above step (2). The layer formed of the uncured core composition can be dried or pre-baked, exposed after exposure, or the like, as needed, similarly to the core film 21. (5) The intermediate coating layer and the coating layer are formed by using the dry film 30 (the base film 31, the coating layer 33, and the composition for the uncured intermediate layer) prepared in the above step (2). The laminate of layer 34) forms the intermediate cladding layer 36 and the cladding layer 33 described above. Specifically, on the lower cladding layer 15 and the core portion 22, the dry film 30 is laminated such that the layers 34 made of the composition for the uncured intermediate layer are opposed to each other ((〇) in Fig. 4, The core portion 22 is bonded to the above-mentioned coating layer 33 ((g) in Fig. 4). Then, the layer 34 formed of the composition for the intermediate layer is hardened to the intermediate cladding layer 36 by light irradiation. ((h) in Fig. 4), the film-shaped optical waveguide 1 is obtained. When the dry film 30 has the cover film 35, the cover film 35 is peeled off, and the lower cover layer 15 and the core portion 22 are layered. Further, the base film 31 can be directly peeled off as the support film 3 of the film-shaped optical waveguide 1 and the dry film 30 layer is bonded to the lower cladding layer 15 and the core portion 22, and is not hardened. The layer 34 formed of the composition for the intermediate layer has the possibility of protruding from the lower cladding layer 15 and removes the protruding portion. In the formation of the intermediate cladding layer 36, the amount of light, the kind, and the light (UV) irradiation device, pre-baking and post-baking conditions, etc., and the upper part of step (2) described in -51 - 200928468 The formation conditions of the coating layer are the same. By laminating and laminating the dry film 30 as described above, the layer 34 made of the composition of the uncured intermediate layer is used as a spacer with the core portion 22 of the hardened body, and is held in the lower portion. Between the cladding layer 15 and the cladding layer 33, the layer 34 formed of the composition for the intermediate layer is cured by light in this state, whereby the intermediate cladding layer 36 having a uniform thickness can be formed. Since the thickness of the cladding layer (the lower cladding layer 15, the intermediate cladding layer 36, and the upper cladding layer 33) around the core portion 22 can be made uniform, the optical characteristics of the light propagating the core portion 22 can be improved. Further, the film-shaped optical waveguide can be used after peeling off the support films 2 and 3. [Examples] Hereinafter, the present invention will be described more specifically. [1. Preparation of each component of the photocurable resin composition] The following materials were prepared as (meth) Acrylic urethane oligomer, reactive diluent monomer, photopolymerization initiator, organic solvent, ethylene polymer having ethylenically unsaturated group, and other additives. [(Meth)acrylic acid amide Ester oligomer; the coating is hardened with light The component (A) of the resin composition, the component (a) of the photocurable resin composition for the intermediate layer, and the component (2) of the photocurable resin composition for the core are fed into the reaction vessel in which the stirrer is placed, and fed into 16.6. Parts by mass of isophorone diisocyanate, 74.7 parts by mass of polypropylene glycol having an average molecular weight of 2,000, 0.01 parts by mass of 2,6-di-t-butyl-p-cresol, and cooling -52-200928468 to 5~ 10 ° C. 5 parts by mass of di-n-butyltin dilaurate was added under stirring, and the temperature was adjusted to 30 ° C or lower and stirred for 2 hours, and then the temperature was raised to 5 ° C and stirred for 2 hours. 8.7 parts by mass (the total amount is 1 part by mass) of 2-hydroxyethyl acrylate was added dropwise, and after the completion of the dropwise addition, the reaction was carried out at 50 ° for 1 hour, and then the temperature was raised to 65 ° C for 2 hours. When the residual isocyanuric acid is 〇_1% by mass or less, the reaction is completed, and A-1 is obtained. A-2 to A-9 were obtained in the same manner. The names and dosages of raw materials used in the manufacture of A-2 to A-9 are listed in Table 1 〇-53- 200928468 ο❿ [1嗽: Α-9 1 I 1 1 1 1 v〇oo v〇1—^ 1 inch (N 〇Α-8 1 1 1 1 1 74.7 16.6 1 00 〇Α -7 1 1 1 1 74.7 16.6 1 00 〇Α -6 1 1 i 1 74.7 1 16.6 1 〇〇〇 ITi < 1 1 1 1 1 1 42.9 1 A-4 i 1 1 40.8 1 1 1 35.5 23.7 1 m < 1 94.5 1 1 1 1 m ΓΛ (N CS 1 .A-2 :77.5 1 1 1 1 1 m ro ON 1 &lt 74.7 1 1 1 1 16.6 1 Γ- oo 1 Unit: parts by mass of polypropylene glycol u 1 polypropylene glycol 2) 1 polyoxyethylene bisphenol A ether 3) 1,6-hexanediol and 1,5-pentanediol Copolymerized polycarbonate diol 4) ίη* 5 11 Distillate K <ίπ Inlay 6 11 03 ^0 S View 11 in r\ « l· <Τ) 3-Methyl-1,5-penta Copolymerized polycarbonate diol of alcohol with isophthalic acid ft) Copolymerized polycarbonate diol of 1,3-propanediol and 1,4-butanediol 7) _1 isophorone diisocyanate toluene diisocyanate acrylic acid 2-hydroxyethyl acetate methoxypropyl acetate 1 a 1 1 oootw-i-φ扨 镒:§ inch sloNM§d stretched negative avoidance ffl-ssll·complete S:®HK Step on (l

Ooo^s^f Μ ^^3 000<N¥^^irle-2i · oeo-2 Ilod>%ln:a N shed liff^hi-^sn distillate! i躐4Π embedded wipe-N氍frM 擀酲鄯isHXKT slightly fr-e(9000.3⁄43⁄4^3⁄4 - os^u -οΐι-οοο^ϊφ—^ oo^i^f ^ - 005Q1D i^ifmooo.os^f IFSIfr8i " SUES -54- 200928468 [Reaction Diluted monomer; component (B) of photocurable resin composition for coating layer, component (b) of photocurable resin composition for intermediate layer, and component (3) of photocurable resin composition for core]

(1) N-vinyl-2-pyrrolidone; manufactured by ISP, V-PYROL

(2) N-vinyl caprolactam; manufactured by ISP, V-CAP

(3) Isobornyl acrylate; manufactured by Osaka Organic Chemical Industry Co., Ltd., IBX A (4) Bisphenol A EO adduct diacrylate; manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat 700 (5) 2,2-double-4 -(2-Hydroxy-3-propenyloxypropylphenyl)propane; manufactured by Showa Polymer Co., Ltd., VR-77 (6) 1,9-nonanediol diacrylate; manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat 260

(7) 9,9-bis[4-(2-acryloxyethoxy)phenyl]anthracene; manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A-BPEF

(8) 1,6-hexanediol diacrylate; manufactured by Kyoeisha Chemical Co., Ltd., Lightacrylate 1,6-HX-A (9) EO modified trimethylolpropane triacrylate; Osaka Organic Chemical Industry Co., Ltd. Manufactured, Biscoat 360 (1〇) ginseng (propylene oxy) isocyanurate; manufactured by Toagosei Co., Ltd., Aronix M-3 1 5 (11) dipentaerythritol hexamethacrylate; manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA [ Polymerization initiator; component (C) of photocurable resin composition for coating layer, -55-200928468 component (c) of photocurable resin composition for intermediate layer, component of photocurable resin composition for core (4)] (1) Irgacure 3 69; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, manufactured by Steam Batt Chemical Company (2) Lrgacure 184 ; 1_hydroxycyclohexyl phenyl ketone, manufactured by Kabat Chemical Co., Ltd. [organic solvent; component (D) of photocurable resin composition for coating layer, component of photocurable resin composition for intermediate layer (d) Component of photocurable resin composition for core (5)] (1) methoxypropyl acetate [B with ethylenically unsaturated group] Polymer (component) (E) of the photocurable resin composition for the coating layer, component (e) of the photocurable resin composition for the intermediate layer, and component (1) of the photocurable resin composition for the core] Example 1 A flask with a dry ice/methanol reflux vessel was purged with nitrogen and fed with 1.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, 90 g. Methyl isobutyl ketone as an organic solvent' was stirred until the polymerization initiator dissolved. Next, after feeding 20 g of 2-hydroxyethyl methacrylate, 25 g of dicyclopentenyl acrylate, 40 g of methyl methacrylate and 15 g of n-butyl acrylate, stirring was started slowly. Subsequently, the temperature of the solution was raised to 70 ° C, and polymerization was carried out at this temperature for 6 hours. Subsequently, 0.1 2 g of di-n-butyltin dilaurate, 〇_〇 5 g of 2,6-di-t-butyl-p-cresol was fed into the resulting solution and stirred to maintain the temperature below 60 ° C. 23.7 g of 2-methyl-56-200928468-based acryloxyethyl isocyanate was added dropwise. After completion of the dropwise addition, the reaction was carried out at 60 t for 5 hours to obtain a polymer solution having a methacryl oxime group in the side chain. Subsequently, the reaction product was added dropwise to a large amount of hexane to solidify the reaction product. Then, the coagulum was redissolved in tetrahydrofuran of the same mass and re-solidified with a large amount of hexane. After the re-dissolution-solidification operation was carried out three times in total, the obtained coagulum was vacuum-dried at 4 ° C for 48 hours to obtain a standard copolymer E-mixing example 2, and a flask equipped with a dry ice/methanol reflux vessel was replaced with nitrogen. 3 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, 100 g of methyl isobutyl ketone as an organic solvent were fed, and stirred until the polymerization initiator dissolved. Next, 20 g of 2-hydroxyethyl methacrylate, 1 g of methacrylic acid, 10 g of dicyclopentenyl acrylate, 25 g of styrene, and 35 g of n-butyl acrylate were fed, and stirring was started slowly. Subsequently, the temperature of the solution was raised to 8 ° C to carry out polymerization at this temperature for 6 hours. Subsequently, 0.13 g of di-n-butyltin dilaurate, 5 g of 2,6-di-t-butyl-p-cresol were added to the resulting solution to maintain the temperature below 60 ° C. 23.7 g of 2-methylpropenyloxyethyl isocyanate was added dropwise. After the completion of the dropwise addition, the reaction was carried out at 60 ° C for 5 hours to obtain a polymer solution having a methacryl oxime group in the side chain. Subsequently, the reaction product was added dropwise to a large amount of hexane to solidify the reaction product. Then, the coagulum was redissolved in tetrahydrofuran of the same mass to re-solidify in a large number of homes. After the re-dissolution-solidification operation was carried out three times in total, the obtained coagulum was vacuum dried at 40 °C for 48 hours to obtain the title copolymer E-2. -57- 200928468 Preparation Example 3 A flask equipped with a dry ice/methanol refluxer was replaced with nitrogen, and 3 g of 2,2'-azobisisobutyronitrile as a polymerization initiator was introduced, and 100 g of an organic solvent was added. The isobutyl ketone is stirred until the polymerization initiator dissolves. Then 'Feed 2 g of 2-hydroxyethyl methacrylate, 10 g of methacrylic acid, 20 g of styrene, 40 g of 4-(1-methyl-1-phenylethyl)phenoxyethyl acrylate After 10 g of n-butyl acrylate, stirring was started slowly. Subsequently, the temperature of the solution was raised to 80 80 ° C, and polymerization was carried out at this temperature for 6 hours. Subsequently, 0.13 g of di-n-butyltin dilaurate and 0.5 g of 2,6-di-t-butyl-p-cresol were fed into the resulting solution, and the temperature was maintained below 60 ° C under stirring. 23.7 g of 2-methylpropenyloxyethyl isocyanate was added dropwise. After completion of the dropwise addition, the mixture was reacted at 60 ° C for 5 hours to obtain a polymer solution having a methyl methacrylate group in the side chain. Subsequently, the reaction product was added dropwise to a large amount of hexane to solidify the reaction product. Then, the coagulum was redissolved in tetrahydrofuran of the same mass and φ ' was solidified again with a large amount of hexane. After the re-dissolution-solidification operation was carried out three times in total, the obtained coagulum was vacuum dried at 40 ° C for 48 hours to obtain the title copolymer E-3. The above-mentioned raw material names and blending amounts used in the production of the copolymers E-1 to E-3 are shown in Table 2. -58- 200928468 [Table 2] Unit: Parts by mass E-1 E-2 E-3 Monomer methacrylic acid via ethyl ester 20 20 20 Methacrylic acid • 10 10 Dicyclopentenyl acrylate 25 10 Styrene _ 25 20 4-(1-methyl-1-phenylethyl)phenoxyethyl acrylate - 40 n-butyl acrylate 15 35 10 methyl methacrylate 40 _ Reactive component 2-methyl propylene Ethoxyethyl isocyanate 23.7 23.7 23.7 The above components were uniformly mixed at a mixing ratio shown in Table 3 to obtain a photocurable resin composition j-1 for a lower cladding layer, an upper cladding layer, and an intermediate cladding layer. ~J-1 3, core photocurable resin composition K-1 to K-2.

-59- 200928468 6❹ [Color K-2 1 Γ[(Meth)acrylic acid urethane oligomer] 丨15.0 1 1 ( t * 1 1 [[Reactive dilute monomer] 丨' 1 25.0 I 1 • 丨 [Polymerization Initiator] I 〇W1 (N 1 [organic solvent] 1 1 60.0 I 1 [ethylene-based polymer containing ethylenically unsaturated group] 1 ( 57.0 1 100.0 j 20.0 I 1 I 1 • 1 1 1 1 1 15.0 • 1 ' 〇cn I 60.0 I 1 I 62.0 I 1 1 100.0 1 m >—> I 1 I 1 1 1 50.0 I 1 1 1 1 〇1 1 Ο W-) <s I 60.0 I 1 40.0 1 1 1 1 100.0 1 J-12 1 • 1 I 1 1 1 25.0 1 1 1 1 1 1 U2—.〇1 I o rn j 60.0 II 60.0 II • 丨100.0 1 J-ll I 1 19.4 II 1 1 1 1 1 1 1 1 LJ9^I Vi Ο <N LJ8-3 I 58.3 I < 1 1 100.0 1 J-10 | 1 I 1 1 1 1 1 « 4 194 1 • • Os (N 1 58.3 68.0 i 1 1 1 100.0 1 Ch 1 t I 1 1 1 « 1 1 1 291 1 • 〇s (N 1 58·3 1 1 68.0 1 1 1 1 100.0 1 00 >—» 1 1 I 1 1 1 1 1 I 70.0 | 1 p 1 100 1 | 10.0 I ' 〇rn 1 40.0 | 1 I 1 1 100.0 1 1 1 I 1 1 1 1 60.0 | 1 25-° J 120 I 1 1 o rn 1 25.0 1 t • 1 loo.o ι 'sO 1 1 I • 1 1 70.0 1 1 120 1 1 1 10.0 I 1 1 〇c*S | 25.0 | • 1 1 1 loo.o] Λ 1 1 I • 1 ί 70.0 1 1 1 10-° 1 1 1 > 1 17·° 1 1 o rn | 25.0 | 1 1 1 1 loo.o 1 —> 400 1 1 Ο rn lo.o 1 1 • 1 130 1 〇〇 \ 150 1 p 1 1 1 W> 〇Vi (N 1 1 1 [100.0 1 rn 44.0 | 1 • 1 1 1 1 1 〇〇\ 1 240 1 • 1 〇>τΐ 1 150 1 • • 〇rn • 1 ιοο.όΠ (N 65.0 1 1 1 1 1 1 1 ' 100 ' 1 1 1 1 1 〇1 15.0 ] o • | 25.0 | 1 • 1 [!〇〇·〇I 2 • 44.0 | t 1 ιο·όΠ 1 1 ' 1 〇σί 1 1 〇iri t 1 1 29.0 I 1 1 1 o rn 1 1 1 1 ιοό^1 _ 1» 5 Μ_Ί Μ_ Μ_ Vt < _ \M_ [A>8 Ί M_ |N-Vinyl -2-pyrrolidone | fN-vinyl caprolactam 丨 [isobornyl acrylate | | bisphenol A EO adduct diacrylate | [2, 2 · bis-4 (2-amino-3-) Propylene methoxypropyl phenyl) propane | | i, 9-nonanediol diacrylate 丨|9,9_bis[4-(2-propyleneoxyethoxy)phenyl]indole | ,6-hexanediol diacrylate] | Trimethylolpropane triacrylate | 1 gin (propylene oxy) isourethane 1 丨 dipentaerythritol hexaacrylate | o Ό m 2 3 ΰΟ 3 A 1 methoxypropyl acetate 1 ώ <N ώ CO ώ total (excluding organic solvent) | -60- 200928468 [2. Formation of film-shaped optical waveguide] [Example 1] (1) Preparation of dry film for intermediate cladding layer and upper cladding layer The photocurable resin composition J-1 is coated on the base film made of polyethylene terephthalate (PET) by spin coating to form a photocurable resin composition J-1. Coating film. Subsequently, the coating film was irradiated with ultraviolet rays having a wavelength of 3 65 nm and an illuminance of 20 mW/cm 2 for 100 seconds, and photocured to form a coating layer having a thickness of 1 μm. Next, the photocurable resin composition J-1 1 was applied onto the upper cladding layer by spin coating, and then pre-baked at 1 ° C for 1 minute using a hot plate to form a A layer formed of the cured photocurable resin composition J-1 1 to obtain a base film, an upper cladding layer (cured product of photocurable resin composition J-1), and an uncured photocurable resin composition A dry film formed by laminating layers of J-11. (2) Formation of lower cladding layer First, a photocurable resin composition J-1 is applied onto a support film (thickness ΙΟΟμηη) made of polyethylene terephthalate (PET) by spin coating. A coating film formed of the photocurable resin composition j1 is formed. Next, the coating film was irradiated with ultraviolet rays having a wavelength of 3 65 nm and an illuminance of 20 mW/cm 2 for 100 seconds, and photo-cured to form a coating layer having a thickness of 1 μm. (3) Formation of core portion Next, the core photocurable resin composition Κ-2 was applied onto the lower cladding layer by spin coating, and pre-baked at 100 ° C for 10 minutes. A coating film is formed. The coating film was irradiated with ultraviolet rays having a wavelength of 3 65 nm and an illuminance of 20 mW/cm 2 for 75 seconds through a mask having a linear pattern having a width of 50 μm, and was photohardened. Next, the substrate having the cured coating film was immersed in a developing liquid composed of acetone to dissolve the unexposed portion of the coating film. Subsequently, by post-baking at 150 ° C for 1 hour, a core portion (thickness 50 μm) having a linear pattern having a width of 5 μm was formed. Win (4) Formation of intermediate cladding layer and upper cladding layer ❿ Next, on the lower cladding layer and the core portion, the layer formed by the uncured photocurable resin composition J-11 is opposed to The above dry film is laminated by laminating the core portion in contact with the upper cladding layer in the dry film. Subsequently, the layer formed of the uncured photocurable resin composition J-1 was cured by ultraviolet rays having a wavelength of 3 65 nm and an illuminance of 20 mW/cm 2 for 100 seconds to form an intermediate coating layer having a thickness of 50 μm, which was obtained by support. A laminate of a film, a lower cladding layer, a core portion, an intermediate cladding layer, an upper cladding layer, and a ruthenium-supporting film. (5) Peeling of the substrate The cured product formed by the above steps (1) to (4) is peeled off from the support film to obtain a sequential lamination of the lower cladding layer, the core portion, and the intermediate cladding layer and the upper cladding layer. A film-shaped optical waveguide. [Examples 2 to 8 and Comparative Examples 1 to 4] A photocurable resin composition for forming a coating layer (lower cladding layer, upper cladding layer, intermediate-62-200928468 coating layer) and used for The film-shaped optical waveguide was formed in the same manner as in Example 1 except that the composition of the photocurable resin forming the core portion was changed as shown in Table 4. [Evaluation of Film-Shaped Optical Waveguides] The film-shaped optical waveguides were evaluated as follows (Examples 1 to 8 and Comparative Examples 1 to 4) e [1. Bending durability] The prepared film-shaped optical waveguide (width 5 mm, length) L〇cm, thickness 70μπι), bending test was carried out in an environment of a temperature of 23 ° C and a humidity of 50%. The test conditions were subjected to a bending test in an environment of a temperature of 23 t and a humidity of 50%. The test conditions were a bending angle of ±135°, a bending speed of 1 //min, a load of 10 0 g, and a bending radius of 1 mm. In addition, the number of bends is bent from the 0 degree position at the beginning (the horizontal state of the film-shaped optical waveguide) to a position of +13 5 degrees, ^ and then the position at 0 degree is bent to the position of -135 degrees, and then restored to the degree of twist. The action of the position is once. The number of times the film-shaped optical waveguide was broken was measured, and the case where the number of times of bending exceeded 100,000 times without breaking or cracking was recorded as "〇", and the case where the number of times of bending was broken or cracked within 100,000 times was recorded as "x". [2. Waveguide loss] For the prepared film-shaped optical waveguide, light having a wavelength of 850 nm was incident from one end thereof. Next, by measuring the amount of light emitted from the other end, the waveguide loss per unit length is obtained by the reduction-63-200928468 (cutback) method. When the waveguide loss is 0.5 dB/cm or less, it is marked as "〇", and when it exceeds 〇5 dB/cm, it is recorded as "X". The above results are shown in Table 4.

-64 - 200928468

❹G [inch 嗽: 镒 [constitution of film-shaped optical waveguide] M2 M2 K-2 [Evaluation] X 〇cn a Ml J-11 K-2 X 〇CN Group J-10 J-10 K-2 X 〇Os ; ON 1 1 X 〇00 揖IK 00 J-13 K-2 〇〇 舾 h hA J-12 1 1-3 1-3 1-3 M3 «-Η 〇〇»r> Mildew* ·-» M2 〇 〇i 辑 U »—ϊ J-11 K-2 〇〇m 习 U cn »—S J-10 Kl 〇〇 (N series W (N *—j J-11 〇〇i in J-11 K- 2 〇〇 lower cladding layer and upper cladding layer composition intermediate cladding layer composition core portion bending durability (bending radius 1 mm) waveguide loss -65- 200928468 From Table 4, the present invention can be understood The film-shaped optical waveguides (Examples 1 to 8) are excellent in bending durability. On the other hand, a photocurable resin composition containing no (meth)acrylic acid urethane oligomer is used as the lower cladding layer. The material of the upper cladding layer and the intermediate cladding layer was inferior in bending durability in Comparative Example 1. Further, either or both of (meth)acrylic acid urethane oligomer and reactive diluent monomer were used. The amount of adjustment is Comparative examples 2 to 4, which are materials of the lower cladding layer, the upper cladding layer, and the intermediate cladding layer, have poor bending durability, and the photocurable resin composition other than the invention has a poor bending durability. A cross-sectional view showing an example of a film-shaped optical waveguide of the present invention is shown in Fig. 2. Fig. 2 is a flow chart showing an example of a method for producing a dry film for forming a lower cladding layer. Fig. 3 shows the formation of an intermediate cladding layer and an upper cladding layer. A flow chart showing an example of a method for producing a dry film. 〇_ Fig. 4 is a flow chart showing an example of a method for producing a film-shaped optical waveguide of the present invention. [Description of main components] 1 : Film-shaped optical waveguide 2·· Support film 3: support film 4: reticle 66-200928468 5: Light 10: dry film for forming lower cladding layer 1 1 : base film 1 2 : composition for lower layer 1 3 : composition of composition for uncured lower layer Layer 14: Lower layer film 15: Lower cladding layer 21: Core film 22: Core portion 30: Intermediate coating layer and upper coating layer forming dry film 31: Base film 32: Upper layer film 3 3 : Upper cladding layer 3 4: from the middle of the unhardened With layers 35 composed of: the cover film 36: an intermediate cladding layer -67-

Claims (1)

200928468 X. Patent Application Park 1. A film-shaped optical waveguide characterized by comprising a lower cladding layer, a core portion, an intermediate cladding layer and an upper cladding layer, wherein the lower cladding layer and the upper cladding layer are included The cured product of the photocurable resin composition of the following components (A) to (C) is composed of: (A) 30 to 80% by mass of a (meth)acrylic acid urethane oligomer, (B) 15 ~69% by mass of a reactive diluent monomer, (C)O1 to 10% by mass of a photopolymerization initiator, (wherein the total amount of the solid content of the photocurable resin composition is 1% by mass); The intermediate coating layer is composed of a cured product of a photocurable resin composition containing the following components (a) to (d): (a) 5 to 80% by mass of (meth)acrylic acid urethane Oligomer, (b) 1 to 40% by mass of a reactive diluent monomer, (c) 0.1 to 10% by mass of a photopolymerization initiator, and 0 (d) 15 to 75% by mass of an ethylenically unsaturated group The ethylene-based polymer (wherein the total amount of the solid content of the photocurable resin composition is 1% by mass). 2. The film-shaped optical waveguide of claim 1, wherein component (A) contains (A-1) a polyol compound, (A-2) a polyisocyanate compound, and (A-3) a hydroxyl group (A) (meth)acrylic acid urethane oligomer of the reaction product of acrylate. 3. The film-shaped optical waveguide of claim 2, wherein the (A-1) polyol compound is selected from the group consisting of aliphatic polyether polyols, aromatic polyether polyols-68-200928468 alcohols, polyester polyols, and poly A film-like optical waveguide of any one of the group of the present invention, which comprises a photo-curable resin in which a lower cladding layer and an upper cladding layer are formed. When the amount of the solid content of the photocurable resin composition is not more than 1% by mass, the content of the ethylene-based polymer having an ethylenically unsaturated group is not more than 10% by mass. Unsaturated vinyl polymer. Ο -69-