JP2009300688A - Resin composition for forming cladding layer, resin film for forming cladding layer using the same, and optical waveguide and optical module using these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for forming a cladding layer excellent in flexibility and twisting resistance, to provide a resin film for forming such a cladding layer, and to provide an optical waveguide and an optical module produced using the resin composition and the resin film. <P>SOLUTION: The optical waveguide and the optical module are produced using the resin composition for forming a cladding layer of an optical waveguide including (A) polyamide-imide and (B) a polymerizable compound, and the resin film for forming a cladding layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition for forming a cladding layer, a resin film for forming a cladding layer, and an optical waveguide and an optical module using the same.

In high-speed and high-density signal transmission between electronic devices and between wiring boards, signal transmission interference and attenuation become barriers in conventional transmission using electric wiring, and the limits of high-speed and high-density are beginning to appear. In order to overcome this problem, a technique for optically connecting electronic elements and wiring boards, so-called optical interconnection, has been studied.
In order to transmit an optical signal over a short distance such as inside or between devices, a flexible film optical waveguide is desired. In particular, when an optical waveguide is wired inside a small portable device, the component film is often wired so that the surface of the component faces in order to save space. The polymer film optical waveguide can be bent with a small curvature radius. Is required.
In order to improve the flexibility of the flexible optical waveguide or the followability at the interface when the shape is restored, an optical waveguide using a low elastic modulus material has been developed. For example, Patent Documents 1 and 2 propose a film optical waveguide with high bending resistance and high twist resistance in which the bending elastic modulus of the optical waveguide is 1000 MPa or less and the film thickness is 150 μm or less. However, since the optical waveguide is manufactured using a stamper, there is a disadvantage that the degree of freedom in design is low and it is difficult to change the design.

Japanese Patent No. 3870976 Japanese Patent No. 3906870

  In view of the above-described problems of the prior art, the present invention provides a clad layer-forming resin composition excellent in bending resistance and twist resistance, a clad layer-forming resin film, an optical waveguide and an optical module produced using them. The purpose is to provide.

As a result of intensive studies, the present inventors have solved the above problem by manufacturing an optical waveguide using a resin composition for forming a clad layer containing (A) polyamideimide and (B) a polymerizable compound. I found that I could do it.
That is, the present invention relates to a resin composition for forming a cladding layer of an optical waveguide containing (A) a polyamideimide and (B) a polymerizable compound, and a resin for forming a cladding layer using the resin composition for forming a cladding layer. Film, at least one of lower clad layer and upper clad layer, optical waveguide in which clad layer forming resin composition or clad layer forming resin film is formed, and optical module using the optical waveguide Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for clad layer formation which is excellent in bending resistance and twist resistance, the resin film for clad layer formation, the optical waveguide produced using these, and an optical module can be provided.

In the following, the present invention will be described in more detail.
The polyamideimide in the component (A) of the present invention is preferably a silicone-modified polyamideimide and / or a butadiene-modified polyamideimide.
The silicone-modified polyamideimide is a polymer having a siloxane skeleton, an imide skeleton, and an amide bond. For example, R ¹ and R ² in the repeating unit represented by the following general formula (1) are represented by the following general formula (2 ), A polyether skeleton represented by the following general formula (3), an aliphatic or alicyclic skeleton represented by the following general formula (4), and the following general What has the aromatic skeleton represented by Formula (5) is mentioned.

(In the formula, R ¹ and R ² each independently represent a divalent organic group represented by any one of the following general formulas (2) to (5), and R ³ and R ⁴ each independently represent 2 carbon atoms. A trivalent aliphatic group having 20 carbon atoms, a trivalent alicyclic group having 3 to 20 carbon atoms, or a trivalent aromatic group having 6 to 20 carbon atoms.)

(In the formula, R ⁵ and R ⁶ each independently represent a divalent organic group, and R ^{7 to} R ¹⁰ each independently represent a monovalent aliphatic group having 1 to 20 carbon atoms or an aromatic group having 6 to 18 carbon atoms. Represents a group, and a represents an integer of 1 to 50.)

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and b + c represents an integer of 1 to 50. This includes the case where each repeating unit is present at random.)

(Wherein R ¹² represents a single bond, an oxygen atom, a sulfur atom, or

In which R ^{13 to} R ¹⁶ each independently represents a hydrogen atom or a methyl group, and d represents an integer of 1 to 20. )

(Wherein R ¹⁷ is a single bond, an oxygen atom, a sulfur atom, or

R ^{18 to} R ²¹ and R ²³ each independently represents a hydrogen atom, or any group of a methyl group, a trifluoromethyl group, and a hydroxyl group, and R ²² represents

The bivalent group of any of these is shown.
R ²⁴ is a single bond, an oxygen atom, a sulfur atom, or

And R ²⁵ represents a hydrogen atom or a methyl group. )
In the general formula (1), examples of the trivalent aliphatic group having 2 to 20 carbon atoms represented by R ³ and R ⁴ include:

And may be substituted with an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 19 carbon atoms, or the like.
In the general formula (1), as the trivalent alicyclic group having 3 to 20 carbon atoms represented by R ³ and R ⁴ , for example,

And may be substituted with an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 15 carbon atoms, or the like.
In the general formula (1), examples of the trivalent aromatic group having 6 to 20 carbon atoms represented by R ³ and R ⁴ include:

And may be substituted with an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 14 carbon atoms, or the like.

In the general formula (2), examples of the divalent organic group represented by R ⁵ and R ⁶ include alkylene groups having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group; a phenylene group, a tolylene group, Examples include an arylene group having 6 to 18 carbon atoms such as a xylylene group.

In the general formula (2), examples of the monovalent aliphatic group having 1 to 20 carbon atoms represented by R ^{7 to} R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and structural isomers thereof.
In the general formula (2), examples of the aromatic group having 6 to 18 carbon atoms represented by R ^{7 to} R ¹⁰ include a phenyl group, a benzyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like, and a halogen atom , An amino group, a nitro group, a cyano group, a mercapto group, an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and the like.

  Silicone-modified polyamideimide is (i) a method in which a diimide dicarboxylic acid containing a diimide dicarboxylic acid having a siloxane skeleton is reacted with a diisocyanate compound, and (ii) a diamine compound containing a diamine having a siloxane skeleton is reacted with a tricarboxylic acid chloride. And (iii) a method of reacting a diisocyanate compound containing a diisocyanate having a siloxane skeleton with a tribasic acid chloride.

  As the method (i), for example, a siloxane diamine is reacted with at least one of a polyether diamine, an aliphatic diamine, an alicyclic diamine, and an aromatic diamine, if necessary, and a tribasic acid anhydride. The diimide dicarboxylic acid obtained in this manner can be obtained by reacting at least one of aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.

Examples of the siloxane diamine include amino-modified silicone oil PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 130 g / eq), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 450 g / eq), X-22-161A (Shin-Etsu Chemical Co., Ltd., amine equivalent 840 g / eq), X-22-161B (Shin-Etsu Chemical Co., Ltd., amine equivalent 1,500 g / eq), KF-8012 (Shin-Etsu Chemical Co., Ltd.) Company-made, amine equivalent 2,200 g / eq), BY16-853 (manufactured by Toray Dow Corning Silicone, amine equivalent 650 g / eq product name), BY16-853B (manufactured by Toray Dow Corning Silicone, amine equivalent 2,200 g) / Eq) and the like are commercially available.
Of these, the amine equivalent of siloxane diamine is preferably 100 to 2,500 g / eq from the viewpoint of flex resistance, torsion resistance, and compatibility with the polymerizable compound (B). Is more preferably 1,000 to 1,600 g / eq, and particularly preferably 100 to 1,600 g / eq.
These compounds can be used alone or in combination of two or more.

  Examples of the polyether diamine include Jeffamine D-230 (Mitsui Chemicals Fine Co., Ltd., amine equivalent 115 g / eq), Jeffamine D400 (Mitsui Chemicals Fine Co., Ltd., amine equivalent 200 g / eq), Jeffamine D2000. (Mitsui Chemicals Fine Co., Ltd., amine equivalent 1,000 g / eq), Jeffamine D4000 (Mitsui Chemicals Fine Co., Ltd., amine equivalent 2,000 g / eq) and the like are commercially available.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane. 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, and structural isomers thereof.
These compounds can be used alone or in combination of two or more.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,3,5-trimethylcyclohexane, bis (4- Aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, (4,4'-diamino) dicyclohexyl ether, (4,4'- Diaminocyclohexyl) ketone, (4,4′-diamino) dicyclohexylsulfone, bis [4- (4-aminocyclohexyloxy) cyclohexyl] methane, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, 2,2-bis [4- (4-aminocyclohexyloxy) Cyclohexyl] hexafluoropropane, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ether, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ketone bis [4- (4-aminocyclohexyloxy) cyclohexyl] sulfone, 1 , 4-bis (4-aminocyclohexyloxy) benzene, 2,2′-dimethylbicyclohexyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) dicyclohexyl-4,4′-diamine, 2, , 6,2 ', 6'-tetramethyldicyclohexyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyldicyclohexyl-4,4'-diamine, 3,3'-dihydroxydicyclohexyl- 4,4′-diamine, 2,5-bis (aminomethyl) bicyclo [ .2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, and the like structural isomers thereof.
These compounds can be used alone or in combination of two or more.

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, and 1,5-diamino. Naphthalene, 2,6-diaminonaphthalene, benzidine, bis (4-aminophenyl) methane, 4,4′-diaminodiphenylmethane, 1,2-bis (4-aminophenyl) ethane, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl sulfone, 1, 4-bis (4-aminophenyl) benzene, 1,4-bis (4-amino-2-trifluoromethyl) Phenoxy) benzene, 4,4′-bis (4-aminophenyl) biphenyl, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-3) -Trifluoromethylphenoxy) biphenyl, bis [4-bis (4-aminophenoxy) phenyl] methane, 1,2-bis [4-bis (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- Bis (4-aminophenoxy) phenyl] propane, 2,2-bis [4-bis (4-aminophenoxy) phenyl] hexafluoropropane, 4,4′-bis (4-aminophenoxy) diphenyl ether, 1,4- Bis (4-aminophenyl) octafluorobutane, 2,2-bis [4- (4-aminophenoxy) -3,5-ditrifluoromethyl Enyl] hexafluoropropane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) decafluorobutane, 4,4′-bis (4-aminophenoxy) diphenyl ketone 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 1,4-bis [4-bis (4-amino) Phenoxy) phenyl] benzene, 4,4′-bis [4-bis (4-aminophenoxy) phenyl] biphenyl, diaminoanthraquinone, and structural isomers thereof.
These compounds can be used alone or in combination of two or more.

Examples of the tribasic acid anhydride include aliphatic tribasic acid anhydrides such as carboxylic succinic anhydride, carboxylic maleic anhydride, and 1-carboxyl glutaric anhydride; hexahydrotrimellitic anhydride, tetrahydrotrimellitic acid Alicyclic tribasic acid anhydrides such as anhydride, 5-carboxy-norbornane-2,3-dicarboxylic acid anhydride, 5-carboxy-5-norbornene-2,3-dicarboxylic acid anhydride; trimellitic acid anhydride And aromatic tribasic acid anhydrides; and structural isomers thereof.
These compounds can be used alone or in combination of two or more.

  If necessary, in addition to the diimide dicarboxylic acid obtained from the diamine and the tribasic acid anhydride, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid, and dimer acid; Aromatic dicarboxylic acids such as acid, phthalic acid and naphthalenedicarboxylic acid can be used in combination.

Examples of the aliphatic diisocyanate include 1,4-tetramethylene isocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, and 1,10-decamethylene diisocyanate. 1,12-dodecamethylene diisocyanate, and structural isomers thereof.
These compounds can be used alone or in combination of two or more.

Examples of the alicyclic diisocyanate include 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,5-bis (isocyanatomethyl) norbornene, bis (4-isocyanatocyclohexyl) methane, and 1,2. -Bis (4-isocyanatocyclohexyl) ethane, 2,2-bis (4-isocyanatocyclohexyl) propane, 2,2-bis (4-isocyanatocyclohexyl) hexafluoropropane, and structural isomers thereof It is done.
These compounds can be used alone or in combination of two or more.

Examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate, 4,4′-bis (3-methylphenyl) methane diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like. And the structural isomers.
These compounds can be used alone or in combination of two or more.

  The silicone-modified polyamideimide of the component (A) used in the present invention is, for example, the siloxane diamine and, if necessary, the polyether diamine, the aliphatic diamine, the alicyclic diamine, and the aromatic diamine. At least one of them and the tribasic acid anhydride are reacted in the presence of an aprotic polar solvent at 50 to 90 ° C. for 0.2 to 1.5 hours, and further, an aromatic hydrocarbon which can be azeotroped with water In an aprotic polar solvent at a ratio of 0.1 to 0.5 mass, and an imide ring closure reaction by dehydration reflux at 120 to 180 ° C. to produce diimide dicarboxylic acid, wherein the aliphatic diisocyanate, At least one of the alicyclic diisocyanate and the aromatic diisocyanate is added to the mixture of the diimide dicarboxylic acid and about 20 to 250 ° C. It can be prepared by reacting about 0.5 to 3 hours.

  Moreover, after manufacturing the said diimide dicarboxylic acid, the aromatic hydrocarbon which can be azeotroped with water is removed from the solution by heating the solution at about 150-250 degreeC, and this is reacted with the said diisocyanate. Can also be manufactured. The modified polyamideimide is preferably a varnish containing an aprotic polar solvent.

  Furthermore, the molar ratio of the diamine and the tribasic acid anhydride is preferably 1 / 2.20 to 1 / 2.05, and more preferably 1 / 2.15 to 1 / 2.10. If this molar ratio is 1 / 2.20 or more, the molecular weight of the resin can be increased without the tribasic acid anhydride remaining, which is preferable. If it is 1 / 2.05 or less, the molecular weight of the resin can be increased without diamine remaining, which is preferable.

  Next, the molar ratio of the diimide dicarboxylic acid and the diisocyanate is preferably 1 / 1.50 to 1 / 1.05, and more preferably 1 / 1.3-1 to 1 / 1.1. If this molar ratio is in the above range, the molecular weight of the resin can be increased, which is preferable.

The aprotic polar solvent is preferably an organic solvent that does not react with the diamine and the tribasic acid anhydride. For example, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ- Examples include butyrolactone, sulfolane, cyclohexanone, and propylene glycol monomethyl ether acetate.
Examples of the aromatic hydrocarbon include toluene and xylene. These organic solvents can be used alone or in combination of two or more.

  The water content contained in these aprotic polar solvents is preferably 0.1 to 0.2% by mass. If the water content is 0.2% by mass or less, the tribasic acid produced by hydration of the tribasic acid anhydride can sufficiently advance the reaction and increase the molecular weight of the polymer. It is.

As the diamine compound containing a diamine having a siloxane skeleton used in the above method (ii), the above-mentioned compounds can be mentioned. As other diamines, those described above can be used.
Examples of the tribasic acid chloride include hexahydrotrimellitic acid chloride, tetrahydrotrimellitic acid chloride, norbornane-2,3,5-tricarboxylic acid chloride, norbornene-2,3,5-tricarboxylic acid chloride, and trimellitic acid chloride. And structural isomers thereof.
These compounds can be used alone or in combination of two or more.
The production method can be produced by the well-known acid chloride method.

As a diisocyanate compound containing a diisocyanate having a siloxane bond used in the method (iii), there is a diisocyanate compound corresponding to the siloxane diamine. As other diisocyanate compounds, those described above can be used.
Examples of the tribasic acid anhydride include the compounds described above. The production method can be produced by a reaction of a diamine compound and a diisocyanate compound which are well known in the art.

  Next, the butadiene-modified polyamideimide used for the component (A) of the present invention will be described. The butadiene-modified polyamideimide is a polymer having a polybutadiene skeleton, an imide skeleton, and an amide bond, and includes, for example, a repeating unit represented by the following general formula (1) and the following general formulas (6) and / or (7). Those having a repeating unit represented. In polybutadiene, some or all of the double bonds may be hydrogenated.

(Wherein R ^{1 to} R ⁴ are the same as described above.)

(In the formula, each R ²⁶ independently represents a divalent organic group represented by any one of the above general formulas (2) to (5), and the bond represented by the dotted line and the solid line is a single bond or a double bond, respectively. A wavy line indicates a cis or trans configuration when the bond represented by the adjacent dotted and solid lines is a double bond, m, n and p are each independently a butadiene unit and / or Indicates the number of hydrogenated butadiene units, including the case where each unit is present at random. M + n + p represents an integer of 1 to 200.)

(In the formula, each R ²⁷ independently represents a divalent organic group represented by any one of the general formulas (2) to (5), and the dotted line and the wavy line have the same meaning as described above. W, x And y each independently represents the number of butadiene units and / or hydrogenated butadiene units, z represents the number of acrylonitrile units, and includes the case where each unit is present at random. Indicates an integer.)

  Such a butadiene-modified polyamideimide can be produced by a method according to the method for producing a silicone-modified polyamideimide described above, for example, polybutadiene having carboxyl groups at both ends, and hydrogen having carboxyl groups at both ends. A mixture containing diimidedicarboxylic acid and at least one of a polybutadiene, an acrylonitrile-butadiene rubber having carboxyl groups at both ends, and a hydrogenated acrylonitrile-butadiene rubber body having carboxyl groups at both ends, and the diisocyanate are reacted. It can manufacture by the method to make.

Examples of the carboxylic acid-terminated polybutadiene include C-1000 (manufactured by Nippon Soda Co., Ltd., weight average molecular weight 1,800) and the like that are commercially available.
Examples of the carboxylic acid-terminated hydrogenated polybutadiene include CI-1000 (manufactured by Nippon Soda Co., Ltd., weight average molecular weight 1,800) and the like that are commercially available.
Examples of the carboxylic acid-terminated acrylonitrile-butadiene rubber include Hiker CTBN 1300 × 8 (manufactured by Ube Industries, Ltd., weight average molecular weight 3,500, acrylonitrile amount 18% by mass), Hiker CTBN 1300 × 13 (manufactured by Ube Industries, Ltd., weight average molecular weight 3 , 500, acrylonitrile amount 26 mass%) and the like are commercially available.
The carboxylic acid-terminated acrylonitrile-butadiene rubber preferably has an acrylonitrile content in the range of 5 to 60% by mass, and more preferably in the range of 15 to 40% by mass.

At least among the polybutadiene having carboxyl groups at both ends, the hydrogenated polybutadiene having carboxyl groups at both ends, the acrylonitrile-butadiene rubber having carboxyl groups at both ends, and the hydrogenated acrylonitrile-butadiene rubber body having carboxyl groups at both ends. One, the molar ratio of the mixture containing the diimide dicarboxylic acid and the diisocyanate is preferably 1 / 1.50 to 1 / 1.05, preferably 1 / 1.3 to 1 / 1.1. Is more preferable. If this molar ratio is in the above range, the molecular weight of the resin can be increased, which is preferable.
As the solvent, the above-mentioned aprotic solvent can be used, and the description described in the above-mentioned method for producing a silicone-modified polyamideimide can be used for the use amount, reaction conditions, and the like.

  The weight average molecular weight of the component (A) polyamideimide is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, and 30,000 to 100,000. Is particularly preferred. When the weight average molecular weight is 10,000 or more, the strength and flexibility in the film state are improved, and an increase in tackiness can be suppressed. On the other hand, if it is 300,000 or less, the compatibility with the polymerizable compound (B) is good. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography method, and is converted with the analytical curve created using standard polystyrene.

The resin composition for forming a cladding layer of the present invention contains (B) a polymerizable compound.
(B) It does not specifically limit as a polymeric compound, The compound etc. which have an ethylenically unsaturated group in an epoxy resin and a molecule | numerator are mentioned. Examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylate and bismaleimide. These polymerizable compounds can be used alone or in combination of two or more.

The epoxy resin is not particularly limited, and for example, epoxy resins described in an epoxy resin handbook (edited by Masaki Shinbo, Nikkan Kogyo Shimbun) can be widely used. Specifically, for example, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD Type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, etc. bifunctional phenol glycidyl ether type epoxy resin; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated 2,2 Hydrogenated bifunctional phenol glycidyl ether type epoxy resin such as' -biphenol type epoxy resin, hydrogenated 4,4'-biphenol type epoxy resin; phenol novolac type epoxy resin , Cresol novolac type epoxy resin, dicyclopentadiene-phenol type epoxy resin, dicyclopentadiene-cresol type epoxy resin, tetraphenylol ethane type epoxy resin and more polyfunctional phenol glycidyl ether type epoxy resin; polyethylene glycol type Bifunctional aliphatic alcohol glycidyl ether type epoxy resin such as epoxy resin, polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, 1,6-hexanediol type epoxy resin; cyclohexanediol type epoxy resin, cyclohexanedimethanol type epoxy resin , Bifunctional alicyclic alcohol glycidyl ether type epoxy resin such as tricyclodecane dimethanol type epoxy resin; trimethylolpropane type epoxy resin Polyfunctional aliphatic alcohol glycidyl ether type epoxy resin having three or more functions such as poxy resin, sorbitol type epoxy resin, glycerin type epoxy resin; bifunctional aromatic glycidyl ester such as diglycidyl phthalate; tetrahydrophthalic acid diglycidyl ester, Bifunctional alicyclic glycidyl esters such as hexahydrophthalic acid diglycidyl ester; bifunctional aromatic glycidyl amines such as N, N-diglycidylaniline, N, N-diglycidyltrifluoromethylaniline; N, N, N ′ , N′-tetraglycidyl-4,4-diaminodiphenylmethane, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, o-triglycidyl-p-aminophenol, etc. Functional aromatic glycidylamine; Bifunctional alicyclic epoxy resins such as cyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinylcyclohexene dioxide; 1 of 2,2-bis (hydroxymethyl) -1-butanol , 2-Epoxy-4- (2-oxiranyl) cyclohexane adduct, etc. Trifunctional or higher polyfunctional alicyclic epoxy resin; Triglycidyl isocyanurate trifunctional or higher polyfunctional heterocyclic epoxy resin; Organopolysiloxane Examples thereof include silicon-containing bifunctional or trifunctional or higher polyfunctional epoxy resins such as type epoxy resins.
Among these, from the viewpoint of transparency and compatibility with polyamideimide, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, Bifunctional phenol glycidyl ether type liquid epoxy resin such as bisphenol AD type epoxy resin; preferably the above bifunctional alicyclic liquid epoxy resin.
These compounds can be used alone or in combination of two or more.

There is no restriction | limiting in particular as said (meth) acrylate, For example, any of a monofunctional thing, a bifunctional thing, or a polyfunctional thing more than trifunctional can be used.
There is no restriction | limiting in particular as monofunctional (meth) acrylate, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) Acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate , Octyl heptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Aliphatic (meth) acrylates such as chloro-2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl Alicyclic (meth) acrylates such as (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate; phenyl (meth) acrylate, Nylphenyl (meth) acrylate, p-cumylphenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2 -Aromatic (meth) acrylates such as naphthoxy) propyl (meth) acrylate; 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) acryloyloxyethyl-N- Mosquito Examples thereof include heterocyclic (meth) acrylates such as rubazole; ethoxylated products thereof; propoxylated products thereof; ethoxylated propoxylated products thereof; modified caprolactones thereof and the like.
Among these, from the viewpoint of transparency and compatibility with polyamideimide, the above aliphatic (meth) acrylates; the above alicyclic (meth) acrylates; the above heterocyclic (meth) acrylates; A propoxylated product thereof; an ethoxylated propoxylated product thereof; a modified product of these caprolactones.

There is no restriction | limiting in particular as bifunctional (meth) acrylate, For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 2-methyl-1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate Aliphatic (meth) acrylates such as: cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F Alicyclic (meth) acrylates such as meth) acrylate; aromatics such as bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, bisphenol AF di (meth) acrylate, and fluorene type di (meth) acrylate Heterocyclic (meth) acrylates such as isocyanuric acid di (meth) acrylate; ethoxylated products thereof; propoxylated products thereof; ethoxylated propoxylated products thereof; modified caprolactone products thereof; neopentyl glycol type Aliphatic epoxy (meth) acrylates such as epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol F type epoxy (meth) Alicyclic epoxy (meth) acrylates such as acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol AF type epoxy (meth) acrylate, fluorene type epoxy Aromatic epoxy (meth) acrylates such as (meth) acrylates may be mentioned.
Among these, from the viewpoint of transparency and compatibility with polyamide-imide, the above aliphatic (meth) acrylate; the above alicyclic (meth) acrylate; the above heterocyclic (meth) acrylate; the ethoxylated products thereof; These ethoxylated propoxy compounds; these caprolactone-modified products; the above aliphatic epoxy (meth) acrylates; and the above alicyclic epoxy (meth) acrylates.

The trifunctional or higher polyfunctional (meth) acrylate is not particularly limited. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra ( Aliphatic (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; heterocyclic (meth) acrylates such as isocyanuric acid tri (meth) acrylate; these ethoxys These propoxylated products; These ethoxylated propoxylated products; These caprolactone modified products; Phenol novolac epoxy (meth) acrylate, Cresol novolac epoxy ( Aromatic epoxy (meth) acrylates such as data) acrylate.
Among these, from the viewpoint of transparency and compatibility with polyamideimide, the above aliphatic (meth) acrylate; the above heterocyclic (meth) acrylate; the ethoxylated product thereof; the propoxylated product thereof; Propoxylated products; these caprolactone modified products are preferred.
These compounds can be used alone or in combination of two or more.

  The bismaleimide is not particularly limited as long as it contains two or more maleimide groups in the molecule. For example, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylene Bismaleimide, N, N′-p-phenylenebismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4′- [3,3′-dimethylbiphenylene] bismaleimide, N, N′-4,4 ′-[3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′- Diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2 , 2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1 -Bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4 '-Cyclohexylidene-bis [1- (4-maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidopheno) Xyl) -2,6-bis (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4 , 4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene, 4,4′-methylene-bis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′ -(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1 -(Maleimidophenoxy) -benzene], 4,4 ′-(1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylidene-bis [1- (maleimido) Enoxy) -3-methylbenzene], 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3 , 5-Dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3 -Ethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) Phenyl] hexafluoropropane, bis [3-methyl-4- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- 4- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1.02,6] decane, 4,8-bis [ 4- (4-Maleimidophenoxy) phenyl] -tricyclo- [5.2.1.02,6] decane, 3,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2. 1.02,6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1.02,6] decane, 1,8-bis 4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3,5-dimethyl-4- (4 -Maleimidophenoxy) phenyl] menthane and the like. Among these, from the viewpoint of transparency and compatibility with polyamideimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenylpropane bismaleimide, N, N ′ -4,4'-diphenyl ether bismaleimide is preferred. These compounds can be used alone or in combination of two or more.

Among the components (B), the amount of the epoxy resin used is preferably 5 to 250 parts by mass with respect to 100 parts by mass of the (A) polyamideimide. Within this range, good bending resistance and twisting resistance can be exhibited without impairing the flexibility of the polyamideimide, and sufficient handling at high temperatures can be obtained. Therefore, 10-200 mass parts is more preferable, and 20-150 mass parts is especially preferable.
(B) As for the usage-amount of the compound which has an ethylenically unsaturated group in the molecule | numerator among (B) component, 5-250 mass parts is preferable with respect to 100 mass parts of (A) polyamideimide. Within this range, good bending resistance and twisting resistance can be exhibited without impairing the flexibility of the polyamideimide, and sufficient handling at high temperatures can be obtained. Therefore, 10-200 mass parts is more preferable, and 20-150 mass parts is especially preferable.
From the above viewpoint, the amount of the polymerizable compound (B) used in the present invention is preferably 5 to 250 parts by mass, more preferably 10 to 200 parts by mass, and more preferably 20 to 200 parts by mass with respect to 100 parts by mass of (A) polyamideimide. 150 parts by mass is particularly preferred.

  In the present invention, an epoxy resin curing agent (C) can be used as necessary. The epoxy resin curing agent is effective because it is excellent in impact resistance under high temperature and high pressure when combined with an epoxy resin.

(C) There is no restriction | limiting in particular as an epoxy resin hardening | curing agent, A phenol type hardening | curing agent, an amine type hardening | curing agent, etc. are mentioned.
The phenolic epoxy resin curing agent is not particularly limited. For example, hydroquinone, resorcinol, catechol, bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol AF, bisphenol AD, biphenol, dihydroxynaphthalene, binaphthol, fluorene type bisphenol, etc. Bifunctional phenols: phenol novolak resin, cresol novolak resin, triazine ring-containing phenol novolak resin, triazine ring-containing cresol novolak resin, bisphenol A novolak resin, tetrabromobisphenol A novolak resin, bisphenol AF novolak resin, bisphenol AD novolak resin, biphenol Novolac resin, fluorene type bisphenol novolac resin, di Black cyclopentadiene - - phenol novolak resin, dicyclopentadiene novolak resins such as cresol novolak resins; phenolic resole resins, such as resole resins and cresol resol resin.
Among these, from the viewpoint of transparency and compatibility with polyamideimide, bifunctional phenols such as hydroquinone, resorcinol, catechol, bisphenol A, and bisphenol F; novolac resins such as phenol novolac resin, cresol novolac resin, and bisphenol A novolac resin It is preferable that

The amine curing agent is not particularly limited, and is a chain aliphatic amine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, dicyandiamide, tetramethylguanidine, triethanolamine; isophorone Diamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8, Cycloaliphatic amines such as 10-tetraoxaspiro [5.5] undecane; xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 2,2-bis [4- (4-a And aromatic amines such as minophenoxy) phenyl] propane. Among these, dicyandiamide and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferable from the viewpoint of transparency and compatibility with polyamideimide.
These compounds can be used alone or in combination of two or more.

In this invention, it is preferable that the usage-amount of a phenol type epoxy resin hardening | curing agent among (C) component is the range whose equivalent ratio of the phenolic hydroxyl group per epoxy group of an epoxy resin is 0.1-3, More preferably, it is 0.5-1.5. Moreover, it is preferable that the equivalence ratio of the active hydrogen of the amino group per epoxy group of an epoxy resin is the range of 0.1-3 for the usage-amount of an amine epoxy resin hardening | curing agent, and 0.5-1. 5 is more preferable.
If the usage-amount of (C) component is this range, hardening (crosslinking) of resin will become enough.

The resin composition for forming a clad layer of the present invention may further contain (D) a curing accelerator as necessary.
The (D) curing accelerator used in the present invention is not particularly limited, and examples thereof include secondary amines such as tri-n-butylamine, benzylmethylamine, and methylaniline; triethylamine, tri-n-propylamine, Tertiary amines such as isopropylamine, tri-n-butylamine, diethylisopropylamine, benzyldimethylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine; pyrrolidine, N-methylpyrrolidine, Piperidine, N-methylpiperidine, morpholine, N-methylmorpholine, piperazine, N, N′-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] Non-5-ene, 1,8-diazabicyclo [5.4.0] undeca Cyclic amines such as -ene; 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5- Dihydroxymethylimi Sol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)] ethyl-s-triazine, 2,4-diamino-6- [2′- Imidazole compounds such as ethyl-4′-methylimidazolyl- (1 ′)] ethyl-s-triazine; trimellitic acid adducts of the imidazole compounds; isocyanuric acid adducts of the imidazole compounds; hydrobromic acid additions of the imidazole compounds Body; tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, Jill trimethylammonium bromide benzyltrimethylammonium, and the like quaternary ammonium salts such as benzyl iodide trimethylammonium.
Among these, from the viewpoint of transparency and curability, the imidazole compound; the trimellitic acid adduct of the imidazole compound; and the isocyanuric acid adduct of the imidazole compound are preferable.
These compounds can be used alone or in combination of two or more.

  (D) It is preferable that the compounding quantity of a hardening accelerator shall be 0-5.0 mass% with respect to a total amount with an epoxy resin and an epoxy resin hardening | curing agent, and it shall be 0.05-3.0 mass%. More preferably, it is more preferable to set it as 0.2-3.0 mass%. When the blending amount of the curing accelerator is 5.0% by mass or less, the storage stability is improved and the pot life is sufficient.

In this invention, (E) radical polymerization initiator can be used as needed. (E) The radical polymerization initiator is not particularly limited as long as it initiates polymerization by heating or irradiation with actinic rays such as ultraviolet rays and visible rays. For example, a thermal radical polymerization initiator or a photo radical polymerization initiator is used. be able to.
The thermal radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1 -Bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane Peroxyketals such as 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; α, α′-bis (t-butyl Peroxy) diisopropylbenzene, dicumyl peroxide, t- Dialkyl peroxides such as tilcumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide and benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxide Peroxycarbonates such as oxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate; t-butyl peroxypivalate, t- Hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t -Hexilper Oxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-3,5 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, Peroxyesters such as 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane and t-butylperoxyacetate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-Dimethylvaleronitrile), 2,2'-azobi (4-methoxy-2'-dimethylvaleronitrile) azo compounds and the like.
Of these, diacyl peroxide, peroxyester, and azo compound are preferred from the viewpoints of curability and transparency.

There is no restriction | limiting in particular as radical photopolymerization initiator, For example, benzoinketals, such as 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one; 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4 [4- Α-hydroxy ketones such as (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2- (2-hydroxyethoxy) ) Ethyl, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ) Glyoxyesters such as ethyl; 2-benzyl-2-dimethylamino-1- (4-morpholin-4-ylphenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-Morpholin-4-ylphenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl]-(4-morpholin) -2-ylpropane- Α-amino ketones such as 1-one; 1,2-octanedione, 1- [4- (phenylthio), 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Oxime esters such as benzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime); bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis ( , 6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, phosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) ) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N '-Tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'- Benzophenone compounds such as aminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2, Quinone compounds such as 3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethyl benzo Benzoin compounds such as benzyl; benzyl compounds such as benzyldimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis (9,9′-acridinylheptane): N-phenylglycine, coumarin and the like .
In the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole sites may give the same and symmetric compounds, but give differently asymmetric compounds. May be.
Among these, from the viewpoint of curability and transparency, the α-hydroxyketone; the glyoxyester; the oxime ester; and the phosphine oxide are preferable.
The above heat and photo radical polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

  (E) It is preferable that the compounding quantity of a radical polymerization initiator is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. If it is 0.01 mass part or more, hardening will be enough, and if it is 10 mass parts or less, sufficient light transmittance will be obtained. From the above viewpoint, the amount is more preferably 0.05 to 7 parts by mass, and particularly preferably 0.1 to 5 parts by mass.

  Further, if necessary, in the resin composition for forming a cladding layer of the present invention, an antioxidant, a yellowing inhibitor, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, a filler, etc. These so-called additives may be added at a rate that does not adversely affect the effects of the present invention.

  The resin composition for forming a clad layer of the present invention is preferably used for at least one of a lower clad and an upper clad of an optical waveguide.

The resin composition for forming a cladding layer of the present invention may be diluted with a suitable organic solvent and used as a resin varnish for forming a cladding layer. The solvent for varnishing is not particularly limited as long as it can dissolve the resin composition for forming a cladding layer of the present invention. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, p-cymene, etc. Chain ethers such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether and dibutyl ether; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol and propylene glycol Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyro Esters such as Kuton; Carbonates such as ethylene carbonate and propylene carbonate; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Polyhydric alcohol alkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; Polyhydric alcohol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone;
These organic solvents can be used alone or in combination of two or more. Moreover, it is preferable that the solid content density | concentration in a resin varnish is 10-80 mass% normally.

  When the resin composition for forming a cladding layer of the present invention is prepared, it is preferably mixed by stirring. Although there is no restriction | limiting in particular in the stirring method, From the viewpoint of stirring efficiency, stirring using a propeller is preferable. Although there is no restriction | limiting in particular in the rotational speed of the propeller at the time of stirring, It is preferable that it is 10-1,000 rpm. If it is 10 rpm or more, each component will be sufficiently mixed, and if it is 1,000 rpm or less, entrainment of bubbles due to rotation of the propeller will be reduced. From the above viewpoint, it is more preferable that it is 50-800 rpm, and it is especially preferable that it is 100-500 rpm. Although there is no restriction | limiting in particular in stirring time, It is preferable that it is 1 to 24 hours. If it is 1 hour or more, each component will be fully mixed, and if it is 24 hours or less, the varnish preparation time can be shortened and productivity can be improved.

  The prepared clad layer-forming resin composition or resin varnish is preferably degassed under reduced pressure. Although there is no restriction | limiting in particular in the defoaming method, For example, the method of using a vacuum pump, a bell jar, and the defoaming apparatus with a vacuum apparatus is mentioned. Although there is no restriction | limiting in particular in the pressure at the time of pressure reduction, The pressure in which the low boiling point component contained in a resin composition does not boil is preferable. Although there is no restriction | limiting in particular in vacuum degassing time, It is preferable that it is 3 to 60 minutes. If it is 3 minutes or more, bubbles dissolved in the resin composition can be removed, and if it is 60 minutes or less, the organic solvent contained in the resin composition does not volatilize and the defoaming time is shortened. And productivity can be improved.

Hereinafter, a cured film obtained by curing the resin composition for forming a cladding layer of the present invention will be described.
The tensile elastic modulus at 25 ° C. of the cured film obtained by curing the resin composition for forming a cladding layer of the present invention is preferably 1 to 2000 MPa, more preferably 10 to 1500 MPa, and further preferably 20 to 1000 MPa. When the elastic modulus of the cured film is 2000 MPa or less, when the film is bent in the thickness direction, it can be bent with a small radius of curvature. On the other hand, when it is 1 MPa or more, the cured film returns to its original shape without being stretched when a bending test or a twist test is performed, which is preferable. Since the film optical waveguide using the cured resin film for forming the cladding layer is absorbed by the upper and lower cladding layers even when a mechanical tensile force is applied, the deformation of the core can be reduced, and the transmission characteristics of the film waveguide can be reduced. Deterioration can be suppressed.

The tensile elongation at break in a tensile test at 25 ° C. of a cured film obtained by curing the resin composition for forming a cladding layer of the present invention is preferably 10 to 600%, more preferably 15 to 400%, and more preferably 20 to 200%. Is more preferable. When the tensile elongation at break is 10% or more, it becomes brittle and does not break at the time of bending, which is preferable. If it is 600% or less, the cured film does not easily stretch by the bending test and does not return to the original shape, which is preferable. The tensile elongation at break means the elongation at the time when the film is broken in the film tensile test.
If this clad layer forming resin composition is used in an optical waveguide, even if a mechanical tensile force is applied, it is absorbed by the upper and lower clad layers, so that the deformation of the core can be reduced, and the transmission characteristics of the optical waveguide can be reduced. Deterioration can be suppressed.

  In a repeated bending test of a cured film obtained by curing the resin composition for forming a cladding layer of the present invention, after performing a bending test 100,000 times with a curvature radius of 1 to 5 mm, for example, 2 mm, It is preferable that no mechanical breakage occurs. More preferably, no mechanical breakage occurs after the bending test is performed 1 million times. If no mechanical breakage occurs in the cured film, the optical waveguide using this film as the cladding layer can perform stable optical transmission for a long period of time, and it should be applied to parts that are always movable, such as the hinge part of mobile phones. Can do. In order to reduce the size of the device, it is required that the optical waveguide does not break even at a smaller radius of curvature. From this viewpoint, it is more preferable that no mechanical breakage occurs when the radius of curvature is 0.5 mm. Mechanical breakage can be confirmed by magnifying glass, under a microscope, or by visual observation.

  In the repeated twist test of the cured film obtained by curing the resin composition for forming a clad layer of the present invention, it is preferable that no mechanical breakage occurs in the cured resin film for forming a clad layer after the 100,000 times twist test. More preferably, no mechanical breakage occurs after the 1,000,000 times twist test. If no mechanical breakage occurs in the cured film, the optical waveguide using this film as the cladding layer can perform stable light transmission for a long period of time. For example, it should be applied to a mobile part such as a hinge part of a mobile phone. Can do. Mechanical breakage can be confirmed by magnifying glass, under a microscope, or by visual observation.

  The total light transmittance of a cured film having a thickness of 110 μm obtained by curing the resin composition for forming a cladding layer of the present invention is preferably 50% or more. If the transmittance is 50% or more, the visibility of the core portion in the optical waveguide is good. For example, when the optical waveguide is processed by a dicing saw, the processing can be easily positioned. From the above viewpoint, the transmittance is more preferably 60% or more, and particularly preferably 70% or more. The upper limit of the total light transmittance is not particularly limited.

  It is preferable that the cured film having a thickness of 110 μm obtained by curing the resin composition for forming a cladding layer of the present invention has a haze (haze value) of 50% or less. If the haze is 50% or less, the visibility of the core portion in the optical waveguide is good. For example, when the outer shape of the optical waveguide is processed by a dicing saw, the processing is easily positioned. From the above viewpoint, the haze is more preferably 40% or less, and particularly preferably 30% or less.

  It is preferable that the refractive index in wavelength 830nm in the temperature of 25 degreeC of the cured film formed by superposing | polymerizing and hardening | curing the resin composition for clad layer formation of this invention is 1.400-1.700. If the refractive index is 1.400 to 1.700, the refractive index is not significantly different from that of a normal optical resin, so that versatility as an optical material is not impaired. From the above viewpoint, the refractive index of the cured film is more preferably 1.425 to 1.675, and particularly preferably 1.450 to 1.650.

Hereinafter, the resin film for forming a clad layer of the present invention will be described.
The resin film for forming a clad layer of the present invention uses the resin composition for forming a clad layer, and contains the components (A) and (B), and (C) to (E) as necessary. It can manufacture easily by apply | coating the resin composition for clad layer forming to a suitable support film. Moreover, when the said resin composition for clad layer formation is diluted with the said organic solvent, it can manufacture by apply | coating a resin composition to a support film and removing an organic solvent.

There is no restriction | limiting in particular as a support film, For example, Polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Polyolefins, such as polyethylene and a polypropylene; Polycarbonate, polyamide, a polyimide, Polyamideimide, Polyetherimide, Polyether sulfide, Poly Examples include ether sulfone, polyether ketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and liquid crystal polymer. Among these, from the viewpoint of flexibility and toughness, it may be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone. preferable.
In addition, from the viewpoint of improving releasability from the resin layer, a film that has been subjected to release treatment with a silicone compound, a fluorine-containing compound, or the like may be used as necessary.

  The thickness of the support film may be appropriately changed depending on the intended flexibility, but is preferably 3 to 250 μm. When it is 3 μm or more, the film strength is sufficient, and when it is 250 μm or less, sufficient flexibility is obtained. From the above viewpoint, the thickness of the support film is more preferably 5 to 200 μm, and particularly preferably 7 to 150 μm.

  A clad layer-forming resin film produced by applying a clad layer-forming resin composition on a support film is composed of a support film, a resin layer, and a protective film, with a protective film attached to the resin layer as necessary. A three-layer structure may be used.

  The protective film is not particularly limited, but from the viewpoint of flexibility and toughness, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene are preferably used. In addition, you may use the film in which the mold release process was given with the silicone type compound, the fluorine-containing compound, etc. from a viewpoint of peelability improvement with a resin layer as needed.

  The thickness of the protective film may be appropriately changed depending on the intended flexibility, but is preferably 10 to 250 μm. When it is 10 μm or more, the film strength is sufficient, and when it is 250 μm or less, sufficient flexibility is obtained. From the above viewpoint, the thickness of the protective film is more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

  Although it does not specifically limit about the thickness of the resin layer of the resin film for clad layer formation of this invention, It is preferable that it is 5-500 micrometers normally by the thickness after drying. If the thickness is 5 μm or more, the strength of the resin film or the cured product of the resin film is sufficient because the thickness is sufficient, and if it is 500 μm or less, the drying can be performed sufficiently so that the amount of residual solvent in the resin film does not increase. When the cured resin film is heated, it does not foam.

  The clad layer-forming resin film thus obtained can be easily stored, for example, by being rolled up. Moreover, a roll-shaped film can be cut out into a suitable size and stored in a sheet shape.

Hereinafter, application examples when the resin film for forming a cladding layer of the present invention is used for an optical waveguide will be described.
The resin film for forming a clad layer of the present invention is preferably used for at least one of a lower clad and an upper clad of an optical waveguide.
Next, the resin composition for forming a core part used in the optical waveguide of the present invention uses a resin composition that is designed so that the core part has a higher refractive index than the cladding layer and can form a core pattern with actinic rays. A photosensitive resin composition is preferable.
The core part-forming resin film can be produced using the core part-forming resin composition by the same method as the cladding layer-forming resin film. The support film used in the production process of the core portion forming resin film is not particularly limited as long as it can transmit the actinic ray for exposure used for core pattern formation. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. Polyester such as phthalate; Polyolefin such as polyethylene and polypropylene; Polycarbonate, Polyamide, Polyimide, Polyamideimide, Polyetherimide, Polyethersulfide, Polyethersulfone, Polyetherketone, Polyphenylenesulfide, Polyarylate, Polysulfone, Liquid crystal polymer Etc.
Among these, the polyester and the polyolefin are preferable from the viewpoints of the transmittance of exposure actinic rays, flexibility, and toughness. Furthermore, it is more preferable to use a highly transparent support film from the viewpoint of improving the transmittance of exposure actinic rays and reducing the side wall roughness of the core pattern. Examples of such highly transparent support films include Cosmo Shine A1517 and Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.
In addition, from the viewpoint of improving releasability from the resin layer, a film that has been subjected to release treatment with a silicone compound, a fluorine-containing compound, or the like may be used as necessary.

  The thickness of the support film of the core portion forming resin film is preferably 5 to 50 μm. If it is 5 μm or more, the strength as a support is sufficient, and if it is 50 μm or less, the gap between the photomask and the core portion forming resin layer is not increased during the formation of the core pattern, and the pattern resolution is good. From the above viewpoint, the thickness of the support film is more preferably 10 to 40 μm, and particularly preferably 15 to 30 μm.

  The core part-forming resin film produced by applying the core part-forming resin composition onto the support film is attached to the resin layer as necessary, and the support film, the resin layer, and the protective film. It is good also as a 3 layer structure which consists of.

  The core part-forming resin film thus obtained can be easily stored by, for example, winding it into a roll. Moreover, a roll-shaped film can be cut out into a suitable size and stored in a sheet shape.

Hereinafter, the optical waveguide of the present invention will be described.
A sectional view of the optical waveguide is shown in FIG. The optical waveguide 1 is formed on a substrate 5 and has a core part 2 made of a core part-forming resin composition having a high refractive index, a lower clad layer 4 made of a resin composition for forming a clad layer having a low refractive index, and An upper cladding layer 3 is used.
The resin composition for forming a cladding layer and the resin film for forming a cladding layer of the present invention are preferably used for at least one of the lower cladding layer 4 and the upper cladding layer 3 of the optical waveguide 1.

  By using the resin film for forming the cladding layer and the resin film for forming the core part, the flatness of each layer, the interlayer adhesion between the cladding and the core, and the resolution (correspondence between thin lines or narrow lines) when forming the optical waveguide core pattern It can be further improved, and it is excellent in flatness, and it becomes possible to form a fine pattern with a small line width and line.

  In the optical waveguide 1, the material of the base material 5 is not particularly limited. For example, a glass epoxy resin substrate, a ceramic substrate, a glass substrate, a silicon substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, a substrate with a metal layer, Examples thereof include a plastic film, a plastic film with a resin layer, and a plastic film with a metal layer.

The optical waveguide 1 can be a flexible optical waveguide using a flexible and tough substrate as the substrate 5, for example, a support film of a resin film for forming a clad layer as the substrate. Moreover, you may make the base material 5 function as a protective film of the optical waveguide 1 at this time. By using a support film substrate as the substrate 5, flexibility and toughness can be imparted to the optical waveguide 1. At this time, the clad layer forming resin is preferably formed on a support film that has been subjected to an adhesion treatment. Furthermore, by making the base material 5 function as a protective film, the optical waveguide 1 is not subjected to dirt or scratches, so that the ease of handling is improved.
From the above viewpoint, the base material 5 having a function as a protective film is disposed outside the upper cladding layer 3 as shown in FIG. 1B, or the lower cladding layer 4 as shown in FIG. And the base material 5 which has a function as a protective film may be arrange | positioned on the outer side of both of the upper clad layers 3.
If the optical waveguide 1 has sufficient flexibility and toughness, the substrate 5 having a function as a protective film may not be disposed as shown in FIG.

The thickness of the lower clad layer 4 is not particularly limited, but is preferably 2 to 200 μm. If it is 2 μm or more, it becomes easy to confine the propagating light inside the core, and if it is 200 μm or less, the entire thickness of the optical waveguide 1 is not too large. The thickness of the lower cladding layer 4 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the lower surface of the lower cladding layer 4.
Although there is no restriction | limiting in particular about the thickness of the resin film for lower clad layer formation, Thickness is adjusted so that the thickness of the lower clad layer 4 after hardening may become said range.

  Although there is no restriction | limiting in particular about the height of the core part 2, It is preferable that it is 10-150 micrometers. When the height of the core is 10 μm or more, the alignment tolerance is not reduced in coupling with the light emitting / receiving element or the optical fiber after the optical waveguide is formed, and when the core portion is 150 μm or less, the light is received and emitted after the optical waveguide is formed. In coupling with an element or an optical fiber, coupling efficiency is not reduced. From the above viewpoint, the height of the core part is more preferably 15 to 130 μm, and particularly preferably 20 to 120 μm. In addition, there is no restriction | limiting in particular about the thickness of the resin film for core part formation, but thickness is adjusted so that the height of the core part after hardening may become said range.

  The thickness of the upper clad layer 3 is not particularly limited as long as the core portion 2 can be embedded, but the thickness after drying is preferably 12 to 500 μm. The thickness of the upper clad layer 3 may be the same as or different from the thickness of the lower clad layer 4 that is formed first, but is thicker than the thickness of the lower clad layer 4 from the viewpoint of embedding the core portion 2. It is preferable. The thickness of the upper cladding layer 3 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the upper surface of the upper cladding layer 3.

  In the repeated bending test of the flexible optical waveguide of the present invention, it is preferable that no mechanical breakage occurs in the flexible optical waveguide after the bending test is performed 100,000 times with a curvature radius of 1 to 5 mm, for example, 2 mm. More preferably, no mechanical breakage occurs after the bending test is performed 1 million times. If mechanical breakage does not occur in the optical waveguide, stable optical transmission can be performed for a long period of time. For example, the optical waveguide can be applied to a part that is always movable, such as a hinge part of a mobile phone. In order to reduce the size of the device, it is required that the optical waveguide does not break even at a smaller radius of curvature. From this viewpoint, it is more preferable that no mechanical breakage occurs when the radius of curvature is 0.5 mm. Mechanical breakage can be confirmed by magnifying glass, under a microscope, or by visual observation.

The film optical waveguide of the present invention preferably has a cladding layer having a small tensile modulus of elasticity of 1 to 2000 MPa, so that the followability at the interface when the film optical waveguide bends or recovers its shape is improved. Can do.
In the repeated twist test of the flexible optical waveguide of the present invention, it is preferable that no mechanical breakage occurs in the flexible optical waveguide after the 100,000-time twist test. More preferably, no mechanical breakage occurs after the 1,000,000 times twist test. If mechanical breakage does not occur in the optical waveguide, stable optical transmission can be performed for a long period of time. For example, the optical waveguide can be applied to a part that is always movable, such as a hinge part of a mobile phone. Mechanical breakage can be confirmed by magnifying glass, under a microscope, or by visual observation.

In the optical waveguide of the present invention, the relative refractive index difference between the core portion and the cladding layer is preferably 1 to 10%. When it is 1% or more, the light propagating through the core portion at the time of bending does not leak into the cladding layer. If it is 10% or less, the propagation light does not spread too much at the connection portion such as the optical waveguide and the optical fiber, and the coupling loss does not increase. From the above viewpoint, it is more preferably 1.5 to 7.5%, and particularly preferably 2 to 5%. The relative refractive index difference was determined by the following formula.
Specific refractive index difference (%) = [(refractive index of core part) ² − (refractive index of clad layer) ² ] / [2 × (refractive index of core part) ² ] × 100

  In the optical waveguide of the present invention, the light propagation loss is preferably 0.3 dB / cm or less. If it is 0.3 dB / cm or less, the loss of light becomes small and the intensity of the transmission signal is sufficient. From the above viewpoint, it is more preferably 0.2 dB / cm or less.

The optical waveguide of the present invention is excellent in bending resistance, twist resistance, transparency, reliability, and heat resistance, and can also be used as an optical transmission line of an optical module. As the form of the optical module, for example, an optical waveguide with an optical fiber in which optical fibers are connected to both ends of the optical waveguide, an optical waveguide with a connector in which connectors are connected to both ends of the optical waveguide, and an optical waveguide and a printed wiring board are combined. Examples include an opto-electric composite substrate, an opto-electric conversion module that combines an optical waveguide, an optical / electric conversion element that converts an optical signal and an electrical signal, and a wavelength multiplexer / demultiplexer that combines an optical waveguide and a wavelength division filter.
In the photoelectric composite substrate, the printed wiring board to be combined is not particularly limited, and examples thereof include a rigid substrate such as a glass epoxy substrate and a ceramic substrate, a flexible substrate such as a polyimide substrate and a polyethylene terephthalate substrate.

Hereinafter, the manufacturing method for forming the optical waveguide 1 using the clad layer forming resin composition and / or the clad layer forming resin film of the present invention will be described. In the following description, the clad layer forming resin and the core portion forming resin are collectively referred to as “optical waveguide forming resin”.
There is no restriction | limiting in particular as a method of manufacturing the optical waveguide 1 of this invention, For example, the resin layer for optical waveguide formation is formed on a base material using the resin composition for optical waveguide formation, or the resin film for optical waveguide formation. For example.

  The substrate used in the present invention is not particularly limited, but is a glass epoxy resin substrate, ceramic substrate, glass substrate, silicon substrate, plastic substrate, metal substrate, substrate with resin layer, substrate with metal layer, plastic film, resin Examples thereof include a plastic film with a layer and a plastic film with a metal layer.

The method for forming the optical waveguide forming resin layer is not particularly limited. For example, using the optical waveguide forming resin composition, spin coating, dip coating, spraying, bar coating, roll coating, Examples of the coating method include a curtain coating method, a gravure coating method, a screen coating method, and an inkjet coating method.
When the resin composition for forming an optical waveguide is diluted with a suitable organic solvent, a step of drying may be added after forming the resin layer as necessary. Examples of the drying method include heat drying and reduced pressure drying. Moreover, you may use these together as needed.

As another method of forming the optical waveguide forming resin layer, there is a method of forming by an lamination method using an optical waveguide forming resin film using the optical waveguide forming resin composition.
Among these, from the viewpoint that an optical waveguide having excellent flatness and having a fine pattern with a small line width and a small line pattern can be formed, a method of producing by a lamination method using a resin film for forming an optical waveguide is preferable.

Hereinafter, although the manufacturing method for forming the optical waveguide 1 using the resin film for optical waveguide formation for a lower clad layer, a core part, and an upper clad layer is demonstrated, this invention is not restrict | limited to this.
First, as a first step, a resin film for forming a lower cladding layer is laminated on the substrate 5. There is no restriction | limiting in particular as a lamination | stacking method in a 1st process, For example, the method of laminating | stacking by crimping, heating using a roll laminator or a flat plate laminator etc. is mentioned. The flat plate laminator in the present invention refers to a laminator in which a laminated material is sandwiched between a pair of flat plates and pressed by pressing the flat plate. For example, a vacuum pressurizing laminator can be suitably used. The heating temperature here is preferably 20 to 130 ° C., and the pressure bonding pressure is preferably 0.1 to 1.0 MPa, but these conditions are not particularly limited. When a protective film exists in the resin film for lower clad layer formation, it laminates | stacks, after removing a protective film.

  When laminating using a vacuum pressurizing laminator, a lower clad layer forming resin film may be temporarily pasted onto the substrate 5 in advance using a roll laminator. Here, from the viewpoint of improving adhesion and followability, it is preferable to perform temporary bonding while pressing, and when pressing, a laminator having a heat roll may be used while heating. The laminating temperature is preferably 20 to 130 ° C. When it is 20 ° C. or higher, the adhesion between the resin film for forming the lower clad layer and the substrate 5 is improved, and when it is 130 ° C. or lower, the resin layer does not flow too much at the time of roll lamination, and the required film Thickness is obtained. From the above viewpoint, the laminating temperature is more preferably 40 to 100 ° C. The pressure during lamination is preferably 0.2 to 0.9 MPa, and the lamination speed is preferably 0.1 to 3 m / min, but these conditions are not particularly limited.

The lower clad layer forming resin layer laminated on the substrate 5 is cured by light and / or heat to form the lower clad layer 4. The removal of the support film of the lower clad layer forming resin film may be performed either before or after curing.
The irradiation amount of actinic rays when the lower clad layer-forming resin layer is cured with light is preferably 0.1 to 5 J / cm ² , but there is no particular limitation on this condition. Moreover, when actinic rays permeate | transmit a base material, in order to make it harden | cure efficiently, the double-sided exposure machine which can irradiate actinic rays simultaneously from both surfaces can be used. Moreover, you may irradiate actinic light, heating. In addition, as a process after photocuring, you may perform a 50-200 degreeC heat processing as needed.
The heating temperature when the lower clad layer forming resin layer is cured by heat is preferably 50 to 200 ° C., but this condition is not particularly limited.

When the support film for the resin film for forming the lower clad layer functions as the protective film 5 for the optical waveguide 1, it is cured under the same conditions as described above by light and / or heat without laminating the resin film for forming the lower clad layer. Then, the lower cladding layer 4 may be formed.
The protective film for the resin film for forming the lower cladding layer may be removed before curing or after curing.

  As the second step, a core part-forming resin film is laminated on the lower cladding layer 4 by the same method as in the first step. Here, the core part forming resin layer is preferably made of a photosensitive resin composition that is designed to have a higher refractive index than the lower clad layer forming resin layer and can form a core pattern with actinic rays.

As a third step, the core portion 2 (core pattern) is exposed. The method for exposing the core 2 is not particularly limited. For example, a method of irradiating actinic rays in an image form through a negative mask pattern called artwork, a direct actinic ray without passing through a photomask using laser direct drawing And the like.
Examples of the active light source include a light source that effectively emits ultraviolet light, such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a mercury vapor arc lamp, a metal halide lamp, a xenon lamp, and a carbon arc lamp. Other examples include light sources that effectively emit visible light, such as photographic flood bulbs and solar lamps.

It is preferable that the irradiation amount of the actinic ray at the time of exposing the core part 2 is 0.01-10 J / cm < ² >. When it is 0.01 J / cm ² or more, the curing reaction proceeds sufficiently, the core portion 2 is not washed away by development, and when it is 10 J / cm ² or less, the core portion 2 becomes thick due to excessive exposure. This is preferable because a fine pattern can be formed. From these viewpoints, the dose of active ray is more preferably from 0.03~5J / cm ^2, and particularly preferably 0.05~3J / cm ^2.
The exposure of the core part 2 may be performed through the support film of the core part forming resin film, or may be performed after removing the support film.

  Moreover, you may perform post-exposure heating as needed from a viewpoint of the resolution of the core part 2 and adhesive improvement after exposure. The time from ultraviolet irradiation to post-exposure heating is preferably within 10 minutes, but this condition is not particularly limited. The post-exposure heating temperature is preferably 40 to 160 ° C., and the time is preferably 30 seconds to 10 minutes, but these conditions are not particularly limited.

As a 4th process, when exposed through the support film of the resin film for core part formation, this is removed and it develops using the developing solution suitable for the composition of the resin layer for core part formation.
The development method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these image development methods together as needed.
The developer is not particularly limited, and is an organic solvent-based developer such as an organic solvent or a semi-aqueous developer composed of an organic solvent and water; an alkaline aqueous solution, an alkaline aqueous solution composed of an alkaline aqueous solution and one or more organic solvents. And alkaline developers. The development temperature is adjusted according to the developability of the core layer forming resin layer.

The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; chain ethers such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and dibutyl ether. Cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; ethylene carbonate, propylene carbonate Which carbonic acid ester; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol Polyhydric alcohol alkyl ethers such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Polyether alcohol acetate such as ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N, Examples include amides such as N-dimethylacetamide and N-methylpyrrolidone.
These organic solvents can be used alone or in combination of two or more. Further, a surface active agent, an antifoaming agent or the like may be mixed in the organic solvent.

The semi-aqueous developer is not particularly limited as long as it is composed of one or more organic solvents and water.
The concentration of the organic solvent is usually preferably 2 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the semi-aqueous developer.

The base of the alkaline aqueous solution is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; Alkali metal bicarbonates such as lithium hydrogen, sodium bicarbonate, potassium bicarbonate; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; Sodium salts such as sodium acid and sodium metasilicate; ammonium salts such as ammonium carbonate and ammonium hydrogen carbonate; tetramethylammonium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 3-propanediol, and organic bases such as 1,3-diamino-propanol-2-morpholine.
These bases can be used alone or in combination of two or more.
The pH of the alkaline aqueous solution used for development is preferably 9-14. Moreover, you may mix surfactant, an antifoamer, etc. in alkaline aqueous solution.

The alkaline quasi-aqueous developer is not particularly limited as long as it is composed of an alkaline aqueous solution and one or more organic solvents. The pH of the alkaline quasi-aqueous developer is preferably as small as possible within a range where development can be sufficiently performed, preferably pH 8 to 13, and more preferably pH 9 to 12.
The concentration of the organic solvent is usually preferably 2 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the alkaline quasi-aqueous developer.

As a treatment after development, the organic solvent, a semi-aqueous cleaning solution composed of the organic solvent and water, or water may be used as necessary.
The cleaning method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these washing | cleaning methods together as needed.
The said organic solvent can be used individually or in combination of 2 or more types. In the semi-aqueous cleaning liquid, the concentration of the organic solvent is usually preferably 2 to 90% by mass. The washing temperature is adjusted in accordance with the developability of the core portion forming resin layer.

As processing after development or washing, exposure and / or heating may be performed as necessary from the viewpoint of improving curability and adhesion of the core portion 2. The heating temperature is preferably 40 to 200 ° C., and the irradiation amount of active light is preferably 0.01 to 10 J / cm ² , but these conditions are not particularly limited.

  As a fifth step, an upper clad layer forming resin film is laminated on the lower clad layer 4 and the core portion 2 by the same method as the first and second steps. Here, the upper clad layer forming resin layer is designed to have a lower refractive index than the core portion forming resin layer. The thickness of the upper clad forming resin layer is preferably larger than the height of the core portion 2.

Next, the upper clad layer forming resin layer is cured by light and / or heat to form the upper clad layer 3 in the same manner as in the first step.
The irradiation amount of actinic rays when the upper clad layer-forming resin layer is cured by light is preferably 0.1 to 30 J / cm ² , but this condition is not particularly limited. Moreover, when actinic rays permeate | transmit a base material, in order to make it harden | cure efficiently, the double-sided exposure machine which can irradiate actinic rays simultaneously from both surfaces can be used. Moreover, you may irradiate actinic light, heating as needed, and you may heat-process as a process after photocuring. The heating temperature during and / or after irradiation with actinic rays is preferably 50 to 200 ° C., but these conditions are not particularly limited.
The heating temperature when the upper clad layer forming resin layer is cured by heat is preferably 50 to 200 ° C., but this condition is not particularly limited.
In addition, when the removal of the support film of the resin film for upper clad layer formation is required, you may remove before hardening or after hardening.
The optical waveguide 1 can be manufactured through the above steps.

The following examples of the present invention will be described more specifically, but the present invention is not limited to these examples.
Production Example 1
[Production of silicone-modified polyamideimide A-1]
In a flask equipped with a stirrer, a moisture meter with a cock connected to a cooling pipe, a gas introduction pipe, and a thermometer, 32.0 parts by mass of siloxane diamine (X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.), poly 40.0 parts by mass of oxypropylenediamine (Jeffamine D2000 manufactured by Mitsui Chemicals Fine Co., Ltd.), 0.94 parts by mass of 4,4′-diaminocyclohexylmethane, 17.9 parts by mass of trimellitic anhydride, and N-methyl-2 -238 parts by mass of pyrrolidone was weighed and stirred at 80 ° C for 30 minutes while introducing nitrogen gas.
100 parts by mass of toluene was added and stirred at 160 ° C. for 6 hours to produce diimide dicarboxylic acid by imide ring closure reaction by dehydration and reflux, and then toluene was distilled off.
After cooling, 13.3 parts by mass of 4,4′-diphenylmethane diisocyanate was added and stirred at 150 ° C. for 2 hours to allow the amidation reaction to proceed.
After cooling, 1.6 parts by mass of trimellitic anhydride is added, and stirred at 80 ° C. for 1 hour to react the terminal isocyanate group with trimellitic anhydride, and a silicone-modified polyamideimide resin A having a carboxyl group at the terminal -1 solution (solid content 30% by mass) was obtained.
The obtained A-1 solution was reprecipitated using water / methanol (50/50 mass ratio), and the precipitated A-1 was separated by filtration. After drying at 40 ° C. for 12 hours in a vacuum oven, the product was dissolved in cyclohexanone to obtain an A-1 solution (solid content: 40% by mass).

[Measurement of weight average molecular weight]
It was 37,000 as a result of measuring the weight average molecular weight (standard polystyrene conversion) of the obtained silicone modification polyamideimide using GPC (Tosoh Corporation SD-8022 / DP-8020 / RI-8020). In addition, Hitachi Chemical Co., Ltd. Gelpack GL-A150-S / GL-A160-S was used for the column.

Production Example 2
[Production of silicone-modified polyamideimide A-2]
92.8 parts by mass of siloxane diamine (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a flask equipped with a stirrer, a moisture meter with a cock connected to a condenser, a gas inlet tube, and a thermometer. 2,2-bis [4- (4-aminophenoxy) phenyl] propane 24.6 parts by weight, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane 16.9 parts by weight, anhydrous tri 81.4 parts by mass of merit acid and 517.6 parts by mass of N-methyl-2-pyrrolidone were weighed and stirred at 80 ° C. for 30 minutes while introducing nitrogen gas.
100 parts by mass of toluene was added, and the mixture was stirred at 160 ° C. for 2 hours to produce diimide dicarboxylic acid by imide ring closure reaction by dehydration and reflux, and then toluene was distilled off.
After cooling, 35.9 parts by mass of 4,4′-diphenylmethane diisocyanate and 32.0 parts by mass of 4-tolylene diisocyanate are added, and the mixture is stirred at 190 ° C. for 2 hours to advance the amidation reaction. A resin A-2 solution (solid content: 25% by mass) was obtained.
As a result of measuring the weight average molecular weight of A-2 by the same method as in Production Example 1, it was 44,000.

Production Example 3
[Production of butadiene-modified polyamideimide A-3]
In a flask equipped with a stirrer, a moisture meter with a cock connected to a condenser, a gas inlet tube, and a thermometer, 44.5 parts by mass of 4,4′-diaminocyclohexylmethane, 82.1 mass of trimellitic anhydride And 1200 parts by mass of N-methyl-2-pyrrolidone were weighed and stirred at 80 ° C. for 30 minutes while introducing nitrogen gas.
100 parts by mass of toluene was added, and the mixture was stirred at 160 ° C. for 2 hours to produce diimide dicarboxylic acid by imide ring closure reaction by dehydration and reflux, and then toluene was distilled off.
After cooling, 102.7 parts by mass of both-end carboxyl group polybutadiene (C-1000, Nippon Soda Co., Ltd.), 115.5 parts by mass of both-end carboxyl group hydrogenated polybutadiene (CI-1000, Nippon Soda Co., Ltd.), and 4,4 91.0 parts by mass of '-diphenylmethane diisocyanate was added and stirred at 190 ° C. for 2 hours to advance the amidation reaction to obtain a butadiene-modified polyamideimide resin A-3 (solid content: 32% by mass) solution.
It was 48,000 as a result of measuring the weight average molecular weight of A-3 by the method similar to manufacture example 1.

Example 1
[Preparation of Clad Layer Forming Resin Varnish CLV-1]
(A) Polyamideimide as the A-1 solution (solid content 40% by mass) 212.5 parts by mass (solid content 85 parts by mass), (B) As the polymerizable compound, dicyclopentadiene-phenol type epoxy resin (DIC) HP-7200L manufactured by Co., Ltd., 15 parts by mass of epoxy equivalent 250 g / eq), (D) 0.01 part by mass of 1-cyanoethyl-2-phenylimidazole (2PZ-CN manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator After stirring and mixing, degassing was performed under reduced pressure to obtain a clad layer forming resin varnish CLV-1.

[Preparation of Cladding Layer Forming Resin Film CLF-1]
Clad layer-forming resin varnish CLV-1 is coated on a release treatment surface of a surface release treatment PET film (A53 manufactured by Teijin DuPont Films Ltd., thickness 50 μm) (Multicoater TM-MC manufactured by Hirano Techseed Co., Ltd.). And then dried at 100 ° C. for 20 minutes, and then a surface release treatment PET film (A31 manufactured by Teijin DuPont Films Ltd., thickness 25 μm) is pasted as a protective film to obtain a resin film CLF-1 for forming a clad layer It was. At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine. In this embodiment, the thickness after curing is 30 μm for the resin film for forming the lower cladding layer, and the upper cladding layer. The resin film for forming was adjusted to 80 μm, and the cured film for refractive index measurement was adjusted to 50 μm.

[Tensile test, bending endurance test, twist endurance test, and production of cured film for total light transmittance and haze measurement]
Using a roll laminator (HLM-1500 manufactured by Hitachi Chemical Technoplant Co., Ltd.), the lower clad layer forming resin film CLF-1 from which the protective film (A31) has been removed is used for forming the upper clad layer from which the protective film (A31) has been removed. On the resin film CLF-1, it laminated | stacked on the conditions of pressure 0.4MPa, temperature 80 degreeC, and speed 0.4m / min. After curing at 160 ° C. for 1 hour, the support film (A53) was removed to obtain a cured film having a thickness of 110 μm.

[Tensile test]
The obtained cured film (width 10 mm, length 70 mm) was subjected to a tensile test (distance between grips 50 mm) using a tensile tester (RTM-100 manufactured by Orientec Co., Ltd.) at a temperature of 25 ° C. and a tensile speed of 50 mm / min, in accordance with JIS K 7127.
(1) Tensile modulus The tensile modulus was calculated by the following equation using the first linear portion of the tensile stress-strain curve.
Tensile stress difference (N) ÷ original average cross-sectional area of the cured film (mm ²⁾ ÷ difference (2) Tensile elongation at break of the strain between the same two points between two points of the tensile modulus (MPa) = a straight line The elongation at break was calculated according to the following formula.
Tensile elongation at break (%) = (distance between grips at break (mm) −initial distance between grips (mm)) ÷ initial distance between grips (mm) × 100

[Bending durability test]
A bending durability test of the obtained cured film (width 5 mm, length 100 mm) was performed using a bending durability tester (manufactured by Daisho Electronics Co., Ltd.), a bending angle of 0 to 180 °, a bending radius of 2 mm, and a bending speed of 2 times / second. The bending durability test was performed under the conditions described above, and the presence or absence of breakage of the cured film was observed. Evaluation was made according to the following criteria.
○: Not broken after 100,000 times ×: Broken after less than 100,000 times

[Twist durability test]
A twist endurance test of the obtained cured film (width 2 mm, length 40 mm) was performed using a bending endurance tester (manufactured by Daisho Electronics Co., Ltd.) with a twist angle of ± 180 °, a distance between grippers of 20 mm, and a twist rate of 0. A twisting durability test was performed under the condition of 5 times / second, and the presence or absence of breakage of the cured film was observed. Evaluation was made according to the following criteria.
○: Not broken after 100,000 times ×: Broken after less than 100,000 times

[Measurement of total light transmittance and haze]
The total light transmittance and haze of the obtained cured film were measured using a color separation / turbidity measuring device (COH 400 manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluation was made according to the following criteria.
(1) Total light transmittance ○: 50% or more ×: Less than 50% (2) Haze ○: 50% or less ×: More than 50%

[Preparation of resin varnish COV-1 for core formation]
As binder polymer, propylene glycol monomethyl ether acetate solution of phenoxy resin (YP-70 manufactured by Tohto Kasei Co., Ltd., solid content 40% by mass) 63 parts by mass (solid content 25 parts by mass), and as the polymerizable compound, ethoxylated fluorene type di Propylene glycol monomethyl ether acetate solution of acrylate (Shin Nakamura Chemical Co., Ltd. A-BPEF / PGMAC70, solid content 70% by mass) 54 parts by mass (solid content 38 parts by mass), bisphenol A type epoxy acrylate (Shin Nakamura Chemical Co., Ltd.) EA-1020) 38 parts by mass, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Ciba Japan) as photo radical polymerization initiator Irgacure 2959) 1 part by mass And 1 part by mass of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819, manufactured by Ciba Japan Co., Ltd.) was stirred and mixed, and then degassed under reduced pressure to obtain a resin varnish COV-1 for forming a core part. It was.

[Preparation of Core Part Forming Resin Film COF-1]
The core part-forming resin varnish COV-1 was applied to the non-treated surface of a PET film (A1517 manufactured by Toyobo Co., Ltd., thickness 16 μm) using the coating machine, at 80 ° C. for 10 minutes, and at 100 ° C. It was dried for 10 minutes, and then a surface release treatment PET film (A31 manufactured by Teijin DuPont Films Ltd., thickness 25 μm) was applied as a protective film to obtain a resin film COF-1 for forming a core part. At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine, but in this example, the thickness after curing was adjusted to 50 μm.

[Production of cured film for refractive index measurement]
(1) Clad Layer Forming Resin Film After curing the clad layer forming resin film CLF-1 at 160 ° C. for 1 hour, the support film (A53) and the protective film (A31) are removed to obtain a cured film having a thickness of 50 μm. Obtained.
(2) Core part forming resin film Using a UV exposure machine (MAP-1200-L, manufactured by Dainippon Screen Co., Ltd.) for the core part forming resin film COF-1, 2000 mJ / cm ^{2 of} ultraviolet rays (wavelength 365 nm) was irradiated. did. The support film (A1517) and the protective film (A31) were removed, and after heat treatment at 160 ° C. for 1 hour, a cured film having a thickness of 50 μm was obtained.

[Measurement of refractive index]
The refractive index at a wavelength of 830 nm at a temperature of 25 ° C. of the obtained cured film was measured using a prism coupler (manufactured by SAIRON TECHNOLOGY, SPA-4000).

[Calculation of relative refractive index]
The refractive index at a wavelength of 830 nm at a temperature of 25 ° C. of the obtained cured film was measured using a prism coupler (manufactured by SAIRON TECHNOLOGY, SPA-4000).
The relative refractive index difference was calculated by the following formula.
Relative Refractive Index Difference (%) = [(Refractive Index of Resin Cured Film for Forming Core Part) ² − (Refractive Index of Resin Cured Film for Forming Clad Layer) ² ] ÷ [2 × (of Resin Cured Film for Forming Core Part Refractive index) ² ] × 100

[Fabrication of optical waveguide]
After removing the protective film (A31) of the resin film CLF-1 for forming the lower cladding layer, it was cured at 160 ° C. for 1 hour to form a lower cladding layer.

Subsequently, using the roll laminator, the core part-forming resin film COF-1 from which the protective film (A31) has been removed is placed on the lower cladding layer at a pressure of 0.4 MPa, a temperature of 80 ° C., and a speed of 0.4 m / min. It laminated | stacked on conditions. Furthermore, using a vacuum pressurization type laminator (MVLP-500 / 600 manufactured by Meiki Seisakusho Co., Ltd.), pressure bonding was performed under the conditions of a pressure of 0.4 MPa, a temperature of 80 ° C., and a pressurization time of 30 seconds.
Next, the film was irradiated with ultraviolet rays (wavelength 365 nm) of 500 mJ / cm ² through the negative photomask having a width of 50 μm with the above-described ultraviolet exposure machine, and then heated after exposure at 80 ° C. for 5 minutes. The support film (A1517) was removed, and the core was developed using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 70/30 mass ratio), and then propylene glycol monomethyl ether and then isopropanol were used. Washed and dried by heating at 100 ° C. for 1 hour.

  Next, the upper cladding layer-forming resin film CLF-1 from which the protective film (A31) has been removed using the vacuum pressurizing laminator is applied on the core and the lower cladding layer at a pressure of 0.4 MPa, a temperature of 80 ° C. Lamination was performed under a pressure time of 30 seconds. After removing the support film (A53) of the resin film for lower clad layer formation CLF-1, it was cured at 160 ° C. for 1 hour to form an upper clad layer. Subsequently, the support film (A53) of the upper clad layer-forming resin film CLF-1 was removed to obtain an optical waveguide. Thereafter, an optical waveguide having a waveguide length of 10 cm was cut out using a dicing saw (DAD-341 manufactured by DISCO Corporation).

Example 2
[Preparation of Clad Layer Forming Resin Varnish CLV-2 and Production of Clad Layer Forming Resin Film CLF-2]
(A) Polyamideimide as the A-1 solution (solid content 40% by mass) 150 parts by mass (solid content 60 parts by mass), (B) As the polymerizable compound, bisphenol A type epoxy resin (YD manufactured by Toto Kasei Co., Ltd.) -8125, epoxy equivalent 170 g / eq) 12.7 parts by mass, trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts by mass, (C) as epoxy resin curing agent, bisphenol A novolac resin Methyl ethyl ketone solution (DIC Corporation, phenolic hydroxyl group equivalent 118 g / eq) 12.1 parts by mass (solid content 7.3 parts by mass), (D) 1-cyanoethyl-2-phenylimidazole (Shikoku Chemical Industries, Ltd.) as a curing accelerator (2PZ-CN) 0.3 parts by mass, (E) As a radical polymerization initiator, bis (2,4 6- trimethyl benzoyl) phenyl phosphine oxide (Ciba Japan Co., Ltd. Irgacure 819) 2 parts by mass, after stirring and mixing, and vacuum degassing, to obtain a cladding layer-forming resin varnish CLV-2.
In the same manner as in Example 1, a clad layer forming resin film CLF-2 was obtained.

[Tensile test, bending endurance test, twist endurance test, and production of cured film for total light transmittance and haze measurement]
Using a roll laminator (HLM-1500 manufactured by Hitachi Chemical Technoplant Co., Ltd.), the lower clad layer forming resin film CLF-2 from which the protective film (A31) has been removed, and the upper clad layer forming from which the protective film (A31) has been removed On the resin film CLF-2, it laminated | stacked on the conditions of pressure 0.4MPa, temperature 80 degreeC, and speed 0.4m / min. Next, ultraviolet rays (wavelength 365 nm) were irradiated with 2000 mJ / cm ² using the ultraviolet exposure machine. After curing at 160 ° C. for 1 hour, the support film (A53) was removed to obtain a cured film having a thickness of 110 μm.

[Production of cured film for refractive index measurement]
The clad layer forming resin film CLF-2 was irradiated with 2000 mJ / cm ^{2 of} ultraviolet rays (wavelength 365 nm) using the ultraviolet exposure machine. After curing at 160 ° C. for 1 hour, the support film (A53) and the protective film (A31) were removed to obtain a cured film having a thickness of 50 μm.

[Tensile test, bending endurance test, twist endurance test, total light transmittance and haze measurement, and refractive index measurement]
In the same manner as in Example 2, a tensile test, a bending durability test, a twisting durability test, a total light transmittance and a haze measurement, and a refractive index measurement were performed. The results are shown in Table 2 and Table 3.

[Fabrication of optical waveguide]
Using the ultraviolet exposure machine, the lower clad layer forming resin film CLF-2 was irradiated with 2000 mJ / cm ² of ultraviolet rays (wavelength 365 nm). After removing the protective film (A31), it was cured at 160 ° C. for 1 hour to form a lower cladding layer, and the core part was formed in the same manner as in Example 1 using the core part forming resin film COF-1. Formed.
Next, the upper clad layer forming resin film CLF-2 from which the protective film (A31) has been removed using the vacuum pressurizing laminator is applied to the core and lower clad layer at a pressure of 0.4 MPa, a temperature of 80 ° C. Lamination was performed under a pressure time of 30 seconds. Ultraviolet rays (wavelength 365 nm) were irradiated at 2000 mJ / cm ² to remove the support film (A53) of the resin film CLF-2 for forming the lower cladding layer, and then cured at 160 ° C. for 1 hour to form an upper cladding layer. Subsequently, the support film (A53) of the upper clad layer-forming resin film CLF-1 was removed to obtain an optical waveguide. Thereafter, an optical waveguide having a waveguide length of 10 cm was cut out using a dicing saw (DAD-341 manufactured by DISCO Corporation).

Examples 3 to 6 and Comparative Example 1
According to the compounding ratio shown in Table 1, clad layer forming resin varnish CLV-3-7 was prepared, and the clad layer forming resin film CLF-3-3 was prepared in the same manner as in Example 1 or 2 and under the conditions shown in Table 2. 7 was produced. Table 2 shows the results of carrying out a tensile test, a bending durability test, a twisting durability test, a total light transmittance and a haze measurement of the cured film.
Then, the optical waveguide was produced by the same method as Example 1 or 2 using these optical waveguide formation resin films. Table 3 shows the combination of the core portion forming resin film and the clad layer forming resin film used for the production of the optical waveguide, the result of measuring the refractive index of each cured film, and the relative refractive index difference.

* 1: Silicone-modified polyamideimide A-1 solution produced in Production Example 1 * 2: Silicone-modified polyamideimide A-2 solution produced in Production Example 2 * 3: butadiene-modified polyamideimide A-3 produced in Production Example 3 Solution * 4: Propylene glycol monomethyl ether acetate solution of phenoxy resin (manufactured by Tohto Kasei Co., Ltd.)
* 5: Dicyclopentadiene-phenol type epoxy resin (manufactured by DIC Corporation, epoxy equivalent 250 g / eq)
* 6: Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 170 g / eq)
* 7: Hydrogenated bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 210 g / eq)
* 8: Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 9: Ethoxylated trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 10: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 11: Diphenylmethane bismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
* 12: Methyl ethyl ketone solution of bisphenol A novolak resin (manufactured by DIC Corporation, phenolic hydroxyl group equivalent 118 g / eq)
* 13: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Wakayama Seika Co., Ltd.)
* 14: 1-cyanoethyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
* 15: 2-ethyl-4-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.)
* 16: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Ciba Japan Co., Ltd.)
* 17: 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinylphenyl) -butan-1-one (manufactured by Ciba Japan Co., Ltd.)
* 18: Di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation)

* 19: wavelength 365nm
* 20: ○ ... No break after 100,000 times, x ... Break after 100,000 times * 21: ○ ... No break after 100,000 times, x ... Break less than 100,000 times * 22: ○ ... 50 % Measured under the conditions of less than 50% and a film thickness of 110 μm * 23: ◯ Measured under the conditions of 50% or more, less than 50% and a film thickness of 110 μm

[Measurement of optical propagation loss]
The optical propagation loss of the optical waveguides (waveguide length 10 cm) obtained in Examples 1 to 6 and Comparative Example 1 is the VCSEL (FLS-300-01-VCL manufactured by EXFO) with the light source having a wavelength of 850 nm as the central wavelength. ), A light receiving sensor (Q82214 manufactured by Advantest Corporation), an incident fiber (GI-50 / 125 multimode fiber, NA = 0.20) and an outgoing fiber (SI-114 / 125, NA = 0.22), It was measured by the cutback method (measurement waveguide lengths 10, 5, 3, 2 cm). Evaluation was made according to the following criteria.
○: 0.3 dB / cm or less ×: larger than 0.3 dB / cm

Further, the bending durability test and the twisting durability test of the obtained optical waveguide (width 5 mm, length 10 cm) were performed under the same conditions as described above. Evaluation was made according to the following criteria.
○: No fracture after 100,000 times ×: Less than 100,000 times The results are shown in Table 4.

* 1: ○ ... 0.3 dB / cm or less, x ... greater than 0.3 dB / cm * 2: ○ ... no breakage after 100,000 times, x ... breakage less than 100,000 times

  From Table 2, the cured film of the resin composition for forming a clad layer of the present invention is excellent in bending resistance and twisting resistance, and an optical waveguide manufactured using these is also excellent in bending resistance and twisting resistance. I understand. On the other hand, it can be seen that a cured film of a resin composition for forming a cladding layer that does not belong to the present invention and an optical waveguide produced using the resin composition are inferior in bending resistance and twisting resistance.

  A film formed by curing the resin composition for forming a cladding layer of the present invention and an optical waveguide using the same have excellent bending resistance and twisting resistance due to the above configuration. Therefore, it can be applied to a wide range of fields such as optical interconnection.

It is sectional drawing explaining the form of the optical waveguide of this invention.

Explanation of symbols

1. 1. Optical waveguide 2. Core part 3. Upper clad layer 4. Lower clad layer Base material

Claims (25)

  A resin composition for forming a cladding layer of an optical waveguide containing (A) polyamideimide and (B) a polymerizable compound.   The resin composition for forming a clad layer according to claim 1, wherein the (A) polyamideimide contains a silicone-modified polyamideimide and / or a butadiene-modified polyamideimide.   (B) The resin composition for forming a clad layer according to claim 1, wherein the polymerizable compound contains an epoxy resin.   The resin composition for forming a clad layer according to claim 3, further comprising (C) an epoxy resin curing agent.   (C) The resin composition for clad layer formation of Claim 4 in which an epoxy resin hardening | curing agent contains a phenol type epoxy resin hardening | curing agent.   (C) The resin composition for forming a clad layer according to claim 4 or 5, wherein the epoxy resin curing agent contains an amine-based epoxy resin curing agent.   Furthermore, the resin composition for clad layer formation in any one of Claims 3-6 containing (D) hardening accelerator.   (D) The resin composition for forming a clad layer according to claim 7, wherein the curing accelerator contains an imidazole compound.   (B) The resin composition for clad layer formation in any one of Claims 1-8 in which a polymeric compound contains the compound which has an ethylenically unsaturated group in the molecule | numerator.   The resin composition for forming a clad layer according to claim 9, further comprising (E) a radical polymerization initiator.   The resin composition for forming a clad layer according to any one of claims 1 to 10, comprising 5 to 250 parts by mass of (B) a polymerizable compound with respect to 100 parts by mass of (A) polyamideimide.   The resin composition for forming a clad layer according to claim 5, wherein the phenolic epoxy resin curing agent is contained so that an equivalent ratio of phenolic hydroxyl groups per epoxy group of the epoxy resin is in the range of 0.1 to 3. .   7. The clad layer forming material according to claim 6, wherein the amine-based epoxy resin curing agent is contained so that an equivalent ratio of active hydrogens of amino groups per epoxy group of the epoxy resin is in a range of 0.1 to 3. 8. Resin composition.   The resin composition for forming a clad layer according to claim 10, wherein (E) the radical polymerization initiator is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).   The resin composition for forming a cladding layer according to any one of claims 1 to 14, wherein a cured film obtained by curing the resin composition for forming a cladding layer has a tensile elastic modulus at 25 ° C of 1 to 2000 MPa.   The resin composition for forming a cladding layer according to any one of claims 1 to 15, wherein a cured film obtained by curing the resin composition for forming a cladding layer has a tensile elongation at break at 10C of 10 to 600%. .   The resin for forming a clad layer according to any one of claims 1 to 16, wherein the cured film formed by curing the resin composition for forming a clad layer is not broken after being subjected to a bending durability test with a bending radius of 2 mm 100,000 times. Composition.   The resin composition for forming a clad layer according to any one of claims 1 to 17, wherein the cured film formed by curing the resin composition for forming a clad layer has no break after performing a twisting durability test 100,000 times.   The resin film for clad layer formation using the resin composition for clad layer formation in any one of 1-18.   An optical waveguide in which at least one of a lower clad layer and an upper clad layer is formed of the clad layer forming resin composition according to any one of 1 to 18.   An optical waveguide in which at least one of a lower clad layer and an upper clad layer is formed by the clad layer forming resin film according to claim 19.   Between the lower clad layer and the upper clad layer of the optical waveguide, a core part is formed of a photosensitive resin composition having a higher refractive index than both clad layers, and the relative refractive index difference between the core part and the clad layer is 1 to The optical waveguide according to claim 20 or 21, wherein the optical waveguide is 10%.   The optical waveguide according to claim 21 or 22, wherein at least one of the clad layer forming resin films comprises a clad layer forming resin and a support film, and the support film is disposed outside the clad layer with respect to the core layer.   The optical waveguide according to claim 23, wherein the resin film for forming a cladding layer is formed by forming a resin composition for forming a cladding layer on a support film subjected to an adhesion treatment.   The optical module using the optical waveguide in any one of Claims 20-24.

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