TW200825123A - Flexible light guide and laminate board for optical/electrical composite wiring board - Google Patents

Abstract

A flexible optical/electrical composite wiring board excelling in repeated flexure and ensuring high reliability is obtained through combining of a light guide of polyimide resin with a flexible copper-clad laminate. The light guide has a cladding layer and a core layer. The cladding layer is formed from a light guide material composed mainly of a siloxane-modified polyimide resin. The core layer is formed from a light guide material exhibiting a refractive index different from that of the cladding layer. A material composed mainly of a siloxane-modified polyimide resin is suitable as the light guide material for the core layer. Use of a resin composition containing a photosensitive resin as the light guide material for the core layer would enable easily forming of desired pattern. The optical/electrical composite wiring board can be obtained by superimposing a cladding layer and a core layer on a flexible printed wiring board so that the core layer is surrounded by the cladding layer.

Description

[Technical Field] The present invention relates to a flexible optical waveguide formed of a material of a polyimide resin-based material and a laminate for an optical-electric composite wiring board forming the optical waveguide. [Prior Art]

# In recent years, the optical communication technology for high-speed and large-capacity data communication has made remarkable progress, and its optical communication network has continued to expand. Optical communication technology has now been used for long-distance communication and medium-range communication in the region, but in the future it will be applied to optical signal transmission between the inside of the machine and between machines. In portable devices, small machines, and the like, since various members are densely arranged, it is necessary to pass through a narrow gap between the members for wiring. Therefore, a flexible printed wiring board is widely used as an electrical wiring. Similarly, an optical wiring board (optical circuit wiring board) composed of a flexible optical waveguide is desired for transmitting optical signals within a short distance between the inside of the machine and the machine. Therefore, it has been desired to develop a flexible optical-electric composite wiring board in which an optical wiring board composed of such a flexible optical waveguide and an electrical wiring board formed of a flexible printed wiring board are integrated. Several optical waveguide materials have been proposed for use in optical-electric composite wiring boards. [Patent Document 1] JP-A-2004-149724 (Patent Document 3) JP-A-2005-43497 (Patent Document 3) discloses a photocurable type and a thermosetting ring. Oxygen resin thin -5 - 200825123 Optical waveguide formed by film hardening. Since the optical waveguide material forms a crosslinked structure via a hardening reaction, the flexibility is insufficient, and it is particularly difficult to apply to a portion of the hinge portion of a mobile phone or the like which must have repeatability. Further, since the epoxy resin has a high water absorption rate, it is feared that the characteristics of the high temperature and high humidity state deteriorate.

Patent Document 2 is an optical waveguide in which a polyimide resin is proposed. Since the optical waveguide material contains fluorine in the polyimine structure, when it is composited with the flexible printed wiring board, it is likely to be inferior in adhesion to the flexible substrate interface. Further, the fluorine-based material is generally expensive, and it is disadvantageous in terms of cost when it is put into practical use. Patent Document 3 proposes an optical waveguide in which the upper cladding layer is a two-layer optical layer, and is inferior in flexibility because it is an inorganic material. [Problem to be Solved by the Invention] The present invention has been made in view of the above problems, and in order to make the flexible optical φ-electric composite wiring board practical, it provides flexibility (low elasticity) and An optical waveguide formed of a polyimide resin having a low water absorption property, and a laminate for an optical-electric composite wiring board having such light wave and conductivity and having excellent repeatability and reliability. (Means for Solving the Problem) The inventors of the present invention have found that the above object can be attained by using a polyimine resin having a specific structure, and the present invention has been accomplished. That is, in the present invention, in the optical waveguide having the cover layer and the core layer, the cover layer of the -6 - 200825123 is a polyimine resin having a constituent unit represented by the following general formulas (1) and (2). A flexible optical waveguide formed of an optical waveguide material of a main component. 【化1】 Ο 0

[Chemical 2]

(3) (4) # (5) (However, An and Ah are independent expressions of the tetravalent aromatic group represented by formula (3), and Ars is a divalent aromatic group represented by formula (4) or formula (5) The group base 'R〗 is independently represented by a carbon number of 1 to 6 one-valent hydrocarbon groups, R3 is a divalent hydrocarbon group independently representing 2 to 6 carbon atoms, and Han 4 is an independently represented hydrocarbon group having 1 to 6 carbon atoms. X and Y are independently shown as a single bond or a divalent group selected from a carbon number of 1 to 15 one-valent hydrocarbon groups, 0, S, CO, S02^c〇nh, and 111 is a number representing 1 to 5〇, η is an integer representing 〇~4, and p and q are the molar ratios of the constituent units of 200825123, P is a range of 0.05 to 0.99, and q is a range of 0.01 to 0.95. The optical waveguide of the present invention is preferably one or more of the following. 1) The core layer is formed using the above optical waveguide material having a refractive index different from that of the cover layer. 2) The elastic modulus of the polyimide resin is in the range of 0.2 to 3.0 GPa.

3) The refractive index difference Δ of the optical waveguide material forming the core layer and the cladding layer is 〇. 0 1 or more. 4) The optical waveguide has a core layer and a cover layer covering the core layer, and the cover layer has a lower refractive index than the core layer. Moreover, the present invention is a laminate for an optical-electric composite wiring board or an optical-electric composite flexible member in which the optical waveguide described above is formed on a flexible copper-clad laminate or a flexible wiring board. Wiring board. Here, the flexible copper clad laminate means a laminate before forming a circuit, and the flexible wiring board is a wiring board which means a circuit. The circuit can be formed by starving the copper box layer of the flexible copper-clad laminate. The optical waveguide of the present invention has a core layer and a cover layer. The cover layer is an optical waveguide material using a polyimine resin having a structural unit represented by the above general formulas (1) and (2) (hereinafter, also referred to as a decane-modified polyimine resin) as a main component. Formed. The alkane-modified polyimine resin used in the present invention has the structural unit represented by the above general formulas (1) and (2). In the general formulae (1) and (2), ΑΓι and Ar2 are independent expressions of the tetravalent aromatic group represented by the formula (3), and An is represented by the formula (4) or (5).

200825123

The divalent aromatic group shown, r3 is independently a carbon number 2 hydrocarbon group, and R4 is independently a number of carbon atoms of 1 to 6 valence hydrocarbons 1 to 50. Here, the case where there is a constitutive unit may be independently changed in the above range. When there are several constituent units, Ari, Ar2, Ar3, and R3- independently change in the above range. Further, when the oxime is modified by a plurality of molecules, the molecules can be changed independently. Further, in the following description of Y and X, R, in the formula (3), the formula (4) and the formula (5), X2 represents a single bond, or a divalent hydrocarbon group having 1 to 15 carbon atoms, hydrazine or CONH The selected divalent group, I is independently a g-valent hydrocarbon group, and η is an integer representing 0 to 4. a divalent aromatic group as shown in the above), and may also be a fragrant group of the formula (5), and may have an An and Ar2 in one molecule or several molecules as a tetravalent group represented by the formula (3) Since the group is usually synthesized by an aromatic tetracarboxylic acid such as an aromatic tetracarboxylic dianhydride, Am and Ar2 can be referred to as an aromatic tetracarboxylic acid, and A r 1 to A r 2 are used for the synthesis. Aroma is understood. However, the decane reforming agent used in the present invention is not limited to the polycondensation obtained by such a synthesis method, and Ar! and Ar2 may be the same or different and composed of Ari or a tetravalent group.

In the formula (3), Y represents a single bond, a carbon number P: ～6 of a divalent group, m represents a number of R3, R4, etc., and a molecule of R4 may also be a bismuth imine resin in the above range The same is true for the 1 and η, and the number is 1 to 6 for the S, CO, and S〇2, and the Ar3 is the divalent aromatic group of the formula (4). Residues of amine reaction type. Poly-imine iminoimine resin due to tetracarboxylic acid. Ar2 may also be from ～15 5 bis-9 - 200825123 Hydrocarbyl, hydrazine, S, CO, S〇2 Or the divalent group selected by CONH. Preferably, the table τικ single bond or one of the valence groups selected by 0, CO and S〇2. The valence of the smoky group is preferably a carbon number of 1 to 6 The alkyl group (inclusive of the meaning of the alkylene group) and the phenyl group are extended. The aromatic tetracarboxylic acid which preferably provides An and Ar2 is represented by acid dianhydride.

# Specifically, 2,2',3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride is preferably exemplified. 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylate Acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3',3,4'· Diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) ether dianhydride, and the like. Further, 3, 3", 4, 4"-, 2, 3, 3", 4"- or 2, 2", 3, 3"-p-terphenyltetracarboxylic dianhydride, 2, 2 may also be mentioned. - bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)methane dianhydride, double (2,3- or 3 , 4-dicarboxyphenyl) phthalic anhydride, 1,1-bis(2,3_ or 3,4-dicarboxyphenyl)ethane dianhydride. An aromatic tetracarboxylic acid of An and Ar2 may also be provided, and other tetracarboxylic acids may be used in combination. When the other tetracarboxylic acid is used, it is used in an amount of 50 mol% or less, preferably 20 mol% or less based on the total aromatic tetracarboxylic acid. Such other tetracarboxylic acids are exemplified by the acid dianhydride form. Also included are pyromellitic dianhydride, 2,3,5,6-cyclohexane di wild, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6 ·Tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5 ,8- -10· 200825123 )Tetrachlorinated naphthalene ",4,5,8-(or 2,3,6,7-)tetracarboxylic dianhydride, 2,3,8,9-,3,4, 9,10-, 4,5,10,11- or 5,6,11,12-fluorene-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyridinium -2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4, 4-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetra The carboxylic acid dianhydride, the 2,3,6,7-decansic acid dianhydride, etc. _ In the general formula (1), the divalent aromatic group represented by Ar3 may be referred to as a residue of a diamine. X, R, and η in Ar3 or (4) and (5) can be understood by explaining the diamine used in the synthesis. Further, the constituent unit represented by the general formula (1) may be The valence aromatic group is formed by several constituent units. X may be the same as the above, but may be different. X may be as described above. Preferably, it is a single bond, or 〇, s, co, so2 The divalent group selected by conh, ch2, C(CH3)2 and 9,9'-fluorenyl. The '9,9'-fluorenyl group is represented by the following formula: [Chemical 3]

In the divalent aromatic group containing X, ' Ri is independently a hydrocarbon group having 1 to 6 carbon atoms, preferably a group having 1 to 6 carbon atoms, an alkenyl group, a cyclic fluorenyl group or a phenyl group. More preferably, the number of carbon atoms is 1 to 3, the alkyl group or the phenyl group. η is an integer ′ of 〇 〜4, preferably 0 〜 2 ′ is more preferably 〇. -11 - 200825123 When Ar3 is a divalent aromatic group represented by the formula (5), a preferred diamine of Ar3 is provided. Specific examples thereof include 2,2-bis-[4-(4-aminophenoxy)phenyl]propane, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, and a double [4-(4-Aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)]biphenyl, double [4-(3-Aminophenoxy)biphenyl, bis[1-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)yl)biphenyl, bis[4 - (4-Aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[ 4-(3-Aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]benzophenone, bis-[4-(3-aminophenoxy)benzophenone , bis[4-(4-aminophenoxy)]benzophenone, bis[4-(3-aminophenoxy)]benzophenone, bis[4,4'-(4-aminophenoxy)] Benzoaniline, bis[4,4'-(3-aminophenoxy)]phenylanilide, 9,9-bis-[4-(4-aminophenoxy)phenyl]anthracene, 9,9- Bis-[4-(3-aminophenoxy)phenyl]anthracene. φ indicates that when Ar3 is a divalent aromatic group represented by the formula (4), a diamine of a preferred Ar3 is provided. Specifically, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2,6-dimethylaniline, 4,4'-methylene-2 ,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4, diaminodiphenylethane, 3,3 '-Diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodithiobenzene, 3 , 3'-diaminodithiobenzene, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl ether, -12- 200825123, 4-a makeup soil ~ benzoquinone, benzidine, 3,3, diaminobiphenyl, 3,3,-dimethyl-4,4' -~Aminobiphenyl, 3,3,dimethoxybenzidine, 4,4,,diamino-p-terphenyl, 3,3'diamino-p-terphenyl, 9,9_ Bis(4-aminophenyl)-9H-indole. Among them, '4,4,diaminodiphenyl ether (DAPE), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, It bis [4·(3-aminophenoxy) Phenyl]phenyl], 9,9-bis(4-aminophenyl)-911-anthracene, 1,3-bis(4-||phenoxy)benzene (TPE_R), and the like. Other aromatic diamines other than the above may be used in a small amount (50 mol% or less, preferably 2 mol% or less). Further, an unsaturated group such as 2, 2, divinyl-4,4,-diamino-biphenyl-like vinyl group or the like is preferably a substituted diamine. Examples of such other aromatic diamines include, for example, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis(4-aminophenoxy)benzene, 1, 3-bis(4-aminophenoxy)benzene, 4,4,-[1,4-phenylenebis(1-methylethylidene)]diphenylamine, 4,4,·[1,3· Phenyl bis(1-methylethylidene) @ diphenylamine, bis(p-aminocyclohexyl)methane, bis(p-/3 ·amino-t-butylphenyl) ether, bis ( p-Methyl-6-aminepentyl)benzene, p-bis-(2-methyl-4-aminepentyl)benzene, p-bis(1,1·dimethylaminepentyl) • benzene, 1, 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(fluorene-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2, 5-diamine, p-xylene_ 2,5-diamine, m-xylylenediamine, p-dimethylamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino hydrazine, piperene, and the like. In the general formula (2), the terminal is a second 13- of the structure of the political oxygen institute containing R3.

200825123 The valence group, which can be called the residue of a diamine. Therefore, R3, R4 and m containing a decane structure or a general formula (2) are understood to be understood from the description of the diamine structure containing a decane used in the above synthesis. Further, the constituent unit represented by the formula (2) may be formed of a plurality of constituent units containing the naphthene structural group. In the divalent group of the general formula (2) containing a decane structure, the number is from 1 to 50, preferably from 5 to 30. If the number is less than 1, the modulus of elasticity (bending property) is small, and if it exceeds 50, the reactivity with tetracarboxylic acid is lowered, and the molecular weight of the polymer is lowered, so that the bending property is particularly high. R3 is a divalent hydrocarbon group having 2 to 6 carbon atoms, preferably a carbon alkyl group. R4 is an alkyl group having 1 to 6 carbon atoms or a phenyl group being a methyl group or a phenyl group. Examples of the diamine having a preferred oxane structure include ω (2-aminoethyl) polydimethyl siloxane, ω, ω'-bis (3-aminopropyl dimethyl oxane, ω, Ω'-bis(4-aminophenyl)polydimethylindole bis(3-aminopropyl)polydiphenyl fluorene, '-dipropyl) polydimethylphenyl chopping house. The oxime-modified polyimine resin used in the present invention is a constituent unit represented by the formulae (1) and (2), and the molar ratio q of the unit of the general formula (1) is 0.01 to 0.95. It is preferably 0.5 to the range. The constituent unit represented by the general formula (2) has a molar ratio of from 0.05 to 0.99, preferably from 0.1 to 0.8. The presence of the molyoxime-modified polyimine resin is the same as that of the constituent units of the general formulas (1) and (2), or the other constituent units are the same as the two, and the general divalent , m is, the low acid dianhydride lowers ^ 2 ~ 6, preferably, - bis) polyoxyalkylene, (3, the amine has a general structure of 0.8: Ρ is ratio, as shown above) -14- 200825123 Wai is better. Further, when there are other constituent units, P + q is 0.5 or more, preferably 0.8 or more. Further, p/(p + q) is preferably in the range of 〇·1 to 〇·8. The alkane-modified polyimine resin used in the present invention preferably has a modulus of elasticity of 0.2 to 3.0 GPa, preferably 0.3 to 3.0 GPa. Further, the glass transition temperature (Tg) is preferably 120 ° C or higher, preferably 140 to 300 ° C.

In the present invention, the core layer of the optical waveguide may be formed of a fluorene-modified polyimine, but it is advantageous to use a photosensitive material which can form an arbitrary pattern by photolithography in the core layer. Examples of such a photosensitive material include a polyamic acid resin having a constituent unit represented by the following general formula (6) and general formula (7), a monomer having an unsaturated bond, and a photopolymerization initiator as a main component. A resin obtained by curing a photosensitive resin composition. The core layer of the optical waveguide of the present invention is preferably a resin obtained by curing the photosensitive resin composition. Hereinafter, the resin obtained by the hardening may also be referred to as a decane-modified cross-linked polyimine resin. (6) -N—4. ,Λ-Ν—Ar3-· HO-f Αη)!—OH -0 〇_NJJ 2—HN—R3-4si-〇}-Si—R3- hS^ Voh t r4 (7)

P In the above general formula (6) or general formula (7), 'Ari, Ar2, R3, and R4 have the same meanings as the above general formulas (1) and (2), and it is desirable to use Ar3 of the general formula (6) ( A part of R4 in the divalent-15-200825123 aromatic group represented by the formula (4) or the formula (5) or R4 in the general formula (7) is an alkenyl group, and imparts photopolymerizability. The alkenyl group is a group represented by CH2 = CH-R6-, and R6 represents a direct bond, an alkyl group having 1 to 6 carbon atoms or a phenyl group, but it is preferably bonded directly to the reactivity.

As the monomer having an unsaturated bond, a photopolymerizable monomer can be used, and in terms of transparency, refractive index, and the like, an acrylate such as a polyfunctional acrylate is preferable. The amount thereof is in the range of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the polyamic acid resin. The decane-modified polyimine resin can be synthesized by a known method. For example, in an organic solvent, one or more aromatic tetracarboxylic dianhydrides can be obtained by reacting two or more kinds of diamines in a ratio of about equimolar. An example of a method for producing a polyfluorene-containing resin containing a siloxane. First, an aromatic acid dianhydride is added to a solvent and dissolved. While stirring, two or more kinds of diamines containing a decane diamine were gradually added under a nitrogen atmosphere and under ice cooling. Thereafter, the reaction is stirred for 2 to 8 hours to obtain a polyamine resin solution containing a siloxane. The above solvent must be inert to both the aromatic polyphthalic acid component and the decane component. Representative of such solvents are diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether, tetrahydrofuran and the like ether solvent, and N,N-dimethylformamide, N,N-dimethyl a guanamine-based solvent such as acetalamine, N-methyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone, and more than one of these solvents may be used, and a diethylene glycol dimethyl ether solvent may be used. A solvent containing 10% by weight or more, preferably 30% by weight or more is suitable. The resulting polyoxyphthalic acid resin containing a siloxane is heat treated or -16-200825123

When the β dehydrating agent is treated, it can be dehydrated and closed to form a polyfluorene-based resin containing a nonane. The heat treatment is carried out, for example, in a nitrogen atmosphere, and heating at 70 to 350 ° C for 2 to 5 hours. It is preferred to carry out stepwise heating in a nitrogen atmosphere at 150 ° C for 30 minutes, at 250 ° C for 30 minutes, and at 32 ° C for 1 hour. Further, by selecting a combination of a diamine and a tetracarboxylic anhydride, a polyimine resin which is soluble in a solvent can be obtained, and the mixture can be dehydrated and closed in advance, and then dissolved in a solvent to form a solution. The solution viscosity (dimethylammonium solution: concentration: 25 wt%) of the polyamidamide resin containing a siloxane is preferably in the range of 2,000 to 50,000 cPa·s. At this time, by adjusting the order of addition of the reaction raw materials, a segmented or random type of decane-modified polyimine resin can be obtained. Further, by changing the amount of use of the diamine containing a siloxane structure, the refractive index of the siloxane-modified polyimine resin can be controlled. In other words, when the amount of the diamine containing a siloxane structure is increased and the structural unit represented by the general formula (2) and the general formula (7) is increased, a phenomenon in which the refractive index is lowered is found. The optical waveguide of the present invention has a core layer and a cover layer. Typically, the cover layer covers the periphery of the core and the cover layer has a lower refractive index than the core layer. The optical waveguide of the present invention is formed by at least a coating layer comprising an optical waveguide material containing the above-mentioned decane-modified polyimine resin as a main component. The core layer may also be formed of an optical waveguide material which does not contain the above-mentioned decane-modified polyimine resin, but in order to impart flexibility, the phthalocyanine-modified polyimine resin is preferably contained, preferably its precursor The oxime-modified cross-linked polyimine resin produced by the photosensitive polyamine resin is preferably formed as an optical waveguide material which is a main component of the resin. Further, the decane-modified crosslinked polyimine resin, -17-200825123, refers to a polyimine resin which is formed by reacting an unsaturated group with a monomer or a resin having another unsaturated group. At this time, an optical waveguide material containing a fluorene-modified polyimine resin having a fluorene-rich composition represented by the general formula (2) is formed into a coating layer, and is modified by at least a siloxane. An optical waveguide of a ruthenium imine resin or an oxidized ortho-modified cross-linked polyimine resin (having a molar ratio of a molar ratio of a molar ratio of a molar ratio of a precursor and a polyimine resin) The material forms the core layer. Hereinafter, an optical waveguide material forming a layer covering 0 is referred to as a covering material, and an optical waveguide material forming a core layer is referred to as a core material. The refractive index of the optical waveguide material containing the decane-modified polyimine resin is preferably in the range of 1.45 to 1.65, and the refractive index difference Δ between the covering material and the core material is 0.01 or more, preferably 〇·〇2 or more. It is better. The optical waveguide material containing the decane-modified polyimine resin of the present invention may contain 50% by weight or more, preferably 60% by weight or more of the decane-modified polyimine resin. The other materials other than the decane-modified polyimine resin are transparent resins such as polyacrylates and epoxy resins, and micro-powdered dioxins, etc., which form a core layer. The photosensitive resin composition which is preferably used is a polyamine which has a constituent unit represented by the above general formula (6) and general formula (7). An acid resin and a photopolymerization initiator are contained as a main component, and acrylic acid is contained as needed. a monomer such as an ester (may also be a polymerizable resin component), a sensitizer, a solvent, etc. The photosensitive resin composition (preferably a solution thereof) is used to photoharden and yttrium to form an optical waveguide. Further, at this time, after the polymerization, at least a part of the vinyl group of the polyoxyphthalic acid resin containing a siloxane is reacted with an unsaturated group of another monomer or resin, and the resin after hardening is referred to as -18. - 200825123 Alkane modified cross-linked polyimine resin.

Here, as the acrylate which can be used, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethoxyethyl acrylate can be used. Ester, 2-ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, isodecyl acrylate, stearyl acrylate, lauryl acrylate, glycidyl acrylate, allyl acrylate, acrylic acid B Oxygen ester, methoxyacrylate, N,N'-dimethylamine ethyl acrylate, benzyl acrylate, 2-hydroxyethyl phthalate, dicyclopentadienyl acrylate, dicyclopentadienyl acrylate Monoacrylate, and dicyclopentadienyl acrylate, dicyclopentadienyl oxyethyl acrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6 - Butanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate , diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxytrimethyl Ester neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(propylene oxyethoxy) bisphenol A, bis(propylene oxyethoxy) tetrabromobisphenol a, tripropylene glycol diacrylate Polyfunctional acrylates such as ester, trimethylolpropane triacrylate, pentaerythritol triacrylate, bis(2-hydroxyethyl)isocyanate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate . In the photosensitive resin composition, the acrylate is in an amount of from 1 to 50 parts by weight, preferably from 5 to 40 parts by weight, based on 100 parts by weight of the polyphthalic acid resin containing a phthalic acid. -19- 200825123

# Photopolymerization initiator, for example, acetophenone, 2,2-dimethoxyethyl benzene, p-dimethylamino acetophenone, candione, benzyl, benzoin, benzoin methyl ether , benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzyl dimethyl ketal, thioxanthone, 2-chloro group Thioxanthone, 2-methylthioxanthone, 2-hydroxy-2-methyl-1-phenyl-1·one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Various photopolymerization initiators such as propan-1-one, methylbenzate, and 1-hydroxycyclohexyl phenyl ketone. The photopolymerization initiator is preferably used in an amount of 1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the phthalic acid-containing polyphthalic acid resin. Further, it is also advantageous to use a sensitizer. In this case, various amines such as benzophenone can be used as the sensitizer. The sensitizer is used in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the polyphthalic acid resin containing a siloxane. When the decane-modified polyimine resin or the resin composition containing the same as a main component is used in a solution form, it can be used in the same manner as the photosensitive resin composition in a solution form of a non-photosensitive polyamine resin composition. It is better. Further, such a photosensitive or non-photosensitive resin composition can be adjusted in viscosity or the like via various organic solvents and the like. Preferred examples of the organic solvent used in the case of use include triethylene glycol dimethyl ether, diglyme, dimethyl acetamide, N-methyl pyrrolidone, and propylene glycol. Methyl ether acetate (pegmia), ethyl lactate or a mixed solvent thereof. The solvent is used in an amount of 1 part by weight based on the solid content of the resin composition, preferably in the range of 1 Torr to 1 Torr. Further, at a normal temperature containing 1% by weight or more of the solvent, -20-200825123 shows a liquid resin composition, which is called a varnish-like resin composition. Further, when an organic solvent as a reaction solvent is used in the production of a polyamic acid resin, it is calculated in a solvent type. Further, in the range where the characteristics of the optical waveguide are not deteriorated, other resins as described below can be used in addition to the above. In other words, the epoxy resin is not particularly limited as long as it has a plurality of epoxy groups in one molecule, and commercially available liquid epoxy resins and solid epoxy resins can be suitably used. Specific examples of the epoxy resin include an alicyclic epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, and a biphenyl epoxy resin having a biphenyl skeleton. 3, epoxy resin with Nai ring, dicyclopentadiene epoxy resin with a cyclopentane skeleton, phenol novolak epoxy resin, cresol novolac epoxy resin, triphenylmethane ring Oxygen resin, bromine-containing epoxy resin, aliphatic epoxy resin, triglycidyl isocyanurate, or the like, and one or more of them may be used. The amount thereof is less than 40 parts by weight, preferably 30 parts by weight or less, based on 100 parts by weight of the polyimine resin or the polyamide resin. Further, in the resin, the resin composition or the resin solution containing the precursor resin of the optical waveguide material of the present invention, if necessary, a thixotropic material or an inorganic layer may be added in a range not impairing the characteristics of the light-waveguide. Filling agent, defoaming agent, etc. The material for an optical waveguide of the present invention formed of the above resin composition is a fluorene-modified polyimine resin or a hydrazine which is produced by imidating the oxime-modified polyimine precursor. An oxane-modified cross-linked polyimine resin is used as a main component. Here, the term "main component" means that it is contained in an amount of 50% by weight or more, preferably 60% by weight or more. More preferably, it is 15 to 35 parts by weight of an epoxy resin or an acrylate with respect to 100 parts by weight of the main component -21 - 200825123. The optical waveguide of the present invention is formed on the lower cladding layer to form a core layer having a specified thickness, and an optical layer waveguide is obtained by providing an upper cladding layer or the like as a cover layer. The optical-electric composite wiring laminate of the present invention is such that a lower cover layer is provided on the flexible copper-clad laminate, and a core layer of a specified thickness and width is formed on the cover layer, and the upper cover layer is covered by a cover, etc. Available. In addition, the optical-electric composite wiring board is obtained by circuit-processing the copper foil of the laminate for the present invention. [Embodiment] Next, a method of an optical waveguide will be described with reference to a flowchart shown in Figs. For example, a group solution (referred to as a coating material for a covering material) as a covering material is applied onto a substrate 1 such as glass, and pre-dried at a temperature of 50 to 120 ° C, and the obtained film is peeled off from the substrate, and The release film was once again adhered to the substrate with a heat-resistant tape or the like, and then heat-treated at a temperature of -200 ° C for 20 to 120 minutes to be cured, and the lower cover layer 2 was obtained ( FIG. 1 ). Next, as shown in FIG. 2, in the lower cladding layer 2, the core composition solution (referred to as a core material solution) is formed into a core layer shape by screen printing or the like, and is 120 to 20 (TC temperature). Heat treatment for 20 minutes to harden the core layer 3. The core material forming the core layer has a higher refractive index of the cover material of the lower cover layer 2. The degree and method of the plate are used to form a moderately thin film. 120 film core material forming finger ^ 120 shape shape -22- 200825123 or, as shown in Figure 3 in the lower cover layer 2, coating the core material solution 3', and pre-drying at a temperature of 50~120 °C, Thereafter, the photomask 4 forming the specified mask pattern is selectively exposed, and the unexposed portion is imaged with an aqueous alkali solution, and heat-treated at a temperature of 120 to 200 ° C for 20 to 20 minutes to harden it. The core layer 3 is formed. Further, a film obtained by pre-drying a core material composed of a photosensitive polyimide-containing polyimide resin layer is laminated on the upper cover layer 2, and is selectively exposed and imaged. Hardening can also form a core layer. Next, as shown in FIG. 4, on the core layer, the same covering material for forming the lower cladding layer 2 is coated with a solution, and heat-treated at a temperature of 1 2 〇 to 200 ° C for 20 to 120 minutes. The film is formed by hardening the upper cover layer 5' and then peeling off the substrate 1 to obtain the film-shaped optical waveguide 6 of the present invention. The lower cover layer 2 and the upper cover layer 5 are made of the same material, and the two are connected by a portion having no core layer. Therefore, it is integrated, and the boundary cannot be determined in the drawing. ^ Further, the pre-dried film obtained by forming the lower cladding layer is laminated on the core layer and heat-treated at a specified temperature. The upper cover layer. The majority of the cover layer of the optical waveguide thus obtained is a flexible material. Therefore, the amount of increase in light transmission loss after repeating the tens of thousands of times of the bending process is expected to be The method for producing a laminate for flexible light-electric composite wiring according to the present invention is described below with reference to 5 and 6. The laminate for flexible wiring 7-23- 20082 5123 is a layer having a copper foil layer 8 and a polyimide layer 9. The polyimide layer 9 is provided with a lower cladding layer 2, the core layer 3 is formed next, and the upper cladding layer 5 is provided to obtain a layer for optical-electric composite wiring. The example of 5 is a method of exposing, developing, thermosetting, or the like of the core layer 3, and the example of FIG. 6 is a method of forming the core layer 3 into a designated core layer shape. The film shape obtained by the optical waveguide forming method is transmitted through the adhesive layer as needed, and is adhered to the surface of the layer 9 of the flexible wiring layer, and the optical-electric composite wiring can be obtained. [Examples] The invention is further illustrated in detail by way of example. The abbreviations used in the examples are the following compounds. BTDA: 3,3,,4,4,-benzophenonetetracarboxylic dianhydride (# ODPA : 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride DSDA: 3,3',4 , 4'-diphenylfluorene tetracarboxylic dianhydride. BPDA : 3,3,,4,4,-biphenyltetracarboxylic dianhydride BAPP: 2,2-bis[4-(4-aminophenoxy) Phenyl]propene oxime DAPE: Diaminodiphenyl ether DVDABP· 2,2-I-Bis-4,4'-diaminobiphenyl PSX-1: Polydimethyl oxime with a number average molecular weight of about 750 In the diamine residue portion of the general formula (2), r4 is _Ch3(CH2)3-, m is 7~8), and the same as above is covered with the same anti-100. The figure forms the i-ply plate 10 of the designated screen printing optical waveguide 6 ply 7. In addition, the diamine (R3 is -24-200825123 PSX-2: a polydimethyl oxime containing a vinyl group having a number average molecular weight of about 850) Alkyldiamine (in the diamine residue portion of the general formula (2), R4 is _CH3 or -CH=CH2, R3 is -(CH2:h-, m is 7-8, and has an average of 1 in one molecule) Vinyl) BAFL : 9,9-bis(4-aminophenyl)-9H·芴DMAC: dimethylacetamide

EOCN: cresol novolac type epoxy resin (epoxy equivalent 191 § / called) BrenS : brominated novolac type epoxy resin (epoxy equivalent 275 g / called) SR-35 0 : trimethylolpropane trimethyl Acrylate (manufactured by Nippon Kayaku Co., Ltd.) Irg369: photopolymerization initiator (manufactured by Ciba Geigy Co., Ltd.) Production Example 1 30.8 g (0.1 mol) of DSDA was dissolved in DMA 290 g in a reactor equipped with a nitrogen injection tube, and The reactor was iced. 60 g (0.08 mol) of PSX-1 was dropped therein for 1 hour under a nitrogen atmosphere. Furthermore, 'BAPP 8·2 g (0.02 mol) was added, and after the completion of the dropwise addition, the temperature in the reactor was returned to room temperature, and the mixture was stirred under a nitrogen atmosphere for 5 hours to obtain a polyamine containing oxime. Resin solution. The viscosity of the dimethylacetamide solution (resin concentration: 2 5.1 wt%) of the polyamine resin containing the decyl alkoxide at 25 ° C was 2,500 cPa · s measured by a Ε-type viscometer. Further, a solution of a resin composition was obtained by mixing a polyoxyphthalic acid resin solution containing a siloxane (100 parts by weight based on a polyamine resin containing a decyl alkane) with 20 parts by weight of EOCN. -25-

§ 200825123 Production Examples 2 to 3 Using the same method as in Production Example 1, a polyamine resin solution containing a halogenated alkane was obtained as shown in Table 1. Further, a resin of 100 parts by weight of BrenS, a part by weight of an aerosol, 5 parts by weight of cerium oxide, and 1 part by weight of an antifoaming agent in a polyoxyphthalic acid resin solution having a siloxane are obtained as a solution of a resin composition. Production Examples 4 to 6 Using the same method as in Production Example 1, a polyamine resin solution containing a siloxane was obtained as shown in Table 1. Further, the resin 1 containing a polyoxyphthalic acid resin solution of a siloxane was obtained by combining the additives shown in Table 1 to obtain the photosensitive resin composition, and the production examples 7 to 8 were obtained except that no decane diamine was used. Using the production method, the resin raw materials and additives shown in Table 1 were used, and a solution of the resin composition was obtained. Production Example 9 Using the same method as in Production Example 1, a polyamine resin solution containing a siloxane was obtained as shown in Table 1. Further, the resin 1 of the polyamine resin solution containing a siloxane is obtained by combining the additives shown in Table 1 to obtain a resin material of the photosensitive resin composition as a solution of each of the resin compositions obtained as described above. The solution was prepared with respect to the obtained resin component in an amount of 5 parts by weight based on the amount of the sol. 1 In the same manner, the resin raw materials which are reacted and blended are mixed with respect to the obtained parts by weight. The specified column -26- 200825123 is thinned. Manufacturing Example 10

On the glass substrate, the resin composition solutions obtained in Production Examples 1 to 3 and 7 to 8 were applied by a bar coater, and predried at 120 ° C for 20 minutes to peel off the obtained film from the glass substrate. Further, the peeled film was attached to a glass substrate using a heat-resistant tape (manufactured by Capton), and then cured at 180 ° C for 30 minutes to form a film having a thickness of 20 μm. Production Example 11 The photosensitive resin composition solutions obtained in Production Examples 4 to 6 and 9 were applied on a glass substrate by a bar coater, and predried at 120 ° C for 20 minutes to obtain a film obtained on a glass substrate. Stripped. Further, after the peeled film was attached to a glass substrate using a heat-resistant tape (manufactured by Capton), the film was irradiated with UV light using an exposure machine (Hitech, high-pressure mercury lamp), and a film of 20 μm thick was formed by 18 (TC hardening for 30 minutes). The characteristics of the film obtained by the above method were evaluated as follows: 1) Refractive index: The refractive index of each film (20 μm thick) was measured at 63 Onm. Further, the refractive index after bending treatment of 100,000 times under the conditions of a bending angle of 1, 70 ° and a number of revolutions of 60 μm was measured using a bending tester. 2) Light transmittance: Each film (20 μm thick) was measured for light transmittance at 85 Å. Further, the light transmittance after the bending treatment was measured by the same method as the refractive index measurement of 1). 3) Tg: The dynamic viscoelasticity of each film was measured, and the peak temperature of wave -27-200825123 of tan $ was regarded as T g . 4) Elasticity: The tensile modulus of each film was measured by a tensile tester Autograph AG-500A (manufactured by Shimadzu Corporation). 5) Water absorption rate: The water absorption rate of each film was measured in accordance with JIS specifications. The type and amount of the resin raw material, the solution viscosity of the polyaminic acid resin, and the type and amount of the additive to be added in the polyaminic acid resin solution (relative to 100 parts by weight of the resin in the polyamic acid resin solution) And film properties are shown in Table 1. § -28- 200825123 t # [1«] Manufacturing Example 9 BTDA 80 BPDA 20 DVDABP 20 PSX-1 60 BAFL 20 3000 SR-350 30 Irg369 5 5 § 5 | | SS Manufacturing Example 8 DSDA 100 DAPE 100 PSX-1 0 25000 4.9 245 0.8 1.568 1.567 96 96 Manufacturing Example 7 BTDA 100 BAPP 100 PSX-1 0 23000 4.58 235 0.6 1.564 1.563 96 95 Manufacturing Example 6 DSDA 100 DVDABP 40 PSX-2 60 _ 9600 SR-350 30 Irg369 5.00 1 1.54 185 0.1 1.506 1.506 99 99 Manufacturing Example 5 ODPA 100 DVDABP 70 PSX-1 30 16000 SR-350 30 Irg369 5 2.76 225 0.1 1.517 1.523 98 98 Manufacturing Example 4 DSDA 100 DVDABP 90 PSX-1 10 17600 SR-350 30 Irg369 5 2.84 230 0.1 1.542 1.534 98 98 Manufacturing Example 3 BTDA 100 BAPP 65 PSX-1 35 _ 8400 Bren-S 30 Aerosol 5 cerium oxide cerium 5 Defoamer 10 1.37 180 0.1 1.579 1.579 99 99 Manufacturing Example 2 DSDA 100 BAPP 80 PSX -1 20 15000 Bren-S 30 Aerosol 5 Ceria-filling agent 5 Defoamer 10 2.65 225 0.1 1.598 1.597 98 98 Manufacturing Example 1 DSDA 100 BAPP 20 PSX-1 80 _1 2500 EOCN 20 0.35 150 0,1 1.496 1.496 98 98 Polyimine resin raw material (% by mole) Anhydride diamine (% by mole) _ 2 * % ψ ^ Sg ? 1 - am 镞 Additives (parts by weight) | η ^ 鹚 鹚 鹚 鹚 Ρ 刮 刮 m m m m m m m m m m 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 - 200825123 As shown in Table 1, the optical waveguide material composed of a siloxane-modified polyimine resin can control the refractive index difference through a wide range of the content of the siloxane component, and the light transmittance is high. The change in refractive index and light transmittance before and after the repeated bending treatment is small. On the other hand, an optical waveguide material composed of a polyimine resin which does not contain a decane component has a small refractive index difference and a low light transmittance, and is therefore unsuitable as an optical waveguide.

§ Example 1 A solution of the resin composition obtained in Production Example 1 was used as a cover layer on a glass substrate, coated with a screen printing machine, pre-dried at 1200 ° C for 20 minutes, and the obtained film was Peel off on the glass substrate. Further, the peeled film was attached to a glass substrate using a heat-resistant tape (manufactured by Capton), and then cured at 180 ° C for 30 minutes to form a lower cover layer of 20 μm thick. Next, the film-like cover layer was attached to a screen printing machine, and the resin composition solution obtained in Production Example 2 was used as a core layer to form a printing plate having a specified printing pattern (a pattern of a core layer). The coating was applied at the designated layer on the cover layer, and then hardened at 180 ° C for 30 minutes to form a core layer (size: film thickness 2 μm, width 100 μm) on the cover layer. Next, on the core layer, a solution of the same resin composition used for forming the lower cover layer was applied by a screen printing machine, and hardened at 180 ° C for 30 minutes to form a 20 μm thick upper cover layer. Thereafter, the heat-resistant adhesive tape which was temporarily adhered was peeled off to obtain a film-shaped optical waveguide. -30-200825123 Example 2 A film-shaped optical waveguide was obtained in the same manner as in Example 1 except that the resin composition solution obtained in Production Example 3 was used as the core layer.

§ The resin composition solution obtained in Production Example 1 was applied on a glass substrate by a screen printing machine, pre-dried at 120 ° C for 20 minutes, and the obtained film was peeled off from the glass substrate. Further, the peeled film was attached to a glass substrate using a heat-resistant tape (manufactured by Capton), and then cured at 180 ° C for 30 minutes to form a 20 μm thick lower cover layer. Next, the photosensitive resin composition solution obtained in Production Example 4 was applied onto a film by a screen printing machine, pre-dried at 12 ° C for 1 minute, and thereafter, a pattern of the specified mask was used. The mask is exposed using an exposure machine (Hitech, high pressure mercury lamp). Thereafter, a 1% aqueous solution of sodium carbonate was used, and 30 was used. (:, imaging was performed under conditions of 150 seconds) and heat-treated at a temperature of 180 ° C for 30 minutes to harden it to form a core layer. Next, on the core layer, the resin composition obtained in Production Example 1 was used. The solution was applied and dried at 180°. (: a 20 μm thick upper cover layer was formed by hardening for 30 minutes. Thereafter, the temporarily adhered heat-resistant tape was peeled off to obtain a film-shaped optical waveguide. Example 4 except that the resin obtained in Production Example 5 was used. The composition solution was used to form a film-like optical waveguide in the same manner as in Example 3 except that the core layer was used for forming the core layer. The fifth embodiment was used except that the resin composition solution obtained in Production Example 6 was used as the core layer. In the same manner as in Example 3, a film-like optical waveguide was obtained in the same manner as in the flexible printed wiring board (Sinite Chemical Co., Ltd. flexible copper-clad laminate; ESP AN EX single-sided type: Poly The polyimide composition having an amine film thickness of 25 μm and a copper foil of 18 μm was coated with a screen printing machine using a screen printing machine, pre-dried at 120 ° C, and further at 180 ° C. Hardened for 30 minutes to form 20 Μπι厚下下覆层. § Next, the resin composition solution obtained in Production Example 2 was applied through a printing plate forming a designated printing pattern at a designated portion on the cover layer, and hardened at 180 ° C for 30 minutes. A core layer (size: film thickness: 20 μm, width: 100 μm) was formed on the cover layer. Next, on the core layer, the resin composition solution obtained in Production Example 1 was applied and hardened at 180 ° C. A laminate for a flexible optical-electric composite wiring board having an optical waveguide formed on a flexible substrate was formed by forming a 20 μm thick upper cladding layer in 30 minutes. Example 7 - 32 - 200825123 The above flexible printed wiring board Using the polyimide surface of the laminate, the resin composition solution obtained in Production Example 1 was coated with a screen printing machine, pre-dried with 12 (TC, and then hardened at 180 ° C for 30 minutes to form a 20 μπ thick layer. Lower cover layer.

Next, the photosensitive resin composition solution obtained in Production Example 4 was applied onto the lower cover layer, and pre-dried at 120 ° C for 10 minutes. Thereafter, a mask having a specified mask pattern was used and an exposure machine was used. (Hitech, high pressure mercury lamp) is exposed. The unexposed portion was developed with a 1% sodium carbonate aqueous solution at 150 ° C for 150 to 200 seconds, and heat-treated at 180 ° C for 30 minutes to harden it to form a core layer (size: film thickness 20 μηι, width 100) Next, on the core layer, the resin composition solution obtained in Production Example 1 was applied, and hardened at 180 ° C for 30 minutes to form a top cover layer of 20 μm thick, which was obtained in a flexible manner. A laminate for a flexible optical-electric composite wiring board in which an optical waveguide is formed on a substrate. § Example 8 In the same manner as in Example 7, except that the photosensitive resin composition solution of Production Example 9 was used instead of the photosensitive resin composition of Production Example 4, the optical waveguide was formed on the flexible substrate. A laminate for a light-electric composite wiring board. [Industrial Applicability] The combination of an optical waveguide formed of a polyimide resin and a flexible copper-clad laminate-33-200825123 can provide high reliability with high repeatability and high reliability. Slight light-electric composite wiring board is put into practical use. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the manufacture of an optical waveguide. Fig. 2 is a flow chart showing the manufacture of an optical waveguide. Fig. 3 is a flow chart showing the manufacture of an optical waveguide.

Fig. 4 is a flow chart showing the manufacture of an optical waveguide. 5 is a flow chart showing the manufacture of a laminate for an optical-electric composite wiring board. FIG. 6 is a flow chart showing the manufacture of a laminate for an optical-electric composite wiring board. [Main component symbol description] 1 : Substrate β 2 : lower cladding layer 3 : core layer, 4 : (light) cover. 5 : upper cover layer 6 : optical waveguide 7 : laminate for flexible wiring 8 : copper layer 9 : polyimine layer 10 : for photo-electric composite wiring board Laminate-34-

Claims (1)

200825123 X. Patent Application No. 1 · An optical waveguide characterized in that in an optical waveguide having a cover layer and a core layer, the cover layer is a polymer having a constituent unit represented by the following general formulas (1) and (2) An optical waveguide material having a quinone imine resin as a main component, [Chemical 1] t Ο Q R3 斗 〇 W—V ο ο r4 r4 Ρ (2) -35- 200825123 Base, X and Y are independently a single bond or a divalent group selected from a divalent hydrocarbon group of 1 to 15 carbon atoms, hydrazine, S, CO, S02 or CONH, and m represents 1 to 50 The number η is an integer representing 0 to 4 independently, and p and q are the molar ratios of the respective constituent units, p is a range of 0.05 to 0.99, and q is a range of 0.01 to 0.95. 2. The optical waveguide of claim 1, wherein the core layer and the cover layer are formed using optical waveguide materials having mutually different refractive indices as recited in claim 1 of the patent application. 3. The optical waveguide of claim 2, wherein the refractive index difference Δ of the optical waveguide material forming the core layer and the cladding layer is 0.01 or more. The optical waveguide of any one of the above-mentioned claims, wherein the optical waveguide is a cover layer having a core layer and a cover core layer, and the cover layer has a refractive index lower than that of the core layer. 5. The optical waveguide of claim 1, wherein the polyamidene resin has an elastic modulus in the range of 0.2 to 3. OGPa. 6. The optical waveguide of claim 1, wherein the core layer is a polyamic acid resin having a composition unit of the following general formula (6) and general formula (7); a monomer having an unsaturated bond and a photopolymerization initiator. The optical waveguide material containing the resin obtained by curing the photosensitive resin composition as a main component as a main component is formed by -36- (6) 200825123 (7) t 3] However, An and Ar2, Ar3, R3 and R4 have the same meanings as the above general formulas (1) and (2), but at least a part of R1 in Ar3 or R4 in the general formula (7) is an alkenyl group or an alkene. Phenyl). A laminate for an optical-electric composite wiring board, characterized in that the optical waveguide according to any one of the first to sixth aspects of the invention is formed on a flexible copper-clad laminate. 8. An optical-electric composite flexible wiring board characterized in that the optical waveguide according to any one of the first to sixth aspects of the invention is formed on a flexible wiring board. -37-