JP2003287634A - Material for plastic optical waveguide and optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing polybenzoxazole material for a plastic optical waveguide which is excellent in electric characteristics, heat resistance and transparency, which realizes a large area at a low cost, and which can freely control the refractive index. <P>SOLUTION: The material for a plastic optical waveguide comprises a compound having repeating units expressed by general formula (1), the compound having the repeating unit with the number m for repetition and the repeating unit with the number n having ≥0.3% difference in refractive index as a compound from the repeating unit with the number m, or comprises a resin produced by closing rings in the above compound. In formula (1), X represents a tetravalent organic group, each of Y<SB>1</SB>and Y<SB>2</SB>represents a divalent organic group and different from each other, and m and n satisfy m>0, n≥0 and 1000≥(m+n)≥2. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic optical waveguide material and an optical waveguide. More specifically, it relates to a plastic optical waveguide that couples and transmits laser light and the like with low loss, and can be applied to an interconnection / optical communication device using the same.

[0002]

2. Description of the Related Art Conventionally, materials such as glass (quartz) and plastic have been studied as optical waveguide materials.
Among them, the optical waveguide made of quartz has advantages such as low loss and high heat resistance, and therefore, it has been extensively studied and actually used in the fields of optical fibers, optical interconnections and optical communication devices.

On the other hand, an optical waveguide made of plastic is easier to manufacture and has a larger area than a quartz optical waveguide, and a plastic optical waveguide using a polymer such as polymethylmethacrylate, polycarbonate and an ultraviolet curable resin is considered. Has been done.

[0004]

However, in the above-mentioned conventional quartz optical waveguide, it is essentially difficult to reduce the cost because it takes a long process to manufacture. In addition, since a high heat treatment of about 1000 ° C. is required in the manufacturing process, there is a problem that fusion with the electric circuit board is poor and it is difficult to increase the area.

In the case of a plastic optical waveguide made of polymethacrylate, polycarbonate, or an ultraviolet curable resin, the heat resistance of the constituent material is around 100 ° C., so that the use environment is limited and the plastic optical waveguide is incorporated as a mounting circuit. Had to pass through a soldering process at several hundreds of degrees Celsius, resulting in poor fusion with an electric circuit board.

[0006] Moreover, although it is a plastic material,
Some attempts have been made to use polyimide having a heat resistance of 0 ° C. or higher for a plastic optical waveguide,
In the current polyimide, due to its unique molecular structure, light loss due to absorption due to the structure was extremely large.
Also, in the polyimide resin, there is a resin with high crystallinity due to its structure, and if the film thickness is thin, there is little influence, but when the film thickness used for the optical waveguide becomes, the film becomes brittle due to its high crystallinity. Or, the refractive index may change.

Therefore, the present invention is excellent in electrical characteristics, heat resistance and transparency, is low in price, has a small optical loss, can realize a large area, and can control the optical refractive index. It is to provide a material for a plastic optical waveguide and an optical waveguide.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in view of the above-mentioned conventional problems, and as a result, as a result, an optical waveguide whose optical refractive index is adjusted by using a copolymer having a specific structure. It has been found that the purpose can be achieved by using the material for use, and the present invention has been completed.

That is, the present invention is as follows: A compound having a repeating unit represented by the general formula (1), having a repeating unit of m and a repeating unit n having a difference in refractive index as a compound of 0.3% or more from the repeating unit, or A plastic optical waveguide material comprising a resin obtained by ring-closing the compound,

[0010]

[Chemical 20] [In the formula, X represents a tetravalent organic group. Y ₁ and Y ₂ represent a divalent organic group and are different groups. m> 0, n ≧ 0
Then, 1000 ≧ (m + n) ≧ 2. ]

2. The plastic optical waveguide according to claim 1, wherein the compound has a tetravalent group selected from the groups represented by the general formulas (2) to (7) as X in the general formula (1). material,

[0012]

[Chemical 21]

[0013]

[Chemical formula 22]

[0014]

[Chemical formula 23]

[0015]

[Chemical formula 24]

[0016]

[Chemical 25]

[0017]

[Chemical formula 26]

[In the structures represented by the formulas (2) to (7), the hydrogen atom on the benzene ring is at least one hydrogen atom selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. It may be substituted with a group. Formula (7)
In the above, Z ₁ represents a single bond or a divalent group selected from the groups represented by formulas (8) to (10). ]

[0019]

[Chemical 27]

[0020]

[Chemical 28] [In Formula (9), a represents the integer of 1-5. ]

[0021]

[Chemical 29]

[In the structures represented by the formulas (9) and (10), at least one hydrogen atom on the benzene ring is selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. It may be substituted with a group. ]

3. The plastic optical waveguide material according to item 1, wherein the compound has a tetravalent group represented by the general formula (11) as X in the general formula (1).

[0024]

[Chemical 30] [In the formula, the hydrogen atom on the benzene ring may be substituted with at least one group selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. ]

4. The compound is Y ₁ in the general formula (1),
The plastic optical waveguide material according to any one of items 1 to 3, wherein Y ₂ has a divalent group selected from the groups represented by formulas (12) to (15). ,

[0026]

[Chemical 31]

[0027]

[Chemical 32]

[0028]

[Chemical 33] [In Formula (14), i, j, and k represent integers from 2 to 10. ]

[0029]

[Chemical 34]

[In the structures represented by the formulas (12), (13) and (15), the hydrogen atom on the benzene ring and the formula (1)
The hydrogen atom in the structure represented by 4) may be substituted with at least one group selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom.
In formula (15), Z ₂ is a single bond or general formula (16) to
A divalent group selected from the groups represented by (18) is shown. ]

[0031]

[Chemical 35]

[0032]

[Chemical 36] [In Formula (17), b represents the integer of 1-5. ]

[0033]

[Chemical 37]

[In the structures represented by the formulas (17) and (18), at least one hydrogen atom on the benzene ring is selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. It may be substituted with a group. ]

5. An optical waveguide in which the core layer and the cladding layer are formed of a compound having a repeating unit represented by the general formula (1), wherein the ratio of the repeating units m and n in the general formula (1) makes An optical waveguide having an adjusted optical refractive index, and

[0036]

[Chemical 38] [In the formula, X represents a tetravalent organic group. Y ₁ and Y ₂ represent a divalent organic group and are different groups. m> 0, n ≧ 0
Then, 1000 ≧ (m + n) ≧ 2. ]

6. The optical waveguide according to claim 5, wherein the core layer has a refractive index higher than that of the cladding layer.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The polybenzoxazole precursor used in the present invention is obtained by the acid chloride method, activation from a bisaminophenol compound or a diaminodihydroxy compound or a derivative thereof such as an esterified product or an etherified product and a dicarboxylic acid. It can be obtained by an ester method or a method such as a condensation reaction in the presence of a dehydration condensation agent such as polyphosphoric acid or dicyclohexylcarbodiimide.

In the example of the diaminodihydroxy compound used in the present invention, as X in the general formula (1), particularly a tetravalent group represented by the formula (2), 1,3-diamino- 4,6-dihydroxybenzene, 1,4-diamino-3,6-dihydroxybenzene, 3-diamino-
4,6-dihydroxydifluorobenzene, 1,4-diamino-3,6-dihydroxydifluorobenzene,
1,4-diamino-2,3-dihydroxydifluorobenzene, 1,2-diamino-3,6-dihydroxydifluorobenzene, 1-methyl-2,4-diamino-3,
5-dihydroxybenzene, 1-methyl-2,5-diamino-3,6-dihydroxybenzene, 1-methyl-
2,4-diamino-3,5-dihydroxyfluorobenzene, 1-methyl-2,5-diamino-3,6-dihydroxyfluorobenzene, 1,4-dimethyl-2,5-
Diamino-3,6-dihydroxybenzene, 1-trifluoromethyl-2,4-diamino-3,5-dihydroxybenzene, 1-trifluoromethyl-2,5-diamino-3,6-dihydroxybenzene, 1-tri Fluoromethyl-2,4-diamino-3,5-dihydroxyfluorobenzene, 1-trifluoromethyl-2,5-diamino-3,6-dihydroxyfluorobenzene, 1,4
-Bis (trifluoromethyl) -2,5-diamino-
3,6-dihydroxybenzene, 1,3-diamino-
4,6-dihydroxydichlorobenzene, 1,4-diamino-3,6-dihydroxydichlorobenzene, 1,4
-Diamino-2,3-dihydroxydichlorobenzene,
Examples thereof include 1,2-diamino-3,6-dihydroxydichlorobenzene and the like, and derivatives thereof such as ester compounds and ether compounds, but are not limited thereto. These diaminodihydroxy compounds can be used alone or in combination.

In the example of the diaminodihydroxy compound used in the present invention, as X in the general formula (1), particularly a tetravalent group represented by the formula (3), 2,7-diamino- 3,6-dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 3,6-diamino-2,5-dihydroxynaphthalene, 2,7- Diamino-1,8-dihydroxynaphthalene, 1-methyl-3,6-diamino-2,7-dihydroxynaphthalene, 1,5-dimethyl-3,7-diamino-2,6-dihydroxynaphthalene, 1-methyl-3 , 6-Diamino-2,5-dihydroxynaphthalene, 1-trifluoromethyl-3,6-diamino-2,7-dihydroxynaphthalene, 1,5-bi (Trifluoromethyl) 3,7
-Diamino-2,6-dihydroxynaphthalene, 1-trifluoromethyl-3,6-diamino-2,5-dihydroxynaphthalene, 2,7-diamino-3,6-dihydroxytetrafluoronaphthalene, 2,6-diamino-
3,7-dihydroxytetrafluoronaphthalene, 1,
6-diamino-2,5-dihydroxytetrafluoronaphthalene, 3,6-diamino-2,5-dihydroxytetrafluoronaphthalene, 2,7-diamino-1,8-
Dihydroxytetrafluoronaphthalene, 2,7-diamino-3,6-dihydroxytetrachloronaphthalene,
2,6-diamino-3,7-dihydroxytetrachloronaphthalene, 1,6-diamino-2,5-dihydroxytetrachloronaphthalene, 3,6-diamino-2,5-
Dihydroxytetrachloronaphthalene, 2,7-diamino-1,8-dihydroxytetrachloronaphthalene,-
Examples thereof include, but are not limited to, 3,6-diamino-2,5-dihydroxynaphthalene, and derivatives thereof such as ester compounds and ether compounds. These diaminodihydroxyl compounds can be used alone or in combination.

In the example of the bisaminophenol compound used in the present invention, as X in the general formula (1), particularly, the compound represented by the formula (4)
As a constituent of the tetravalent group represented by (6),
9,9-bis (4-((4-amino-3-hydroxy))
Phenoxy) phenyl) fluorene, 9,9-bis (4
-((3-amino-4-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis-((4-amino-3
-Hydroxy) phenyl) fluorene, 9,9-bis-
((3-Amino-4-hydroxy) phenyl) fluorene, 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) -3-phenyl-phenyl) -fluorene, 9,9-bis ( 4-((3-amino-4-hydroxy) phenoxy) -3-phenyl-phenyl) -fluorene, 9,9-bis-((2-amino-3-hydroxy-4-phenyl) -phenyl) -fluorene, 9, 9
-Bis-((2-hydroxy-3-amino-4-phenyl) -phenyl) -fluorene and the like,
Further, derivatives thereof such as ester compounds and ether compounds can be mentioned, but the invention is not limited thereto. These diaminodihydroxyl compounds can be used alone or in combination.

In the example of the bisaminophenol compound used in the present invention, as X in the general formula (1), particularly, the compound represented by the formula (7)
And Z ₁ has a divalent group represented by the formula (8): 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3 '-Diamino-4,4'-dihydroxybiphenyl, 3,4'
-Diamino-4,3'-dihydroxybiphenyl, 4,
4'-diamino-3,3'-dihydroxy-5,5'-
Dimethylbiphenyl, 3,3'-diamino-4,4'-
Dihydroxy-5,5'-dimethylbiphenyl, 4,
4'-diamino-3,3'-dihydroxy-6,6'-
Dimethylbiphenyl, 3,3'-diamino-4,4'-
Dihydroxy-6,6'-dimethylbiphenyl, 3,
4'-diamino-4,3'-dihydroxy-5,5'-
Dimethylbiphenyl, 3,4'-diamino-4,3'-
Dihydroxy-6,6'-dimethylbiphenyl, 4,
4'-diamino-3,3'-dihydroxy-5,5'-
Trifluoromethylbiphenyl, 3,3'-diamino-
4,4'-dihydroxy-5,5'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-trifluoromethylbiphenyl,
3,3'-diamino-4,4'-dihydroxy-6,
6'-trifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'-trifluoromethylbiphenyl, 3,4'-diamino-4,3'-
Dihydroxy-6,6'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-
5,5'-difluorobiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-difluorobiphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-difluoro Biphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-difluorobiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'-difluorobiphenyl, 3,4 '-Diamino-4,3'-dihydroxy-6,6'-difluorobiphenyl,4,4'-diamino-3,3'-dihydroxy-5,5'-dichlorobiphenyl,3,3'-diamino-4,4'-Dihydroxy-5,5'-dichlorobiphenyl,4,4'-diamino-3,3'-dihydroxy-6,6'-dichlorobiphenyl,3,3'-diamino-4,4'-dihydroxy-6,6'-dichlorobipheni3,4'-diamino-4,3'-dihydroxy-5,5'-dichlorobiphenyl,3,4'-diamino-4,3'-dihydroxy-6,6'-dichlorobiphenyl, bis (4- Amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl)
Ether, bis (4-amino-3-hydroxy-5-methylphenyl) ether, bis (3-amino-4-hydroxy-5-methylphenyl) ether, bis (4-amino-3-hydroxy-5-trifluoro) Methylphenyl) ether, bis (3-amino-4-hydroxy-5)
-Trifluoromethylphenyl) ether, bis (4-
Amino-3-hydroxy-5-fluorophenyl) ether, bis (3-amino-4-hydroxy-5-fluorophenyl) ether, bis (4-amino-3-hydroxy-2,5,6-trifluorophenyl) ether,
Bis (3-amino-4-hydroxy-2,5,6-trifluorophenyl) ether, bis (4-amino-3-)
Hydroxy-5-chlorophenyl) ether, bis (3
-Amino-4-hydroxy-5-chlorophenyl) ether, bis (4-amino-3-hydroxy-2,5,6
-Trichlorophenyl) ether, bis (3-amino-
4-hydroxy-2,5,6-trichlorophenyl) ether, bis (3-amino-4-hydroxyphenyl)
Sulfide, bis (4-amino-3-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxy-
5-methylphenyl) sulfide, bis (4-amino-
3-hydroxy-5-methylphenyl) sulfide, bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) sulfide, bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) sulfide, bis (3-amino-4-hydroxy-5-fluorophenyl) sulfide, bis (4-amino-3-hydroxy-5-fluorophenyl) sulfide, bis (3-
Amino-4-hydroxy-2,5,6-trifluorophenyl) sulfide, bis (4-amino-3-hydroxy-2,5,6-trifluorophenyl) sulfide,
Bis (3-amino-4-hydroxy-5-chlorophenyl) sulfide, bis (4-amino-3-hydroxy-)
5-chlorophenyl) sulfide, bis (3-amino-
4-hydroxy-2,5,6-trichlorophenyl) sulfide, bis (4-amino-3-hydroxy-2,
5,6-trichlorophenyl) sulfide, bis (3-
Amino-4-hydroxyphenyl) sulfone, bis (4
-Amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxy-5-methylphenyl)
Sulfone, bis (4-amino-3-hydroxy-5-methylphenyl) sulfone, bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) sulfone,
Bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) sulfone, bis (3-amino-4-hydroxy-5-fluorophenyl) sulfone, bis (4
-Amino-3-hydroxy-5-fluorophenyl) sulfone, bis (3-amino-4-hydroxy-2,5,
6-trifluorophenyl) sulfone, bis (4-amino-3-hydroxy-2,5,6-trifluorophenyl) sulfone, bis (3-amino-4-hydroxy-5)
-Chlorophenyl) sulfone, bis (4-amino-3-)
Hydroxy-5-chlorophenyl) sulfone, bis (3
-Amino-4-hydroxy-2,5,6-trichlorophenyl) sulfone, bis (4-amino-3-hydroxy-2,5,6-trichlorophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) Ketone, bis (4-amino-3-hydroxyphenyl) ketone, bis (3-amino-4-hydroxy-5-methylphenyl)
Ketone, bis (4-amino-3-hydroxy-5-methylphenyl) ketone, bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) ketone, bis (4-amino-3-hydroxy-5-) Trifluoromethylphenyl) ketone, bis (3-amino-4-hydroxy-5-fluorophenyl) ketone, bis (4-amino-3-hydroxy-5-fluorophenyl) ketone, bis (3-amino-4-hydroxy) -2,5,6-trifluorophenyl) ketone, bis (4-amino-3-hydroxy-2,5,6-trifluorophenyl) ketone,
Bis (3-amino-4-hydroxy-5-chlorophenyl) ketone, bis (4-amino-3-hydroxy-5-)
Chlorophenyl) ketone, bis (3-amino-4-hydroxy-2,5,6-trichlorophenyl) ketone, bis (4-amino-3-hydroxy-2,5,6-trichlorophenyl) ketone, bis (3- Amino-4-hydroxyphenyl) methane, 2,2-bis (4-amino-3)
-Hydroxyphenyl) methane, bis (3-amino-4)
-Hydroxy-5-methylphenyl) methane, bis (4
-Amino-3-hydroxy-5-methylphenyl) methane, bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) methane, bis (4-amino-3-)
Hydroxy-5-trifluoromethylphenyl) methane, bis (3-amino-4-hydroxy-5-fluorophenyl) methane, bis (4-amino-3-hydroxy-5-fluorophenyl) methane, bis (3-amino −
4-hydroxy-2,5,6-trifluorophenyl)
Methane, bis (4-amino-3-hydroxy-2,5,
6-trifluorophenyl) methane, bis (3-amino-4-hydroxy-5-chlorophenyl) methane, bis (4-amino-3-hydroxy-5-chlorophenyl)
Methane, bis (3-amino-4-hydroxy-2,5,
6-trichlorophenyl) methane, bis (4-amino-)
3-hydroxy-2,5,6-trichlorophenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2 , 2-bis (3-amino-4-hydroxy-5-methylphenyl) propane,
2,2-bis (4-amino-3-hydroxy-5-methylphenyl) propane, 2,2-bis (3-amino-4)
-Hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-5)
-Trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-5-fluorophenyl) propane, 2,2-bis (4-amino-3-hydroxy-5-fluorophenyl) propane, 2,2-bis (3-amino-4-hydroxy-2,5,6-trifluorophenyl) propane, 2,2-bis (4-amino-
3-hydroxy-2,5,6-trifluorophenyl)
Propane, 2,2-bis (3-amino-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (4-
Amino-3-hydroxy-5-chlorophenyl) propane, 2,2-bis (3-amino-4-hydroxy-2,
5,6-Trichlorophenyl) propane, 2,2-bis (4-amino-3-hydroxy-2,5,6-trichlorophenyl) propane, 2,2-bis (4-amino-3)
-Hydroxyphenyl) hexafluoropropane, 2,
2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (2-amino-3-)
Hydroxyphenyl) hexafluoropropane, 2,2
-Bis (3-amino-2-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (2
-Amino-3-hydroxyphenyl) -2- (3-amino-2-hydroxyphenyl) hexafluoropropane, 2- (2-amino-3-hydroxyphenyl) -2
-(3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (2-amino-3-hydroxyphenyl) -2- (4-amino-3-hydroxyphenyl)
Hexafluoropropane, 2- (3-amino-2-hydroxyphenyl) -2- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-amino-2-hydroxyphenyl) -2- (4 -Amino-3-
(Hydroxyphenyl) hexafluoropropane, 2-
(3-Amino-4-hydroxyphenyl) -2- (4-
Amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5)
-Methylphenyl) hexafluoropropane, 2,2-
Bis (4-amino-3-hydroxy-5-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis ( 4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-fluorophenyl) hexafluoropropane, bis (4-amino-3-) Hydroxy-
5-fluorophenyl) hexafluoropropane, 2,
2-bis (3-amino-4-hydroxy-2,5,6-
Trifluorophenyl) hexafluoropropane, 2,
2-bis (4-amino-3-hydroxy-2,5,6-
Trifluorophenyl) hexafluoropropane, 2,
2-bis (3-amino-4-hydroxy-5-chlorophenyl) hexafluoropropane, 2,2-bis (4-
Amino-3-hydroxy-5-chlorophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-2,5,6-trichlorophenyl) hexafluoropropane, 2,2-bis (4-amino) Examples include, but are not limited to, 3-hydroxy-2,5,6-trichlorophenyl) hexafluoropropane and the like. Derivatives of these ester compounds and ether compounds can also be mentioned.

Of these, 2,2- which forms a tetravalent group represented by the general formula (11) as X in the general formula (1).
Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (2-amino-3-hydroxyphenyl) hexa Fluoropropane, 2,2-bis (3-amino-2-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (2-amino-3- Hydroxyphenyl) -2- (3-amino-2-hydroxyphenyl) hexafluoropropane, 2- (2-amino-3-hydroxyphenyl) -2- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2 -(2-amino-
3-hydroxyphenyl) -2- (4-amino-3-hydroxyphenyl) hexafluoropropane, 2- (3
-Amino-2-hydroxyphenyl) -2- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-amino-2-hydroxyphenyl) -2
-(4-amino-3-hydroxyphenyl) hexafluoropropane, 2- (3-amino-4-hydroxyphenyl) -2- (4-amino-3-hydroxyphenyl)
Hexafluoropropane, 2,2-bis (3-amino-
4-hydroxy-5-methylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-5-methylphenyl) hexafluoropropane, 2,
2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2
-Bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-
Bis (3-amino-4-hydroxy-5-fluorophenyl) hexafluoropropane, bis (4-amino-3)
-Hydroxy-5-fluorophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-2,5,6-trifluorophenyl) hexafluoropropane, 2,2-bis (4-amino- 3-hydroxy-2,5,6-trifluorophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-chlorophenyl) hexafluoropropane, 2,
2-bis (4-amino-3-hydroxy-5-chlorophenyl) hexafluoropropane, 2,2-bis (3-
Amino-4-hydroxy-2,5,6-trichlorophenyl) hexafluoropropane and 2,2-bis (4-amino-3-hydroxy-2,5,6-trichlorophenyl) hexafluoropropane are more preferable. .

In the example of the bisaminophenol compound used in the present invention, as X in the general formula (1), particularly, the compound represented by the formula (7)
A group represented by formula ( ₁ ) wherein Z ₁ has a divalent group represented by formula (9) is 1,2-bis (4
-Amino-3-hydroxyphenoxy) benzene, 1,
2-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-)
Hydroxyphenoxy) benzene, 1,4-bis (4-
Amino-3-hydroxyphenoxy) benzene, 1,4
-Bis (3-amino-4-hydroxyphenoxy) benzene, 1,2-bis (4-amino-3-hydroxyphenoxy) tetrafluorobenzene, 1,2-bis (3-
Amino-4-hydroxyphenoxy) tetrafluorobenzene, 1,3-bis (4-amino-3-hydroxyphenoxy) tetrafluorobenzene, 1,3-bis (3
-Amino-4-hydroxyphenoxy) tetrafluorobenzene, 1,4-bis (4-amino-3-hydroxyphenoxy) tetrafluorobenzene, 1,4-bis (3-amino-4-hydroxyphenoxy) tetrafluorobenzene, 1,2-bis (4-amino-3-hydroxyphenoxy) tetrafuchlorobenzene, 1,2-bis (3-amino-4-hydroxyphenoxy) tetrachlorobenzene, 1,3-bis (4-amino-3-hydroxy) Phenoxy) tetrachlorobenzene, 1,3-bis (3-amino-4-hydroxyphenoxy) tetrachlorobenzene, 1,4-bis (4-amino-3-hydroxyphenoxy) tetrachlorobenzene, 1,4-bis (3-amino -4-hydroxyphenoxy) tetrachlorobenzene, etc. DOO can not be construed as being limited thereto. Derivatives of these ester compounds and ether compounds can also be mentioned.

In the example of the bisaminophenol compound used in the present invention, as X in the general formula (1), particularly as represented by the formula (7)
A group represented by the formula (1), wherein Z ₁ has a divalent group represented by the formula (10), 1,2-bis (4-amino-3-hydroxyphenoxy) biphenyl, , 2-bis (3-amino-4-hydroxyphenoxy) biphenyl, 1,3-bis (4-amino-3-hydroxyphenoxy) biphenyl, 1,3-bis (3-
Amino-4-hydroxyphenoxy) biphenyl, 1,
4-bis (4-amino-3-hydroxyphenoxy) biphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) biphenyl, 2-bis (4-amino-3-)
Hydroxyphenoxy) octafluorobiphenyl,
1,2-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 1,3-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl, 1,3-bis (3-amino-4-) Hydroxyphenoxy) octafluorobiphenyl, 1,4-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 2-bis (4 -Amino-3-hydroxyphenoxy) octachlorobiphenyl, 1,2-bis (3-amino-4-hydroxyphenoxy) octachlorobiphenyl, 1,3-
Bis (4-amino-3-hydroxyphenoxy) octachlorobiphenyl, 1,3-bis (3-amino-4-hydroxyphenoxy) octachlorobiphenyl, 1,4
-Bis (4-amino-3-hydroxyphenoxy) octachlorobiphenyl, 1,4-bis (3-amino-4-)
Examples thereof include, but are not limited to, hydroxyphenoxy) octachlorobiphenyl. These bisaminophenol compounds can be used alone or in combination.

In the polybenzoxazole precursor used in the present invention, one kind or two kinds of diaminodihydroxy compounds or bisaminophenol compounds having the structures represented by the formulas (2) to (10), Alternatively, one or more of each may be mixed and used.

As Y ₁ and Y ₂ in the general formula (1), a divalent group represented by the formula (12) is particularly preferable.
Phthalic acid, isophthalic acid, terephthalic acid, 2-methylisophthalic acid, 3-methylphthalic acid, 2-methylterephthalic acid, 2,4,5,6-tetramethylisophthalic acid,
3,4,5,6-tetramethylphthalic acid, 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 3,4,5,5 6-tetrafluorophthalic acid, 2-
Trifluoromethylisophthalic acid, 3-trifluoromethylphthalic acid, 2-trifluoromethylterephthalic acid,
2,4,5,6-trifluoromethylisophthalic acid,
3,4,5,6-Trifluoromethylphthalic acid, 2-chloroisophthalic acid, 3-chlorophthalic acid, 2-chloroterephthalic acid, 2,4,5,6-tetrachloroisophthalic acid, 3,4,5,5 Examples thereof include 6-tetrachlorophthalic acid, but are not limited thereto. These dicarboxylic acid compounds can be used alone or in combination.

As the dicarboxylic acid used in the present invention, as Y ₁ and Y ₂ in the general formula (1), particularly a divalent group represented by the formula (13), 1,4-dicarboxylic acid is used. Carboxynaphthalene, 1,5-dicarboxynaphthalene,
1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 1,
4-dicarboxyhexafluoronaphthalene, 1,5-
Dicarboxyhexafluoronaphthalene, 1,6-dicarboxyhexafluoronaphthalene, 1,7-dicarboxyhexafluoronaphthalene, 1,8-dicarboxyhexafluoronaphthalene, 1,4-dicarboxyhexachloronaphthalene, 1,5-di Examples thereof include carboxyhexachloronaphthalene, 1,6-dicarboxyhexachloronaphthalene, 1,7-dicarboxyhexachloronaphthalene, and 1,8-dicarboxyhexachloronaphthalene, but are not limited thereto. These dicarboxylic acid compounds can be used alone or in combination.

The dicarboxylic acid used in the present invention includes, as Y ₁ and Y ₂ in the general formula (1), particularly succinic acid and glutaric acid as a divalent group represented by the formula (14). Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, dodecanedioic acid, tridecanedioic acid, 1,12-dodecanedicarboxylic acid, tetrafluorosuccinic acid, hexafluoroglutaric acid, Octafluoroadipic acid, perfluoropimelic acid, perfluorosuberic acid, perfluoroazelaic acid, perfluorosebacic acid, 1,9-perfluorononanedicarboxylic acid, perfluorododecanedioic acid, perfluorotridecanedioic acid, 1 , 12-Perfluorododecanedicarboxylic acid, tetrachlorosuccinic acid, hexachloroglutaric acid Octachloroadipic acid, perchloropimelic acid, perchlorosuberic acid, perchloroazelaic acid, perchlorosebacic acid, 1,9-perchlorononanedicarboxylic acid, perchlorododecanedioic acid, perchlorotridecanedioic acid, 1, 12-perchlorododecanedicarboxylic acid, 1,4-perfluorocyclohexanedicarboxylic acid, 1,3-perfluorocyclohexanedicarboxylic acid, 1,2-perfluorocyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples include cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-perchlorocyclohexanedicarboxylic acid, 1,3-perchlorocyclohexanedicarboxylic acid, and 1,2-perchlorohexanedicarboxylic acid, but are not limited thereto. What is done is not. These dicarboxylic acid compounds can be used alone or in combination.

As the dicarboxylic acid used in the present invention, Y ₁ and Y ₂ in the general formula (1) constitute a group particularly represented by the formula (15), and Z ₂ is represented by the formula (16). Done 2
As those having a valent group, 4,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 2,4'-oxybisbenzoic acid,
3,4'-oxybisbenzoic acid, 2,3'-oxybisbenzoic acid, 4,4'-oxybisoctafluorobenzoic acid, 3,3'-oxybisoctafluorobenzoic acid,
3,4'-oxybisoctafluorobenzoic acid, 2,
4'-oxybisoctafluorobenzoic acid, 3,4'-
Oxybisoctafluorobenzoic acid, 2,3'-oxybisoctafluorobenzoic acid, 4,4'-oxybisoctachlorobenzoic acid, 3,3'-oxybisoctachlorobenzoic acid, 3,4'-oxybis Octachlorobenzoic acid, 2,4'-oxybisoctachlorobenzoic acid, 3,
4'-oxybisoctachlorobenzoic acid, 2,3'-oxybisoctachlorobenzoic acid, bis (4-carboxyphenyl) -sulfide, bis (3-carboxyphenyl) -sulfide, bis (2-methyl-4-) Carboxyphenyl) -sulfide, bis (2-methyl-3-carboxyphenyl) -sulfide, bis (3-methyl-4)
-Carboxyphenyl) -sulfide, bis (4-methyl-3-carboxyphenyl) -sulfide, bis (5
-Methyl-4-carboxyphenyl) -sulfide, bis (5-methyl-3-carboxyphenyl) -sulfide, bis (6-methyl-4-carboxyphenyl) -sulfide, bis (6-methyl-3-carboxyphenyl) -Sulfide, bis (2-trifluoromethyl-4)
-Carboxyphenyl) -sulfide, bis (2-trifluoromethyl-3-carboxyphenyl) -sulfide, bis (3-trifluoromethyl-4-carboxyphenyl) -sulfide, bis (4-trifluoromethyl-3-carboxy) Phenyl) -sulfide, bis (5-
Trifluoromethyl-4-carboxyphenyl) -sulfide, bis (5-trifluoromethyl-3-carboxyphenyl) -sulfide, bis (6-trifluoromethyl-4-carboxyphenyl) -sulfide, bis (6-trifluoro) Methyl-3-carboxyphenyl)
-Sulfide, bis (4-carboxyoctafluorophenyl) -sulfide, bis (3-carboxyoctafluorophenyl) -sulfide, bis (4-carboxyoctachlorophenyl) -sulfide, bis (3-carboxyoctachlorophenyl) -sulfide, bis (4
-Carboxyphenyl) -sulfone, bis (3-carboxyphenyl) -sulfone, bis (2-methyl-4-carboxyphenyl) -sulfone, bis (2-methyl-3)
-Carboxyphenyl) -sulfone, bis (3-methyl-4-carboxyphenyl) -sulfone, bis (4-methyl-3-carboxyphenyl) -sulfone, bis (5
-Methyl-4-carboxyphenyl) -sulfone, bis (5-methyl-3-carboxyphenyl) -sulfone,
Bis (6-methyl-4-carboxyphenyl) -sulfone, bis (6-methyl-3-carboxyphenyl) -sulfone, bis (2-trifluoromethyl-4-carboxyphenyl) -sulfone, bis (2-trifluoro) Methyl-3-carboxyphenyl) -sulfone, bis (3-
Trifluoromethyl-4-carboxyphenyl) -sulfone, bis (4-trifluoromethyl-3-carboxyphenyl) -sulfone, bis (5-trifluoromethyl-4-carboxyphenyl) -sulfone, bis (5-trifluoro) Methyl-3-carboxyphenyl) -sulfone, bis (6-trifluoromethyl-4-carboxyphenyl) -sulfone, bis (6-trifluoromethyl-)
3-carboxyphenyl) -sulfone, bis (4-carboxyoctafluorophenyl) -sulfone, bis (3
-Carboxyoctafluorophenyl) -sulfone, bis (4-carboxyoctachlorophenyl) -sulfone, bis (3-carboxyoctachlorophenyl) -sulfone, bis (4-carboxyphenyl) -ketone, bis (3-carboxyphenyl) -ketone , Bis (2-methyl-4-carboxyphenyl) -ketone, bis (2-
Methyl-3-carboxyphenyl) -ketone, bis (3
-Methyl-4-carboxyphenyl) -ketone, bis (4-methyl-3-carboxyphenyl) -ketone, bis (5-methyl-4-carboxyphenyl) -ketone,
Bis (5-methyl-3-carboxyphenyl) -ketone, bis (6-methyl-4-carboxyphenyl) -ketone, bis (6-methyl-3-carboxyphenyl)-
Ketone, bis (2-trifluoromethyl-4-carboxyphenyl) -ketone, bis (2-trifluoromethyl-3-carboxyphenyl) -ketone, bis (3-trifluoromethyl-4-carboxyphenyl) -ketone,
Bis (4-trifluoromethyl-3-carboxyphenyl) -ketone, bis (5-trifluoromethyl-4-carboxyphenyl) -ketone, bis (5-trifluoromethyl-3-carboxyphenyl) -ketone, bis ( 6
-Trifluoromethyl-4-carboxyphenyl) -ketone, bis (6-trifluoromethyl-3-carboxyphenyl) -ketone, bis (4-carboxyoctafluorophenyl) -ketone, bis (3-carboxyoctafluorophenyl) -Ketone, bis (4-carboxyoctachlorophenyl) -ketone, bis (3-carboxyoctachlorophenyl) -ketone, bis (4-carboxyphenyl) -methane, bis (3-carboxyphenyl) -methane, bis (2-methyl) -4-carboxyphenyl) -methane, bis (2-methyl-3-carboxyphenyl) -methane, bis (3-methyl-4-carboxyphenyl) -methane, bis (4-methyl-3-carboxyphenyl) -methane , Bis (5-methyl-4-carboxyphenyl) -me Emissions, bis (5-methyl-3-carboxyphenyl) - methane, bis (6-methyl-4-carboxyphenyl) - methane, bis (6-methyl-3-
Carboxyphenyl) -methane, bis (2-trifluoromethyl-4-carboxyphenyl) -methane, bis (2-trifluoromethyl-3-carboxyphenyl)
-Methane, bis (3-trifluoromethyl-4-carboxyphenyl) -methane, bis (4-trifluoromethyl-3-carboxyphenyl) -methane, bis (5-trifluoromethyl-4-carboxyphenyl) -methane , Bis (5-trifluoromethyl-3-carboxyphenyl) -methane, bis (6-trifluoromethyl-4)
-Carboxyphenyl) -methane, bis (6-trifluoromethyl-3-carboxyphenyl) -methane, bis (4-carboxyoctafluorophenyl) -methane,
Bis (3-carboxyoctafluorophenyl) -methane, bis (4-carboxyoctachlorophenyl) -methane, bis (3-carboxyoctachlorophenyl)-
Methane, 2,2-bis (4-carboxyphenyl) -propane, 2,2-bis (3-carboxyphenyl) -propane, 2,2-bis (2-methyl-4-carboxyphenyl) -propane, 2, 2-bis (2-methyl-3-
Carboxyphenyl) -propane, 2,2-bis (3-
Methyl-4-carboxyphenyl) -propane, 2,2
-Bis (4-methyl-3-carboxyphenyl) -propane, 2,2-bis (5-methyl-4-carboxyphenyl) -propane, 2,2-bis (5-methyl-3-carboxyphenyl) -propane , 2,2-bis (6-methyl-4-carboxyphenyl) -propane, 2,2-
Bis (6-methyl-3-carboxyphenyl) -propane, 2,2-bis (2-trifluoromethyl-4-carboxyphenyl) -propane, 2,2-bis (2-trifluoromethyl-3-carboxyphenyl) ) -Propane, 2,2-bis (3-trifluoromethyl-4-carboxyphenyl) -propane, 2,2-bis (4-trifluoromethyl-3-carboxyphenyl) -propane, 2,2-bis ( 5-trifluoromethyl-4-carboxyphenyl) -propane, 2,2-bis (5-trifluoromethyl-3-carboxyphenyl) -propane, 2,2-bis (6-methyl-4-carboxyphenyl)- Propane, 2,2-bis (6-trifluoromethyl-3-carboxyphenyl) -propane, 2,2-bis (4-carboxyoctane Fluorophenyl) -propane, 2,2-bis (3-carboxyoctafluorophenyl) -propane, 2,2-bis (4-carboxyoctachlorophenyl) -propane, 2,2-bis (3-carboxyoctachlorophenyl)- Propane, 2,2-
Bis (4-carboxyphenyl) -hexafluoropropane, 2,2-bis (3-carboxyphenyl) -hexafluoropropane, 2,2-bis (2-methyl-4-)
Carboxyphenyl) -hexafluoropropane, 2,
2-bis (2-methyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (3-methyl-4)
-Carboxyphenyl) -hexafluoropropane,
2,2-bis (4-methyl-3-carboxyphenyl)
-Hexafluoropropane, 2,2-bis (5-methyl-4-carboxyphenyl) -hexafluoropropane, 2,2-bis (5-methyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (6-Methyl-4-carboxyphenyl) -hexafluoropropane, 2,2-bis (6-methyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (2-
Trifluoromethyl-4-carboxyphenyl) -hexafluoropropane, 2,2-bis (2-trifluoromethyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (3-trifluoromethyl-4-)
Carboxyphenyl) -hexafluoropropane, 2,
2-bis (4-trifluoromethyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (5
-Trifluoromethyl-4-carboxyphenyl) -hexafluoropropane, 2,2-bis (5-trifluoromethyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (6-trifluoromethyl-4)
-Carboxyphenyl) -hexafluoropropane,
2,2-bis (6-trifluoromethyl-3-carboxyphenyl) -hexafluoropropane, 2,2-bis (4-carboxyoctafluorophenyl) -hexafluoropropane, 2,2-bis (3-carboxyocta) Fluorophenyl) -hexafluoropropane, 2,2
Examples thereof include, but are not limited to, -bis (4-carboxyoctachlorophenyl) -hexafluoropropane and 2,2-bis (3-carboxyoctachlorophenyl) -hexafluoropropane. These dicarboxylic acid compounds can be used alone or in combination.

As the dicarboxylic acid used in the present invention, Y ₁ and Y ₂ in the general formula (1) particularly constitute a group represented by the formula (15), and Z ₂ is represented by the formula (17). Done 2
As those having a valent group, 1,2-bis (4-carboxyphenoxy) benzene, 1,2-bis (3-carboxyphenoxy) benzene, 1,3-bis (4-carboxyphenoxy) benzene, 1, 3-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,2-bis (4-carboxyphenoxy) tetrafluoro Benzene, 1,2-
Bis (3-carboxyphenoxy) tetrafluorobenzene, 1,3-bis (4-carboxyphenoxy) tetrafluorobenzene, 1,3-bis (3-carboxyphenoxy) tetrafluorobenzene, 1,4-bis (4
-Carboxyphenoxy) tetrafluorobenzene,
1,4-bis (3-carboxyphenoxy) tetrafluorobenzene, 1,2-bis (4-carboxyphenoxy) tetrachlorobenzene, 1,2-bis (3-carboxyphenoxy) tetrachlorobenzene, 1,3-bis (4 -Carboxyphenoxy) tetrachlorobenzene,
Examples include 1,3-bis (3-carboxyphenoxy) tetrachlorobenzene, 1,4-bis (4-carboxyphenoxy) tetrachlorobenzene, and 1,4-bis (3-carboxyphenoxy) tetrachlorobenzene, but are not limited thereto. It is not something that will be done. These dicarboxylic acid compounds can be used alone or in combination.

As the dicarboxylic acid used in the present invention, Y ₁ and Y ₂ in the general formula (1) constitute a group particularly represented by the formula (15), and Z ₂ is represented by the formula (18). Done 2
As those having a valent group, 1,2-bis (4-carboxyphenoxy) biphenyl, 1,2-bis (3-carboxyphenoxy) biphenyl, 1,3-bis (4-
Carboxyphenoxy) biphenyl, 1,3-bis (3
-Carboxyphenoxy) biphenyl, 1,4-bis (4-carboxyphenoxy) biphenyl, 1,4-bis (3-carboxyphenoxy) biphenyl, 1,2-
Bis (4-carboxyphenoxy) octafluorobiphenyl, 1,2-bis (3-carboxyphenoxy) octafluorobiphenyl, 1,3-bis (4-carboxyphenoxy) octafluorobiphenyl, 1,3-bis (3-carboxy Phenoxy) octafluorobiphenyl, 1,4-bis (4-carboxyphenoxy) octafluorobiphenyl, 1,4-bis (3-carboxyphenoxy) octafluorobiphenyl, 1,2-bis (4-carboxyphenoxy) octachlorobiphenyl 1,2-bis (3-carboxyphenoxy) octachlorobiphenyl, 1,3-bis (4-carboxyphenoxy) octachlorobiphenyl, 1,3-bis (3-
Carboxyphenoxy) octachlorobiphenyl, 1,
4-bis (4-carboxyphenoxy) octachlorobiphenyl, 1,4-bis (3-carboxyphenoxy)
Examples thereof include, but are not limited to, octachlorobiphenyl and the like. These dicarboxylic acids can be used alone or in combination.

In the method for producing the copolymer used in the present invention, an example of the synthesis by the acid chloride method is given. First, the above dicarboxylic acid is chlorinated in the presence of a catalyst such as N, N-dimethylformamide in an excessive amount. The reaction is carried out with thionyl at room temperature to 75 ° C., and excess thionyl chloride is distilled off by heating and reducing pressure. Then, the residue is recrystallized with a solvent such as hexane to obtain dicarboxylic acid chloride which is an acid chloride. Then, the bisaminophenol compound or diaminodihydroxy compound is usually dissolved in a polar solvent such as N-methyl-2-pyrrolidone, and in the presence of an acid acceptor such as pyridine, dicarboxylic acid chloride and -3
The compound can be obtained by reacting at 0 ° C. to room temperature. Further, this compound can be ring-closed to a resin by heating or the like.

In the compound having a repeating unit represented by the general formula (1) used in the present invention, the difference in the refractive index between the repeating unit of m and the compound is 0.3%.
It is a compound having the above repeating unit n, and the cured product can be adjusted to an appropriate refractive index by adjusting the ratio of the repeating unit m and the repeating unit n. Used. The total number of each repeating unit is set to be suitable for forming an optical waveguide. The ratio of the repeating unit of m to the repeating unit of n is 0.0
It is preferable to adjust the refractive index in the range of 5 to 0.95, but it suffices if the refractive index can be adjusted to a preferable value as the core layer and the cladding layer of the optical waveguide. The compound having the structure represented by the general formula (1) may be used in combination with each of the layers in the optical waveguide.

The plastic optical waveguide material of the present invention is
In addition to the above compounds, various additives such as a surfactant and a coupling agent can be added and used if necessary.

Further, the compound of the present invention can be used as a positive type photosensitive resin composition by using together with a naphthoquinonediazide compound as a photosensitizer, and Y ₁ of the general formula (1), or Y _{2 in the} general formula (2)
When there is a group having a photocrosslinkable group such as a methacryloyl group in the above structure, it can be used as a negative photosensitive resin composition by using a photoinitiator.

The plastic optical waveguide material of the present invention is
It can be applied to a single mode optical waveguide on a substrate which is generally manufactured, or a structure similar to a multimode optical waveguide. For example, there are a slab type, a ridge type, a buried type and the like. It can also be applied as a flexible film optical waveguide or the like.

The optical waveguide of the present invention can be obtained by using, as the core layer and the cladding layer, a plastic optical waveguide material whose optical refractive index is adjusted by the ratio of the repeating units m and n of the compound. At this time, the refractive index of the optical waveguide material adjusted depending on the structure of the optical waveguide is different. For example, when producing a single mode optical waveguide, the difference in refractive index between the optical waveguide materials used in the core layer and the cladding layer is 0.3% to
1.5%, 1. when manufacturing a multimode optical waveguide.
It is preferable to use a material adjusted to 0% or more in order to reduce light loss.

A method of manufacturing an embedded single mode optical waveguide in the optical waveguide structure will be described with reference to FIG.

First, a solution of the above-mentioned optical waveguide material for lower cladding is applied onto a substrate 1 made of silicon or the like by a method such as spin coating to form a lower cladding layer 2. The lower clad layer 2 thus obtained is cured by heating or the like to be ring-closed to obtain a resin. Next, the same method as that for forming the lower clad layer 2 on the lower clad layer 2 using a solution of an optical waveguide material of a compound having a higher refractive index than the compound used as the lower clad layer. Thus, the core layer 3 is formed. Next, a mask layer 4 for forming a core pattern is formed on the core layer 3 (see FIG. 1).
(A)). As the material for the mask layer, metals such as Al and Ti, SiO ₂ , spion glass (SOG), Si-containing resist, and photosensitive polybenzoxazole can be used.

Next, a resist is applied onto the mask layer 4 and prebaked, exposed, developed and afterbaked to obtain a patterned resist layer 5 (FIG. 1).
(B)). Next, after removing the mask layer 4 not protected by the resist layer 5 by etching (FIG. 1C), the resist layer 5 is removed by an etching solution, and the mask layer 4 is used to remove the fluorine-containing polybenzoxene of the core layer 3. Oxazole is removed by dry etching (FIG. 1 (d)). When Si-containing resist or photosensitive polybenzoxazole is used for the mask layer 4, it is not necessary to use photoresist.

Next, the remaining mask layer 4 is removed by dry etching or using a peeling liquid. (Fig. 1
(E)). Further, a solution of the same optical waveguide material as that used for the lower clad material is applied thereon by spin coating or the like to form an upper clad layer 6, which is cured by heating or the like to form a ring-closed resin. The upper clad layer 6 is obtained (FIG. 1 (f)). In this way, a single mode optical waveguide made of a plastic optical waveguide material having good optical waveguide characteristics such as optical loss can be manufactured.

[0063]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Refractive Index in Each Repeating Unit] Reference Example 1 73.4 parts (0.2 mo) of 2,2′-bis (4-amino-3-hydroxyphenyl) hexafluoropropane
l) was dissolved in 200 parts of dried dimethylacetamide, 39.6 parts (0.5 mol) of pyridine was added, and then 100 parts of cyclohexane was added to 100 parts of cyclohexane at −15 ° C. under dry nitrogen.
2'-Bis (trifluoromethyl) -4,4'-biphenylenedicarboxylic acid chloride 89.4 parts (0.2mo
What melt | dissolved l) was dripped over 30 minutes. After the dropping was completed, the temperature was returned to room temperature and the mixture was stirred at room temperature for 5 hours. afterwards,
The reaction solution was added dropwise to 7 L of distilled water, and the precipitate was collected and dried to give the polybenzoxazole precursor (A) 11
0.5 part was obtained. About the obtained precursor, gel permeation chromatography (hereinafter abbreviated as GPC)
And the molecular weight measured by using the above polymer on a silicon substrate by a spin coating method, and cured by heating at 320 ° C. to obtain a cured product at 1300 nm with a prism coupler manufactured by Metricon Corporation.
Table 1 shows the refractive index measured at the wavelength of.

Reference Examples 2 to 42 Diaminodihydroxy compounds shown in Tables 1 to 3 are 23.4 '(0.2 mol) of 2,2'-bis (4-amino-3-hydroxyphenyl) hexafluoropropane in Reference Example 1. Replaced with 0.2 mol, and 89.4 parts (0.2 mol) of 2,2′-bis (trifluoromethyl) -4,4′-biphenylenedicarboxylic acid chloride was used in Table 1.
The polybenzoxazole precursor was obtained and evaluated in the same manner as in Reference Example 1 except that 0.2 mol of dicarboxylic acid chloride shown in 3 to 3 was replaced. The evaluation results are shown in Tables 1 to 3.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[Synthesis of Material for Optical Waveguide] Examples 1 to 23 In Example 1, 2,2′-bis (trifluoromethyl) -4,4′-biphenylenedicarboxylic acid chloride was used as a dicarboxylic acid shown in Tables 4 to 5. Mixture of chloride 0.2m
A polybenzoxazole copolymer precursor was synthesized and an optical waveguide material was obtained and evaluated in the same manner as in Reference Example 1 except that it was replaced with ol. The evaluation results are shown in Tables 4-5.

[0070]

[Table 4]

[0071]

[Table 5]

Examples 24 to 42 In Reference Example 7, 2,2'-bis (trifluoromethyl) -4,4'-biphenylenedicarboxylic acid chloride was mixed with a dicarboxylic acid chloride mixture shown in Tables 6 to 0.2m.
A polybenzoxazole copolymer precursor was synthesized and an optical waveguide material was obtained and evaluated in the same manner as in Reference Example 1 except that it was replaced with ol. The evaluation results are shown in Tables 6-7.

[0073]

[Table 6]

[0074]

[Table 7]

Examples 43 to 61 In Reference Example 13, 2,2'-bis (trifluoromethyl) -4,4'-biphenylenedicarboxylic acid chloride was mixed with dicarboxylic acid chlorides shown in Tables 8 to 0.2m.
A polybenzoxazole copolymer precursor was synthesized and an optical waveguide material was obtained and evaluated in the same manner as in Reference Example 1 except that it was replaced with ol. The evaluation results are shown in Tables 8-9.

[0076]

[Table 8]

[0077]

[Table 9]

Examples 62 to 80 In Reference Example 19, 2,2'-bis (trifluoromethyl) -4,4'-biphenylenedicarboxylic acid chloride was mixed with a mixture of dicarboxylic acid chlorides shown in Tables 10 to 0.1.
Similar to Reference Example 1 except that 2 mol was substituted,
An optical waveguide material was obtained by synthesizing a polybenzoxazole copolymer precursor and evaluated. The evaluation results are shown in Tables 10-11.

[0079]

[Table 10]

[0080]

[Table 11]

Examples 81 to 99 In Reference Example 25, 2,2'-bis (trifluoromethyl) -4,4'-biphenylene dicarboxylic acid chloride was mixed with a mixture of dicarboxylic acid chlorides shown in Tables 12 to 0.3.
Similar to Reference Example 1 except that 2 mol was substituted,
An optical waveguide material was obtained by synthesizing a polybenzoxazole copolymer precursor and evaluated. The evaluation results are shown in Tables 12 to 13.

[0082]

[Table 12]

[0083]

[Table 13]

Examples 100 to 118 In Reference Example 31, 2,2'-bis (trifluoromethyl) -4,4'-biphenylene dicarboxylic acid chloride was mixed with a mixture of dicarboxylic acid chlorides shown in Tables 14 to 15.
Similar to Reference Example 1 except that 2 mol was substituted,
An optical waveguide material was obtained by synthesizing a polybenzoxazole copolymer precursor and evaluated. The evaluation results are shown in Tables 14 to 15.

[0085]

[Table 14]

[0086]

[Table 15]

Examples 119 to 137 In Reference Example 37, 2,2'-bis (trifluoromethyl) -4,4'-biphenylene dicarboxylic acid chloride was mixed with a mixture of dicarboxylic acid chlorides shown in Tables 16 to 0.1.
Similar to Reference Example 1 except that 2 mol was substituted,
An optical waveguide material was obtained by synthesizing a polybenzoxazole copolymer precursor and evaluated. The evaluation results are shown in Tables 16-17.

[0088]

[Table 16]

[0089]

[Table 17]

Reference Example 2, Examples 1 to 9 and Reference Example 3 were 4,4 '.
-The copolymerization ratio of oxybisbenzoic acid chloride and 4,4'-hexafluoroisopropylidene diphenyl-1,1'-dicarboxylic acid chloride was changed from 0 to 1.0, and the refractive index was plotted. As shown in FIG.

From this, it is understood that the refractive index can be freely controlled by changing the copolymerization ratio. Also, the same control was possible by changing the copolymerization ratio of other dicarboxylic acid chlorides. Therefore, by using the copolymer of the present invention, it is possible to provide a plastic optical waveguide material in which the refractive index can be freely controlled and the refractive index of the core portion and the clad portion can be freely designed.

[Production of Optical Waveguide] Example 138 The polybenzoxazole precursor (4-8) synthesized in Example 8 was applied as a material for an optical waveguide on a silicon substrate by a spin coating method to form a film. did. The formed thin film was cured by heating at 320 ° C. for 1 hour to form a lower clad layer. Then, a core layer was formed on the lower clad layer by spin coating using the optical waveguide material (4-6) obtained in Example 6. No intermixing was observed between the lower clad film and the core film. The formed core layer was cured by heating at 320 ° C. for 1 hour.

Next, an aluminum layer having a thickness of 0.3 μm was vapor-deposited on the core layer to form a mask layer. further,
A positive photoresist (a diazonaphthoquinone-novolak resin system, manufactured by Tokyo Ohka Co., Ltd., trade name OFPR-800) was applied on the aluminum layer by a spin coating method, and then prebaked at about 95 ° C. Next, a photomask (Ti) for pattern formation is arranged, and after irradiating with ultraviolet rays using an ultra-high pressure mercury lamp, a positive resist developing solution (T
MAH: Tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka, trade name NMD-3) was used for development. Then, post bake was performed at 135 degreeC. As a result, a linear resist pattern having a line width of 8 μm was obtained. Next, the aluminum layer was wet-etched to transfer the resist pattern to the aluminum layer.
Further, the core layer was processed by dry etching using the patterned aluminum layer as a mask. next,
The aluminum layer was removed with an etching solution. Further, the same polybenzoxazole precursor (4-8) as that of the lower clad layer was applied onto the exposed surface of the core layer by spin coating. This coating film was heat-treated at 320 ° C. for 1 hour to form an upper clad. Finally, both ends of the optical waveguide were cut off with a dicing saw to form light input / output end faces. In this way, an embedded single mode optical waveguide was obtained on the silicon substrate.

The insertion loss of the buried type single mode optical waveguide obtained above was measured to find that the wavelength was 1.3 μm.
0.3 dB / cm or less and 0.3 dB / c at 1.55 μm
It was m or less. Further, the polarization dependence of the insertion loss was 0.5 dB / cm or less at both the wavelength of 1.3 μm and the wavelength of 1.55 μm. Furthermore, the loss of this optical waveguide is 75 ° C / 9
Even under the condition of 0% RH, it did not change for more than 1 month.

In Examples 139 to 158, the optical waveguide materials shown in Table 18 were combined, and optical waveguides were produced in the same manner as in Example 138. The evaluation results are shown in Table 18.

Comparative Example 1 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 6.4 parts (20.0 mmol) and pyromellitic dianhydride 4.4 parts (20.0 mmol) , And 86.6 parts of dimethylacetamide, and the mixture was stirred and reacted at room temperature for 3 days in a nitrogen atmosphere to react the polyamic acid (1
8-1) was obtained. The molecular weight of this polyamic acid was measured by GPC and found to be 14,000. The refractive index was 1.576.

Polyamic acid (18-1) obtained above
Is used as the core layer and the precursor (1-1) of the fluorinated polybenzoxazole obtained in Reference Example 1 is used as the upper and lower clad layers, and otherwise the same as in Example 138. A mode optical waveguide was prepared and evaluated. The results are shown in Table 18.

[0098]

[Table 18]

[0099]

According to the present invention, there can be provided a plastic optical waveguide material in which the refractive index of the optical waveguide material can be freely controlled and the core portion and the cladding portion of the optical waveguide can be freely designed. Further, it is particularly useful for an optical waveguide having a high transparency in the near infrared wavelength region used for optical communication and having a small optical loss.

[Brief description of drawings]

FIG. 1 is a process chart showing an example of a method for producing an embedded optical waveguide according to the present invention.

FIG. 2 is a graph showing an example of the relationship between the copolymerization ratio and the refractive index of the present invention.

[Explanation of symbols]

1 substrate 2 Lower clad layer 3 core layers 4 Mask layer for forming core pattern 5 Resist layer 6 Upper clad layer

Continued front page    F term (reference) 2H047 PA02 PA24 QA05 TA11 TA31                 4J043 PA04 PA19 QB23 QB34 SA06                       SA42 SA43 SA44 SA47 SA52                       SA54 SA71 SB03 TA42 TA44                       TA47 TA66 TA67 UA042                       UA121 UA122 UA131 UA132                       UA141 UA142 UA151 UA152                       UA161 UA162 UA171 UA172                       UA181 UA182 UA231 UA261                       UA262 UB011 UB012 UB021                       UB022 UB052 UB061 UB062                       UB121 UB122 UB131 UB132                       UB141 UB142 UB151 UB152                       UB281 UB282 UB301 UB302                       VA012 VA022 VA042 VA052                       VA082 VA092 XA19 XB19                       YA06 ZA51 ZB21

Claims (6)

[Claims] 1. A compound having a repeating unit represented by the general formula (1), wherein the repeating unit of m has a difference in refractive index between the repeating unit of m and the compound of 0.3% or more. A material for a plastic optical waveguide, which comprises a compound having: or a resin obtained by ring-closing the compound. [Chemical 1] [In the formula, X represents a tetravalent organic group. Y ₁ and Y ₂ represent a divalent organic group and are different groups. m> 0, n ≧ 0
Then, 1000 ≧ (m + n) ≧ 2. ] 2. A compound wherein X in the general formula (1) is
4 selected from the groups represented by formulas (2) to (7)
The plastic optical waveguide material according to claim 1, which has a valent group. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [In the structures represented by the formulas (2) to (7), the hydrogen atom on the benzene ring is substituted with at least one group selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. It may be done. In formula (7), Z ₁ represents a single bond or a divalent group selected from the groups represented by formulas (8) to (10). ] [Chemical 8] [Chemical 9] [In Formula (9), a represents the integer of 1-5. ] [Chemical 10] [In the structures represented by the formulas (9) and (10), the hydrogen atom on the benzene ring is at least one group selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. It may be replaced. ] 3. The compound is represented by the formula (1), wherein X is
The plastic optical waveguide material according to claim 1, which has a tetravalent group represented by the general formula (11). [Chemical 11] [In the formula, the hydrogen atom on the benzene ring may be substituted with at least one group selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. ] 4. The compound has a divalent group selected from the groups represented by formulas (12) to (15) as Y ₁ and Y _{2 in} formula (1). The material for plastic optical waveguides according to claim 1. [Chemical 12] [Chemical 13] [Chemical 14] [In Formula (14), i, j, and k represent integers from 2 to 10. ] [Chemical 15] [In the structures represented by the formulas (12), (13) and (15), the hydrogen atom on the benzene ring and the hydrogen atom in the structure represented by the formula (14) are a methyl group or a fluorine atom. It may be substituted with at least one group selected from a trifluoromethyl group and a chlorine atom. Formula (15)
In the above, Z ₂ represents a single bond or a divalent group selected from the groups represented by formulas (16) to (18). ] [Chemical 16] [Chemical 17] [In Formula (17), b represents the integer of 1-5. ] [Chemical 18] [In the structures represented by the formulas (17) and (18), the hydrogen atom on the benzene ring is at least one group selected from a methyl group, a fluorine atom, a trifluoromethyl group and a chlorine atom. It may be replaced. ] 5. The core layer and the clad layer are represented by the general formula (1):
An optical waveguide formed of a compound having a repeating unit represented by the formula (1), wherein the optical refractive index of each layer is adjusted by the ratio of repeating units m and n in the general formula (1). [Chemical 19] [In the formula, X represents a tetravalent organic group. Y ₁ and Y ₂ represent a divalent organic group and are different groups. m> 0, n ≧ 0
Then, 1000 ≧ (m + n) ≧ 2. ] 6. The optical waveguide according to claim 5, wherein the core layer has a refractive index higher than that of the cladding layer.