JP2002037885A - Positive-type fluorinated polyimide precursor and positive-type photosensitive fluorinated polyimide precursor composition - Google Patents

Abstract

[PROBLEMS] To provide an optical waveguide satisfying low optical loss at near infrared wavelength, high heat resistance and low moisture absorption, and a photosensitive fluorine-containing polyimide precursor composition for an optical waveguide which can be provided by easy processing. The purpose is to provide things. The above problem can be solved by using a fluorine-containing polyamide ester obtained by polymerizing an alkoxy group or the like, particularly, a t-butoxy ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluorine-containing polyimide precursor, and more particularly, to a positive type polyimide precursor having excellent optical properties, heat resistance and long-term reliability suitable for optical waveguides and the like and capable of forming a pattern by photolithography or the like. The present invention relates to a photosensitive polyimide precursor, a composition thereof, and an optical waveguide using the same.

[0002]

2. Description of the Related Art In optical communication, which has been rapidly growing in recent years, important optical components include an optical branching coupler (optical coupler), an optical multiplexer / demultiplexer, an optical isolator, an optical fiber amplifier, and the like. Is promising. The most efficient and reliable passive optical waveguide device to date is a glass waveguide, but it has problems in workability such as including a high-temperature process of 1000 ° C or more, and studies on manufacturing an optical waveguide using a polymer material Many have also been made. Among them, the fluorinated polyimide resin is considered as an optical waveguide material because of its small light loss in the near-infrared region (1.2-1.6 μm) and excellent high heat resistance and low moisture absorption. Is taking a bath. (For example, JP-A-2-281037, JP-A-4-8734, JP-A-4-9807
JP-A-5-164929 and JP-A-5-164929
However, in these methods, in order to form a relief structure of a waveguide pattern, for example, a pattern is formed with a photosensitive resin on a polyimide layer, and RIE (reactive ion etching) or the like is used. Since a complicated method of etching and peeling off excess photosensitive resin is used, the number of steps in the waveguide manufacturing process increases, which affects the manufacturing cost and yield.

On the other hand, FMHoulihan et al. (Macromolecules,
In 1989, vol22, P4477-P4483) reported a polyesteramide modified with a t-butoxy group. However, since it does not contain fluorine, it becomes poor in hygroscopicity when converted to polyimide after exposure, There is an inconvenience that the transmittance outside is too low to be applied to an optical waveguide or the like.

[0004]

In order to solve the above-mentioned problems of the prior art, a low loss in the near-infrared region, which is useful as a material for an optical waveguide or the like, is obtained. Another object of the present invention is to provide a positive photosensitive fluorine-containing polyimide precursor composition and an optical waveguide which can be processed by photolithography.

[0005]

The present inventors have synthesized various photosensitive polyimide precursors for the purpose of applying an optical waveguide and examined the applicability.
It has been found that a fluorinated polyamide ester having a butoxy group is a material that can impart positive-type photosensitivity and can form a good optical waveguide and the like.

That is, the present invention provides: 1) (A) the following general formula (Formula 7):

[0007]

Embedded image [Where k is an integer of 1 or more, and m and n are such that m + n is 1
Each of the above is an integer of 0 or more. R1 and R3 are represented by the following formula (Formula 8):

[0008]

Embedded image Or any of the groups represented by
2, R4 has the following formula (Formula 9):

[0009]

Embedded image Is a single or a mixture of any of the groups represented by
Wherein R5 is the same or different and is hydrogen, deuterium,
X is at least one selected from fluorine and a perfluoroalkyl group, wherein X is a direct bond or the following formula (Formula 10):

[0010]

Embedded image (Where R7 is a perfluoroalkylene group, and n is 1
And R6 represents a deuterium, fluorine or perfluoroalkyl group. A) a polyimide precursor containing a repeating unit represented by formula (1) and containing fluorine. 2) R in the above chemical formula (Chemical formula 7) is 1 to 10 carbon atoms
1) The polyimide precursor according to 1), which is at least one selected from the group consisting of an alkyl group, a cycloalkyl group and a cycloether group. 3) R in the chemical formula (Formula 7) is -CR ¹ R ² R ³
(Where R ¹ , R ² , and R ³ are the same or different and are each a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. Also, it is possible that all of R ¹ , R ² , and R ³ are hydrogen atoms. No.) The polyimide precursor according to 1), wherein 4) The polyimide precursor according to 1), wherein R in the chemical formula (Chem. 7) is a t-butyl group. 5) R1 and / or R1 of the polyimide precursor (A) component
Or a part or all of R3 is represented by the following formula (Formula 11)

[0011]

Embedded image The polyimide precursor according to any one of 1) to 4), which contains a structure represented by the following formula: 6) R2 and / or R4 of the component (A) are represented by the following formula (Formula 12)

[0012]

Embedded image The polyimide precursor according to any one of 1) to 5), wherein 7) In the chemical formula (7) in the component (A), m / n> 0.
5. The polyimide precursor according to 1) to 6), which is 5. 8) A polyimide precursor composition further comprising (B) a photoacid generator and, if necessary, a sensitizer, in addition to the polyimide precursor according to any one of 1) to 7). 9) Used to form a pattern by exposure 8)
The positive photosensitive polyimide precursor composition according to the above. 10) The positive photosensitive polyimide precursor composition according to 9), which is used as a material for an optical waveguide. 11) An optical waveguide obtained from the positive photosensitive polyimide precursor composition according to 10).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) in the present invention has the following general formula (Formula 13)

[0014]

Embedded image [Where k is an integer of 1 or more, and m and n are such that m + n is 1
Each of the above is an integer of 0 or more. R1 and R3 are represented by the following formula (Formula 14):

[0015]

Embedded image Or any of the groups represented by
2, R4 has the following formula (Formula 15):

[0016]

Embedded image Is a single or a mixture of any of the groups represented by
Wherein R5 is the same or different and is hydrogen, deuterium,
X is at least one selected from fluorine and a perfluoroalkyl group, wherein X is a direct bond or the following formula (Formula 16):

[0017]

Embedded image (Where R7 is a perfluoroalkylene group, and n is 1
And R6 represents a deuterium, fluorine or perfluoroalkyl group. This is a polyimide precursor containing a repeating unit represented by the formula (1) and containing fluorine. In the polyimide precursor having the structure of the general formula, hydrogen in the alkyl group is replaced with fluorine or the like, and vibration absorption based on a C-H bond of the alkyl group or the like causing light loss in the near infrared region is small. Become. However, the absorption based on the C—H bond of the hydrogen atom directly bonded to the benzene ring is considered to have little absorption and not affect the effect of the present invention, and therefore contains hydrogen directly bonded to the benzene ring. It doesn't matter if all hydrogen is deuterium, fluorine,
It is preferred that the compound is substituted with at least one or more selected from perfluoroalkyl groups.

The component (A) can be produced, for example, from an ester compound and a diamine component using an acid dianhydride component as a raw material, and if necessary, from an acid dianhydride and a diamine. An acid is obtained, and a part or all of the carboxyl group may be modified into an ester group. An ester compound giving a structure of the general formula and a diamine component, and if necessary, an acid dianhydride are appropriately selected and copolymerized. I just need. As the acid dianhydride and the acid dianhydride to be copolymerized as raw materials for obtaining such an ester compound, an acid dianhydride containing fluorine is suitable in terms of low loss of near-infrared light and lowering the moisture absorption rate. .

Examples of the fluorine-containing dianhydride component include (trifluoromethyl) pyromellitic dianhydride, di (trifluoromethyl) pyromellitic dianhydride, and di (heptafluoropropyl) pyromellitic Acid dianhydride, pentafluoroethyl pyromellitic dianhydride, bis {3,5-di (trifluoromethyl) phenoxy} pyromellitic dianhydride, 2,2-bis (3,4-
Dicarboxyphenyl) hexafluoropropane dianhydride, 5,5'-bis (trifluoromethyl) -3,
3 ', 4,4'-tetracarboxybiphenyl dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxybiphenyl dianhydride, , 5'-bis (trifluoromethyl)
-3,3 ', 4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone dianhydride, bis {( (Trifluoromethyl) dicarboxyphenoxy｝ benzene dianhydride, bis ｛(trifluoromethyl) dicarboxyphenoxy｝ trifluoromethylbenzene dianhydride, bis (dicarboxyphenoxy) trifluoromethylbenzene dianhydride, bis (dicarboxy) Phenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2,2
-Bis {(4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} biphenyl dianhydride, bis} (trifluoromethyl) dicarboxyphenoxy {Bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl dianhydride and the like.

If all monovalent elements bonded to carbon such as a phenyl ring as well as an alkyl group in the molecule are fluorine or perfluoroalkyl groups, absorption in the near infrared region can be improved. Small and preferred. In order to obtain such an acid dianhydride, a tetracarboxylic acid or a derivative thereof is converted into an anhydride by a usual method, and if heated to, for example, 100 ° C. or more, a desired perfluorinated dihydrate can be obtained. Such acid anhydrides, acid chlorides and the like include: 2,5-difluoropyromellitic acid, 2-trifluoromethyl-5-fluoropyromellitic acid, 2,5-di (trifluoromethyl)
Pyromellitic acid, 2,5-di (pentafluoroethyl)
Pyromellitic acid, hexafluoro-3,3 ', 4,4'
-Biphenyltetracarboxylic acid, hexafluoro-3,
3 ', 4,4'-benzophenonetetracarboxylic acid,
2,2-bis (3,4-dicarboxytrifluorophenyl) hexafluoropropane, 1,3-bis (3,4
-Dicarboxytrifluorophenyl) hexafluoropropane, 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene, hexafluoro-3,3 '(or 4,4')-oxybisphthalic acid And the like.

As the copolymer component of the component (A), an acid anhydride component containing no fluorine may be used.
Para-phenyl-3,4,3 ", 4" -tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenylethertetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, Meta-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride,
3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, -(2,3-dicarboxyphenyl) -3
-(3,4-dicarboxyphenyl) -1,1,3,3
-Tetramethyldisiloxane dianhydride.

The ester compound starting from an acid anhydride, which is a copolymer component of the component (A), may be produced by any route. For example, it can be produced by the following method. That is, after dissolving the acid dianhydride in a solvent, the mixture is mixed with a metal alkoxide, heated and preferably placed under reflux.
After reacting under reflux for 0.5 to 24 hours, a reaction precipitate is obtained. This precipitate is dissolved in water. When an acid is added to the aqueous solution to adjust the pH to 3 to 6.5, preferably 4 to 6, an ester compound as a final product is obtained. If necessary, this is purified by a general purification method such as recrystallization or column chromatography separation. If the heating temperature is 20 ° C. or higher, a reaction product can be obtained, but in order to shorten the reaction time, 50 ° C. or higher, particularly a reflux temperature, is preferable.

The solvent used here is not particularly restricted but is preferably, for example, tetrahydrofuran, ethyl acetate or the like.
Further, it is preferable to use 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride as the acid anhydride, since the hygroscopicity and the transmittance of near-infrared light are improved. The metal alkoxide to be used is not particularly limited, either. However, t-
Butoxide salts are preferred, and potassium tert-butoxide is particularly preferred from the viewpoint of general versatility of raw materials.

The ester compound which is a copolymer component of the component (A) can also be obtained by dissolving the acid anhydride in a solvent, if necessary, mixing with an alcohol, heating and, if necessary, refluxing. After reacting under reflux for 0.5 to 24 hours, a reaction product is obtained. The unreacted alcohol and the solvent are removed from the reaction product by a usual method to obtain an ester compound as a final product. The heating temperature is 20
If the temperature is higher than 50 ° C., a reaction product can be obtained, but in order to shorten the reaction time, the temperature is higher than 50 ° C., particularly preferably reflux temperature.

If necessary, this is purified by a general purification method such as recrystallization or column chromatography separation.

The acid dianhydride used as a raw material for the ester compound is selected from the viewpoints of the hygroscopicity of polyimide and the low absorption of near-infrared light.

[0027]

Embedded image Particularly, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride is preferred from the viewpoint of versatility. Further, the ester compound obtained using the acid anhydride represented by the chemical formula (17) as a raw material is preferably 20 mol% or more of all the acid anhydrides, so that the hygroscopicity and the transmittance of near-infrared light are improved. Preferred from the point.

It is necessary that the diamine used in producing the polyimide precursor (A) in the present invention does not contain a hydrogen atom of an alkyl group, an allyl group, a propargyl group or a hydroxyl group. Further, a diamine containing fluorine is preferable from the viewpoint of reducing the loss of near-infrared light and reducing the moisture absorption. Examples of the fluorine-containing diamine component include 4- (1H, 1H, 11H-eicosafluoroundecanooxy) -1,3-diaminobenzene and 4- (1H, 1H-perfluoro-1-butanoxy) -1,3-. Diaminobenzene, 4- (1H, 1H
-Perfluoro-1-heptanoxy) -1,3-diaminobenzene, 4- (1H, 1H-perfluoro-1-octanoxy) -1,3-diaminobenzene, 4-pentafluorophenoxy-1,3-diaminobenzene , 4-
(2,3,5,6-tetrafluorophenoxy) -1,
3-diaminobenzene, 4- (4-fluorophenoxy) -1,3-diaminobenzene, 4- (1H, 1H,
2H, 2H-perfluoro-1-hexanoxy) -1,
3-diaminobenzene, 4- (1H, 1H, 2H, 2H
-Perfluoro-1-dodecanoxy) -1,3-diaminobenzene, (2,5) -diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine, diaminotetra (trifluoromethyl) benzene,
Diamino (pentafluoroethyl) benzene, 2,5-
Diamino (perfluorohexyl) benzene, 2,5-
Diamino (perfluorobutyl) benzene, 2,2'-
Bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,
4'-diaminobiphenyl, octafluorobenzidine, 4,4'-diaminodiphenyl ether, 2,2-
Bis (4-aminophenyl) hexafluoropropane,
1,3-bis (anilino) hexafluoropropane,
1,4-bis (anilino) octafluorobutane, 1,
5-bis (anilino) decafluoropentane, 1,7-
Bis (anilino) tetradecafluoroheptane, 2,
2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether,
3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,
3'-bis (trifluoromethyl) -4,4'-diaminobenzophenone, 4,4'-diamino-p-terphenyl, 1,4-bis (p-aminophenyl) benzene,
p- (4-amino-2-trifluoromethylphenoxy) benzene, bis (aminophenoxy) bis (trifluoromethyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (3-aminophenoxy) phenyl} hexafluoropropane, 2,2-
Bis {4- (2-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) -3,5-dimethylphenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) -3,5-ditrifluoromethylphenyl @ hexafluoropropane, 4,4'-bis (4-amino-2-
Trifluoromethylphenoxy) biphenyl, 4,4 '
-Bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone,
4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis {4-
(4-amino-3-trifluoromethylphenoxy) phenyl} hexafluoropropane, bis {(trifluoromethyl) aminophenoxy} biphenyl, bis [{(trifluoromethyl) aminophenoxy} phenyl] hexafluoropropane, bis2 -[(Aminophenoxy) phenyl] hexafluoroisopropyl dibenzene, 4,4'-bis (4-aminophenoxy) octafluorobiphenyl and the like.

All monovalent elements bonded to carbon such as an alkyl group other than an amino group and a phenyl ring in the molecule are fluorine,
Alternatively, if it is a perfluoroalkyl group, the absorption in the near-infrared is small and thus it is preferable. For example, 3,4,5,6-tetrafluoro-1,2-phenylenediamine, 2,4,4
5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,4′-diaminooctafluorobiphenyl, bis (2,3,5, 6-tetrafluoro-4-
Aminophenyl) ether, bis (2,3,5,6-tetrafluoro-4-aminophenyl) sulfone, hexafluoro-2,2'-bis (trifluoromethyl)-
4,4'-diaminobiphenyl and the like.

Further, a diamine component containing no fluorine may be contained as a copolymer component.
-Diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, metaphenylenediamine, paraphenylenediamine, 1,5-naphthalenediamine,
2,6-naphthalenediamine, bis- (4-aminophenoxyphenyl) sulfone, bis- (4-aminophenoxyphenyl) sulfide, bis- (4-aminophenoxyphenyl) biphenyl, 1,4-bis- (4-amino Phenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether-3
-Sulfonamide, 3,4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,
4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-
3'-sulfonamide, 3,3'-diaminodiphenylsulfon-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 3,4 '
-Diaminodiphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-
Sulfonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenylether-3-carbonamide, 3,4'-diaminodiphenylether -4-carbonamide, 3,4 '
Diaminodiphenyl ether-3'-carbonamide, 3,3'-diaminodiphenylether-4-carbonamide, 4,4'-diaminodiphenylmethane-3
-Carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diamino Diphenylsulfone-3-carbonamide, 3,
4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide- 3-carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,
3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-
3'-sulfonamide, 1,4-diaminobenzene-2
-Carbonamide, 4,4'-bis (4-aminophenoxy) biphenyl, bis {4- (3-aminophenoxy) phenyl} sulfone and the like. The acid anhydride component and the diamine component may be used in combination of two or more.

In the present invention, it is necessary that any or all of the above ester compounds, acid dianhydrides and diamines contain a fluorine-containing compound. Particularly preferred examples of the combination include an ester compound synthesized from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride as an ester compound or a 2,2
An ester compound synthesized from bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and an ester compound synthesized from pyromellitic dianhydride; 2,2-bis (3,4- Dicarboxyphenyl) hexafluoropropane dianhydride or 2,2-
A mixture of bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride,
As the diamine, 4,4'-diaminodiphenyl ether is preferable. In particular, by mixing and copolymerizing 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride or an ester compound synthesized therefrom, refractive index and linear expansion are obtained. It is preferable because the coefficient and the like can be set to desired values.

The solution containing the polyimide precursor (A) is used with the ester compound and, if necessary, the acid dianhydride and the diamine component so that the ester compound, the acid dianhydride and the diamine are substantially equimolar. And polymerized in an organic polar solvent. When a mixture of a plurality of diamines and carboxylic dianhydrides is used, the sum of the moles of a plurality or a single diamine and the sum of the moles of a plurality or a single carboxylic dianhydride are equal or almost equal. To do. This polyimide precursor is obtained by first dissolving or diffusing a diamine and an ester compound and, if necessary, a carboxylic dianhydride in an organic polar solvent, preferably in an inert atmosphere such as argon or nitrogen. It is common to mix an ester compound and an equivalent or more of a condensing agent. The order of addition of each monomer is not particularly limited, and the ester compound and, if necessary, the acid dianhydride are added to the organic polar solvent first, the diamine component is added, and a solution of the polyamide ester may be used. An appropriate amount may be first added to the organic polar solvent, and then the ester compound and, if necessary, the acid dianhydride may be added. The acid dianhydride may be reacted after the ester compound has been reacted with the diamine first, or the ester compound may be reacted after the acid dianhydride has been reacted with the diamine. When using multiple or single diamines and multiple or single ester compounds or carboxylic dianhydrides as ester compounds, there are various addition methods known to those skilled in the art. For example, JP-A-5-70590,
This is a method disclosed in JP-A-5-25273, JP-A-5-271410 and the like. The diamine is converted to a diisocyanate at a high temperature (40 ° C. to 2 ° C.) without using a condensing agent.
(00 ° C.) for polymerization. In some cases, a polyamic acid is obtained from an acid dianhydride and a diamine, and a part or all of the carboxyl group may be modified into an ester group. When a pattern is formed, the ratio of the ester compound to the acid dianhydride is preferably m / n> 0.5 in the chemical formula (1) from the viewpoint that a good pattern can be obtained. If m / n is 0.5 or less, a clear relief pattern may not be shown.

Examples of the organic polar solvent used in the reaction for producing the component (A) include dimethyl sulfoxide and dimethyl sulfoxide.
Sulfoxide solvents such as diethylsulfoxide, N, N
Formamide solvents such as -dimethylformamide and N, N-diethylformamide, acetamido solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, phenol, Examples thereof include phenolic solvents such as o-, p-, m- or p-cresol, xinol, halogenated phenol, and catechol, and hexamethylphosphoramide, γ-butyrolactone, and the like.
Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

As the above-mentioned condensing agent, those used for condensation synthesis of polyamide can be generally used. Examples include phosphites, phosphorous chlorides, phosphoric amides, phosphoric esters, phosphoric anhydrides and the like. Triphenyl phosphite and its derivatives as phosphites, phosphorus trichloride and phosphorus oxychloride as phosphorus chlorides, and 2,3-dihydro-2-thioxo-3-benzoxazolylphosphone as phosphoric amides Acids and the like. The condensing agent is 2 to 3 equivalents of the ester compound, preferably 2.1 to 2.
Add 3 equivalents. If necessary, pyridine, triethylamine or the like is added to enhance the activity of the condensation reaction.
The amount added is generally approximately equivalent to the condensing agent.

The concentration of the solution is 5 to 40% by weight (10 to 40% by weight).
The polymer solution preferably has a rotational viscosity (25 ° C.) of 50 to 5000 poise.

The component (A), when imidized in the photolithography step, has substantially no hydrogen bonded to a carbon atom such as an alkyl group, so that the largest light loss in the near infrared region is caused. By reducing the vibration absorption based on the C—H bond of the alkyl group, etc., and by introducing an imide bond into the main chain structure to form a polyimide, sufficient heat resistance (260 ° C. or higher) for producing an optical waveguide is obtained. ).

When the photoacid generator (B) is blended with the polyimide precursor of the present invention, photosensitivity can be imparted to the resulting composition. In addition, when the component (B) is used, a good pattern can be obtained, and almost no residue remains in the polyimide when imidized. Therefore, particularly when used as an optical waveguide, light in the near infrared region can be obtained. The property of reducing loss can be sufficiently obtained. Therefore, the composition containing the component (A) and the component (B) of the present invention can be suitably used as a material for an optical waveguide.

The photoacid generator (B) is a compound that generates an acid upon irradiation with light or actinic radiation, and the generated acid releases the protective group alkoxy group in the component (A). . Examples of such a compound include JP-A-5-13
4415, JP-A-5-150459, JP-A-5-458
78 and the like, and examples thereof include a sulfonium salt and an iodonium salt. Specifically, diphenyliodonium, 4,4'-di-butylphenyliodonium, triphenylsulfonium, trifluoroacetate such as t-butyltriphenylsulfonium, trifluoromethanesulfonate, toluenesulfonate, and Compounds having a substituent on the phenyl group of these onium salts may be mentioned. Specific examples of compounds that generate an acid upon irradiation with light or the like include benzoin tosylate, orthonitrobenzyl paratoluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, tri (tert-butylphenyl) sulfonium trifluoromethanesulfonate, benzene Diazonium paratoluenesulfonate, 4- (di-n-
Propylamino) -benzonium tetrafluoroborate, 4-P-tolyl-mercapto-2,5-diethoxy-benzenediazonium hexafluorophosphate, tetrafluoroborate, diphenylamine-4-
Diazonium sulfate, 4-methyl-6-trichloromethyl-2-pyrone, 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone,
4- (4-methoxy-styryl) -6- (3,3,3,-
(Trichloro-propenyl) -2-pyrone, 2-trichloromethyl-benzimidazole, 2-tribromomethyl-quinolone, 2,4-dimethyl-1-tribromoacetyl-benzene, 4-dibromoacetyl-benzoic acid, o-
Naphthoquinonediazide-4-sulfonic acid chloride, di (p-tert-butylbenzene) diphenyliodonium trifluoromethanesulfonate, 1,4-bis-dibromomethyl-benzene, tris-dibromomethyl-S-triazine, 2- (6-methoxy- Naphthyl-2
-Yl) -4,6-bis-trichloromethyl-S-triazine, 2- (naphthyl-1-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (naphthyl-
2-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxyethyl-naphthyl-1-yl)-
4,6-bis-trichloromethyl-S-triazine, 2- (benzopyran-3-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-methoxy-anthrac-1-yl)- 4,6-bis-trichloromethyl-S
-Triazine, 2- (phenanth-9-yl) -4,6
-Bis-trichloromethyl-S-triazine, and the like.

These are used alone or in combination of two or more. In order to further improve the light sensitivity, a sensitizer can be added.

The composition containing the components (A) and (B) of the present invention can be used as a photosensitive material capable of forming a pattern by exposure. In the case of the component (A), the presence of hydrogen ions generated from the component (B) upon exposure removes an alkoxy group, so that the solvent solubility in a developing solution described later increases. It becomes a positive type photosensitive material.

The amount of the component (B) is preferably 0.01 to 30% by weight of the component (A).
More preferably, the content is 0.05 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

To obtain the composition of the present invention, the above polyimide precursors (A) and (B) are mixed in a solvent, preferably under an inert atmosphere such as argon or nitrogen. The solution preferably has a rotational viscosity (25 ° C.) of 50 to 5000 poise. At this time, a solvent may be added or removed in order to adjust the viscosity. It is preferable to use the same solvent as that used for producing the polyimide precursor.

As described above, the photosensitive polyimide precursor composition of the present invention can be used for an optical waveguide. The obtained optical waveguide preferably has at least one of the core layer and the cladding layer in an optical waveguide having a core layer and a cladding layer, and particularly preferably the core layer is a polyimide obtained from the composition containing the component (A). Next, a method for manufacturing an optical waveguide will be described.

First, a lower clad layer is formed on a substrate by a usual method, and the photosensitive polyimide precursor composition is applied thereon by spin coating, dipping, spraying, screen printing, or the like. By heating and drying most of the solvent at 50 ° C to 100 ° C, a coating film having no tackiness can be obtained. The thickness of the coating film is not particularly limited, but is preferably from 4 to 70 μm, more preferably from 6 to 40 μm, depending on the design of the optical waveguide. On the coating film, after exposure to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the exposed portion is developed and dissolved with an appropriate developer to dissolve,
By removing, a desired relief pattern can be obtained. Generally, an upper clad layer is formed thereon.

The substrate to be used may be on a plate or in a film form. The material is a silicon wafer, a metal substrate, a ceramic substrate, a polymer substrate, or the like. The material of the polymer substrate is polyimide resin, polyamide imide resin, polyether imide resin, polyamide resin, polyester resin, polycarbonate resin, polyketone resin, polysulfone resin,
Examples include polyphenylene ether resin, polyolefin resin, polystyrene resin, polyphenylene sulfide resin, fluororesin, polyarylate resin, liquid crystal polymer resin, epoxy resin, cyanate resin and the like. A polyimide resin, an epoxy resin, and a cyanate resin are preferable from the viewpoint of heat resistance and adhesiveness with an optical waveguide material.

The actinic rays or actinic rays to be irradiated include, for example, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, an i-ray stepper, other ultraviolet rays, a visible light source,
Wires, electron beams and the like can also be used.

As the developing solution, for example, a good solvent (N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), a mixed solvent of the above good solvent and a poor solvent (lower alcohol, ketone, water, aromatic hydrocarbon, etc.), a basic solution ( Aqueous solution of sodium hydroxide, aqueous solution of sodium carbonate, aqueous solution of tetramethylammonium hydroxide, aqueous solution of triethanolamine, etc.). In some cases, development can be performed using only lower alcohols. Among these, a basic solution is preferred from the viewpoint of ease of development.

After development, rinsing with water or a poor solvent, if necessary, and drying at about 100 ° C. are preferable to make the pattern stable. Further, by heating this relief pattern further, a patterned high heat-resistant polyimide can be formed. In addition, it is necessary that the component (B) and the monomer removed by the heating at this time do not substantially remain in the polyimide. The term “substantially no residual” means a low latitude amount that does not cause an increase in light absorption rate or a decrease in heat resistance. The heating temperature at this time is 200
To 500 ° C, more preferably 250 to 400 ° C. When the heating temperature is less than 200 ° C., a photoinitiator added to impart photosensitivity or a monomer that has been eliminated tends to be reduced in optical properties, mechanical properties, and thermal properties remaining in the polyimide, If it exceeds 500 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease. The heating time at this time is 0.05 to
Preferably, it is 10 hours. This heating time is 0.
If the time is less than 05 hours, the mechanical and thermal properties of the polyimide film tend to decrease, and if it exceeds 10 hours, the mechanical and thermal properties of the polyimide film tend to decrease.
In many cases, heating by increasing the temperature stepwise is superior in mechanical strength.

The optical loss of the obtained optical waveguide is 1 dB / cm.
Or less, preferably 0.5 dB / cm or less, more preferably 0.3 dB / cm or less. Optical loss is 1dB /
If it is larger than cm, if the pattern of the optical waveguide is large, it may not withstand practical use. At this time, it is necessary that the compound does not substantially contain a hydrogen atom bonded to a carbon atom such as an alkyl group and a hydrogen atom of a hydroxyl group and a carboxyl group. The term “substantially not contained” is an amount that does not deteriorate optical characteristics such as light loss.

[0050]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The raw materials used were commercial products. The source of each raw material is shown. 2,2'-bis (trifluoromethyl)-
4,4'-diaminobiphenyl (Central Glass), dimethylacetamide (Wako Pure Chemical Industries), pyromellitic dianhydride (Wako Pure Chemical Industries), 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane dianhydride (manufactured by Clariant Japan), 4,4 '
-Diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), tetrahydrofuran (Nacalai Tex), potassium t-butoxide (Wako Pure Chemical), hydrochloric acid (Wako Pure Chemical), silica gel (Nacalai Tex), acetone (Nacalai Tex), methyl ethyl ketone (Nakarai Tex) ), Condensing agent (2,3
-Dihydro-2-thioxo-3-benzoxazolyl)
Phosphonic acid diphenyl ester (Tokyo Kasei)), sulfonium salt-based acid generator Adeka Optomer SP170 (Adeka), 15% by weight aqueous solution of tetramethylammonium hydroxide (Wako Pure Chemical Industries), methanol (Wako Pure Chemical Industries) Light loss, heating 5% weight loss temperature, and refractive index were measured by the following methods. Light loss: A film sample was measured with a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). Heating 5% weight loss temperature: The film sample was measured with a thermogravimeter (TG / DTA200, manufactured by Seiko Denshi). Refractive index: precision Abbe refractometer 3T for film sample
(NAR-3T manufactured by Atago Co., Ltd.). (Synthesis of ester compound I) In a three-necked flask equipped with a reflux tube, 20.4 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added.
(mmol) was added and stirred under a nitrogen atmosphere for 10 minutes to dissolve. While stirring, 10.3 g of potassium t-butoxide (9.
2 mmol), and the mixture was heated and stirred under reflux for 6 hours. After cooling to room temperature, the precipitate was separated by filtration, vacuum-dried to remove tetrahydrofuran, and dissolved in 200 ml of pure water. Hydrochloric acid was added to the solution, and the precipitate obtained by adjusting the pH to 6 (measured with a pH test paper) was separated by filtration, and the water was removed by vacuum drying. This compound was mixed at a mixing ratio of 75% by weight /
The target compound was obtained by column chromatography using a 25% by weight acetone / methyl ethyl ketone mixed solvent as a developing solvent and silica gel as a filler. The obtained compound was prepared by dissolving 10% by weight of a target compound in dimethyl sulfoxide D6 (manufactured by Aldrich) and dissolving JNM (manufactured by JEOL Ltd.) based on tetramethylsilane (manufactured by Aldrich).
-Measured with a PMX60 NMR spectrometer.
As a result, peaks were obtained at 1.5 ppm (hydrogen peak of t-butoxy group) and 7.7 ppm (hydrogen peak of benzene ring). This indicated that 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was esterified to be the target compound. (Synthesis of ester compound II) 10.0 g (46 m) of pyromellitic dianhydride was placed in a three-necked flask equipped with a reflux tube.
mol) was added and stirred under a nitrogen atmosphere for 10 minutes to dissolve. While stirring, 10.3 g of potassium t-butoxide (92%) was added to this solution.
mmol), and the mixture was heated and stirred under reflux for 6 hours. After cooling to room temperature, the precipitate was separated by filtration, vacuum-dried to remove tetrahydrofuran, and dissolved in 200 ml of pure water. Hydrochloric acid was added to the solution, and the precipitate obtained by adjusting the pH to 6 (measured with a pH test paper) was separated by filtration, and the water was removed by vacuum drying. This compound was mixed at a mixing ratio of 50% by volume /
After recrystallization from 120 g of a 50% by weight pure water / ethanol mixed solvent, the residue was dried under vacuum to obtain the target compound. The proton NMR of the target compound was measured, and peaks were obtained at 1.5 ppm (hydrogen peak of t-butoxy group) and 7.7 ppm (hydrogen peak of benzene ring). This indicated that pyromellitic dianhydride was esterified to be the target compound. (Synthesis of polyimide precursor I) In a vessel under a nitrogen atmosphere, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3.20 g, 10 mmol) and compound I (5.92 g, 10 mmol) Is dissolved in dimethylacetamide (36.5 g), and triethylamine (2.12 g, 21 mmol) and a condensing agent ((2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonic acid diphenyl ester, 9 .20g, 24mmo
l) was added and the vessel was stirred at room temperature (about 20 ° C) for 24 hours. Next, after mixing the above solution with toluene and filtering the precipitate,
Vacuum drying was performed to obtain a polyimide precursor I. (Synthesis of polyimide precursor II) 4,4'-diaminodiphenyl ether (2.00 g,
10 mmol) and Compound I (5.92 g, 10 mmol)
l) was dissolved in dimethylacetamide (31.7 g), and triethylamine (2.12 g, 21 mmol) and a condensing agent ((2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonic acid diphenyl ester, 9.
20g, 24mmol) and add the container to room temperature (about 20 ° C)
For 24 hours. Next, the above solution was mixed with toluene, and the precipitate was filtered and dried under vacuum to obtain a polyimide precursor II. (Synthesis of Polyimide Precursor III) 2,2'-bis (trifluoromethyl) -4,4'-
Diaminobiphenyl (3.20 g, 10 mmol) and Compound I (2.96 g, 5 mmol) Compound II (1.8
3,5 mmol) with dimethylacetamide (31.2)
g) and dissolved in triethylamine (2.12 g, 2
1 mmol) and a condensing agent (diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, 9.20 g, 24 mmol) were added, and the vessel was stirred at room temperature (about 20 ° C.) for 24 hours. . Next, the above solution was mixed with toluene, and the precipitate was filtered and dried under vacuum to obtain a polyimide precursor III. (Synthesis of polyimide precursor IV) 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3.20 g, 10 mmol) was added to dimethylacetamide (31.2 g) in a vessel under a nitrogen atmosphere. After dissolving, pyromellitic dianhydride (1.09 g, 5 mmol) was mixed, stirred at 0 ° C for 2 hours, and then brought to room temperature (about 20 ° C).
The compound (2.96 g, 5 mmol), triethylamine (2.12 g, 21 mmol) and a condensing agent ((2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonic acid diphenyl ester, 9.20
g, 24 mmol) at room temperature (about 20 ° C.).
Stir for 4 hours. Next, the above solution was mixed with toluene, and the precipitate was filtered and dried under vacuum to obtain a polyimide precursor IV. (Synthesis of Polyamide Ester V) In a vessel under a nitrogen atmosphere, 4,4'-diaminodiphenyl ether (2.00
g, 10 mmol and compound 2 (3.66 g, 10 mmol
l) in dimethylacetamide (22.6 g), triethylamine (2.12 g, 21 mmol) and a condensing agent ((2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonic acid diphenyl ester, 9.
20g, 24mmol) and add the container to room temperature (about 20 ° C)
For 24 hours. Next, the above solution was mixed with toluene, and the precipitate was filtered and dried under vacuum to obtain a polyimide precursor V. Example 1 18 g of dimethylformamide was added to 2 g of the polyimide precursor solution (I) obtained in Synthesis Example 1.
4 g of a sulfonium salt-based acid generator (ADEKA OPTOMER SP170) was mixed with this solution in a dark room and stirred for about 1 hour to obtain a positive photosensitive fluorinated polyimide precursor composition.
Spin coating on aluminum plate, 5 under nitrogen atmosphere
The photosensitive film was obtained by drying at 0 ° C. for 10 minutes, at 70 ° C. for 10 minutes, and at 100 ° C. for 10 minutes. This film has a width of 10
365n through a photomask having a pattern of μm
After irradiating for 60 seconds with a high pressure lamp having an intensity of 10 mW / cm 2 in a wavelength range of m, an organic alkali solution (tetramethyl ammonium hydroxide 15 wt% aqueous solution 10 wt%, pure water 40 wt%, methanol 50 wt% mixed solution) )
And the irradiated part was removed. The film was placed under nitrogen at 100 ° C. for 10 minutes, 150 ° C. for 10 minutes, and 200 ° C. for 10 minutes.
10 minutes at 250 ° C., 10 minutes at 300 ° C., 10 minutes at 350 ° C., and 10 minutes at 400 ° C.
m, a good relief structure having a thickness of 10 μm was obtained. Also,
Without exposure, a 10 μm fluorinated polyimide film was similarly heated to produce a fluorinated polyimide film. The polyimide film was measured for light loss at a wavelength of 1.3 μm, a temperature at which the weight of the polyimide film was reduced by 5% by weight, and a refractive index. Table 1 shows the results.

Example 2 A good relief structure was obtained in the same manner as in Example 1 except that the polyimide precursor II was used. Similarly, a film was prepared, and the light loss, the heating 5% by weight weight loss temperature, and the refractive index were measured. Table 1 shows the results.

Example 3 An excellent relief structure was obtained in the same manner as in Example 1 except that the polyimide precursor (III) was used. Similarly, a film was prepared, and the light loss, the heating 5% by weight weight loss temperature, and the refractive index were measured. Table 1 shows the results. (Example 4) A good relief structure was obtained in the same manner as in Example 1 except that the polyimide precursor (IV) was used. Similarly, a film was prepared, and the light loss, the heating 5% by weight weight loss temperature, and the refractive index were measured. Table 1 shows the results.

Comparative Example 1 A relief structure was obtained in the same manner as in Example 1 except that the polyimide precursor (V) was used. Similarly, a film was prepared, and the light loss, the heating 5% by weight weight loss temperature, and the refractive index were measured. Table 1 shows the results.

[0055]

[Table 1] As can be seen from the results of the table, Examples 1 to 5 can be put to practical use in all items, but Comparative Example 1 has large optical loss and cannot be put to practical use as an optical waveguide material. Also, as shown in Example 2, good physical properties can be obtained even when polymerization is performed by changing the kind of diamine. By copolymerizing as in Examples 1 and 3, the refractive index can be changed arbitrarily, and this is suitable as an optical waveguide material. Also, as in Example 4, it is possible to copolymerize all of the ester compounds with part of the acid dianhydride.

[0056]

By using the fluorine-containing polyimide precursor for an optical waveguide of the present invention, photosensitivity which is easy to process is imparted, and low light loss in near infrared, high heat resistance, low moisture absorption, etc. A good fluorine-containing polyimide optical waveguide can be obtained.

Continued on the front page F term (reference) 2H025 AB14 AB17 AD03 BE00 BE01 BE07 BE08 CB25 CB43 FA17 FA29 2H047 QA05 4J002 CM041 FD206 FD207 4J043 PA04 PA19 QB15 QB26 RA06 RA07 SA06 SA54 SB01 SB02 TA22 TA47 TB01 UA121 UA 121 UA 122 UB051 UB052 UB061 UB062 UB121 UB122 UB131 UB132 UB141 UB142 UB151 UB152 UB171 UB172 UB281 UB282 UB301 UB302 UB401 UB402 VA011 VA012 VA021 VA022 VA031 VA032 VA041 VA042 VA061 VA062 XA0712 X07 ZVA12A

Claims (11)

[Claims] (A) The following general formula (Chemical formula 1): [Where k is an integer of 1 or more, and m and n are such that m + n is 1
Each of the above is an integer of 0 or more. R1 and R3 are represented by the following formula (Formula 2): Or any of the groups represented by
2, R4 is represented by the following formula (Formula 3): Is a single or a mixture of any of the groups represented by
Wherein R5 is the same or different and is hydrogen, deuterium,
X is at least one selected from fluorine and a perfluoroalkyl group, wherein X is directly bonded or represented by the following formula: (Where R7 is a perfluoroalkylene group, and n is 1
And R6 represents a deuterium, fluorine or perfluoroalkyl group. A) a polyimide precursor containing a repeating unit represented by formula (1) and containing fluorine. 2. The polyimide precursor according to claim 1, wherein R in the chemical formula (Formula 1) is at least one selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and a cycloether group. 3. The compound of the formula (1) wherein R is --CR
¹R^TwoR^Three(Where R¹, R ^Two, R^ThreeAre the same or different,
Each is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms
You. Also R¹, R^Two, R^ThreeAre all hydrogen atoms
There is no. 2. The polyimide precursor according to claim 1, wherein 4. The polyimide precursor according to claim 1, wherein R in said chemical formula (Formula 1) is a t-butyl group. 5. The polyimide precursor (A) component R1
And / or part or all of R3 is represented by the following formula: The polyimide precursor according to any one of claims 1 to 4, which has a structure represented by the following formula: 6. R2 and / or R4 of the component (A)
Is the following formula (Chemical formula 6) The polyimide precursor according to any one of claims 1 to 5, which is represented by: 7. The method according to claim 1, wherein m /
7. The polyimide precursor according to claim 1, wherein n> 0.5. 8. A polyimide precursor composition, which further comprises (B) a photoacid generator and, if necessary, a sensitizer, in addition to the polyimide precursor according to any one of claims 1 to 7. 9. The positive photosensitive polyimide precursor composition according to claim 8, which is used for forming a pattern by exposure. 10. The positive photosensitive polyimide precursor composition according to claim 9, which is used as a material for an optical waveguide. 11. An optical waveguide obtained from the positive photosensitive polyimide precursor composition according to claim 10.