JP2001343541A - Optical waveguide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical waveguide which is excellent in heat resistance and hardly causes double refractivity and a producing method thereof. SOLUTION: This optical waveguide has a core and/or a clad which is made of fluorine-contained allyletherketone polymer of formula (I) and/or polycianoallylether of formula (III).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical waveguide. More specifically, the present invention relates to an optical waveguide having excellent heat resistance and workability and low optical loss.

[0002]

2. Description of the Related Art With the practical use of optical communication systems by the development of low-loss optical fibers, development of various optical communication components has been desired. It is also desired to establish an optical wiring technology for mounting these optical components at a high density, particularly an optical waveguide technology.

In general, an optical waveguide has (1) no birefringence phenomenon, (2) small optical loss, (3) easy manufacture, (4) control of the refractive index difference between a core and a clad, And (5) various conditions such as excellent heat resistance are required. As a low-loss optical waveguide, quartz has a very good light transmittance, and the wavelength is 1.3 even when used as a waveguide.
Since it has already been demonstrated with an optical fiber that a low optical loss of 0.1 dB / cm or less can be achieved at μm,
Silica-based optical waveguides have been mainly studied. However,
Quartz-based materials have manufacturing problems, such as the fact that it takes a long time to produce an optical waveguide using this material, that a high temperature is required during production, and that it is difficult to increase the area. Also, plastic optical waveguides such as polymethyl methacrylate (PMMA) can be molded at low temperatures and have the advantage of being expected to be low in price. However, they have poor heat resistance and have sufficiently low loss at long wavelengths. Have not been achieved.

In consideration of such problems, attention has been paid to polyimide having the highest heat resistance among plastics, and an attempt has been made to use it in an optical waveguide by utilizing this property. At this time, as described above, the polyimide is required to have a small optical transmission loss, that is, to have transparency. However, a polyimide having transparency has been reported so far. For example, a SAMPE JOURNA
L) July / August, p. 28 (1985) reports some examples of transparent polyimides. Further, a transparent fluorinated polyimide having a low dielectric constant is disclosed in JP-A-3-72528.
Patent Publication, Japanese Patent No. 2816771 and Japanese Patent Laid-Open No. 4-3
No. 28504 and the like.

[0005] Further, since commercially available polyimides have a CH bond of a phenyl group in the molecular chain, harmonics of the stretching vibration of the CH bond or harmonics of the stretching vibration of the CH bond and the bending vibration. And a large absorption peak still exists in the near infrared region.

However, since the above-mentioned polyimide is insoluble in a solvent, it is necessary to spin-coat a polyamic acid solution and then bake it at 350 ° C. Since the refractive index changes due to stress due to the difference in the coefficient, it is difficult to control the refractive index, and it is necessary to select a material that can withstand the firing temperature for other materials such as a substrate and an element.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an optical waveguide which is excellent in heat resistance and workability and has a small optical loss.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above objects, and as a result, they have been formed of a fluorine-containing aryl ether ketone polymer and / or polycyano aryl ether having a specific structure. It has been discovered that an optical waveguide having a core and / or a clad has excellent heat resistance and workability. Based on this finding, the present invention has been completed.

That is, the above object is achieved by the following formula (I):

[0010]

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Wherein X represents a halogen atom, a lower alkyl group or a lower alkoxy group, q is an integer of 0 to 4, n represents a degree of polymerization, and m is an integer of 0 or 1. R ¹ has the following formula (II):

[0012]

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(Where X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, and q ′ represents 0 to 4)
And p is an integer of 0 or 1. R ² is 2
Represents a valent organic group. ). A fluorine-containing aryl ether ketone polymer represented by｝ and / or
Or the following formula (III):

[0014]

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(Where Y ¹ is an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or a substituent An alkylamino group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms which may have a substituent,
An aryl group having 6 to 20 carbon atoms that may have a substituent, an aryloxy group having 6 to 20 carbon atoms that may have a substituent, 6 to 20 carbon atoms that may have a substituent 20
Represents an arylamino group or an arylthio group having 6 to 20 carbon atoms which may have a substituent; Y ² represents a divalent organic group; and z represents a degree of polymerization. This is achieved by an optical waveguide having a core and / or cladding made of a polycyanoaryl ether represented by the formula (1).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

According to a first concept, the present invention provides the following formula (I):

[0018]

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Wherein X represents a halogen atom, a lower alkyl group or a lower alkoxy group, q is an integer of 0 to 4, n is a degree of polymerization, and m is an integer of 0 or 1. R ¹ has the following formula (II):

[0020]

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(Wherein X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, and q ′ represents 0 to 4)
And p is an integer of 0 or 1. R ² is 2
Represents a valent organic group. ). Fluorine-containing aryl ether ketone polymer represented by｝ (hereinafter, referred to as
Simply referred to as “fluorinated aryl ether ketone polymer”) and / or the following formula (III):

[0022]

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(Where Y ¹ is an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or a substituent An alkylamino group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms which may have a substituent,
An aryl group having 6 to 20 carbon atoms that may have a substituent, an aryloxy group having 6 to 20 carbon atoms that may have a substituent, 6 to 20 carbon atoms that may have a substituent 20
Represents an arylamino group or an arylthio group having 6 to 20 carbon atoms which may have a substituent; Y ² represents a divalent organic group; and z represents a degree of polymerization. The present invention provides an optical waveguide having a core and / or a clad made of a polycyanoaryl ether represented by the formula

In the present invention, the core of the optical waveguide and / or
Alternatively, the fluorine-containing aryl ether ketone polymer constituting the clad has the following formula (I):

[0025]

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Is a polymer represented by the formula:

Each repeating unit of the fluorine-containing aryl ether ketone polymer represented by the above formula (I) has the following formula:

[0028]

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A p-tetrafluorobenzoylene group (also referred to simply as “p-tetrafluorobenzoylene group” in the present specification) represented by the following formula:

[0030]

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The oxyalkylene group represented by the formula (hereinafter simply referred to as "oxyalkylene group") is located at any position (ortho, meta or para position, particularly preferably para position) of the benzene ring. Each has a structure in which any residue of the benzene ring is bonded or unsubstituted with X.

In the above formula (I), X represents a halogen atom such as a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, preferably a fluorine atom; a lower alkyl group such as methyl, ethyl, propyl, isopropyl and butyl. C1 to C6, preferably C1 to C4
Linear or branched alkyl groups, preferably methyl and ethyl, and their halogenated alkyl groups such as trifluoromethyl; lower alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy; 1-6, preferably 1 carbon atom
And 4 straight-chain or branched-chain alkoxy groups, preferably methoxy and ethoxy, and halogenated alkoxy groups thereof such as trifluoromethoxy. Of these, a fluorine atom is particularly preferably used as X. As described above, X is a group substituted for a residual hydrogen atom to which the p-tetrafluorobenzoylene group and the oxyalkylene group are not bonded, and the number of bonds of X to the benzene ring, that is, the formula: The value of q in (I) is 0
Is an integer of ４4.

In the above formula (I), m is an integer of 0 or 1, and R ¹ is the following formula (II):

[0034]

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Is a group represented by

In the above formula (II), X 'is a halogen atom, for example, a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, preferably a fluorine atom; a lower alkyl group,
For example, methyl, ethyl, propyl, isopropyl, butyl and the like have 1 to 6 carbon atoms, preferably 1 carbon atom.
Linear or branched alkyl groups, preferably methyl and ethyl, and their halogenated alkyl groups such as trifluoromethyl; lower alkoxy groups such as carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy and butoxy; A linear or branched alkoxy group having 1 to 6 atoms, preferably 1 to 4 carbon atoms, preferably a halogenated alkoxy group such as methoxy and ethoxy, and trifluoromethoxy. Among these, a fluorine atom is particularly preferably used as X ′. Further, the number of bonds of X ′ to the benzene ring, that is, the value of q ′ in the formula (II) is an integer of 0 to 4. Among them, R ¹ is represented by the following formula (V):

[0037]

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Preferably, the group is represented by

In the above formulas (II) and (V), p is an integer of 0 or 1. R ² represents a divalent organic group, specifically, methylene (—CH ₂
-), ethylene (-CH ₂ CH ₂ -), propylene (-C
_{H 2 CH (CH 3) -} ), trimethylene (-CH ₂ CH ₂ C
H ₂ —), tetramethylene (—CH ₂ (CH ₂ ) ₂ CH)
₂ -), pentamethylene _{(-CH 2 (CH 2) 3} CH
₂ -), hexamethylene _{(-CH 2 (CH 2) 4} CH
₂ -), propenylene (-CH ₂ CH = CH-), vinylene (-CH = CH -), 1,2,3-tri-yl (-CH ₂ CHCH ₂ -), 2, 2, 3, 3, 4,4,4
5,5-octafluorohexamethylene (—CH ₂ (C
F ₂ ) ₄ CH _2- ), and 2,2,3,3,4,4,5,
5,6,6,7,7- dodecafluoro octamethylene _{(-CH 2 (CF 2) 6} CH 2 -) , such as, carbon atoms, usually 1 to 12, preferably a linear or 1-6 A branched, saturated or unsaturated alkylene group; formula: —CH ₂ —
A group represented by CH ₂ —O—CH ₂ —CH ₂ —; and o-, m- or p-benzenedimethylene, o-, m-
Or p-benzenetetrafluorodimethylene, o-,
m- or p-phenylene, divalent naphthalene, biphenyl, anthracene, o-, m- or p-terphenyl, phenanthrene, dibenzofuran, biphenyl ether, biphenyl sulfone, and the following five formulas:

[0040]

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And divalent aromatic groups such as the aromatic groups represented by In the divalent organic group according to the present invention, hydrogen directly bonded to a carbon atom may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group. Of these, divalent aromatic groups are preferred as R ² , and more preferably the following seven:

[0042]

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The aromatic group represented by is used as R ² .

Further, in the above formula (I), n represents the degree of polymerization, and is specifically 2 to 5000, preferably 5 to 500. Further, in the present invention, the fluorinated aryl ether ketone polymer may be composed of the same repeating unit or may be composed of different repeating units.In the latter case, the repeating unit is a block. It may be in the form of a shape or a random shape.

The fluorine-containing aryl ether ketone polymer particularly preferably used in the present invention is represented by the following formula (I)
V):

[0046]

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[0047] Note that the above formula (I
In V), R ¹ and m are the same as defined in the above formula (I).

The method for producing the fluorinated aryl ether ketone polymer according to the present invention will be described in detail below. From this description, it can be seen that the terminal of the fluorinated aryl ether ketone polymer represented by the formula (I) is p-terminal. When the tetrafluorobenzoylene group side is fluorine and the oxyalkylene group side is hydrogen atom, that is, the fluorinated aryl ether ketone polymer represented by the formula (I) has the following formula (I)
X):

[0049]

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A polymer represented by the following formula (X):

[0051]

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It is considered to be a polymer represented by Further, the fluorine-containing aryl ether ketone polymer of the formula (I) used in the present invention may have a crosslinked structure.

Hereinafter, the fluorine-containing aryl ether ketone polymer represented by the above formula (IV) preferably used in the present invention will be described in detail. For example, a substituted compound is used as a starting material instead, or a desired substituent is introduced into a corresponding benzene ring of a product between each step or after completion of all steps in a synthesis method described below using a known method. It can be prepared in a similar manner by those skilled in the art.

In the above formula (IV), when m is 0, the following formula (VI):

[0055]

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Here, n represents a degree of polymerization, and is a fluorine-containing aryl ether ketone polymer represented by the following formula.

In the above formula (IV), when m is 1 and p is 0, the following formula (VII):

[0058]

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Here, n represents a degree of polymerization, and is a fluorinated aryl ether ketone polymer represented by the following formula.

Further, in the above formula (IV), m is 1
And when p is 1, the following formula (VII)
I):

[0061]

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Here, n represents the degree of polymerization, and R ² is as described above. In the above formula (VIII), n represents the degree of polymerization.
0, more preferably 5 to 200.

The method for producing the fluorinated aryl ether ketone polymer according to the present invention is not particularly limited, and any known method, for example, K. Kimura et al., Polymer
The method described in Preprints, Vol. 39, No. 2, 1998 can be used.

More specifically, a method for producing a fluorinated aryl ether ketone polymer when the fluorinated aryl ether ketone polymer according to the present invention is represented by the above formula (VI) or (VII) will be described below. explain.

First, 2,3,4,5,6-pentafluorobenzoyl chloride is converted into an organic solvent in the presence of a Friedel-Crafts catalyst, for example, an alkoxybenzene such as methoxybenzene or ethoxybenzene or 4-methoxydiphenyl ether. P- (2,3,4) by a Friedel-Crafts reaction with 4-alkoxydiphenyl ether such as
5,6-pentafluorobenzoyl) alkoxybenzene or 4-alkoxy-4 ′-(2,3,4,5,6
-Pentafluorobenzoyl) diphenyl ether, and the reaction product is dealkylated to give the following formula:

[0066]

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Here, q is an integer of 0 or 1, and 2,3,4,5,6-pentafluorobenzoyl compound (hereinafter simply referred to as “2,3,4,5,6-pentafluorobenzoyl”) Compounds).

In the Friedel-Crafts reaction, the amount of the alkoxybenzene or 4-alkoxydiphenyl ether used is preferably 0.8 to 1.2 mol per mol of 2,3,4,5,6-pentafluorobenzoyl chloride. Is 0.9 to 1.1 mol. At this time, if the amount of the alkoxybenzene or 4-alkoxydiphenyl ether used is less than 0.8 mol, an excessive amount of 2,3,4,5,6-pentafluorobenzoyl group is introduced into the alkoxybenzene or 4-alkoxydiphenyl ether. Not preferred. On the other hand, if the amount of the alkoxybenzene or 4-alkoxydiphenyl ether exceeds 1.2 mol, a large amount of unreacted alkoxybenzene or 4-alkoxydiphenyl ether remains, which is not preferable in terms of productivity.

Examples of the Friedel-Crafts catalyst effectively used in the above-mentioned Friedel-Crafts reaction include aluminum chloride, antimony chloride, ferric chloride, ferrous chloride, titanium tetrachloride, boron trifluoride, and tin tetrachloride. , Bismuth chloride, zinc chloride, mercury chloride and sulfuric acid.
The amount of Friedel Crafts catalyst used was 2, 3,
It is 0.5 to 10 mol, preferably 1 to 5 mol, per 1 mol of 4,5,6-pentafluorobenzoyl chloride.

The organic solvent used in the Friedel-Crafts reaction must not react with the acid chloride. Examples of such an organic solvent include dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, and nitrobenzene. The concentration of 2,3,4,5,6-pentafluorobenzoyl chloride in this organic solvent is 1 to 50% by mass, preferably 5 to 30% by mass. The reaction is carried out at a temperature of 0 to 150 ° C, preferably 0 to 100 ° C, while keeping the reaction system under stirring.

The product obtained by such a reaction is obtained by pouring water into the reaction mixture, extracting with an extractant such as dichloromethane, dichloroethane or carbon tetrachloride, separating the organic layer from the extract, and extracting the extractant. Is obtained by distillation. Further, by recrystallizing the product, if necessary, with methanol or ethanol,
It may be obtained as white crystals.

Next, the dealkylation treatment will be described below. That is, the dealkylation reaction can be performed using an acid, an alkali, or an organometallic reagent.
As the reagent, for example, hydrogen bromide, hydrogen iodide, trifluoroacetic acid, hydrochloride of pyridine, concentrated hydrochloric acid, magnesium iodide etherate, aluminum chloride, aluminum bromide, boron trichloride, triiodide And boron hydroxide, potassium hydroxide and Grignard reagent. The amount of the reagent used is p- (2,3,4,
5,6-pentafluorobenzoyl) alkoxybenzene or 4-alkoxy-4 ′-(2,3,4,5,6
0.1 mol or more, preferably 0.1 to 30 mol, per 1 mol of (pentafluorobenzoyl) diphenyl ether.
Is a mole.

In the present invention, the dealkylation reaction may be carried out in the absence of a solvent or in a solvent, but is preferably carried out in a solvent in consideration of reaction efficiency and reaction control. .

In the present invention, examples of the solvent effectively used for performing the dealkylation reaction in the solvent include water, acetic acid, acetic anhydride, benzene and tetrahydrofuran. In addition, p-
(2,3,4,5,6-pentafluorobenzoyl) alkoxybenzene or 4-alkoxy-4 '-(2
The concentration of (3,4,5,6-pentafluorobenzoyl) diphenyl ether is 1 to 50% by mass, preferably 5 to 50% by mass.
30% by mass. The reaction is carried out at a temperature of 0-250C, preferably 50-200C.

Further, the thus obtained 2,3,
By heating the 4,5,6-pentafluorobenzoyl compound in an organic solvent in the presence of a basic compound at a reaction temperature of 30 to 250 ° C, preferably 50 to 200 ° C, the compound of the above formula (VI) and A fluorinated aryl ether ketone polymer represented by (VII) is obtained.

As the organic solvent used in the above polymerization reaction, for example, N-methyl-2-pyrrolidinone, N, N-
Examples include polar solvents such as dimethylacetamide and methanol, and toluene. These organic solvents may be used alone or in the form of a mixture of two or more.

Further, in organic solvents, 2,3,4,5,
The concentration of the 6-pentafluorobenzoyl compound is 5 to 5
0 mass%, preferably 10 to 30 mass%.

When toluene or another similar solvent is used in the initial stage of the reaction, water produced as a by-product during phenoxide formation can be removed as an azeotrope of toluene regardless of the polymerization solvent.

The basic compound used in the present invention acts to accelerate the polycondensation reaction by collecting hydrogen fluoride generated by the polycondensation reaction. Examples of such a basic compound include potassium carbonate, lithium carbonate and potassium hydroxide.

In the above polymerization reaction, the amount of the basic compound used is 0.5 to 1 with respect to 1 mol of the 2,3,4,5,6-pentafluorobenzoyl compound used.
0 mol, preferably 0.5 to 5 mol.

After the completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation or the like, and if necessary, the distillate is washed to obtain a desired polymer. Alternatively, the polymer may be obtained by adding the reaction solution to a solvent having a low solubility of the polymer to precipitate the polymer as a solid, and separating the precipitate by filtration.

Next, a method for producing a fluorinated aryl ether ketone polymer when the fluorinated aryl ether ketone polymer according to the present invention is represented by the above formula (VIII) will be described below.

First, 2,3,4,5,6-pentafluorobenzoyl chloride is subjected to a Friedel-Crafts reaction with diphenyl ether in an organic solvent in the presence of a Friedel-Crafts catalyst to give the following formula:

[0084]

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4,4'-bis (2,3,4,
5,6-pentafluorobenzoyl) diphenyl ether (hereinafter simply referred to as “4,4′-bis (2,3,4,5,6
-Pentafluorobenzoyl) diphenyl ether "or" BPDE ").

In the above-mentioned Friedel-Crafts reaction, the amount of diphenyl ether used is 0,3,4,5,6-pentafluorobenzoyl chloride per 1 mol.
It is 4 to 0.6 mol, preferably 0.45 to 0.55 mol. That is, the amount of diphenyl ether used is 0.4
If the molar ratio is less than 2,3, 2,3,3
A 4,5,6-pentafluorobenzoyl group is introduced, which is not preferable. On the other hand, if the amount of diphenyl ether exceeds 0.6 mol, unreacted diphenyl ether remains in a large amount, which is not preferable in terms of productivity.

The Friedel-Crafts catalyst effectively used in the Friedel-Crafts reaction includes aluminum chloride, antimony chloride, ferric chloride, ferrous chloride, titanium tetrachloride, boron trifluoride, tin tetrachloride , Bismuth chloride, zinc chloride, mercury chloride and sulfuric acid.
The amount of Friedel Crafts catalyst used was 2, 3,
It is 0.5 to 10 mol, preferably 1 to 5 mol, per 1 mol of 4,5,6-pentafluorobenzoyl chloride.

As the organic solvent used in the Friedel-Crafts reaction, a solvent that does not react with acid chloride can be used. Examples of such an organic solvent include dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, and nitrobenzene. The concentration of 2,3,4,5,6-pentafluorobenzoyl chloride in this organic solvent is 1 to 50% by mass, preferably 5 to 30% by mass. The reaction is carried out at 0 to 150 ° C., preferably 0 to 10 ° C., while maintaining the reaction system in a stirring state.
It is performed at a temperature of 0 ° C.

The product obtained by such a reaction is obtained by pouring water into the reaction mixture, extracting with an extractant such as dichloromethane, dichloroethane or carbon tetrachloride, separating the organic layer from the extract, and extracting the extractant. Is obtained by distillation. Further, by recrystallizing the product, if necessary, with methanol or ethanol,
It may be obtained as white crystals.

Further, the thus obtained 4,4 ′
-Bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (BPDE) is reacted with an organic solvent in the presence of a basic compound in the following formula (XIV):

[0091]

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However, R ² is represented by the above formulas (II) and (V)
By heating with a divalent phenol compound represented by the same formula (VII)
A fluorinated aryl ether ketone polymer represented by I) is obtained.

In the above reaction, the reaction temperature is 20 to 1
The temperature is 50 ° C, preferably 50 to 120 ° C. At this time, by reacting at such a low temperature, side reactions can be suppressed, and gelation of the polymer can be prevented.

As the organic solvent used in the above polymerization reaction, for example, N-methyl-2-pyrrolidinone, N, N-
Examples include polar solvents such as dimethylacetamide and methanol, and toluene. These organic solvents may be used alone or in the form of a mixture of two or more.

The concentration of 4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether in the organic solvent is 5 to 50% by mass, preferably 10 to 30% by mass. .

When toluene or another similar solvent is used in the initial stage of the reaction, water produced as a by-product during the production of phenoxide can be removed as an azeotrope of toluene regardless of the polymerization solvent.

The basic compound used in the present invention acts to accelerate the polycondensation reaction by collecting hydrogen fluoride generated by the polycondensation reaction, and further converts the phenol compound into a more reactive anion. It has the effect of changing. Examples of such a basic compound include, for example,
Potassium carbonate, lithium carbonate and potassium hydroxide.

In the above polymerization reaction, the amount of the basic compound used is 4,4′-bis (2,3,3
4,5,6-pentafluorobenzoyl) 1 to 20 mol, preferably 1 to 2 mol per 1 mol of diphenyl ether
10 moles.

The divalent phenol compound used in the above polymerization reaction is not particularly limited as long as it is represented by the above formula (XIV). For example, 2,2-bis (4-vidroxyphenyl)- 1,1,1,3,3
3-hexafluoropropane (hereinafter, referred to as “6FBA”), bisphenol A (hereinafter, referred to as “BA”),
9,9-bis (4-hydroxyphenyl) fluorene (hereinafter, referred to as “HF”), bisphenol F (hereinafter, referred to as “HF”)
“BF”), hydroquinone (hereinafter “HQ”), resorcinol (hereinafter “RS”) and 2- (3-oxyphenyl) -2- (4′-oxyphenyl) propane (hereinafter “3”). , 4'-BA ")
And the like. The amount of the dihydric phenol compound used is preferably 0.8 to 1.2 mol, preferably 1 mol of 4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether. Is 0.9 to 1.1 mol.

After the completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation or the like, and if necessary, the distillate is washed to obtain a desired polymer. Alternatively, the polymer may be obtained by adding the reaction solution to a solvent having a low solubility of the polymer to precipitate the polymer as a solid, and separating the precipitate by filtration.

The fluorinated aryl ether ketone polymer produced as described above has the following advantages.
It satisfies the conditions required for an optical waveguide: (2) it can be easily manufactured; (3) it can control the refractive index difference between a core and a clad; and (4) it has excellent heat resistance.

In the present invention, the polycyano aryl ether constituting the core and / or the clad of the optical waveguide is represented by the following formula (III):

[0103]

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Is a polymer represented by the formula:

In the above formula (III), Y ¹ represents an optionally substituted alkyl group having 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
Pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and 2-ethylhexyl, preferably methyl, ethyl, propyl and butyl; alkoxy having 1 to 12 carbon atoms which may have a substituent Groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, furfuryloxy and allyloxy, preferably methoxy, Ethoxy, propoxy, isopropoxy and butoxy; an alkylamino group having 1 to 12 carbon atoms which may have a substituent, for example, methylamino, ethylamino, dimethylamino, diethylamino, propyl Amino, n- butylamino, s
ec-butylamino and tert-butylamino, preferably methylamino, ethylamino, dimethylamino and diethylamino; 1 carbon atom which may have a substituent
To 12 alkylthio groups, for example, methylthio, ethylthio, propylthio and n-butylthio, sec-butylthio, tert-butylthio and iso-propylthio, preferably methylthio, ethylthio and propylthio; the number of carbon atoms which may have a substituent 6-20 aryl groups such as phenyl, benzyl, phenethyl, o
-, M- or p-tolyl, 2,3- or 2,4
Xylyl, mesityl, naphthyl, anthryl, phenanthryl, biphenylyl, benzhydryl, trityl and pyrenyl, preferably phenyl and o-, m- and p-tolyl; 6 to 2 carbon atoms optionally having substituents
An aryloxy group of 0, for example, phenoxy, benzyloxy, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester and phenyl ester; and the like); Naphthoxy, o-, m- or p-methylphenoxy, o-,
m- or p-phenylphenoxy, phenylethynylphenoxy, and cresotic acid and its esters, preferably phenoxy and naphthoxy; an arylamino group having 6 to 20 carbon atoms which may have a substituent, for example, anilino, o -, M- or p-toluidino,
1,2- or 1,3-xylidino, o-, m- or p-methoxyanilino and anthranilic acid and its esters, preferably anilino and o-, m- or p-toluidino; An arylthio group having 6 to 20 carbon atoms, for example, phenylthio, phenylmethanethio, o-, m- or p-tolylthio and thiosalicylic acid and esters thereof,
Preferably it represents phenylthio. Of these, an aryloxy group, an arylthio group and an arylamino group which may have a substituent are preferable, and phenoxy, phenylthio and anilino are most preferable as Y ¹ .

In the above formula (III), Y ¹ is used when it represents a substituted alkyl group, alkoxy group, alkylamino group, alkylthio group, aryl group, aryloxy group, arylamino group or arylthio group. Possible substituents can be appropriately selected according to the desired properties of the target substance, and are not particularly limited. For example, alkyl groups having 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl, tert-butyl, pentyl,
Isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; halogen atoms such as fluorine, chlorine, bromine and iodine;
Examples include a cyano group, a nitro group and a carboxy ester group. Of these, methyl and carboxy ester groups are preferred.

Further, in the above formula (III), Y ²
Represents a divalent organic group, for example, the following formula:

[0108]

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Among these, the following formula:

[0110]

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A divalent organic group represented by the following formula is preferable as Y ² , and particularly, the following formula:

[0112]

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The divalent organic group represented by the formula is preferred as Y ² .

Further, in the above formula (III), n represents the degree of polymerization, and specifically, is from 5 to 1,000, preferably from 10 to 500. The polycyanoaryl ether of the present invention may be composed of the same repeating unit of the structural unit of the above formula (III) or may be composed of different repeating units. In the latter case, The repeating unit may be block-shaped or random.

The method for producing the polycyanoaryl ether of the present invention will be described in detail below. From this description, it can be seen that the terminal of the polycyanoarylether represented by the formula (III) has a benzene ring side containing a fluorine atom. When it is fluorine and the oxygen atom (Y ² ) side is a hydrogen atom,
The polycyano aryl ether represented by the formula (III) has the following formula (XI):

[0116]

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It is considered to be a polymer represented by
Further, the polycyanoaryl ether of the formula (III) used in the present invention may have a crosslinked structure.

The polycyano aryl ether of the present invention is
The fluorinated aryl ether ketone can be produced in the same manner as described above, but specifically, the following formula (XI)
I):

[0119]

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The tetrafluorobenzonitrile derivative represented by the following formula (XIII):

[0121]

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The compound is produced by polymerizing in the presence of a dihydroxy compound represented by the following formula and a basic catalyst. At this time, Y ¹ in the above formula (XII) and the above formula (XII)
The definition of Y ² in I) is the same as the definition of Y ¹ and Y ² in the above formula (III).

In the present invention, the tetrafluorobenzonitrile derivative of the formula (XII) can be produced by a known method. For example, the following formula: Y ¹ H wherein Y ¹ is the same as defined in the above formula (III) In an organic solvent in the presence of a basic compound.
5,6-pentafluorobenzonitrile (herein,
(PFBN)).

In the above reaction, the compound represented by the formula: Y ¹ H and the PFBN may each be used as a single compound or two or more of the compounds represented by the formula: Y ¹ H and / or PFBN. Although it may be used in the form of a mixture, it is preferably used as a single compound in consideration of the purification step and the physical properties of the polymer. In the latter case, the sum of the number of moles of a plurality or a single PFBN used is expressed by a formula of a plurality or a single formula: Y
It is preferable that the amount of the compound represented by the formula: Y ¹ H is equal to or approximately equal to the total number of moles of the compound represented by ¹ H. Specifically, the amount of the compound represented by the formula: Y ¹ H is preferably 0 to 1 mol of PFBN. 0.1-5 mol, more preferably 0.5
２2 mol.

Examples of the organic solvent that can be used in the above reaction include N-methyl-2-pyrrolidinone, N, N
-Polar solvents such as dimethylacetamide, acetonitrile, benzonitrile, nitrobenzene, nitromethane and methanol; and mixed solvents of these polar solvents and non-polar solvents such as toluene and xylene.
These organic solvents may be used alone or in the form of a mixture of two or more. PF in an organic solvent
The concentration of BN is 1 to 40% by mass, preferably 5 to 30%.
% By mass. At this time, when toluene or another similar solvent is used in the initial stage of the reaction, water by-produced during the reaction can be removed as an azeotrope of toluene regardless of the polymerization solvent.

It is desirable that the basic compound used in the above-mentioned reaction acts to collect hydrogen fluoride generated to accelerate the reaction. Examples of such a basic compound include potassium carbonate, calcium carbonate, potassium hydroxide, calcium hydroxide and potassium fluoride. At this time, the amount of the basic compound used is 0.1 to 5 mol, preferably 0.5 to 2 mol, per 1 mol of PFBN used.

Further, the reaction conditions in the above reaction are Y
There is no particular limitation as long as the reaction between the compound represented by ¹ H and PFBN proceeds efficiently. For example, the reaction is usually carried out while keeping the reaction system in a stirring state, usually in the range of 20 to 180. ° C, preferably 40-160 ° C
At a temperature of The reaction time varies depending on other reaction conditions, raw materials to be used, and the like, but is usually 1 to 48 hours, preferably 2 to 24 hours. In addition, the reaction
It may be carried out under normal pressure or reduced pressure, but it is desirable to carry out under normal pressure from the viewpoint of equipment. The product obtained by such a reaction is obtained by pouring distilled water into the reaction mixture,
After extraction with an extractant such as dichloromethane, dichloroethane or carbon tetrachloride, the organic layer is obtained by separating the extract from the extract and distilling off the extractant. Further, if necessary, this product may be obtained as crystals by recrystallization from methanol or ethanol.

The tetrafluorobenzonitrile derivative of the formula (XII) thus synthesized is further subjected to polymerization in the presence of a dihydroxy compound of the formula (XIII) and a basic catalyst, as described above. To produce the desired polycyanoaryl ether of formula (III). At this time, the tetrafluorobenzonitrile derivative of the formula (XII) may be used after being subjected to the above-mentioned purification steps such as extraction, recrystallization, chromatography, and distillation, or may be used as it is without performing the purification step. However, considering the yield of the next step, it is preferable to use after purification.

Formula (XII) used in the above reaction
The dihydroxy compound of I) is the desired product of formula (II)
It is selected according to the structure of the polycyanoaryl ether of I). Formula (XII) preferably used in the present invention
As the dihydroxy compound of I), as shown below, 2,2-bis (4-bidoxyphenyl)-
1,1,1,3,3,3-hexafluoropropane (hereinafter, referred to as “6FBA”), 4,4′-dihydroxydiphenyl ether (hereinafter, referred to as “DPE”), bisphenol F (hereinafter, referred to as “BF”) ), Hydroquinone (hereinafter referred to as "HQ"), bisphenol A (hereinafter referred to as "HQ").
9,9-bis (4-hydroxyphenyl) fluorene (hereinafter, referred to as "HF"), phenolphthalein (hereinafter, referred to as "PP"), 1,4-bis (hydroxyphenyl) cyclohexane (hereinafter, referred to as "PP"). Hereinafter, "CH
B "), and 4,4'-dihydroxybiphenyl (hereinafter, referred to as" BP ").

[0130]

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In the above reaction, the tetrafluorobenzonitrile derivative of the formula (XII) and the dihydroxy compound of the formula (XIII) may each be used as a single compound or two or more tetrafluorobenzonitrile compounds of the formula (XII). Benzonitrile derivatives and / or formula (XI)
Although it may be used in the form of a mixture of dihydroxy compounds of II), it is preferably used as a single compound in consideration of the purification step and the physical properties of the polymer. In the latter case, the total number of moles of plural or single tetrafluorobenzonitrile derivatives of the formula (XII) used is the total number of moles of plural or single dihydroxy compounds of the formula (XIII). Preferably, the amount of the dihydroxy compound of the formula (XIII) is 0.1 to 0.1 mol per 1 mol of the tetrafluorobenzonitrile derivative of the formula (XII).
It is 5 mol, preferably 1-2 mol.

The above reaction may be carried out in an organic solvent or without solvent, but is preferably carried out in an organic solvent. In the former case, examples of the organic solvent that can be used include N-methyl-2-pyrrolidinone, N,
Polar solvents such as N-dimethylacetamide, acetonitrile, benzonitrile, nitrobenzene, nitromethane and methanol; and mixed solvents of these polar solvents with non-polar solvents such as toluene and xylene. These organic solvents may be used alone or in the form of a mixture of two or more. The concentration of the tetrafluorobenzonitrile derivative of the formula (XII) in the organic solvent is 1 to 50% by mass, preferably 5 to 20% by mass.
It is. At this time, when toluene or another similar solvent is used in the initial stage of the reaction, water by-produced during the reaction can be removed as an azeotrope of toluene regardless of the polymerization solvent.

In the present invention, the tetrafluorobenzonitrile derivative of the formula (XII) and the compound of the formula (XII)
The reaction of the dihydroxy compound of I) must be performed in the presence of a basic catalyst. The basic catalyst has the formula (XI)
Preferably, the compound has an action of converting the dihydroxy compound of the formula (XIII) into a more reactive anion so as to promote the polycondensation reaction with the dihydroxy compound of the formula II). Specifically, potassium carbonate, calcium carbonate, hydroxide Potassium, calcium hydroxide, potassium fluoride and the like can be mentioned. The amount of the basic catalyst used is expressed by the formula (X
II) with a tetrafluorobenzonitrile derivative of formula (X)
The amount of the compound represented by the formula (X) is not particularly limited as long as the reaction with the dihydroxy compound III) can proceed favorably.
Usually, 0.1 to 5 moles, preferably 0.5 to 5 moles per 1 mole of the tetrafluorobenzonitrile derivative of II).
2 moles.

The reaction conditions in the above polymerization reaction are not particularly limited as long as the reaction between the tetrafluorobenzonitrile derivative of the formula (XII) and the dihydroxy compound of the formula (XIII) proceeds efficiently. However, for example, the polymerization temperature is preferably 200 ° C. or less,
More preferably 20 to 150 ° C, most preferably 40 to
100 ° C. By reacting at such a low temperature,
It is possible to suppress side reactions and prevent gelation of the polymer without requiring special equipment. The polymerization time varies depending on other reaction conditions, raw materials to be used, and the like, but is preferably 1 to 48 hours, more preferably 2 to 2 hours.
4 hours. Further, the polymerization reaction may be performed under normal pressure or under reduced pressure, but is preferably performed under normal pressure from the viewpoint of facilities.

After the completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation or the like, and the distillate is washed as necessary to obtain a desired polymer. Alternatively, the polymer may be obtained by adding the reaction solution to a solvent having low polymer solubility to precipitate the polymer as a solid, and separating the precipitate by filtration.

The polycyanoaryl ether thus produced has (1) a small optical loss, (2) easy production, (3) a difference in refractive index between the core and the clad, and (4) This satisfies the condition required for an optical waveguide having excellent heat resistance.

In the present invention, the core of the optical waveguide and / or
Alternatively, the clad contains the fluorinated aryl ether ketone polymer and / or polycyano aryl ether thus produced, wherein the core and / or the clad are formed of a single kind of fluorinated aryl ether ketone polymer. Or a mixture of two or more fluorine-containing aryl ether ketone polymers or polycyano aryl ethers, or one or more fluorine-containing aryl ether ketone polymers and It may be composed of a combination with one or more polycyanoaryl ethers, and is appropriately selected in consideration of desired properties such as a refractive index and heat resistance.

The optical waveguide of the present invention may have any one of a core and a clad made of a fluorinated aryl ether ketone polymer and / or a polycyano aryl ether. In consideration of the above, it is preferable that both the core and the clad are made of the above-mentioned fluorine-containing aryl ether ketone polymer and / or polycyano aryl ether.

Further, in the present invention, the core and / or the clad are not only fluorinated aryl ether ketone polymers and / or polycyano aryl ethers, but also remarkably show the gist of the present invention such as heat resistance and suppression of birefringence. Other resins having different structures may be blended without departing from the scope. As other resins used at this time, specifically,
Polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMM
A), general-purpose resins such as ABS resin and AS resin; polyacetate (POM), polycarbonate (PC), polyamide (PA: nylon), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)
Engineering plastics such as polyphenylene sulfide (PPS), polyether sulfone (PES), polyketone (PK), polyimide (P
I), thermoplastic resins such as polycyclohexanedimethanol terephthalate (PCT), polyarylate (PAR) and various liquid crystal polymers (LCP), and thermosetting resins such as epoxy resins, phenol resins, and novolak resins. When other resins are blended in the low dielectric resin composition of the present invention, the blending amount of the other resins is not particularly limited as long as the electrical properties and heat resistance are not significantly reduced. On the other hand, the content is 0 to 49% by mass.

Hereinafter, as one embodiment of the present invention, a method of manufacturing a ridge type optical waveguide in which both the core and the clad are made of a fluorine-containing aryl ether ketone polymer will be described with reference to FIG.
However, the present invention is not limited to the following embodiments, and a ridge-type optical waveguide is produced in the same manner when both the core and the clad are made of polycyanoaryl ether. it can.

First, a fluorine-containing aryl ether ketone polymer is applied on a substrate 1 such as silicon or quartz glass by spin coating to a predetermined thickness to form a lower cladding layer 2. Next, the lower cladding layer 2
A fluorine-containing aryl ether ketone polymer is further applied thereon by spin coating to a predetermined thickness to obtain a core layer 3. Further, after applying an aluminum layer 4 on the core layer by vapor deposition, photoresist coating,
Pre-baking, exposure, development, and after-baking are performed to obtain a patterned resist layer 5. Subsequently, after the aluminum layer portion not covered with the resist layer 5 is removed by wet etching, the fluorine-containing aryl ether ketone polymer of the core layer portion not covered with the resist layer 5 and the corresponding aluminum layer is dry-etched. Remove. Finally, the remaining aluminum layer 4 is removed by wet etching to produce a ridge-type optical waveguide. Thus, a ridge type optical waveguide in which the lower clad layer and the core layer are formed of the fluorinated aryl ether ketone polymer and the upper clad layer is the air layer is obtained.

In the following, as another embodiment of the present invention, a method for manufacturing a buried optical waveguide in which both the core and the clad are made of polycyanoaryl ether will be described with reference to FIG.
However, the present invention is not limited to the following embodiments. In addition, in FIG.
3 have the same meaning as in FIG. 1, and 6 means the upper cladding layer. Also, similar to the first embodiment,
Even when both the core and the clad are made of polycyanoaryl ether, a ridge-type optical waveguide can be manufactured in the same manner.

First, a lower cladding layer 2 is formed by spin-coating a polycyano aryl ether on a substrate 1 to a predetermined thickness by using the same method as in the first embodiment. A core layer 3 is formed on the lower cladding layer 2 by spin coating a polycyano aryl ether to a predetermined thickness. Next, a polycyano aryl ether is further spin-coated on the core layer 3 so as to have a predetermined thickness to form the upper cladding layer 6, whereby a buried optical waveguide according to the present invention can be manufactured. .

In the first and second embodiments, the lower (and upper) cladding layer and the core layer are all formed by spin coating. However, in consideration of excellent heat resistance and suppression of the birefringence phenomenon, it is preferable to form all of the lower (and upper) cladding layer and the core layer by spin coating. As is apparent, at least one of the cladding layer and the core layer may be formed of a fluorinated aryl ether ketone polymer and / or a polycyano aryl ether, and the production method is not particularly limited. As a method used when the clad layer and the core layer are formed by a method other than spin coating, a conventionally known method can be used, and specifically, casting (casting method), flexographic printing, roll coating, Methods include spray coating, bar coating, flexographic printing, and dip coating. Among these methods, spin coating, casting, and bar coating are preferably used in consideration of easy coating, easy control of the film, enlargement of the area, and the like. In the above embodiment, both the lower cladding layer 2 and the core layer 3 are formed by spin coating.
The method for forming the core layer 3 may be the same or different, and is appropriately selected from the above-described methods. Further, when other components as described above are contained in addition to the fluorine-containing aryl ether ketone polymer and / or polycyano aryl ether, for example, casting (casting method), spin coating, roll coating, spray coating, The lower (and upper) cladding layer and core layer can be formed in a similar manner using known methods such as bar coating, flexographic printing, and dip coating.

In the present invention, the material constituting the lower cladding layer and the core layer, and (in the case of the buried type) the upper cladding layer, depends on the wavelength of light and It is preferable to be formed from different types of materials so that the difference in the refractive index is suitable for the intended use.

Further, according to the present invention, a lower cladding layer,
The thicknesses of the core layer and the upper cladding layer vary depending on the structure of the optical waveguide, the wavelength of light, and the application. For example, in the case of a ridge-type optical waveguide, the thicknesses of the lower cladding layer and the core layer are usually 1 mm. ５０50 μm. When the optical waveguide according to the present invention is a buried optical waveguide, the thicknesses of the lower cladding layer, the core layer and the upper cladding layer are usually 1 to 50 μm.

The structure of the optical waveguide manufactured by the method of the present invention is not particularly limited.
The same structure as that of all conventionally manufactured optical waveguides such as a flat type and a lens type is used.

[0148]

The present invention will be described more specifically below with reference to examples.

Example 1 On a silicon wafer having a surface of a silicon oxide layer and having a diameter of 3 inches, the following formula:

[0150]

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After spin coating a varnish containing 10% by mass of the fluorine-containing aryl ether ketone polymer of
A film is formed by drying at 110 ° C. and has a thickness of 10 μm.
Was formed.

The optical waveguide obtained in this way is
It had a heat resistance of 0 ° C. or higher, and hardly any light loss was observed.

[0153]

As described above, the optical waveguide of the present invention is
It is characterized by having a core and / or a clad made of the fluorine-containing aryl ether ketone polymer of the formula (I) and / or the polycyano aryl ether of the formula (III). Therefore, the fluorine-containing aryl ether ketone polymer of the formula (I) and the polycyano aryl ether of the formula (III) are excellent in heat resistance, and are excellent in processability because they are soluble in a solvent. The optical waveguide has excellent heat resistance and almost no light loss.

[Brief description of the drawings]

FIG. 1 is a process chart showing one embodiment of a method for manufacturing a ridge-type optical waveguide according to the present invention.

FIG. 2 is a cross-sectional view of one embodiment of a method for manufacturing a buried optical waveguide according to the present invention.

[Description of numbering]

 DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Lower clad layer, 3 ... Core layer, 4 ... Aluminum layer, 5 ... Resist layer, 6 ... Upper clad layer.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kozo Tajiri 1-25-12 Kannondai, Tsukuba, Ibaraki Prefecture Inside Nippon Shokubai Co., Ltd. (72) Inventor Yasunori Okumura 1-25-25 Kannondai, Tsukuba, Ibaraki 12 Shares F-term (reference) in Nippon Shokubai Co., Ltd. 2H047 KA04 KA05 PA02 PA15 PA24 PA28 QA05 RA08 TA05 TA31 4J005 AA24 BA00 BB02

Claims (1)

[Claims] (1) The following formula (I): Wherein X represents a halogen atom, a lower alkyl group or a lower alkoxy group; q is an integer of 0 to 4;
Represents a degree of polymerization, and m is an integer of 0 or 1. R ¹ has the following formula (II): (However, X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, q ′ is an integer of 0 to 4, p is an integer of 0 or 1, and R ² represents a divalent organic group.) )). And / or a fluorine-containing aryl ether ketone polymer represented by the following formula (III): (However, Y ¹ has 1 carbon atom which may have a substituent.
An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an alkylamino group having 1 to 12 carbon atoms which may have a substituent, C1-C12 alkylthio group, C6-C20 aryl group which may have a substituent, C6-C20 aryloxy group which may have a substituent, substituent Represents an arylamino group having 6 to 20 carbon atoms or an arylthio group having 6 to 20 carbon atoms which may have a substituent; Y ² represents a divalent organic group; Represents the degree of polymerization. An optical waveguide having a core and / or a clad made of a polycyanoaryl ether represented by the following formula: