JP2010085607A - Composition for optical component, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for optical components, excellent in optical characteristics, heat resistance, adhesion characteristics, processability and the like, and to provide optical components excellent in optical characteristics and heat resistance. <P>SOLUTION: The composition for optical components contains (a) a hydroxyamide polymer expressed by general formula (A), (b) inorganic particles having a specific surface area of 30 to 200 m<SP>2</SP>/g, and (c) a solvent. In formula (A), X, Y<SP>1</SP>and Y<SP>2</SP>each represents a group different from one another; and l and m are integers, l representing an integer of 4 or more, m representing an integer of 0 or more and l+m being equal to 4 or more. The arrangement of repeating units in formula (A) may be a block type or a random type. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an optical component composition and an optical component.

  As optical materials typified by optical communication, inorganic materials such as quartz glass and polymer organic materials are being studied. Inorganic materials generally have processability problems such as high-temperature heating required in the optical component manufacturing process. As an organic material, polymethyl methacrylate, polycarbonate, polyimide, polybenzoxazole, and the like are known. From the viewpoint of heat resistance, polymethyl methacrylate and polycarbonate have problems in that their applications are limited and the process becomes complicated due to application.

  Further, fluorinated polyimides and fluorinated polybenzoxazoles have been widely studied (see, for example, Patent Document 1) and are applied as optical materials, but because fluorine is introduced into the structure. In some cases, the material may be limited to the intended use, and a more reliable material is desired.

  As an optical material, polybenzoxazole having a bulky specific structure with favorable transmittance in the visible light region is known (see, for example, Patent Document 2). This is because the light transmittance is improved by introducing a bulky specific structure such as a norbornane skeleton, but on the other hand, the introduction of an aliphatic structure and a hydrophobic structure reduces the heat resistance and its application. There is a problem that application is limited or wettability of the resin to the substrate is lowered, so that there is a problem that coating uniformity is lowered, and there is a problem that the application range is narrow or difficult to put into practical use.

  In addition, in optical waveguides as optical components, waveguides made of inorganic oxides such as SiO are formed conformally from the film forming method. The process is complicated. Further, when polyimide is used (for example, refer to Patent Document 3), since a carbonyl group is included in the polyimide structure, there is a problem that it is affected by moisture absorption. In addition, it is known to use a composite material of polyimide or polybenzoxazole and inorganic particles for an optical waveguide (for example, Patent Document 4). In these, it is necessary to disperse the inorganic particles in the polymer solution, and it is necessary to control the dispersibility of the inorganic particles in the production of the optical waveguide. However, if the amount of inorganic particles added is increased in order to obtain sufficient optical characteristics, there arises a problem that the film forming property is lowered.

International Publication No. 2003/010223 Pamphlet Japanese Patent Laid-Open No. 11-322929 JP 2001-354853 A JP 2007-63502 A

  Under such circumstances, the present invention provides a composition for optical parts that is excellent in optical characteristics, heat resistance, workability, and the like, and further provides an optical part that is excellent in optical characteristics and heat resistance. It is.

As a result of intensive studies to achieve the above object, the present inventors have obtained a uniform structure by using a hydroxyamide polymer having a specific structure, inorganic particles having a specific surface area of 30 to 200 m ² / g, and a solvent. The present inventors have found that the film can be formed and converted into a resin having high optical properties, heat resistance and physical properties, and can meet the purpose, and the present invention has been completed based on this finding.

  That is, the present invention is achieved by the following means (1) to (9).

(1) A composition for optical parts comprising the hydroxyamide polymer (a) represented by the general formula (A), inorganic particles (b) having a specific surface area of 30 to 200 m ² / g, and a solvent (c).

[In the formula (A), X represents a group selected from the groups represented by the following formula (B), and the X in the two repeating units may be the same or different. Y ¹ represents a group selected from the groups represented by the following formulas (C) and (D). Y ² represents a group selected from the groups represented by the following formula (E) and formula (F). l and m are integers where l is an integer of 4 or more, m is an integer of 0 or more, and l + m is an integer of 4 or more. In addition, the arrangement of the repeating units in the formula (A) may be either block or random. ]

[X _{1 in} Formula (B) and Formula (C) represents the following formula (G)

In the formula (E), R represents a group selected from an aryl group or a group represented by an alkyl group having 1 to 10 carbon atoms. P in the formula (D) represents an integer of 1 or more and 4 or less.
Moreover, the hydrogen atom on the ring structure in the group represented by Formula (B), Formula (C), Formula (D), Formula (E), Formula (F), and Formula (G) has 1 to 4 carbon atoms. The alkyl group may be substituted with at least one group selected from alkyl groups. ]

(2) The composition for optical components according to item (1), wherein the hydroxyamide polymer (a) has a weight average molecular weight in terms of standard polystyrene of from 5,000 to 15,000.
(3) The composition for optical components according to (1) or (2), wherein the inorganic particles (b) are titanium oxide or zirconium oxide, the surface of which may be coated.
(4) The composition for optical components according to any one of Items (1) to (3), wherein the hydroxyamide polymer (a) is represented by General Formula (H).

[In the formula (H), X ′ represents a group selected from the groups represented by the following formula (I), and X ′ in two repeating units in the formula may be the same or different. Y ³ represents a group selected from the groups represented by the following formulas (J) and (K). Y ⁴ represents a group selected from the groups represented by the following formula (L). l ′ and m ′ are integers where l ′ is an integer of 4 or more, m ′ is an integer of 0 or more, and l ′ + m ′ is an integer of 4 or more. In addition, the arrangement of the repeating units in the formula (H) may be either block or random. ]

[X _{2 in} Formula (I) and Formula (J) represents the following formula (M)

In the formula (L), R represents a group selected from an aryl group or a group represented by an alkyl group having 1 to 10 carbon atoms. P ′ in the formula (K) represents an integer of 1 or more and 4 or less.
Moreover, the hydrogen atom on the ring structure in the group represented by the formula (I), the formula (J), the formula (K), the formula (L), and the formula (M) is an alkyl group having 1 to 4 carbon atoms. It may be substituted with at least one group selected from ]

(5) The composition for optical components according to any one of Items (1) to (4), wherein the hydroxyamide polymer is represented by General Formula (N).

[In formula (N), X ″ represents a group selected from the groups represented by the following formula (O), and two X ″ in the formula may be the same or different. Y ⁵ represents a group selected from the groups represented by the following formula (P). Y ⁶ represents a group selected from the groups represented by the following (Q). l ″ and m ″ indicate l ″ is an integer of 4 or more, m ″ is an integer of 0 or more, and l ″ + m ″ is an integer of 4 or more. In addition, the arrangement of the repeating units in the formula (N) may be either block or random. ]

[X _{3 in} Formula (O) and Formula (P) represents Formula (R)

In the formula (Q), R represents a group selected from an aryl group or a group represented by an alkyl group having 1 to 10 carbon atoms. Moreover, the hydrogen atom on the ring structure in the group represented by Formula (O), Formula (P), Formula (Q), and Formula (R) is at least one selected from alkyl groups having 1 to 4 carbon atoms. It may be substituted with groups. ]

(6) When forming the film on the surface of the SiOx film formed by the plasma CVD method using the optical component composition, the contact angle between the composition and the SiOx film is 0 ° or more and 10 ° or less. The composition for optical components according to any one of Items (1) to (5).
(7) In the composition for optical components, a coating film was formed at a rotating speed of a spin coater at 1400 rpm in an atmosphere at 23 ° C./humidity 45%, and the average thickness of the film heated at 380 ° C./250 seconds was The solution viscosity at 25 ° C. when the content of the hydroxyamide polymer is adjusted so as to be 500 nm is from 3 mPa · s to 11 mPa · s. The composition for optical components according to any one of the above.
(8) A film is formed using the composition for optical components according to any one of items (1) to (7), and the hydroxyamide polymer in the composition for optical components is subjected to a condensation reaction. Optical parts obtained.
(9) The optical component according to (8), wherein the optical component has a light attenuation coefficient of 0 or more and 0.01 or less at a wavelength of 380 nm.

According to the present invention, a composition for optical parts that is excellent in optical properties, heat resistance, adhesion properties, workability, and the like can be obtained. In addition, since the composition for optical parts is excellent in wettability to a substrate when forming a film, the uniformity of the film formation is excellent, and the properties of the obtained film are also good.
An optical component obtained from the composition for optical components is excellent in optical properties and heat resistance, and an optical device having the optical components is excellent in optical properties and heat resistance.

The present invention is characterized by comprising a hydroxyamide polymer (a) represented by the general formula (A), inorganic particles (b) having a specific surface area of 30 to 200 m ² / g, and a solvent (c). It is a composition for optical components. Thereby, the composition for optical components which is excellent in an optical characteristic, heat resistance, contact | adherence characteristic, workability, etc. can be provided.

  The hydroxyamide polymer (a) represented by the general formula (A) includes at least one bisaminophenol compound having a group selected from the groups represented by the formula (B), and the formula (A). C) and at least one dicarboxylic acid compound having a group selected from the groups represented by the above formula (D) can be reacted and synthesized.

  Further, as the dicarboxylic acid compound, at least one dicarboxylic acid compound having a group selected from the groups represented by the formula (C) and the formula (D), and the formula (E) and the formula (F) The reaction can also be carried out using a dicarboxylic acid compound having a group selected from the groups represented.

  In the synthesis of the hydroxyamide polymer (a), as a method of reacting a bisaminophenol compound with a dicarboxylic acid compound, a conventional acid chloride method, an activated ester method, a dehydrating condensing agent such as polyphosphoric acid or dicyclohexylcarbodiimide A method such as a condensation reaction in the presence of

  The group in the bisaminophenol compound means a group having four bonds that can be bonded to an amino group and a phenolic hydroxyl group. In addition, the group in the dicarboxylic acid compound means a group having two bonds that can bond to a carboxyl group.

  Specific examples of the bisaminophenol compound having a group represented by the formula (B) used in the present invention include 2,5-diaminohydroquinone, 2,3-diaminohydroquinone, 3,6-diaminocatechol, 4,6 -Diaminoresorcinol, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2 -Bis (4-amino-3-hydroxyphenyl) propane, 2,2- (2,3'-amino-3,4'-hydroxyphenyl) propane, 2,2- (3,4'-amino-2, 3'-hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxy Diphenyl sulfone, 2,3′-diamino-3,4′-dihydroxydiphenyl sulfone, 3,4′-diamino-2,3′-dihydroxydiphenyl sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,3'-diamino-3,4'-dihydroxydiphenyl ether, 3,4'-diamino-2,3'-dihydroxydiphenyl ether, 1,3-bis (3-amino-4hydroxyphenoxy) benzene, 1,3-bis (4-amino-3hydroxyphenoxy) benzene, 1,4-bis (3-amino-4hydroxyphenoxy) benzene, 1,4-bis (4 -Amino-3hydroxyphenoxy) benzene, 1,3-bis (3-amino-4hydride) Xylphenylsulfanyl) benzene, 1,3-bis (4-amino-3hydroxyphenylsulfanyl) benzene, 1,4-bis (3-amino-4hydroxyphenylsulfanyl) benzene, 1,4-bis (4-amino-) 3hydroxyphenylsulfanyl) benzene, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,4′-diamino-2,3′-dihydroxy Biphenyl, 2,3′-diamino-3,4′-dihydroxybiphenyl, 3,3′-diamino-2,2′-dihydroxybinaphthyl, 2,2′-diamino-3,3′-dihydroxybinaphthyl, 2,3 '-Diamino-3,2'-dihydroxybinaphthyl, 9,9-bis (4-amino-3-hydroxyph Enyl) fluorene, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bis (4- (3-amino-4-hydroxyphenyl) sulfanylphenyl) fluorene, 9,9-bis ( 4- (4-amino-3-hydroxyphenyl) sulfanylphenyl) fluorene, 9,9-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) fluorene and 9,9-bis (4- (3- Amino-4-hydroxyphenoxy) phenyl) fluorene and the like.

  Among these, in terms of solubility in solvents and heat resistance, 2,5-diaminohydroquinone, 4,6-diaminoresorcinol, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3) -Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2- (2,3'- Amino-3,4′-hydroxyphenyl) propane, 2,2- (3,4′-amino-2,3′-hydroxyphenyl) propane, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, 2,3′-diamino-3,4′-dihydroxydiphenylsulfone, 3,4′- Amino-2,3′-dihydroxydiphenyl sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 2,3′-diamino-3, 4'-dihydroxydiphenyl ether, 3,4'-diamino-2,3'-dihydroxydiphenyl ether, 1,3-bis (3-amino-4hydroxyphenoxy) benzene, 1,3-bis (4-amino-3hydroxyphenoxy) ) Benzene, 1,4-bis (3-amino-4hydroxyphenoxy) benzene, 1,4-bis (4-amino-3hydroxyphenoxy) benzene, 1,3-bis (3-amino-4hydroxyphenylsulfanyl) Benzene, 1,3-bis (4-amino-3hydroxyphenylsulfani ) Benzene, 1,4-bis (3-amino-4hydroxyphenylsulfanyl) benzene, 1,4-bis (4-amino-3hydroxyphenylsulfanyl) benzene, 9,9-bis (4-amino-3-hydroxy) Phenyl) fluorene, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bis (4- (4-amino-3-hydroxyphenyl) sulfanylphenyl) fluorene, 9,9-bis ( 4- (4-amino-3-hydroxyphenyl) sulfanylphenyl) fluorene, 9,9-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) fluorene and 9,9-bis (4- (3- Amino-4-hydroxyphenoxy) phenyl) fluorene is preferred, 3,3′-diamino-4,4′-dihydro Xidiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 1,3-bis (3-amino-4hydroxyphenoxy) benzene, 1,3-bis (4-amino-3hydroxyphenoxy) benzene, 9,9-bis (4-amino-3-hydroxyphenyl) fluorene and 9 , 9-bis (3-amino-4-hydroxyphenyl) fluorene is more preferred. These bisaminophenol compounds may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid compound having a group represented by the formula (C) used in the present invention include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 1 , 4-Naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-sulfonylbisbenzoic acid, 3,3′-sulfonylbisbenzoic acid, 4,4′-thiobisbenzoic acid Acid, 3,3′-thiobisbenzoic acid, 4,4′-oxybisbenzoic acid, 3,3′-oxybisbenzoic acid, bis (4-carboxyphenyl) methane, bis (3-carboxyphenyl) methane, 2,2 -Bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2'-dimethyl-4,4'-biphenyl Dicarboxylic acid, 3,3′-dimethyl-4,4′-biphenyldicarboxylic acid, 2,2′-dimethyl-3,3′-biphenyldicarboxylic acid, 1,3-bis (4-carboxyphenoxy) benzene, 1, 3-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,3-bis (4-carboxyphenylsulfanyl) benzene 1,3-bis (3-carboxyphenylsulfanyl) benzene, 1,4-bis (4-carboxyphenylsulfanyl) benzene, 1,4-bis (3-carboxyphenylsulfanyl) benzene, 4,4′-bis ( 4-carboxyphenoxy) biphenyl, 4,4′-bis (3-carboxyphenoxy) biphe 3,4′-bis (4-carboxyphenoxy) biphenyl, 3,4′-bis (3-carboxyphenoxy) biphenyl, 3,3′-bis (4-carboxyphenoxy) biphenyl, 3,3′-bis (3-carboxyphenoxy) biphenyl, 9,9-bis (3-carboxyphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis (4- (3-carboxyphenyl) sulfanylphenyl ) Fluorene, 9,9-bis (4- (4-carboxyphenyl) sulfanylphenyl) fluorene, 9,9-bis (4-carboxyphenoxyphenyl) fluorene, 9,9-bis (3-carboxyphenoxyphenyl) fluorene, etc. However, it is not limited to these.

  Among these, in terms of solubility in a solvent, isophthalic acid, terephthalic acid, 4,4′-sulfonylbisbenzoic acid, 3,3′-sulfonylbisbenzoic acid, 4,4′-thiobisbenzoic acid, 3,3 '-Thiobisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, bis (4-carboxyphenyl) methane, bis (3-carboxyphenyl) methane, 2,2-bis (4- Carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 1,3-bis (4-carboxyphenoxy) benzene, 1,3-bis (3-carboxyphenoxy) benzene, 1,4-bis ( 4-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,3-bis (4-carboxyphenylsulfurate) Anil) benzene, 1,3-bis (3-carboxyphenylsulfanyl) benzene, 1,4-bis (4-carboxyphenylsulfanyl) benzene, 1,4-bis (3-carboxyphenylsulfanyl) benzene, 9,9- Bis (3-carboxyphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis (4- (3-carboxyphenyl) sulfanylphenyl) fluorene, 9,9-bis (4- ( 4-carboxyphenyl) sulfanylphenyl) fluorene, 9,9-bis (4-carboxyphenoxyphenyl) fluorene and 9,9-bis (3-carboxyphenoxyphenyl) fluorene are preferred, isophthalic acid, 4,4′-sulfonylbis Benzoic acid, 3,3′-sulfonylbisbenzoic acid 4,4′-thiobisbenzoic acid, 3,3′-thiobisbenzoic acid, 4,4′-oxybisbenzoic acid, 3,3′-oxybisbenzoic acid, 1,3-bis (4-carboxyphenoxy) benzene, 1,3-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 9,9-bis (3-carboxyphenyl) Fluorene and 9,9-bis (4-carboxyphenyl) fluorene are more preferred. These dicarboxylic acid compounds may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid compound having a group represented by the formula (D) used in the present invention include 1,3-cyclohexanedicarboxylic acid, cis-1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, 1,3-decalindicarboxylic acid, 1,4-decalindicarboxylic acid, 2,6-decalindicarboxylic acid, 1,3-adamantane Dicarboxylic acid, 5-methyl-1,3-adamantane dicarboxylic acid, 2,2-adamantane dicarboxylic acid, 3,3 ′-(2,2-adamantyl) phenyl dicarboxylic acid, 4,4 ′-(2,2-adamantyl) ) Phenyldicarboxylic acid, 3,3 ′-(2,2-adamantyloxy) phenyldicarboxylic acid, , 4 ′-(2,2-adamantyloxy) phenyl dicarboxylic acid, 3,3 ′-(1,3-adamantyl) phenyl dicarboxylic acid, 4,4 ′-(1,3-adamantyl) phenyl dicarboxylic acid, 3, 3 ′-(1,1′-biadamantane) dicarboxylic acid, 3,5- (1,1′-biadamantane) dicarboxylic acid, 3,3 ′-(1,1′-biadamantane) dicarboxylic acid, 3, 5 ′-(1,1′-biadamantane) dicarboxylic acid, 3 ′, 5 ′, 7,7′-tetramethyl-1,1′-biadamantane-3,5-dicarboxylic acid, 5,5 ′, 7 , 7'-Tetramethyl-1,1'-biadamantane-3,3'dicarboxylic acid and 3 ', 5,7,7'-tetramethyl-1,1'-biadamantane-3,5'-dicarboxylic acid Etc., but are limited to these Not to.

  Among these, 1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid have solubility in solvents and heat resistance. Acid, 5-methyl-1,3-adamantane dicarboxylic acid, 3,3 ′-(1,1′-biadamantane) dicarboxylic acid, 3,5- (1,1′-biadamantane) dicarboxylic acid, 3,3 '-(1,1'-biadamantane) dicarboxylic acid, 3,5'-(1,1'-biadamantane) dicarboxylic acid, 3 ', 5', 7,7'-tetramethyl-1,1'- Biadamantane-3,5-dicarboxylic acid, 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane-3,3′dicarboxylic acid and 3 ′, 5,7,7′-tetramethyl 1,1'-biadamantane-3,5'-dicarboxylic acid. These dicarboxylic acid compounds may be used alone or in combination of two or more.

  In the dicarboxylic acid compound having a group represented by the formula (E) used in the present invention, the R substituent is an aryl group or an alkyl group having 1 to 10 carbon atoms. Specifically, as the aryl group, Examples thereof include a phenyl group, a benzyl group, a tolyl group, an o-xylyl group, an m-xylyl group, and a p-xylyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group, and an adamantyl group. Among these, phenyl group, tolyl group, o-xylyl group, m-xylyl group, p-xylyl group, methyl group, isobutyl group and t-butyl group are preferable, and phenyl group, tolyl group, o-xylyl group, An m-xylyl group and a p-xylyl group are more preferable.

  As a specific example of the dicarboxylic acid compound having a group represented by the formula (E), a specific example of a dicarboxylic acid compound having a phenylethynyl group whose R substituent is a phenyl group is 4-phenylethynylisophthalic acid. 5-phenylethynylisophthalic acid, 2-phenylethynylterephthalic acid, 3-phenylethynylterephthalic acid, 2-phenylethynyl-1,5-naphthalenedicarboxylic acid, 3-phenylethynyl-1,5-naphthalenedicarboxylic acid, 4- Phenylethynyl-1,5-naphthalenedicarboxylic acid, 1-phenylethynyl-2,6-naphthalenedicarboxylic acid, 3-phenylethynyl-2,6-naphthalenedicarboxylic acid, 4-phenylethynyl-2,6-naphthalenedicarboxylic acid, 3,7-bisphenylethynyl-1,5-naphthalene Dicarboxylic acid, 4,8-bisphenylethynyl-2,6-naphthalenedicarboxylic acid, 4-phenylethynyl-2,2′-biphenyldicarboxylic acid, 6-phenylethynyl-2,2′-biphenyldicarboxylic acid, 2-phenyl Ethynyl-4,4′-biphenyldicarboxylic acid, 4,4′-bisphenylethynyl-2,2′-biphenyldicarboxylic acid, 6,6′-bisphenylethynyl-2,2′-biphenyldicarboxylic acid, 2,2 '-Bisphenylethynyl-4,4'-biphenyldicarboxylic acid, 2,2-bis (3-carboxy-4-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-5-phenylethynylphenyl) propane 2,2-bis (4-carboxy-2-phenylethynylphenyl) propane, 2,2-bis (4-carbohydrate) Ci-3-phenylethynylphenyl) propane, bis (3-carboxy-4-phenylethynylphenyl) sulfone, bis (3-carboxy-5-phenylethynylphenyl) sulfone, bis (4-carboxy-2-phenylethynylphenyl) Sulfone, bis (4-carboxy-3-phenylethynylphenyl) sulfone, bis (3-carboxy-4-phenylethynylphenyl) ether, bis (3-carboxy-5-phenylethynylphenyl) ether, bis (4-carboxy- Examples include 2-phenylethynylphenyl) ether, bis (4-carboxy-3-phenylethynylphenyl) ether, and the like, but are not limited thereto.

  Among these, in terms of solubility in solvents, 4-phenylethynylisophthalic acid, 5-phenylethynylisophthalic acid, 2-phenylethynylterephthalic acid, 3-phenylethynylterephthalic acid, 2,2-bis (3-carboxy- 4-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-5-phenylethynylphenyl) propane, 2,2-bis (4-carboxy-2-phenylethynylphenyl) propane, 2,2-bis ( 4-carboxy-3-phenylethynylphenyl) propane, bis (3-carboxy-4-phenylethynylphenyl) sulfone, bis (3-carboxy-5-phenylethynylphenyl) sulfone, bis (4-carboxy-2-phenylethynyl) Phenyl) sulfone, bis (4-carboxy-) -Phenylethynylphenyl) sulfone, bis (3-carboxy-4-phenylethynylphenyl) ether, bis (3-carboxy-5-phenylethynylphenyl) ether, bis (4-carboxy-2-phenylethynylphenyl) ether, bis (4-Carboxy-3-phenylethynylphenyl) ether is preferable, and 4-phenylethynylisophthalic acid, 5-phenylethynylisophthalic acid, 2-phenylethynylterephthalic acid, and 3-phenylethynylterephthalic acid are more preferable. These dicarboxylic acid compounds may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid compound having a group represented by the formula (F) used in the present invention include 4-ethynylisophthalic acid, 5-ethynylisophthalic acid, 2-ethynylterephthalic acid, 3-ethynylterephthalic acid, 2 -Ethynyl-1,5-naphthalenedicarboxylic acid, 3-ethynyl-1,5-naphthalenedicarboxylic acid, 4-ethynyl-1,5-naphthalenedicarboxylic acid, 1-ethynyl-2,6-naphthalenedicarboxylic acid, 3-ethynyl -2,6-naphthalenedicarboxylic acid, 4-ethynyl-2,6-naphthalenedicarboxylic acid, 3,7-diethynyl-1,5-naphthalenedicarboxylic acid, 4,8-diethynyl-2,6-naphthalenedicarboxylic acid, 4 -Ethynyl-2,2'-biphenyldicarboxylic acid, 6-ethynyl-2,2'-biphenyldicarboxylic acid, 2-ethy 4,4′-biphenyldicarboxylic acid, 4,4′-diethynyl-2,2′-biphenyldicarboxylic acid, 6,6′-diethynyl-2,2′-biphenyldicarboxylic acid, 2,2′-diethynyl- 4,4′-biphenyldicarboxylic acid, 2,2-bis (3-carboxy-4-ethynylphenyl) propane, 2,2-bis (3-carboxy-5-ethynylphenyl) propane, 2,2-bis (4 -Carboxy-2-ethynylphenyl) propane, 2,2-bis (4-carboxy-3-ethynylphenyl) propane, bis (3-carboxy-4-ethynylphenyl) sulfone, bis (3-carboxy-5-ethynylphenyl) ) Sulfone, bis (4-carboxy-2-ethynylphenyl) sulfone, bis (4-carboxy-3-ethynylphenyl) sulfone, bis 3-carboxy-4-ethynylphenyl) ether, bis (3-carboxy-5-ethynylphenyl) ether, bis (4-carboxy-2-ethynylphenyl) ether, bis (4-carboxy-3-ethynylphenyl) ether, etc. However, it is not limited to these.

  Among these, 4-ethynylisophthalic acid, 5-ethynylisophthalic acid, 2-ethynylterephthalic acid, 3-ethynylterephthalic acid, and 2,2-bis (3-carboxy-4-ethynylphenyl) in terms of solubility in solvents ) Propane, 2,2-bis (3-carboxy-5-ethynylphenyl) propane, 2,2-bis (4-carboxy-2-ethynylphenyl) propane, 2,2-bis (4-carboxy-3-ethynyl) Phenyl) propane, bis (3-carboxy-4-ethynylphenyl) sulfone, bis (3-carboxy-5-ethynylphenyl) sulfone, bis (4-carboxy-2-ethynylphenyl) sulfone, bis (4-carboxy-3) -Ethynylphenyl) sulfone, bis (3-carboxy-4-ethynylphenyl) ether, bi (3-carboxy-5-ethynylphenyl) ether, bis (4-carboxy-2-ethynylphenyl) ether, bis (4-carboxy-3-ethynylphenyl) ether are preferred, 4-ethynylisophthalic acid, 5-ethynylisophthalate Acid, 2-ethynyl terephthalic acid, and 3-ethynyl terephthalic acid are more preferable. These dicarboxylic acid compounds may be used alone or in combination of two or more.

  In addition, the hydrogen atom on the ring structure in the group represented by Formula (B), Formula (C), Formula (D), Formula (E), Formula (F), and Formula (G) has 1 to 4 carbon atoms. The alkyl group may be substituted with at least one group selected from alkyl groups. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and t-butyl group.

  As a method for producing the hydroxyamide polymer (a) used in the present invention, for example, in the acid chloride method, the acid chloride to be used is first a dicarboxylic acid compound in the presence of a catalyst such as N, N′-dimethylformamide. And an excess amount of thionyl chloride at room temperature to about 100 ° C., the excess thionyl chloride is distilled off by heating and decompression, and the residue is recrystallized with a solvent such as hexane. Can do. The dicarboxylic acid chloride compound thus produced is usually dissolved in a polar solvent such as N-methyl-2-pyrrolidone and N, N′-dimethylacetamide together with the bisaminophenol compound, and an acid acceptor such as pyridine. A hydroxyamide polymer can be obtained by reacting in the presence at room temperature to about −30 ° C. When the hydroxyamide polymer thus obtained is a copolymer, the arrangement of repeating units may be block-like or random.

  For example, as a method for producing a block-like repeating unit, in the case of the acid chloride method, a bisaminophenol compound having a group selected from groups represented by formula (B), formula (C) and formula (D ), After reacting in advance with at least one dicarboxylic acid chloride compound having a group selected from the groups represented by formula (B), the molecular weight is increased, and then the group is further selected from the groups represented by formula (B). It can be obtained by reacting a bisaminophenol compound having a group with at least one dicarboxylic acid chloride having a group selected from the groups represented by formulas (E) and (F).

  Conversely, it has a bisaminophenol compound having a group selected from the groups represented by formula (B) and a group selected from the groups represented by formula (E) and formula (F). After reacting in advance with at least one dicarboxylic acid chloride compound to increase the molecular weight of the polymer, the bisaminophenol compound further having a group selected from the group represented by formula (B) and the formula ( You may make it react with at least 1 sort (s) of the dicarboxylic acid chloride compound which has group chosen from group represented by C) or Formula (D).

  In the case of a random repeating unit, it is selected from a bisaminophenol compound having a group selected from the group represented by formula (B) and a group represented by formula (C) or formula (D). Simultaneously reacting at least one dicarboxylic acid chloride compound having a group with at least one dicarboxylic acid chloride compound having a group selected from the groups represented by formula (E) and formula (F). Can be obtained.

  In the structure represented by the formula (A), l and m are each an integer of 4 or more, m is an integer of 0 or more, and l + m is an integer of 4 or more, and is a bisaminophenol used for the hydroxyamide polymer. Generally, l + m is in the range of 4 to 100, although it varies depending on the combination of the compound and the dicarboxylic acid compound.

  The hydroxyamide polymer (a) represented by the general formula (A) thus obtained has a structure represented by the general formula (H) in terms of solubility in the solvent (c) and heat resistance. The hydroxyamide polymer having a structure represented by the general formula (N) is more preferable.

  In addition, the hydroxyamide polymer (a) represented by the general formula (A) preferably has a weight average molecular weight in terms of standard polystyrene of 5000 or more and 15000 or less, more preferably 8000 or more and 12000 or less. The weight average molecular weight can be used outside the above range, but if it is smaller than the lower limit, heat resistance may be deteriorated during the process after film formation, and if it is larger than the upper limit, solubility in a solvent may be reduced. Moreover, when the solution viscosity in the composition for optical parts of the present invention is increased, wettability to the substrate may be reduced during the formation of the coating film, and the film thickness uniformity may be reduced.

  The said weight average molecular weight says the thing calculated | required in polystyrene conversion, creating a calibration curve with standard polystyrene using a high performance liquid chromatograph. For example, as an apparatus, a TSKgelGMH-HRH high-speed SEC column, UV (λ = 270 nm) detector was used in a high performance liquid chromatograph SC-8020 system manufactured by Tosoh Corporation, and N-Br with 0.5% LiBr added as a mobile phase. It can be measured using a methyl-2-pyrrolidone solution, and a calibration curve of retention time and molecular weight can be prepared with PS-oligomer kit made by Tosoh as standard polystyrene, and the weight average molecular weight in terms of polystyrene of the hydroxyamide polymer can be obtained. it can.

  Moreover, as a reaction method for bringing the weight average molecular weight in terms of standard polystyrene of the hydroxyamide polymer within the above range, for example, in the above production method, the reaction molar ratio of the dicarboxylic acid chloride compound and the bisaminophenol compound is adjusted. Examples thereof include a method for controlling the molecular weight, a method for stopping the reaction by using a carboxylic acid chloride compound or an aminophenol compound for the dicarboxylic acid chloride compound and the bisaminophenol compound, and adjusting the molecular weight to an arbitrary molecular weight. The carboxylic acid chloride compound and aminophenol compound are used to terminate the reaction as a terminal group of the hydroxyamide polymer and prevent the molecular weight from increasing any more. For example, benzoic acid chloride, 2-aminophenol and the like are exemplified. can do.

  In the method of controlling the molecular weight by adjusting the reaction molar ratio of the dicarboxylic acid compound and the bisaminophenol compound, the dicarboxylic acid compound and the bisaminophenol compound used above are also related to the weight average molecular weight in terms of standard polystyrene. The molar ratio varies depending on the structure of the compound, but the reaction molar ratio is adjusted to 0.7 or more and 0.9 or less by increasing the number of moles of one compound, for example, by increasing the number of moles of the aminophenol compound. Preferably, it is 0.75 or more and 0.90 or less, and more preferably 0.8 or more and 0.90 or less. The reaction molar ratio can be used outside the above range, but if it is lower than the lower limit, a relatively low molecular component is often generated. Moreover, when exceeding the said upper limit, there exists a possibility that the weight average molecular weight of standard polystyrene conversion may become larger than the target range.

  In addition, the hydroxyamide polymer (a) used for this invention can produce a condensation reaction by heating, and can obtain a benzoxazole polymer.

Examples of the inorganic particles (b) used in the present invention include aluminum oxide particles, zirconium oxide particles, titanium oxide particles, zinc oxide particles, lead sulfide particles, zinc sulfide particles, barium titanate, potassium titanate, and gallium nitride. . Among these, titanium oxide particles and zirconium oxide particles are preferable in terms of refractive index and transparency. In order to suppress the catalytic activity of these inorganic particles and to improve the dispersibility with the hydroxyamide polymer (a) and the solvent (c), the surface of the particles is coated with silica or alumina. May be.
These inorganic particles may be used alone or in combination of two or more.

The specific surface area of these inorganic particles is 30 to 200 m ² / g, and more preferably 60 to ²⁰⁰ m ² / g. When the specific surface area is smaller than the lower limit, the transparency decreases due to light scattering. On the other hand, if the specific surface area is larger than the upper limit, the surface free energy increases and aggregation tends to occur, so that the uniformity of the film decreases. The specific surface area can be determined by a general BET method.

  As an average particle diameter of an inorganic particle, 1-60 nm is preferable and 1-40 nm is more preferable. The average particle diameter can be measured as an effective diameter by a dynamic light scattering method.

  The solvent (c) used in the present invention is different depending on the structure of the hydroxyamide polymer (a), and examples thereof include ketone solvents, ether solvents, ester solvents and aprotic polar solvents. Examples of the solvent include cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-cyclohexanone, 3,3,5-trimethylcyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, propylene carbonate, diacetone alcohol and γ-butyrolactone; ether solvents Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene group Cole 1-mono-n-butyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether and the like; as ester solvents, propylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, Butyl lactate, methyl-1,3-butylene glycol acetate, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc .; as aprotic polar solvents, N-methyl-2-pyrrolidone, N, N- Dimethylacetamide, dimethyl sulfoxide, etc .; These may be used alone or in combination of two or more. Among these, depending on the structure of the hydroxyamide polymer, a mixture of a solvent other than N-methyl-2-pyrrolidone and the above N-methyl-2-pyrrolidone, a mixture of a solvent other than cyclopentanone and the above cyclopentanone A mixture of cyclohexanone and a solvent other than cyclohexanone can be preferably used.

  In the composition for optical parts of the present invention, the mixing ratio of the hydroxyamide polymer (a), the inorganic particles (b) and the solvent (c) varies depending on the purpose of use of the optical parts, but the inorganic particles (b) The hydroxyamide polymer (a) is preferably 10 parts by mass to 200 parts by mass, and more preferably 50 parts by mass to 150 parts by mass with respect to 100 parts by mass. Although it can be used outside the above range, when the inorganic particles (b) exceed 200 parts by mass, the viscosity increases and a uniform film may not be obtained. On the other hand, if the amount is less than 10 parts by mass, the refractive index does not increase and good optical properties may not be obtained.

  Moreover, 400 mass parts-3000 mass parts are preferable with respect to 100 mass parts of said hydroxyamide polymers (a), and, as for a solvent (c), 900 mass parts-2000 mass parts are more preferable. Although it can be used outside the above range, if the solvent (c) exceeds 3000 parts by mass, a sufficient film thickness may not be obtained. On the other hand, when the amount is less than 400 parts by mass, the solution viscosity of the composition increases, and a uniform film may not be obtained.

The composition for an optical component of the present invention includes, as components other than (a), inorganic particles (b) and solvent (c), a surface treatment agent, a dispersant, a surfactant, a coupling agent represented by a silane system, Additives such as radical initiators that generate oxygen radicals or sulfur radicals by heating can be added. Moreover, it can be used as a photosensitive resin composition by using the hydroxyamide polymer together with, for example, a naphthoquinonediazide compound as a photosensitive agent.
Examples of the surface treatment agent include a silane coupling agent and a chelating agent. Examples of the dispersant include fatty acids such as glycerin, stearic acid, and oleic acid, sodium alkylsulfosuccinate, sodium alkylmetaphosphate, polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polyester, polyether, and polyurethane. .

The composition for optical components of the present invention can be obtained by mixing the hydroxyamide polymer (a) obtained above, the inorganic particles (b), the solvent (c), and additives as required.
In mixing the composition, it is preferable to prepare a dispersion in which inorganic particles (b) and a solvent (c) are mixed in advance and inorganic particles are dispersed in the solvent.

  As a method for uniformly dispersing these inorganic particles in a solvent, for example, a solvent, inorganic particles, and a surface treatment agent or a dispersant as necessary are mixed, and a high-frequency ultrasonic homogenizer or micro beads are used. By the bead mill treatment, a dispersion liquid in which inorganic particles are uniformly dispersed can be obtained.

In the present invention, an optical component can be obtained using the composition for optical components. As an example of production when the optical component is in the form of a film, for example, a composition for optical component is produced using the hydroxyamide polymer (a), inorganic particles (b) and solvent (c) obtained above. Then, this composition for optical components is applied to an appropriate support such as a silicon wafer or a ceramic substrate to form a coating film. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Thereafter, the coating film obtained above is heated, for example, preferably in an inert gas atmosphere such as nitrogen gas or argon gas at a temperature of 40 ° C. or higher and 425 ° C. or lower to remove the solvent, and subsequently 300 ° C. Above, at a temperature of 425 ° C. or less, by heating and / or irradiating active energy rays at a temperature of 300 ° C. or more and 425 ° C. or less, the hydroxyamide polymer in the optical component composition is subjected to a condensation reaction, A film can be formed as a benzoxazole polymer and used as an optical component.
As the active energy ray, for example, an electron beam, a light beam having an arbitrary wavelength from the ultraviolet region to the infrared region can be used.

  Thus, the composition for optical components that can be used for the film for optical components is a film obtained by heating a coating film formed by coating in the same manner as described above at 380 ° C. for 250 seconds, at a wavelength of 380 nm. The light attenuation coefficient in the film is preferably 0 or more and 0.01 or less. The attenuation coefficient means that the smaller the numerical value, the smaller the light absorption in the film. The smaller the attenuation coefficient, the better the transparency, and the better the transparency of the film. The attenuation coefficient can be used even outside the above range, but if it exceeds 0.01, it means that light is absorbed and attenuated in the film, which may be unpreferable depending on the intended use. Preferably, it should be close to 0, 0.008 or less, more preferably 0.005 or less.

  The attenuation coefficient is determined by n & k Technology Inc. The spectroscopic ellipsometer can be measured by an n & k analyzer made by the company or a commercially available spectroscopic ellipsometer. A. Woollam Co. Inc. It can be measured with a spectroscopic ellipsometer. For the measurement of the attenuation coefficient, the value of the wavelength at 380 nm is used. For example, a film obtained by heat-treating a coating film produced by spin coating on a silicon substrate at 380 ° C. for 250 seconds in a nitrogen gas atmosphere is obtained from n & k Technology Inc. Reflectance measurement is performed using an n & k analyzer 1500 manufactured by the company, and an attenuation coefficient at a wavelength of 380 nm can be obtained.

The composition for optical components of the present invention has a hydroxyamide polymer content so that the thickness of the coating film formed under specific conditions is 500 nm and the solution viscosity of the composition is in the following range. It is preferable in terms of film formability to adjust.
The solution viscosity is preferably 3 mPas or more and 11 mPas or less when measured at 25 ° C., more preferably 4 mPas or more and 10 mPas or less, and further preferably 4 mPas or more and 8 mPas or less. Although the solution viscosity can be used outside the above range, if it is lower than the lower limit, there is a high possibility that a relatively low molecular component in the hydroxyamide polymer is contained in a large amount, which may cause a decrease in heat resistance typified by outgas. There is. On the other hand, if the upper limit is exceeded, the wettability to the underlying substrate is lowered, and there is a possibility that the margin during film formation or the film thickness uniformity is lowered.

  As an evaluation method for adjusting the content of the hydroxyamide polymer in the solution viscosity, a composition obtained by dissolving the hydroxyamide polymer obtained above in N-methyl-2-pyrrolidone as a standard solvent is used. The film thickness after forming the coating film on the support at 1400 rpm under an atmosphere of 23 ° C./humidity of 45% and heating the coating film at 380 ° C. for 250 seconds is 500 nm. Thus, the content of the hydroxyamide polymer is adjusted.

  The solution viscosity can be measured with a commercially available E-type viscometer or B-type viscometer, and is used after being calibrated with a standard solution manufactured as a standard substance for calibrating a viscometer standardized by JIS Z 8809. For example, as an E type viscometer, TVE-20L: manufactured by Toki Sangyo Co., Ltd., and as a standard solution, a standard solution JS10 for viscometer calibration manufactured by Toki Sangyo Co., Ltd. can be exemplified.

  Moreover, the composition for optical components has a contact angle with respect to the SiOx film of the composition for optical components when a coating film is formed by coating the surface of the SiOx film formed by the plasma CVD method in the same manner as described above. It is preferably 0 ° or more and 10 ° or less. In the above range, it is better to be close to 0 °, preferably 8 ° or less, more preferably 5 ° or less. The contact angle can be used outside the above range, but if the upper limit is exceeded, the wettability with the substrate surface is poor and the film-forming property is deteriorated. There is a possibility that a problem such as narrowing of the margin occurs.

  The contact angle can be obtained by a general θ / 2 method. Specifically, the droplet of the composition for optical elements is dropped on the substrate, and the contact angle is obtained by doubling the angle connecting the left and right end points and the vertex with the line connecting the left and right end points of the droplet. And As a measuring apparatus, it can measure using the Kyowa Interface Science Co., Ltd. product CA-X type contact angle measuring apparatus, for example.

  The optical component of the present invention is obtained using the composition for optical components. Examples thereof include an optical lens, an optical filter, an optical switch, an optical waveguide, an optical fiber, and a condensing lens.

An example of the structure of an optical waveguide that is one of the optical components of the present invention is not particularly limited, but is described in JP-A-08-139300.
For example, as shown in FIG. 1, an inorganic film (2) typified by a SiOx film is formed as a cladding layer on a semiconductor substrate (1) by a plasma CVD method, and processed into a concave shape as a core by a photoresist method. To do. Then, using the composition for optical components of the present invention, a coating film is formed on the surface of the inorganic film having the concave shape as described above. Examples of the coating method include spin coating with a spinner, spray coating with a spray coater, dipping, printing, roll coating, and the like. Thereafter, the coating film obtained above is pre-baked at a predetermined temperature, and then irradiated with heating and / or active energy rays to form the optical waveguide portion (3).
Next, unnecessary portions are removed by etching or the like as necessary. At this time, patterning may be performed using a resist or the like. Thereafter, an inorganic waveguide (4) typified by a SiOx film is formed on the upper portion by plasma CVD to produce an optical waveguide.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.

Production Example 1
Production of 5-ethynylisophthalic acid dichloride (1) Synthesis of dimethyl 5-trifluoromethanesulfonyloxyisophthalate To a four-necked 5 L flask equipped with a thermometer, a Dimro condenser, a calcium chloride tube, and a stirrer, 190.0 g (0.904 mol) of dimethyl hydroxyisophthalate, 3 L of dehydrated toluene and 214.7 g (2.718 mol) of dehydrated pyridine were charged and cooled to −30 ° C. with stirring. Here, 50.2 g (1.808 mol) of trifluoromethanesulfonic anhydride was slowly added dropwise while taking care not to increase the temperature to -25 ° C or higher. In this case, it took 1 hour to complete the dropping. After completion of the dropwise addition, the reaction temperature was raised to 0 ° C. for 1 hour, and further raised to room temperature and reacted for 5 hours. The obtained reaction mixture was poured into 4 L of ice water, and the aqueous layer and the organic layer were separated. Further, the aqueous layer was extracted twice with 500 mL of toluene, and this was combined with the previous organic layer. This organic layer was washed twice with 3 L of water, dried over 100 g of anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, distilled off toluene with a rotary evaporator, and dried under reduced pressure to give a pale yellow solid of 5-trifluoromethane. 294.0 g of dimethyl sulfonoxyisophthalate was obtained (yield 95%). The crude product was recrystallized from hexane to obtain white needle crystals, which were used for the next reaction.

(2) Synthesis of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol Four-neck equipped with thermometer, Dimroth condenser, nitrogen inlet, and stirrer Into a 1 L flask, 125 g (0.365 mol) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate obtained in the above (1), 1.1 g (0.000041 mol) of triphenylphosphine, 0.275 g of copper iodide (0 .00144 mol) and 33.73 g (0.401 mol) of 3-methyl-1-butyn-3-ol were charged and nitrogen was allowed to flow. 375 mL of dehydrated triethylamine and 200 mL of dehydrated pyridine were added and dissolved by stirring. After continuing to flow nitrogen for 1 hour, 0.3 g (0.00427 mol) of dichlorobis (triphenylphosphine) palladium was quickly added, and the mixture was heated to reflux for 1 hour in an oil bath. Thereafter, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 mL of water, and the precipitated solid was collected by filtration, and further washed twice with 500 mL of water, 500 mL of 5 mol / L hydrochloric acid, and 500 mL of water. The solid was dried under reduced pressure at 50 ° C. to obtain 98.8 g of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol (yield) 98%).

(3) Synthesis of 5-Ethynylisophthalic Acid Dipotassium Salt Into a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 3 L of n-butanol and 182 g of potassium hydroxide (85%) (2.763 mol) ) And heated to reflux to dissolve. To this, 95 g (0.344 mol) of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol synthesized in the above (2) was added and heated under reflux for 30 minutes. did. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 L of ethanol and dried under reduced pressure at 60 ° C. to obtain 88.87 g of dipotassium 5-ethynylisophthalate (yield 97%).

(4) Synthesis of 5-ethynylisophthalic acid dichloride Into a 2 L 4-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 80 g of dipotassium 5-ethynylisophthalic acid obtained in (3) above (0 .3 mol) and 400 L of chloroform were charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Thereafter, 4 mL of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred at 45 to 50 ° C. for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 150 mL of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted twice with 200 mL of diethyl ether and then filtered. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semisolid crude product. This was washed with dry n-hexane and subsequently recrystallized with diethyl ether to obtain 13 g of 5-ethynylisophthalic acid dichloride (yield 19%).

Production Example 2
Preparation of 5-phenylethynylisophthalic acid dichloride (1) Synthesis of 5-bromoisophthalic acid 99.18 g (0.55 mol) of 5-aminoisophthalic acid was added to a 4-neck 1 L flask equipped with a thermometer, stirrer and dropping funnel. ) And 165 mL of 48 wt% hydrobromic acid and 150 mL of distilled water were added and stirred. The flask was cooled to 5 ° C. or less, and 39.4 g (0.57 mol) of sodium nitrite dissolved in 525 mL of distilled water was added dropwise over 1 hour to obtain a diazonium salt aqueous solution. 94.25 g (0.66 mol) of cuprous bromide and 45 mL of 48 wt% hydrobromic acid were placed in a 4 L 3 L flask equipped with a thermometer, a Dimroth condenser, a dropping funnel and a stirrer and stirred. . The flask was cooled to 0 ° C. or lower, and the diazonium salt aqueous solution was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 30 minutes. After allowing to cool, the precipitate was collected by filtration, washed twice with 2 L of distilled water, and the obtained white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 117 g of a crude product of 5-bromoisophthalic acid. Used in the next reaction without purification.

(2) Synthesis of dimethyl 5-bromoisophthalate Into a 500 mL flask equipped with a thermometer, a stirrer, and a Dimroth condenser, 110 g of 5-bromoisophthalic acid obtained in (1) above, 500 mL of methanol, and 10 g of concentrated sulfuric acid were placed. And refluxed for 6 hours. After standing to cool, it was added dropwise to 1 L of distilled water and neutralized with a 5 wt% aqueous sodium hydrogen carbonate solution. The precipitate was separated by filtration and washed twice with 2 L of distilled water, and then the resulting white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 109 g (0.4 mol) of dimethyl 5-bromoisophthalate (yield). 89%).

(3) Synthesis of 5-phenylethynylisophthalic acid dichloride In Production Example 1 (2), 125 g (0.365 mol) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate was converted to 5-bromoisophthalic acid obtained in (2) above. 80.8 g of 1- [3,5-bis (methoxycarbonyl) phenyl] -2-phenylethyne was obtained in the same manner as in Production Example 1 (2) except that 99.7 g (0.365 mol) of dimethyl acid was used. (Yield 75%).
Thereafter, in the same manner as in Production Examples 1 (3) and (4), 5- (2-phenylethynyl) isophthalic acid dipotassium salt was obtained, and then 5- (2-phenylethynyl) isophthalic acid dichloride was obtained.

Production Example 3
Synthesis of 3,3′-thiobisbenzoic acid dichloride (1) Synthesis of 3,3′-thiobisbenzoic acid Into a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 3-iodobenzoic acid 49 .6 g (0.200 mol), potassium carbonate 13.8 g (0.100 mol) and N, N-dimethylformamide 200 mL were added and dissolved at 100 ° C. under a nitrogen gas flow, and then sodium sulfide 8.6 g (0 .110 mol) and 3.8 g (0.020 mol) of copper iodide were added and refluxed for 12 hours. 1 L of water and 20 g of activated carbon were added to the reaction solution and heated at 100 ° C. for 1 hour. The activated carbon was removed by filtration, and the reaction solution was neutralized by adding dropwise 100 mL of 6 mol / L hydrochloric acid, and the precipitate was collected and washed twice with 1 L of distilled water. The obtained precipitate was vacuum-dried at 60 ° C. for 12 hours to obtain 11.52 g of 3,3′-thiobisbenzoic acid. (Yield 42%)

(2) Synthesis of 3,3′-thiobisbenzoic acid dichloride 3,3′-thiobisbenzoic acid obtained in (1) above was added to a 300 mL four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer. 10.97 g (0.04 mol), 0.08 g (0.0004 mol) of benzyltriethylammonium chloride and 50 g (0.42 mol) of thionyl chloride were added and refluxed for 3 hours. Thionyl chloride was distilled off at 100 ° C., and the residue was vacuum-dried at 60 ° C. for 12 hours to obtain 11.8 g of 3,3′-thiobisbenzoic acid dichloride. (Yield 95%)

Production Example 4
Preparation of titanium oxide particle methyl ethyl ketone dispersion Titanium oxide particles (SSP-20, Sakai Chemical Industry Co., Ltd., specific surface area 170 m ² / g) 20 parts by mass, methyl ethyl ketone 78 parts by mass and polypropylene glycol 2 parts by mass are mixed and pulverized. -Bead mill dispersion treatment was performed using a disperser (Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.) to obtain a titanium oxide particle methyl ethyl ketone dispersion.

Production Example 5
Preparation of titanium oxide particle methyl ethyl ketone dispersion Titanium oxide particles (TTO-55 (B) manufactured by Ishihara Sangyo Co., Ltd., specific surface area 35 m ² / g) 20 parts by mass, methyl ethyl ketone 78 parts by mass and polypropylene glycol 2 parts by mass were mixed, Using a fine pulverizer / disperser (Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.), bead mill dispersion treatment was performed to obtain a titanium oxide particle methyl ethyl ketone dispersion.

Production Example 6
Preparation of Zirconium Oxide Particles Methyl Ethyl Ketone Dispersion Solution Zirconium oxide particles (UEP-100 manufactured by Nippon Rare Element Chemical Industry Co., Ltd., specific surface area 90 m ² / g) 20 parts by mass, methyl ethyl ketone 78 parts by mass and polypropylene glycol 2 parts by mass Using a fine grinding / dispersing machine (Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.), bead mill dispersion treatment was performed to obtain a zirconium oxide particle methyl ethyl ketone dispersion.

Production Example 7
Instead of the titanium oxide particles used in Production Example 3, titanium oxide particles (Super Titania F-10 manufactured by Showa Denko KK, specific surface area 9 m ² / g) were used in the same manner as in Production Example 3, A titanium oxide particle methyl ethyl ketone dispersion was obtained.

Production Example 8
In the same manner as in Production Example 3, except that titanium oxide particles (SSP-25 manufactured by Sakai Chemical Industry Co., Ltd., specific surface area 270 m ² / g) were used instead of the titanium oxide particles used in Production Example 3, oxidation was performed. A titanium particle methyl ethyl ketone dispersion was obtained.

Example 1
[Synthesis of hydroxyamide polymer]
Under a nitrogen gas flow, 32.3 g (0.08 mol) of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene was dissolved in 400 g of dried N-methyl-2-pyrrolidone, and the temperature was changed to 0 to 10 ° C. 4,4'-oxybisbenzoic acid chloride 29.5 g (0.1 mol) was added in small portions. After stirring at 0 to 10 ° C. for 3 hours, the mixture was returned to room temperature and stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped in 4 liters of 50% aqueous methanol solution in small droplets, the precipitate was collected, and further repeated 3 times in 4 liters of 50% aqueous methanol solution. Thereafter, the precipitate was dried to obtain a hydroxyamide polymer. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated by the following methods.

(1) Weight average molecular weight in terms of standard polystyrene As a high-performance liquid chromatograph SC-8020 system manufactured by Tosoh Corporation, a TSKgelGMH-HRH high-speed SEC column, LiBr 0.5% N-methyl-2-pyrrolidone mobile phase, UV (Λ = 270 nm) Measurement was performed using a detector, and the weight average molecular weight was determined by conversion using standard polystyrene (PS-oligomer kit manufactured by Tosoh Corporation).

(2) Solution viscosity After dissolving 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 3, and 9.0 g of cyclohexanone in a glass sample bottle, the pore size was 0. The mixture was filtered through a 5 μm Teflon (registered trademark) filter to obtain a composition. The coating film was formed on a support with a spin coater (rotation speed 1400 rpm) in an atmosphere of 23 ° C./humidity 45%, and the coating film was further heated at 380 ° C./250 seconds. Was confirmed to be 500 nm. Next, the composition used in this measurement was precisely weighed in a glass sample container with a lid, and 1.1 ml was measured after dissolution to prepare a sample. The viscometer was an E-type viscometer TVE-20L: manufactured by Toki Sangyo Co., Ltd., measured at 25.0 ° C. using a cone rotor 1 ° 34 ′ × R24, and a cone rotor rotation speed: 50 rpm. Each measurement was performed three times, and the average value was calculated.

[Production of composition and film]
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Using the composition, a coating film is formed on a silicon substrate by spin coating, and the coating film is dried by heating at 200 ° C./90 seconds in an N ² gas atmosphere, and further, 380 ° C./250 seconds. Heat treatment was performed to obtain a film.
Using each of the composition and film obtained above, the contact angle, glass transition temperature, adhesion, and film quality uniformity were evaluated by the measurement methods shown below. Each characteristic is shown in Table 1.

(3) Contact angle The composition obtained above is put into a glass sample container with a lid, and after dissolution, using a CA-X contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. 1 μl was measured, and the contact angle 5 seconds after dropping onto the substrate with the SiOx film was measured by the θ / 2 method. Each measurement was performed three times, and the average value was calculated.

(4) Glass transition temperature About the powder obtained by scraping off the film obtained above, the flow rate of N ² gas was 30 mL / min by MDSC (temperature cycle mode differential operation calorimeter: 2910 MDSC manufactured by TA Instruments). Measured in the temperature range from 40 ° C to 420 ° C while raising the temperature at a rate of temperature rise of 2 ° C / min and a temperature amplitude of ± 2 ° C / min, and calculating from the transition point of the reverse curve It was.

(5) Adhesion The film manufacturing process, as the silicon substrate, except for using SiOx film-coated silicon substrate in the same manner, to produce a film, further SiOx was 100nm film forming the upper layer, N ² gas atmosphere at The film annealed at 400 ° C. for 3 hours was subjected to a tape adhesion test according to JIS K-5400, and evaluated by the number of peeled off (numerator) in 100 squares (denominator).

(6) Uniformity of film quality In the film preparation step, a coating film prepared by spin-coating the composition obtained above on a silicon wafer having a diameter of 200 mm at 1400 rpm as a silicon substrate at 380 ° C. in an N ² gas atmosphere. Heat treatment for 250 seconds, and 19 points (total 37 points) at 10 mm intervals on the XY axis in the wafer surface are both n & k Technology Inc. It measured using the company made n & k analyzer 1500, the refractive index calculated the average value, and the film thickness calculated the variation degree from 3 sigma.

[Evaluation of optical components]
As the optical component, a substrate having a SiOx film (inorganic film (2)) having a recess formed on a silicon substrate (semiconductor substrate (1)) as shown in FIG. 1 is prepared, and a coating film is formed in the recess. However, the evaluation as the optical component was simplified by evaluating the coating film obtained above.
Using the composition obtained above, a coating film is formed by spin coating so as to embed a recess on the silicon substrate, and the coating film is heated at 200 ° C. for 90 seconds in an N ² gas atmosphere. The film was dried and further heat-treated at 380 ° C./250 seconds to obtain a film.
Using the film obtained above, the refractive index and the attenuation coefficient were evaluated by the measurement methods shown below. Each characteristic is shown in Table 2.

(9) Refractive index and attenuation coefficient Using the film obtained above, n & k Technology Inc. The reflectance was measured using an n & k analyzer 1500 manufactured by the company, the reflectance in the wavelength range of 190 nm to 1000 nm was curve fitted, and the calculated refractive index of 633 nm and attenuation coefficient of 380 nm were used.

Example 2
In the synthesis of the hydroxyamide polymer of Example 1, 3,3′-thiobisbenzoic acid dichloride obtained in Production Example 3 instead of 29.5 g (0.1 mol) of 4,4′-oxybisbenzoic acid chloride 31. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 1 g (0.1 mol) was used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Example 3
In the synthesis of the hydroxyamide polymer of Example 1, 26.1 g (0.1 mol) of 1,3-adamantane dicarboxylic acid dichloride was used instead of 29.5 g (0.1 mol) of 4,4′-oxybisbenzoic acid chloride. A hydroxyamide polymer was obtained in the same manner as Example 1 except that it was used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Example 4
In the synthesis of the hydroxyamide polymer of Example 1, instead of 29.5 g (0.1 mol) of 4,4′-oxybisbenzoic acid chloride, 44.3 g of 9,9-bis (4-carboxyphenyl) fluorine chloride ( A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 0.1 mol) was used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Example 5
In the synthesis of the hydroxyamide polymer of Example 1, 11.4 g (0 of 5-ethynylisophthalic acid dichloride obtained in Production Example 1 was used instead of 29.5 g (0.1 mol) of 4,4′-oxybisbenzoic acid chloride. 0.05 mol) and 4,4′-oxybisbenzoic acid chloride 14.8 g (0.05 mol) were used in the same manner as in Example 1 to obtain a hydroxyamide polymer. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Example 6
In the synthesis of the hydroxyamide polymer of Example 1, in place of 29.5 g (0.1 mol) of 4,4′-oxybisbenzoic acid chloride, 15.2 g of 5-phenylethynylisophthalic acid dichloride obtained in Production Example 2 ( A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 0.05 mol) and 14.8 g (0.05 mol) of 4,4′-oxybisbenzoic acid chloride were used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Example 7
In the synthesis of the hydroxyamide polymer of Example 1, 3,3′-diamino-4,4 instead of 32.3 g (0.08 mol) of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene Using 18.6 g (0.08 mol) of '-dihydroxydiphenyl ether, 5-ethynylisophthalic acid dichloride obtained in Preparation Example 1 was used instead of 29.5 g (0.1 mol) of 4,4'-oxybisbenzoic acid chloride. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 4 g (0.05 mol) and 4,4′-oxybisbenzoic acid chloride 14.8 g (0.05 mol) were used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Example 8
In the synthesis of the hydroxyamide polymer of Example 1, 3,3′-diamino-4,4 instead of 32.3 g (0.08 mol) of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene Using 22.4 g (0.08 mol) of '-dihydroxydiphenylsulfone, 5-phenylethynylisophthalic acid dichloride obtained in Preparation Example 2 was used instead of 29.5 g (0.1 mol) of 4,4'-oxybisbenzoic acid chloride. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 15.2 g (0.05 mol) and 4,4′-oxybisbenzoic acid chloride 14.8 g (0.05 mol) were used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Examples 9-16
In preparing the compositions of Examples 1 to 8, in place of 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4, 5.0 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 5 was used. Were obtained in the same manner as in Examples 1 to 8, respectively. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Examples 17-24
In the preparation of the compositions of Examples 1 to 8, except that 2.5 g of the zirconium oxide particle methyl ethyl ketone dispersion obtained in Production Example 6 was used instead of 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4. Were obtained in the same manner as in Examples 1 to 8, respectively. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Comparative Example 1
In preparing the composition of Example 1, a composition was obtained in the same manner as in Example 1 except that 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 was not used. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Comparative Example 2
In the preparation of the composition of Example 1, instead of 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 7 was used. A composition was obtained in the same manner as in Example 1. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Comparative Example 3
In preparing the composition of Example 1, in place of 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 8 was used. A composition was obtained in the same manner as in Example 1. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Comparative Example 4
In the synthesis of the hydroxyamide polymer of Example 1, 2,2-bis (3-amino-) instead of 32.3 g (0.08 mol) of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 29.3 g (0.08 mol) of 4-hydroxyphenyl) hexafluoropropane was used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 2.5 g of the titanium oxide particle methyl ethyl ketone dispersion obtained in Production Example 4 and 9.0 g of cyclohexanone were dissolved and mixed in a glass sample bottle, a 0.5 μm pore size Teflon (registered) (Trademark) filter, and the composition was obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

Comparative Example 5
In the synthesis of the hydroxyamide polymer of Example 1, 2,2-bis (3-amino-) instead of 32.3 g (0.08 mol) of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 29.3 g (0.08 mol) of 4-hydroxyphenyl) hexafluoropropane was used. Using the obtained hydroxyamide polymer, the weight average molecular weight (Mw) and the solution viscosity were evaluated in the same manner as in Example 1.
After 1 g of this hydroxyamide polymer, 5.0 g of the zirconium oxide particle methyl ethyl ketone dispersion obtained in Production Example 6 and 9.0 g of cyclohexanone were mixed in a glass sample bottle to dissolve the hydroxyamide polymer, It filtered with the 0.5 micrometer pore diameter Teflon (trademark) filter, and obtained the composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 1 and 2.

  As is clear from the results summarized in Tables 1 and 2, the Examples showed a high refractive index of 1.7 or more, a low attenuation coefficient, and good optical characteristics. Moreover, good wettability was exhibited at a low contact angle, and properties such as adhesion and heat resistance were also excellent. On the other hand, in Comparative Example 1, since no inorganic particles were added, a sufficient refractive index was not obtained. In Comparative Example 2, the attenuation coefficient is increased due to the inorganic particles having a small specific surface area, and the film thickness uniformity is low, and satisfactory optical characteristics are not obtained. In Comparative Example 3, since the inorganic particles having a large specific surface area are aggregated in the composition, the attenuation coefficient is increased, the film thickness uniformity is low, and satisfactory optical characteristics are not obtained. In Comparative Examples 4 and 5, since the hydroxyamide polymer contains fluorine, the wettability is poor, the adhesion is deteriorated, and a sufficient refractive index is not obtained. It is clear that all of the above cannot be satisfied.

It is sectional drawing for demonstrating the structural example of the optical waveguide which is one of the optical components of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Inorganic film 3 on a semiconductor substrate Optical waveguide part 4 Upper inorganic film

Claims (9)

A composition for optical parts comprising a hydroxyamide polymer (a) represented by the general formula (A), inorganic particles (b) having a specific surface area of 30 to 200 m ² / g, and a solvent (c).

[In the formula (A), X represents a group selected from the groups represented by the following formula (B), and the X in the two repeating units may be the same or different. Y ¹ represents a group selected from the groups represented by the following formulas (C) and (D). Y ² represents a group selected from the groups represented by the following formula (E) and formula (F). l and m represent an integer of 1 or more, m is an integer of 0 or more, and 1 + m is an integer of 4 or more. In addition, the arrangement of the repeating units in the formula (A) may be either block or random. ]

[X _{1 in} Formula (B) and Formula (C) represents the following formula (G)

In the formula (E), R represents a group selected from an aryl group or a group represented by an alkyl group having 1 to 10 carbon atoms. P in the formula (D) represents an integer of 1 or more and 4 or less.
Moreover, the hydrogen atom on the ring structure in the group represented by Formula (B), Formula (C), Formula (D), Formula (E), Formula (F), and Formula (G) has 1 to 4 carbon atoms. The alkyl group may be substituted with at least one group selected from alkyl groups. ]   The composition for optical parts according to claim 1, wherein the hydroxyamide polymer (a) has a weight average molecular weight in terms of standard polystyrene of from 5,000 to 15,000.   The composition for optical components according to claim 1 or 2, wherein the inorganic particles (b) are titanium oxide or zirconium oxide, the surface of which may be coated. The said hydroxyamide polymer (a) is a composition for optical components of any one of Claims 1-3 represented by general formula (H).

[In the formula (H), X ′ represents a group selected from the groups represented by the following formula (I), and X ′ in two repeating units in the formula may be the same or different. Y ³ represents a group selected from the groups represented by the following formulas (J) and (K). Y ⁴ represents a group selected from the groups represented by the following formula (L). l ′ and m ′ are integers where l ′ is an integer of 4 or more, m ′ is an integer of 0 or more and l ′ + m ′ is an integer of 4 or more. In addition, the arrangement of the repeating units in the formula (H) may be either block or random. ]

[X _{2 in} Formula (I) and Formula (J) represents the following formula (M)

In the formula (L), R represents a group selected from an aryl group or a group represented by an alkyl group having 1 to 10 carbon atoms. P ′ in the formula (K) represents an integer of 1 or more and 4 or less.
Moreover, the hydrogen atom on the ring structure in the group represented by the formula (I), the formula (J), the formula (K), the formula (L), and the formula (M) is an alkyl group having 1 to 4 carbon atoms. It may be substituted with at least one group selected from ] The said hydroxyamide polymer is a composition for optical components of any one of Claims 1-4 represented by general formula (N).

[In formula (N), X ″ represents a group selected from the groups represented by the following formula (O), and two X ″ in the formula may be the same or different. Y ⁵ represents a group selected from the groups represented by the following formula (P). Y ⁶ represents a group selected from the groups represented by the following (Q). l ″ and m ″ indicate l ″ is an integer of 4 or more, m ″ is an integer of 0 or more, and l ″ + m ″ is an integer of 4 or more. In addition, the arrangement of the repeating units in the formula (N) may be either block or random. ]

[X _{3 in} Formula (O) and Formula (P) represents the following formula (R)

In the formula (Q), R represents a group selected from an aryl group or a group represented by an alkyl group having 1 to 10 carbon atoms. Moreover, the hydrogen atom on the ring structure in the group represented by Formula (O), Formula (P), Formula (Q), and Formula (R) is at least one selected from alkyl groups having 1 to 4 carbon atoms. It may be substituted with groups. ]   A contact angle between the composition and the SiOx film when the film is formed on the surface of the SiOx film formed by the plasma CVD method using the composition for optical parts is 0 ° or more and 10 ° or less. Item 6. The composition for optical components according to any one of Items 1 to 5.   In the composition for optical parts, a coating film is formed in an atmosphere at 23 ° C./humidity of 45% at a rotation speed of a spin coater of 1400 rpm, and the film is heated at 380 ° C./250 seconds to have an average thickness of 500 nm. The solution viscosity at 25 ° C. when the content of the hydroxyamide polymer is adjusted is 3 mPa · s or more and 11 mPa · s or less, The optical component according to claim 1. Composition.   An optical component obtained by forming a film using the composition for optical components according to claim 1 and subjecting the hydroxyamide polymer in the composition for optical components to a condensation reaction.   The optical component according to claim 8, wherein the optical component has a light attenuation coefficient of 0 or more and 0.01 or less at a wavelength of 380 nm.

Images