JP2009235385A - 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, adhesive characteristics, processability and the like, and to provide the optical components excellent in optical characteristics and heat resistance. <P>SOLUTION: The composition for the optical components comprises a hydroxyamide polymer represented by formula (A) [in formula (A), X represents a group selected from groups represented by following formula (B) (not shown) and two X's in the formula may be the same or different; Y represents at least one group selected from groups represented by following formula (C) (not shown), formula (D) (not shown), formula (E) (not shown)or formula (F) (not shown); Z represents a group selected from groups represented by formula (G) (not shown); m and n are 0 or an integer of ≥1 and m+n is an integer of ≥4; and the sequence of the recurring units in formula (A) is either of block-like and random-like], an alkoxysilane polymer represented by formula (I) and a solvent, wherein the hydroxyamide polymer has ≥5,000 but ≤15,000 weight-average molecular weight expressed in terms of standard polystyrene. <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. In general, inorganic materials are required to have high temperature heating in the manufacturing process and to improve properties as optical materials. 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.

  In addition, fluorinated polyimide and fluorinated polybenzoxazole have been widely studied (see, for example, Patent Documents 1 and 2) and applied as optical materials. However, fluorine is introduced into the structure. Therefore, there are cases where it is limited to the intended use, and a more reliable material is desired.

  In addition, as an optical material, a report has been made on polybenzoxazole having a bulky specific structure with favorable transmittance in the visible light region (see, for example, Patent Document 3). 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 limits its application. Or the wettability of the resin to the substrate is reduced, and there are problems such as limited use of the film-forming property to the base substrate, and the coating uniformity is reduced, and the margin is narrow for practical use. Or there is a problem that it is difficult.

In addition, in an optical waveguide as an optical component, a waveguide made of an inorganic oxide such as SiO (see, for example, Patent Document 4) is formed conformally from the film forming method. It is easily affected and requires a device such as a flattening process, which complicates the process. Further, when polyimide is used, the polyimide structure contains a carbonyl group, so that it may be affected by moisture absorption, and practical application is difficult. Moreover, although the report which uses the composite material of a polyimide or polybenzoxazole and an inorganic particle for an optical waveguide is made (for example, refer patent document 5 and 6), these disperse | distribute an inorganic particle in the solution of a polymer. It is necessary to control dispersibility. From the viewpoint of composition uniformity, problems such as control of characteristic distribution, haze, etc. easily occur, a margin at the time of use is narrow, and cannot be used.
In addition, regarding an integrated circuit device and a manufacturing method thereof (for example, refer to Patent Document 7), a report has been made of using a reaction product of organic polysilica and uncondensed polybenzoxazole as a dielectric composition. Here, it is used as a dielectric material for the back end of line (BEOL) part of an integrated circuit, and when used as an optical component, a silane compound can be introduced only into the polybenzoxazole terminal, and the amount of silica component is limited, Since the molecular weight of the polybenzoxazole resin needs to be adjusted and complicated, there is a problem that it is difficult to balance the characteristics and it is difficult to put it into practical use.

JP 2000-290374 A International Publication No. 2003/010223 Pamphlet Japanese Patent Laid-Open No. 11-322929 Japanese Patent Laid-Open No. 08-139300 JP 2006-222270 A JP 2007-63502 A Japanese Patent Laid-Open No. 10-135200

  Under such circumstances, the present invention provides a composition for optical components that is excellent in optical properties, heat resistance, adhesion properties, workability, and the like, and further provides an optical component that is excellent in optical properties and heat resistance. It is to provide.

  As a result of intensive studies to achieve the above object, the present inventors use a hydroxyamide polymer and an alkoxysilane polymer having a specific structure having a weight average molecular weight of 5000 or more and 15000 or less in terms of standard polystyrene. By expressing a uniform film-forming property, the silanol group produced by hydrolyzing the alkoxysilane polymer undergoes a condensation reaction to crosslink the siloxane, thereby converting it into a resin having high optical properties, heat resistance, and physical properties, Based on this finding, the present invention has been completed.

  That is, the present invention is achieved by the following means (1) to (7).

(1) A composition for optical parts comprising a hydroxyamide polymer represented by formula (A), an alkoxysilane polymer represented by formula (I) and a solvent, wherein the hydroxyamide polymer is converted into a standard polystyrene equivalent. A composition for optical parts, wherein the weight average molecular weight is 5000 or more and 15000 or less.

[In the formula (A), X represents a group selected from the groups represented by the following formula (B), and two X in the formula may be the same or different. Y represents at least one group selected from the groups represented by the following formula (C), formula (D), formula (E) and formula (F). Z represents a group selected from the groups represented by formula (G). m and n are 0 or an integer of 1 or more, and m + n 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 (G) represents Formula (H)

In formula (C) and formula (D), R represents a group selected from a phenyl group or an alkyl group. P in the formula (G) 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), Formula (G), and Formula (H) is It may be substituted with at least one group selected from alkyl groups having 1 to 4 carbon atoms and phenyl groups. ]

[R ₁ and R _{2 in} Formula (I) represent phenyl or a group selected from alkyl groups having 1 or 2 carbon atoms, and R ₁ and R ₂ may be the same or different. q ₁ , r ₁ , s ₁ , q ₂ , r ₂ , and s ₂ are integers of 0 or more, and q ₁ + r ₁ + s ₁ + q ₂ + r ₂ + s ₂ is an integer of 2 or more and 50 or less, and , Q ₁ + r ₁ + q ₂ + r ₂ represents an integer of 1 or more and 50 or less. Further, the arrangement of the repeating units in formula (I) may be either block-like or random. ]

(2) The composition for optical components according to item (1), wherein the hydroxyamide polymer represented by the formula (A) is a hydroxyamide polymer having a terminal group L represented by the formula (J). .

[In the formula (J), X, Y and Z are the same as X, Y and Z in the formula (A).
L is the following formula (K)

In the formula, R ₃ represents an alkyl group having 3 carbon atoms or a phenyl group. R ₄ and R ₅ represent a group selected from a phenyl group or an alkyl group having 1 or 2 carbon atoms, and R ₄ and R ₅ may be the same or different. v represents an integer of 1 or more and 4 or less.
t and u are integers of 0 or more and t + u is an integer of 4 or more. Further, the arrangement of the repeating units in formula (J) may be either block or random. ]

(3) The above-mentioned hydroxyamide polymer is polymerized by reacting a dicarboxylic acid compound and a diamine compound at a molar ratio in the range of 0.70 or more and 0.90 or less. The composition for optical parts as described in (2).
(4) When forming the surface of the SiOx film formed by the plasma CVD method using the composition for optical components, 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 item (3), wherein
(5) In the composition for optical components, a coating film was formed at 1400 rpm in a spin coater at an atmosphere of 23 ° C./humidity 45%, and the average thickness of the film heated at 380 ° C./250 seconds was For optical components according to (3) or (4), the solution viscosity at 25 ° C. when the content of the hydroxyamide polymer is adjusted to 500 nm is 7 mPas or more and 11 mPas or less. Composition.
(6) Forming a film using the composition for optical components according to any one of items (1) to (5), and a hydroxyamide portion of a hydroxyamide polymer in the composition for optical components And an optical component obtained by subjecting a silanol group produced by hydrolysis of an alkoxysilane polymer to a condensation reaction.
(7) The optical component according to (6), 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. An optical component obtained from the optical component composition is excellent in optical properties, heat resistance, adhesion properties, and the like, and an optical device including the optical component is excellent in optical properties and heat resistance. 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.

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

  The present invention is a composition for optical parts comprising a hydroxyamide polymer represented by formula (A), an alkoxysilane polymer represented by formula (I) and a solvent, wherein the hydroxyamide polymer is converted into standard polystyrene Is a composition for optical parts, wherein the weight average molecular weight is from 5,000 to 15,000. This provides an excellent composition for optical components that combines heat resistance, adhesion and processability expressed by a polyhydroxyamide polymer and optical properties expressed by an alkoxysilane polymer when used as an optical component. it can.

The hydroxyamide polymer represented by the formula (A) includes at least one bisaminophenol compound having a group selected from the groups represented by the formula (B), the formula (C), and the formula ( D) is a group selected from the groups represented by formula (E) and formula (F), and is a group that can be bonded to an adjacent carbonyl group and has a group other than the unsaturated hydrocarbon group. It can be obtained by reacting one or more compounds. Moreover, as said dicarboxylic acid compound, the said dicarboxylic acid compound and the dicarboxylic acid compound which has a group chosen from the group represented by Formula (G) can also be used together. As the reaction method, a conventional acid chloride method, an activated ester method, a condensation reaction in the presence of a dehydration condensing agent such as polyphosphoric acid or dicyclohexylcarbodiimide can be used.
In the bisaminophenol compound, the group represented by the formula (B) has four bonds that can bond to an amino group and a phenolic hydroxyl group. In the dicarboxylic acid compound, the groups represented by the formula (C), the formula (D), the formula (E), the formula (F), and the formula (G) have two bonds that can be bonded to a carboxyl group. Have one.

As the bisaminophenol compound having a group represented by the formula (B) used in the present invention, 2,4-diaminoresorcinol,
4,6-diaminoresorcinol,
2,2-bis (3-amino-4-hydroxyphenyl) propane,
2,2-bis (4-amino-3-hydroxyphenyl) propane,
3,3′-diamino-4,4′-dihydroxydiphenyl sulfone,
4,4′-diamino-3,3′-dihydroxydiphenyl sulfone,
3,3′-diamino-4,4′-dihydroxybiphenyl,
4,4′-diamino-3,3′-dihydroxybiphenyl,
2,2′-dihydroxy-3,3′-diamino-1,1′-binaphthyl,
9,9-bis (4-amino-3-hydroxyphenyl) fluorene,
9,9-bis (3-amino-4-hydroxyphenyl) fluorene,
9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene,
9,9-bis (4-((3-amino-4-hydroxy) phenoxy) phenyl) fluorene,
9,9-bis ((4-amino-3-hydroxy) phenyl)) fluorene,
9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene,
9,9-bis (4-((4-amino-3-hydroxy) phenoxy) -3-phenyl-phenyl) -fluorene,
9,9-bis (4-((3-amino-4-hydroxy) phenoxy) -3-phenyl-phenyl) -fluorene,
9,9-bis ((2-amino-3-hydroxy-4-phenyl) -phenyl) -fluorene,
9,9-bis ((2-hydroxy-3-amino-4-phenyl) -phenyl) -fluorene,
9,9-bis (4- (4-amino-3-hydroxyphenyl) sulfanylphenyl) fluorene,
9,9-bis (4- (3-amino-4-hydroxyphenyl) sulfanylphenyl) fluorene,
3,3′-diamino-4,4′-dihydroxydiphenyl ether,
4,4′-diamino-3,3′-dihydroxydiphenyl ether,
Etc. These may be used alone or in combination of two or more.

In the dicarboxylic acid compound having a group represented by the formulas (C) and (D) used in the present invention, R is a phenyl group or an alkyl group, and the alkyl group includes a methyl group, an ethynyl group, Examples include propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclohexyl group and adamantyl group.
As specific examples of such dicarboxylic acid compounds, examples of dicarboxylic acid compounds having a phenylethynyl group in which R is a phenyl group include 3-phenylethynylphthalic acid, 4-phenylethynylphthalic acid, and 2-phenylethynylisophthalic acid. 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-Naphtaliska Bonic acid, 2-phenylethynyl-1,6-naphthalenedicarboxylic acid, 3-phenylethynyl-1,6-naphthalenedicarboxylic acid, 4-phenylethynyl-1,6-naphthalenedicarboxylic acid, 5-phenylethynyl-1,6 Naphthalenedicarboxylic acid, 7-phenylethynyl-1,6-naphthalenedicarboxylic acid, 8-phenylethynyl-1,6-naphthalenedicarboxylic acid, 3,3′-diphenylethynyl-2,2′-biphenyldicarboxylic acid, 4, 4′-diphenylethynyl-2,2′-biphenyldicarboxylic acid, 5,5′-diphenylethynyl-2,2′-biphenyldicarboxylic acid, 6,6′-diphenylethynyl-2,2′-biphenyldicarboxylic acid, 2 , 2′-Diphenylethynyl-3,3′-biphenyldicarboxylic acid, 4,4′-diphenylethynyl -3,3'-biphenyldicarboxylic acid, 5,5'-diphenylethynyl-3,3'-biphenyldicarboxylic acid, 6,6'-diphenylethynyl-3,3'-biphenyldicarboxylic acid, 2,2'-diphenyl Ethynyl-4,4′-biphenyldicarboxylic acid, 3,3′-diphenylethynyl-4,4′-biphenyldicarboxylic acid, 2,2-bis (2-carboxy-3-phenylethynylphenyl) propane, 2,2- Bis (2-carboxy-4-phenylethynylphenyl) propane, 2,2-bis (2-carboxy-5-phenylethynylphenyl) propane, 2,2-bis (2-carboxy-6-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-2-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-4-phenyl) Nylethynylphenyl) propane, 2,2-bis (3-carboxy-5-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-6-phenylethynylphenyl) propane, 2,2-bis (4- Carboxy-2-phenylethynylphenyl) propane, 2,2-bis (4-carboxy-3-phenylethynylphenyl) propane, 4-phenylethynyl-1,3-dicarboxycyclopropane, 5-phenylethynyl-2,2 -Dicarboxycyclopropane, structural isomer of 1,3-bis (4-carboxy-phenoxy) -5-phenylethynyl-benzene, 1,3-bis (4-carboxy-phenyl) -5-phenylethynyl-benzene Structural isomers, 5- (1-phenylethynyl-phenoxy) -isophthalic acid, 5- ( -Phenylethynyl-phenoxy) -isophthalic acid, 5- (3-phenylethynyl-phenoxy) isophthalic acid, 2- (1-phenylethynyl-phenoxy) terephthalic acid, 2- (2-phenylethynyl-phenoxy) terephthalic acid, 2 -(3-phenylethynyl-phenoxy) terephthalic acid, 5- (1-phenylethynyl-phenyl) -isophthalic acid, 5- (2-phenylethynyl-phenyl) -isophthalic acid, 5- (3-phenylethynyl-phenyl) -Isophthalic acid, 2- (1-phenylethynyl-phenyl) -terephthalic acid, 2- (2-phenylethynyl-phenyl) -terephthalic acid, 2- (3-phenylethynyl-phenyl) -terephthalic acid and the like.

Examples of dicarboxylic acid compounds having an alkylethynyl group in which R is an alkyl group include 3-hexynylphthalic acid, 4-hexynylphthalic acid, 2-hexynylisophthalic acid, 4-hexynylisophthalic acid, 5- Hexynylisophthalic acid, 2-hexynylterephthalic acid, 3-hexynylterephthalic acid, 2-hexynyl-1,5-naphthalenedicarboxylic acid, 3-hexynyl-1,5-naphthalenedicarboxylic acid, 4- Hexynyl-1,5-naphthalenedicarboxylic acid, 1-hexynyl-2,6-naphthalenedicarboxylic acid, 3-hexynyl-2,6-naphthalenedicarboxylic acid, 4-hexynyl-2,6-naphthalenedicarboxylic acid, 2-hexynyl-1,6-naphthalenedicarboxylic acid, 3-hexynyl-1,6-naphthalenedicarboxylic acid, 4-hexoxy 1,6-naphthalenedicarboxylic acid, 5-hexynyl-1,6-naphthalenedicarboxylic acid, 7-hexynyl-1,6-naphthalenedicarboxylic acid, 8-hexynyl-1,6-naphthalenedicarboxylic acid, 3 3,3′-dihexynyl-2,2′-biphenyldicarboxylic acid, 4,4′-dihexynyl-2,2′-biphenyldicarboxylic acid, 5,5′-dihexynyl-2,2′-biphenyldicarboxylic acid 6,6′-dihexynyl-2,2′-biphenyldicarboxylic acid, 2,2′-dihexynyl-3,3′-biphenyldicarboxylic acid, 4,4′-dihexynyl-3,3 ′ -Biphenyldicarboxylic acid, 5,5'-dihexynyl-3,3'-biphenyldicarboxylic acid, 6,6'-dihexynyl-3,3'-biphenyldicarboxylic acid, 2,2'-dihexynyl- 4,4'-biphenyl Carboxylic acid, 3,3′-dihexynyl-4,4′-biphenyldicarboxylic acid, 2,2-bis (2-carboxy-3-hexynylphenyl) propane, 2,2-bis (2-carboxy- 4-hexynylphenyl) propane, 2,2-bis (2-carboxy-5-hexynylphenyl) propane, 2,2-bis (2-carboxy-6-hexynylphenyl) propane, 2,2 -Bis (3-carboxy-2-hexynylphenyl) propane, 2,2-bis (3-carboxy-4-hexynylphenyl) propane, 2,2-bis (3-carboxy-5-hexynyl) Phenyl) propane, 2,2-bis (3-carboxy-6-hexynylphenyl) propane, 2,2-bis (4-carboxy-2-hexynylphenyl) propane, 2,2-bis (4- Cal Xyl-3-hexynylphenyl) propane, 4-hexynyl-1,3-dicarboxycyclopropane, 5-hexynyl-2,2-dicarboxycyclopropane, 1,3-bis (4-carboxy-phenoxy) Structural isomer of -5-hexynyl-benzene, structural isomer of 1,3-bis (4-carboxy-phenyl) -5-hexynyl-benzene, 5- (3-hexynyl-phenoxy) -isophthalic acid, 5- ( 1-hexynyl-phenoxy) -isophthalic acid, 5- (2-hexynyl-phenoxy) isophthalic acid, 2- (1-hexynyl-phenoxy) terephthalic acid, 2- (2-hexynyl-phenoxy) terephthalic acid, 2- (3 -Hexynyl-phenoxy) terephthalic acid, 5- (1-hexynyl-phenyl) -isophthalic acid, 5- (2-hexynyl) -Phenyl) -isophthalic acid, 5- (3-hexynyl-phenyl) -isophthalic acid, 2- (1-hexynyl-phenyl) -terephthalic acid, 2- (2-hexynyl-phenyl) -terephthalic acid, 2- (3 -Hexynyl-phenyl) -terephthalic acid and the like, but are not limited thereto.
These may be used alone or in combination of two or more.

  Examples of dicarboxylic acid compounds having groups represented by formula (E) and formula (F) used in the present invention include 3-ethynylphthalic acid, 4-ethynylphthalic acid, 2-ethynylisophthalic acid, and 4-ethynyl. Isophthalic acid, 5-ethynylisophthalic acid, 2-ethynylterephthalic acid, 3-ethynylterephthalic acid, 5-ethynyl-terephthalic acid, 2-ethynyl-1,5-naphthalenedicarboxylic acid, 3-ethynyl-1,5-naphthalenedicarboxylic acid 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, 2-ethynyl-1,6-naphthalenedicarboxylic acid, 3-ethynyl-1,6-naphthalenedicarboxylic acid, 4-ethynyl 1,6-naphthalenedicarboxylic acid, 5-ethynyl-1,6-naphthalenedicarboxylic acid, 7-ethynyl-1,6-naphthalenedicarboxylic acid, 8-ethynyl-1,6-naphthalenedicarboxylic acid, 3,3 ′ -Diethynyl-2,2'-biphenyldicarboxylic acid, 4,4'-diethynyl-2,2'-biphenyldicarboxylic acid, 5,5'-diethynyl-2,2'-biphenyldicarboxylic acid, 6,6'-diethynyl -2,2'-biphenyldicarboxylic acid, 2,2'-diethynyl-3,3'-biphenyldicarboxylic acid, 4,4'-diethynyl-3,3'-biphenyldicarboxylic acid, 5,5'-diethynyl-3 , 3′-biphenyldicarboxylic acid, 6,6′-diethynyl-3,3′-biphenyldicarboxylic acid, 2,2′-diethynyl-4,4′-biphenyldi Rubonic acid, 3,3′-diethynyl-4,4′-biphenyldicarboxylic acid, 2,2-bis (2-carboxy-3-ethynylphenyl) propane, 2,2-bis (2-carboxy-4-ethynylphenyl) ) Propane, 2,2-bis (2-carboxy-5-ethynylphenyl) propane, 2,2-bis (2-carboxy-6-ethynylphenyl) propane, 2,2-bis (3-carboxy-2-ethynyl) Phenyl) propane, 2,2-bis (3-carboxy-4-ethynylphenyl) propane, 2,2-bis (3-carboxy-5-ethynylphenyl) propane, 2,2-bis (3-carboxy-6- Ethynylphenyl) propane, 2,2-bis (4-carboxy-2-ethynylphenyl) propane, 2,2-bis (4-carboxy-3-ethini) Phenyl) propane, 4-ethynyl-1,3-dicarboxycyclopropane, 5-ethynyl-2,2-dicarboxycyclopropane, 1,3-bis (4-carboxy-phenoxy) -5-ethynyl-benzene Isomers, structural isomers of 1,3-bis (4-carboxy-phenyl) -5-ethynyl-benzene, 5- (3-ethynyl-phenoxy) -isophthalic acid, 5- (1-ethynyl-phenoxy) -isophthalate Acid, 5- (2-ethynyl-phenoxy) isophthalic acid, 2- (1-ethynyl-phenoxy) terephthalic acid, 2- (2-ethynyl-phenoxy) terephthalic acid, 2- (3-ethynyl-phenoxy) terephthalic acid, 5- (1-ethynyl-phenyl) -isophthalic acid, 5- (2-ethynyl-phenyl) -isophthalic acid, 5- (3-ethini Ru-phenyl) -isophthalic acid, 2- (1-ethynyl-phenyl) -terephthalic acid, 2- (2-ethynyl-phenyl) -terephthalic acid, 2- (3-ethynyl-phenyl) -terephthalic acid and the like. However, it is not limited to these. These may be used alone or in combination of two or more.

As an example of the dicarboxylic acid compound having a group represented by the formula (G) used in the present invention,
Isophthalic acid, terephthalic acid,
4,4′-biphenyldicarboxylic acid,
3,4'-biphenyldicarboxylic acid,
3,3′-biphenyldicarboxylic acid,
1,4-naphthalenedicarboxylic acid,
2,3-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid,
4,4′-sulfonylbisbenzoic acid,
3,4′-sulfonylbisbenzoic acid,
3,3′-sulfonylbisbenzoic acid,
4,4′-oxybisbenzoic acid,
3,4′-oxybisbenzoic acid,
3,3′-oxybisbenzoic acid,
4,4′-thiobisbenzoic acid,
3,4'-thiobisbenzoic acid,
3,3′-thiobisbenzoic acid,
2,2-bis (4-carboxyphenyl) propane,
2,2-bis (3-carboxyphenyl) propane,
2,2′-dimethyl-4,4′-biphenyldicarboxylic acid,
3,3′-dimethyl-4,4′-biphenyldicarboxylic acid,
2,2′-dimethyl-3,3′-biphenyldicarboxylic acid,
Bis (4- (2-carboxyphenoxy) phenyl) benzene,
Bis (4- (3-carboxyphenoxy) phenyl) benzene,
Bis (4- (4-carboxyphenoxy) phenyl) benzene,
Bis (4- (2-carboxyphenyl) sulfanylphenyl) benzene,
Bis (4- (3-carboxyphenyl) sulfanylphenyl) benzene,
Bis (4- (4-carboxyphenyl) sulfanylphenyl) benzene,
9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene,
9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene,
4,4′-bis (4-carboxyphenoxy) biphenyl,
4,4′-bis (3-carboxyphenoxy) biphenyl,
3,4′-bis (4-carboxyphenoxy) biphenyl,
3,4'-bis (3-carboxyphenoxy) biphenyl,
3,3′-bis (4-carboxyphenoxy) biphenyl,
3,3′-bis (3-carboxyphenoxy) biphenyl,
4,4′-bis ((4-carboxyphenyl) sulfanylphenyl) biphenyl,
4,4′-bis ((3-carboxyphenyl) sulfanylphenyl) biphenyl,
3,4'-bis ((4-carboxyphenyl) sulfanylphenyl) biphenyl,
3,4'-bis ((3-carboxyphenyl) sulfanylphenyl) biphenyl,
3,3′-bis ((4-carboxyphenyl) sulfanylphenyl) biphenyl,
3,3′-bis ((3-carboxyphenyl) sulfanylphenyl) biphenyl 4,4′-bis (4-carboxyphenoxy) -p-terphenyl,
4,4′-bis (4-carboxyphenoxy) -m-terphenyl,
3,4'-bis (4-carboxyphenoxy) -p-terphenyl,
3,3′-bis (4-carboxyphenoxy) -p-terphenyl,
3,4'-bis (4-carboxyphenoxy) -m-terphenyl,
3,3′-bis (4-carboxyphenoxy) -m-terphenyl,
4,4′-bis (3-carboxyphenoxy) -p-terphenyl,
4,4′-bis (3-carboxyphenoxy) -m-terphenyl,
3,4'-bis (3-carboxyphenoxy) -p-terphenyl,
3,3′-bis (3-carboxyphenoxy) -p-terphenyl,
3,4'-bis (3-carboxyphenoxy) -m-terphenyl,
3,3′-bis (3-carboxyphenoxy) -m-terphenyl,
9,9-bis- (2-carboxy-phenyl) fluorene,
9,9-bis- (3-carboxy-phenyl) fluorene,
9,9-bis- (4-carboxy-phenyl) fluorene,
Bis-((2-carboxy-3-phenyl) -phenyl) -fluorene,
Bis-((4-carboxy-3-phenyl) -phenyl) -fluorene,
Bis-((5-carboxy-3-phenyl) -phenyl) -fluorene,
Bis-((6-carboxy-3-phenyl) -phenyl) -fluorene,
9,9-bis (4- (2-carboxy-phenoxy) -phenyl) -fluorene,
9,9-bis (4- (3-carboxy-phenoxy) -phenyl) -fluorene,
9,9-bis (4- (4-carboxy-phenoxy) -phenyl) -fluorene,
9,9-bis ((4- (2-carboxy-phenoxy) -3-phenyl) -phenyl) -fluorene,
9,9-bis ((4- (3-carboxy-phenoxy) -3-phenyl) -phenyl) -fluorene,
9,9-bis ((4- (4-carboxy-phenoxy) -3-phenyl) -phenyl) -fluorene,
9,9-bis (4- (2-carboxyphenyl) sulfanylphenyl) fluorene,
9,9-bis (4- (3-carboxyphenyl) sulfanylphenyl) fluorene,
9,9-bis (4- (4-carboxyphenyl) sulfanylphenyl) fluorene,
1,3-adamantane-dicarboxylic acid,
2,2-adamantane-dicarboxylic acid,
1,2-adamantane-dicarboxylic acid,
3,3 ′-(1,1′-biadamantane) -dicarboxylic acid,
3,5- (1,1′-biadamantane) -dicarboxylic acid,
2,2- (1,1′-biadamantane) -dicarboxylic acid,
2,2 ′-(1,1′-biadamantane) -dicarboxylic acid,
Examples include 2,5- (1,1′-biadamantane) -dicarboxylic acid, but are not limited thereto.
These 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. And may be substituted with at least one group selected from alkyl groups and phenyl groups. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group.

  As the method for producing the hydroxyamide polymer represented by the formula (A) used in the present invention, for example, in the acid chloride method, the acid chloride used is first in the presence of a catalyst such as N, N′-dimethylformamide. The dicarboxylic acid compound and an excess amount of thionyl chloride are reacted at a temperature of room temperature to about 130 ° C., the excess thionyl chloride is distilled off by heating and reduced pressure, and the residue is recrystallized with a solvent such as hexane. Can be obtained. 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.

  Further, as the bisaminophenol compound, at least one bisaminophenol compound having a group selected from the groups represented by the formula (B), and the dicarboxylic acid compound as a formula (C), a formula ( D), one or more dicarboxylic acids having a group selected from the groups represented by formula (E), formula (F) or formula (G). The arrangement of the repeating units of the hydroxyamide polymer thus obtained may be block-like or random.

  Furthermore, in the formula (A), the repeating unit obtained by using the dicarboxylic acid compound having the repeating unit having the unsaturated hydrocarbon group and the group represented by the formula (G) not having the unsaturated hydrocarbon group In the case of a copolymer having a unit, the arrangement of the repeating unit having the unsaturated hydrocarbon group and the repeating unit not having the unit may be blocky or random. For example, as a method for producing a block-like repeating unit, when an acid chloride method is used, a bisaminophenol compound having a group selected from groups represented by formula (B) and a group represented by formula (G) A dicarboxylic acid chloride compound having a group selected from the group consisting of a bisaminophenol compound having a group selected from the group represented by the formula (B) after reacting in advance and increasing the molecular weight; It can be obtained by reacting a dicarboxylic acid chloride compound having a group selected from the groups represented by (B), formula (C), formula (D), formula (E) and formula (F). .

  Conversely, a bisaminophenol compound having a group selected from the groups represented by formula (B), and formula (C), formula (D), formula (E), and formula (F). After reacting in advance with a dicarboxylic acid chloride compound having a group selected from the group to increase the molecular weight of the polymer, bisamino having a group selected from the group represented by formula (B) A phenol compound and a dicarboxylic acid chloride compound having a group selected from the groups represented by formula (G) may be reacted.

  In the case of a random repeating unit, a bisaminophenol compound having a group selected from groups represented by formula (B) and a dicarboxylic acid chloride having a group selected from groups represented by formula (G) By reacting a compound with a dicarboxylic acid chloride compound having a group selected from the groups represented by formula (C), formula (D), formula (E) and formula (F) Obtainable.

  In the hydroxyamide polymer obtained above, m and n in the structure represented by the formula (A) are integers of 0 or more and m + n is an integer of 4 or more, and bisamino used for the synthesis of the polymer Although it varies depending on the phenol compound and dicarboxylic acid compound, it is generally in the range of 1-50.

  The hydroxyamide polymer represented by the formula (A) has a standard polystyrene equivalent weight average molecular weight of 5,000 or more and 15000 or less, preferably 7000 or more and 15000 or less, more preferably 8000 or more and 12000 or less. If the molecular weight is smaller than the lower limit, heat resistance deteriorates during the process after film formation, causing gas generation problems. If the molecular weight is larger than the upper limit, solubility in a solvent is reduced, and the optical property of the present invention is also reduced. When the viscosity of the component composition increases, the wettability to the base substrate decreases during coating film formation, and is affected by the properties of the base material surface. A decrease in uniformity occurs.

  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 making the weight average molecular weight of standard polystyrene conversion of the hydroxyamide polymer represented by the formula (A) into the above range, for example, a reaction molar ratio of a dicarboxylic acid compound and the bisaminophenol compound To adjust the molecular weight, to adjust the molecular weight to an arbitrary molecular weight by using the carboxylic acid chloride compound or the aminophenol compound for the dicarboxylic acid chloride compound and the bisaminophenol compound to stop the reaction Etc. can be illustrated. The carboxylic acid chloride and aminophenol compound are used to terminate the reaction as a terminal and prevent the molecular weight from increasing further, and examples thereof include benzoic acid chloride and 2-aminophenol.

  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 differs depending on the structure of the compound, but it is preferably adjusted to 0.7 or more and 0.9 or less by making the number of moles of one compound excessive, for example, by making the number of moles of aminophenol compound excessive. 0.75 or more and 0.90 or less, 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.

  The hydroxyamide polymer represented by the formula (J) used in the present invention has a group represented by the following formula (K) as the terminal group L of the hydroxyamide polymer represented by the formula (A) obtained above. It is what you have. By having a group represented by the formula (K) having an alkoxysilyl group at the terminal of the hydroxyamide polymer, this is represented by a silanol group generated by hydrolysis or the like in the step of producing an optical component, and represented by the formula (I). The silanol group in the alkoxysilane polymer is preferable because it causes siloxane crosslinking and further improves heat resistance.

［式（Ｋ）中のＲ_３は、炭素数３のアルキル基又はフェニル基を示す。Ｒ_４及びＲ_５は、フェニル基又は、炭素数１又は２のアルキル基の中から選ばれ基を示し、Ｒ_４、Ｒ_５は同一でも異なっても良い。ｖは１以上４以下の整数を示す。］

[R ₃ in Formula (K) represents an alkyl group having 3 carbon atoms or a phenyl group. R ₄ and R ₅ represent a group selected from a phenyl group or an alkyl group having 1 or 2 carbon atoms, and R ₄ and R ₅ may be the same or different. v represents an integer of 1 or more and 4 or less. ]

  Examples of the group represented by the formula (K) include trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, methoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxyethylsilylpropyl group, ethoxysilyldiethylpropyl group, Examples include triphenoxysilylpropyl group, diphenoxyphenylsilylpropyl group, phenoxydiphenylpropyl group, diphenoxymethylsilylpropyl group, phenoxydimethylpropyl group, diphenoxyethylsilylpropyl group, and phenoxydiethylpropyl group. Among these, a trimethoxysilylpropyl group, a dimethoxymethylsilylpropyl group, a triethoxysilylpropyl group, a diethoxyethylsilylpropyl group, and the like are preferable for obtaining the above effects.

  In the hydroxyamide polymer represented by the formula (J), t and u in the structure represented by the formula (J) are integers of 0 or more and t + u is the same as m and n in the formula (A). Although it is an integer of 4 or more and varies depending on the bisaminophenol compound and dicarboxylic acid compound used, it is generally in the range of 1 to 50.

  As a method for producing the hydroxyamide polymer represented by the formula (J), the terminal of the hydroxyamide polymer represented by the formula (A) is sealed with an aminosilane compound having a group represented by the formula (K). It can be obtained by sealing with a stopper. As a specific example, in the production of a hydroxyamide polymer represented by the above formula (A), after reacting a dichanrubonic acid compound and a bisaminophenol compound, an end capping having a group represented by the above formula (K) is used. It can be obtained by reacting a stop material.

  Here, when the terminal of the polyhydroxyamide polymer represented by the formula (A) is a carboxylic acid chloride, the end-capping material includes an amino group that reacts with the end group and a group represented by the formula (K). An aminosilane compound having can be used. In this case, in the above reaction, the aminosilane compound is reacted by adjusting the reaction moles of the dicarboxylic acid compound and the bisaminophenol compound to an excessive amount of dicarboxylic acid. For example, as in the reaction in the polyhydroxyamide polymer represented by the above formula (A), the ratio of the reaction moles of the dicarboxylic acid compound and the bisaminophenol compound is set to the number of moles of the bisaminophenol compound relative to the dicarboxylic acid compound. And preferably adjusted to 0.7 or more and 0.9 or less, more preferably 0.75 or more and 0.90 or less, and further preferably 0.8 or more and 0.90 or less. An amide polymer is synthesized, the reaction is terminated as a carboxylic acid chloride terminal, and then an aminosilane compound as a terminal sealing material is reacted. At this time, the number of moles of the end-capping material relative to the dicarboxylic acid compound is preferably adjusted to 0.20 or more and 0.60 or less, more preferably 0.20 or more and 0.50 or less, and still more preferably, It is good to set it as 0.20 or more and 0.40 or less.

  Specific examples of the aminosilane compound having the group represented by the formula (K) as the terminal sealing material include trimethoxysilylpropylamine, triethoxysilylpropylamine, dimethoxymethylsilylpropylamine, diethoxyethylsilylpropylamine. , Trimethoxysilylphenylamine, triethoxysilylphenylamine, dimethoxymethylsilylphenylamine, diethoxyethylsilylphenylamine and the like.

  The hydroxyamide polymer represented by the formula (A) and the hydroxyamide polymer represented by the formula (J), which are hydroxyamide polymers used in the present invention, are heated to cause condensation reaction and crosslinking of the hydroxyamide group. A benzoxazole polymer can be obtained by causing a crosslinking reaction with a group.

The alkoxysilane polymer represented by the formula (I) used in the present invention is a group represented by a phenyl group or a group having 1 or 2 carbon atoms as R ₁ and R ₂ in the formula (I). It has the group chosen. In the formula (I), R ₁ and R ₂ may be the same or different, and q ₁ , r ₁ , s ₁ , q ₂ , r ₂ , and s ₂ are each an integer of 0 or more and q ₁ + r ₁ + s ₁ + q ₂ + r ₂ + s ₂ represents an integer of 2 or more and 50 or less, and q ₁ + r ₁ + q ₂ + r ₂ represents an integer of 1 or more and 50 or less. Further, the arrangement of the repeating units in formula (I) may be either block-like or random.
Examples of the phenyl group or the alkyl group having 1 or 2 carbon atoms as R ₁ and R ₂ in the formula (I) include phenyl, methyl group, and ethyl group.

Such an alkoxysilane polymer uses one, two, or three types of alkoxysilane compounds in a predetermined amount ratio, and a solution such as an alcohol, water, and an acid such as acetic acid, It can be obtained by hydrolysis, and further by condensation reaction of silanol groups generated by hydrolysis.
By using such an alkoxysilane polymer, silanol groups are condensed and siloxane crosslinking is carried out, so that the heat resistance is particularly improved in the optical component composition of the present invention.

  Examples of the alkoxysilane compound used for the synthesis of the alkoxysilane polymer include tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, trimethoxyphenylsilane, triethoxyphenylsilane, triphenoxyphenylsilane, trimethoxymethylsilane, and triethoxy. Methylsilane, triphenoxymethylsilane, trimethoxyethylsilane, triethoxyethylsilane, triphenoxyphenylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, diphenoxydiphenylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diphenoxydimethylsilane , Dimethoxydiethylsilane, diethoxydiethylsilane, diphenoxydiethylsilane, dimethoxyphenylmethylsila , Diethoxyphenylmethylsilane, diphenoxyphenylmethylsilane, dimethoxyphenylethylsilane, diethoxyphenylethylsilane, diphenoxyphenylethylsilane, dimethoxymethylethylsilane, diethoxymethylethylsilane and diphenoxymethylethylsilane . Of these, tetraethoxysilane, triethoxyphenylsilane, triethoxymethylsilane, and triethoxyethylsilane are preferable.

The composition for optical components of the present invention can be obtained by mixing the hydroxyamide polymer, alkoxysilane polymer and solvent obtained above. The mixing ratio of the hydroxyamide polymer and the alkoxysilane varies depending on the purpose of use and the like, but generally, the weight ratio of the alkoxysilane to the hydroxyamide polymer is, for example, 0.1 times or more and 1.5. It can be used at about twice or less.
In addition, the mixing ratio of the hydroxyamide polymer and the solvent varies depending on the purpose of use, etc., but generally the weight ratio of the solvent to the hydroxyamide polymer is, for example, about 5 times or more and about 20 times or less. Can be used.

  The solvent used in the present invention varies depending on the structure of the hydroxyamide polymer. For example, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-cyclohexanone, 3,3,5-trimethylcyclohexanone, propylene carbonate, Diacetone alcohol, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol 1-mono-n-butyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ester Ter, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3 -Methoxypropionate etc. can be mentioned. These may be used alone or in combination of two or more. Of these, cyclopentanone, cyclohexanone, a mixture of cyclopentanone and a solvent other than the above cyclopentanone, and a mixture of cyclohexanone and a solvent other than the above cyclohexanin are preferably used, depending on the structure of the hydroxyamide polymer. be able to.

  The composition for optical components of the present invention comprises a surfactant, a coupling agent typified by a silane, an oxygen radical as various additives, if necessary, in the hydroxyamide polymer, alkoxysilane polymer and solvent. A radical initiator that generates 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.

In the present invention, an optical component can be obtained using the composition for optical components. Examples of production when the optical component is in the form of a film include, for example, film formation using a composition for optical components, and hydrolysis of the hydroxyamide portion and the alkoxysilane polymer in the optical component composition. It is obtained by condensation reaction of silanol groups.
More specifically, as a method for producing a film as an optical component, for example, first, the composition for optical components obtained above is applied to an appropriate support, such as a silicon wafer or a ceramic substrate, and a coating film is formed. Form. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.
Subsequently, 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 350 ° C. The hydroxyamide polymer and the alkoxysilane polymer in the optical component composition are heated at a temperature of 425 ° C. or lower and / or irradiated with active energy rays at a temperature of 300 ° C. or higher and 425 ° C. or lower. Then, a condensation reaction is carried out to form a film as a benzoxazole polymer / alkoxysilane polycondensate, which can be used as an optical component.

  Thus, the composition for optical components that can be used for a 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./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 absorption of light in the film. The smaller the attenuation coefficient, the better the transparency, and the better the transparency. 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 formed on a silicon substrate by spin coating in a nitrogen gas atmosphere at 380 ° C./250 seconds is a film 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 7 mPas or more and 11 mPas or less when measured at 25 ° C., more preferably 8 mPas or more and 11 mPas or less, and further preferably 8 mPas or more and 10 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 a coating film on the support at 1400 rpm under an atmosphere at 23 ° C./humidity of 45% and heating the coating film at 380 ° C./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 the optical waveguide that is one of the optical components of the present invention is not particularly limited, but examples thereof include those described in JP-A-08-139300.
As the manufacturing method, for example, as shown in FIG. 1, an inorganic film (2) represented by a SiOx film is formed as a cladding layer on a semiconductor substrate (1) by a plasma CVD method, and a photoresist method is used. The core is processed into a concave shape. 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. At this time, 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
Preparation of 5-phenylethynylisophthalic acid dichloride (1) Synthesis of 5-bromoisophthalic acid In a four-necked 1 L flask equipped with a thermometer, a stirrer and a dropping funnel, 99.18 g (0.55 mol) of 5-aminoisophthalic acid was added. ) 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 four-necked 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 obtained above 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 filtered off and washed twice with 2 L of distilled water, and the resulting white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 117 g of a crude product. Used in the next reaction without purification.

(2) Synthesis of dimethyl 5-bromoisophthalate Into a 500 mL flask equipped with 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 for 6 hours. Refluxed. After standing to cool, it was added dropwise to 1 L of distilled water, and this was 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 1- [3,5-bis (methoxycarbonyl) phenyl] -2-phenylethyne In a four-neck 1 L flask equipped with a thermometer, a Dimroth condenser, a nitrogen inlet, and a stirrer, the above ( 99.7 g (0.365 mol) of dimethyl 5-bromoisophthalate obtained in 2), 1.1 g (0.000041 mol) of triphenylphosphine, 0.275 g (0.000014 mol) of copper iodide, 40.9 g of phenylacetylene (0.4 mol) was charged and nitrogen was allowed to flow into the flask. Next, 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 / liter hydrochloric acid, and 500 mL of water. The solid was dried under reduced pressure at 50 ° C. to obtain 90.8 g of 1- [3,5-bis (methoxycarbonyl) phenyl] -2-phenylethyne (yield 85%).

(4) Synthesis of 5-phenylethynylisophthalic acid dipotassium salt In 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) was dissolved and dissolved by heating under reflux. To this, 85 g (0.29 mol) of 1- [3,5-bis (methoxycarbonyl) phenyl] -2-phenylethyne synthesized in the above (3) was added and heated to reflux for 30 minutes. 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 94 g of dipotassium 5-phenylethynylisophthalate (yield 95%).

(5) Synthesis of 5-phenylethynylisophthalic acid dichloride A 5-liter ethynylisophthalic acid dipotassium salt 85 obtained in (4) above was added to a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer. .6 g (0.2 mol) and 1 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 80 to 130 ° C. for 3 hours. After cooling, 2 L of hexane was added, and the resulting precipitate was collected by filtration. The crystals were dissolved in 150 mL of chloroform and 300 mL of hexane under heating. After hot filtration, the crystals were allowed to stand in a refrigerator at 0 ° C. for 48 hours. As a result, 42 g of 5-phenylethynylisophthalic acid dichloride was obtained (55% yield).

Production Example 2
Preparation of 5-ethynylisophthalic acid dichloride (1) Synthesis of dimethyl 5-trifluoromethanesulfonyloxyisophthalate Into 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 increased to 0 ° C. for 1 hour, and the temperature was further raised to room temperature 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 a thermometer, a Dimroth condenser, a nitrogen inlet, and a 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 In a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 3 L of n-butanol, 182 g of potassium hydroxide (85%) (2.763 mol) Was dissolved by heating under reflux. To this, 95 g (0.344 mol) of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol synthesized in (2) above was added and heated to reflux for 30 minutes. 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 four-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 obtained residue was extracted and filtered twice with 200 mL of diethyl ether. 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 2a
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 the mixture was 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 3
[Synthesis of hydroxyamide polymer]
Under a nitrogen gas flow, 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether was dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0 0.22 mol) was cooled to −15 ° C. and 12.9 g (0.0425 mol) of 5-phenylethynylisophthalic acid dichloride synthesized in Production Example 1 and 8.6 g (0.0425 mol) of isophthalic acid dichloride were added. It was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, 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 39 g of a hydroxyamide polymer. Using the obtained hydroxyamide polymer, solubility, weight average molecular weight (Mw) and solution viscosity were evaluated by the following methods. Each characteristic is shown in Table 1.

Production Example 4
In Production Example 3, 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether Instead of 12.9 g (0.0425 mol) of 5-phenylethynylisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 56.6 g (0.1 mol) of 5-phenylethynyl synthesized in Production Example 1 was used. 45 g of hydroxyamide polymer was obtained in the same manner as in Production Example 3 except that 28.8 g (0.095 mol) of isophthalic acid dichloride was used. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Production Example 2. Each characteristic is shown in Table 1.

Production Example 5
[Synthesis of hydroxyamide polymer]
In Production Example 3, instead of 12.9 g (0.0425 mol) of 5-phenylethynylisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 5-ethynylisophthalic acid dichloride synthesized in Production Example 2 was used. 27 g of hydroxyamide polymer was obtained in the same manner as in Production Example 3 except that 6 g (0.0425 mol) and 8.6 g (0.0425 mol) of isophthalic acid dichloride were used. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Production Example 3. Each characteristic is shown in Table 1.

Production Example 5 '
[Synthesis of hydroxyamide polymer]
In Production Example 3, instead of 12.9 g (0.0425 mol) of 5-phenylethynylisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 5-ethynylisophthalic acid dichloride synthesized in Production Example 2 was used. Except for using 6 g (0.0425 mol) and 13.3 g (0.0425 mol) of 3,3′-thiobisbenzoic acid dichloride synthesized in Preparation Example 2a, all in the same manner as in Preparation Example 3, 25 g of hydroxyamide weight Coalescence was obtained. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Production Example 3. Each characteristic is shown in Table 1.

Production Example 6
[Synthesis of alkoxysilane polymer]
Tetraethoxysilane (20.8 g, 0.1 mol) was dissolved in methanol (50 g), water (3.6 g, 0.2 mol) and acetic acid (0.06 g, 0.001 mol) were added, and the reaction was carried out at 25 ° C / 48 hours. And left at 23 ° C. for 7 days. From this reaction solution, 54 g of the solvent was removed under reduced pressure to obtain a solution of 9.3 g of alkoxysilane polymer. The weight average molecular weight (Mw) was evaluated by the following method using the alkoxysilane polymer thus obtained. Each characteristic is shown in Table 1.

Production Example 7
[Synthesis of alkoxysilane polymer]
10.4 g (0.05 mol) of tetraethoxysilane and 8.9 g (0.05 mol) of triethoxymethylsilane are dissolved in 50 g of methanol, and 3.6 g (0.2 mol) of water and 0.06 g of acetic acid (0 0.001 mol) was added, reacted at 25 ° C./48 hours, and allowed to stand at 23 ° C. for 7 days. From this reaction solution, 54 g of the solvent was removed under reduced pressure to obtain 9.0 g of an alkoxysilane polymer solution. The weight average molecular weight (Mw) was evaluated by the following method using the alkoxysilane polymer thus obtained. Each characteristic is shown in Table 1.

Production Example 8
[Synthesis of alkoxysilane polymer]
A solution of 10.4 g (0.05 mol) of tetraethoxysilane, 6.0 g (0.025 mol) of triethoxyphenylsilane, and 4.5 g (0.025 mol) of triethoxymethylsilane in 50 g of methanol, and 3. 6 g (0.2 mol) and 0.06 g (0.001 mol) of acetic acid were added, reacted at 25 ° C./48 hours, and allowed to stand at 23 ° C./7 days. From this reaction solution, 54 g of the solvent was removed under reduced pressure to obtain 12.2 g of a solution of alkoxysilane polymer. The weight average molecular weight (Mw) was evaluated by the following method using the alkoxysilane thus obtained. Each characteristic is shown in Table 1.

Production Example 9
[Synthesis of hydroxyamide polymer]
In Production Example 3, 2,2-bis (3-amino-4hydroxyphenyl) hexafluoropropane was used in place of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether. Instead of 12.9 g (0.0425 mol) of 5-phenylethynylisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 36.6 g (0.1 mol) of 1phthalic dichloride 19.2 g (0.025 mol). Except for using 095 mol), 50 g of hydroxyamide polymer was obtained in the same manner as in Production Example 3. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Production Example 3. Each characteristic is shown in Table 1.

Production Example 10
[Synthesis of hydroxyamide polymer]
In Production Example 3, 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether Instead of 12.9 g (0.0425 mol) of 5-phenylethynylisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 56.6 g (0.1 mol) of 19.2 g (0.025 mol) of isophthalic acid dichloride. Except for using 095 mol), 66 g of hydroxyamide polymer was obtained in the same manner as in Production Example 3. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Production Example 3. Each characteristic is shown in Table 1.

Production Example 11
[Synthesis of hydroxyamide polymer]
Under a nitrogen gas flow, 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether was dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0 Then, the mixture was cooled to −15 ° C., and 36.4 g (0.12 mol) of 5-phenylethynylisophthalic acid dichloride obtained in the same manner as in Production Example 1 was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, and then 8.9 g (0.04 mol) of triethoxysilylpropylamine was added and stirred at −15 ° C. for 1 hour. Then, it returned to room temperature and stirred at room temperature for 1 hour. Thereafter, the reaction solution was dropped into 4 liters of methanol in small droplets, and the precipitate was collected, and further repeated three times in 4 liters of methanol. Thereafter, the precipitate was dried to obtain 51 g of a hydroxyamide polymer. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Production Example 3. Each characteristic is shown in Table 1.

[Evaluation of hydroxyamide polymer and alkoxysilane polymer]
(1) Solubility Solubility in the solvent N-methyl-2-pyrrolidone was evaluated using the hydroxyamide polymer and alkoxysilane polymer obtained above. 1 g of hydroxyamide polymer or alkoxysilane polymer and 2 g of N-methyl-2-pyrrolidone are put into a glass sample container with a lid, mixed manually for 30 seconds, and allowed to stand for 30 minutes to check for insoluble matter. The solubility was judged by visual observation. Here, in Table 1, ◎ means that the mixture was dissolved after manually mixing for 30 seconds, and ◯ means that the mixture was mixed manually for 30 seconds and dissolved after standing for 30 minutes.

(2) Weight average molecular weight in terms of standard polystyrene For the hydroxyamide polymer and alkoxysilane polymer obtained above, as a device, a column for TSKgelGMH-HRH high-speed SEC was used in a high performance liquid chromatograph SC-8020 system manufactured by Tosoh Corporation. , Measured using an N-methyl-2-pyrrolidone mobile phase with 0.5% LiBr, UV (λ = 270 nm) detector, converted using standard polystyrene (PS-oligomer kit manufactured by Tosoh Corporation), and weight average molecular weight Asked.

(3) Solution viscosity As a composition at a ratio of 1 g of hydroxyamide polymer or alkoxysilane polymer and 9 g of N-methyl-2-pyrrolidone, this was prepared in a spin coater (rotation speed 1400 rpm) in an atmosphere of 23 ° C./45% humidity. ), A coating film was formed on the support, and it was confirmed that the thickness of the coating film after heating the coating film at 380 ° C./250 seconds was 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.

Example 1
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 3 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 6 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Using this composition, a coating film is formed by spin coating, and the coating film is dried by heating at 200 ° C./90 seconds in an N ² gas atmosphere, and further subjected to heat treatment at 380 ° C./250 seconds to form a film. And evaluated. The characteristics are shown in Tables 2 and 3.

Example 2
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 4 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 6 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 3
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 5 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 6 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 4
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 11 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 6 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 5
After dissolving and mixing 0.07 g of the hydroxyamide polymer synthesized in Production Example 3, 0.03 g of the alkoxysilane polymer synthesized in Production Example 7 and 1 g of N-methyl-2-pyrrolidone in a glass sample bottle The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 6
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 3 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 8 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 7
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 4 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 7 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 8
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 11 and 0.03 g of the alkoxysilane polymer synthesized in Production Example 7 and 1 g of N-methyl-2-pyrrolidone are dissolved and mixed in a glass sample bottle. The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm to obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Example 9
0.07 g of the hydroxyamide polymer synthesized in Production Example 5 ′, 0.03 g of the alkoxysilane polymer synthesized in Production Example 6 and 1 g of N-methyl-2-pyrrolidone were dissolved and mixed in a glass sample bottle. Then, it filtered with the 0.1 micrometer pore size 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 2 and 3.

Comparative Example 1
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 9 was dissolved and mixed with 1 g of N-methyl-2-pyrrolidone in a glass sample bottle, it was filtered with a Teflon (registered trademark) filter having a pore size of 0.1 μm. To obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

Comparative Example 2
After 0.07 g of the hydroxyamide polymer synthesized in Production Example 10 was dissolved and mixed with 1 g of N-methyl-2-pyrrolidone in a glass sample bottle, it was filtered with a Teflon (registered trademark) filter having a pore size of 0.1 μm. To obtain a composition. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. The characteristics are shown in Tables 2 and 3.

[Evaluation of composition for optical parts]
(4) 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.

(5) 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.

(6) Adhesiveness In the above film production process, a film was produced in the same manner except that a silicon substrate with a SiOx film was used as the silicon substrate, and a SiOx film of 100 nm was formed as an upper layer, and in an N ² gas atmosphere 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).

(8) Uniformity of film quality In the film preparation process, 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 coating film obtained above, the refractive index and the attenuation coefficient were evaluated by the measurement methods shown below. Each characteristic is shown in Table 3.

(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.

  From Table 2, it is excellent in film thickness uniformity represented by adhesiveness and workability, and heat resistance. Also, from Table 3, it is clear that optical component compositions and optical components that are excellent in refractive index and attenuation coefficient can be provided as optical characteristics.

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

Claims (7)

A composition for optical parts comprising a hydroxyamide polymer represented by formula (A), an alkoxysilane polymer represented by formula (I) and a solvent, wherein the hydroxyamide polymer is a weight average molecular weight in terms of standard polystyrene. Is a composition for optical parts, wherein the composition is 5000 or more and 15000 or less.

[In the formula (A), X represents a group selected from the groups represented by the following formula (B), and two X in the formula may be the same or different. Y represents at least one group selected from the groups represented by the following formula (C), formula (D), formula (E) and formula (F). Z represents a group selected from the groups represented by formula (G). m and n are 0 or an integer of 1 or more, and m + n 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 (G) represents Formula (H)

In formula (C) and formula (D), R represents a group selected from a phenyl group or an alkyl group. P in the formula (G) 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), Formula (G), and Formula (H) is It may be substituted with at least one group selected from an alkyl group having 1 to 4 carbon atoms and a phenyl group. ]

[R ₁ and R _{2 in} Formula (I) represent a phenyl group or a group selected from alkyl groups having 1 or 2 carbon atoms, and R ₁ and R ₂ may be the same or different. q ₁ , r ₁ , s ₁ , q ₂ , r ₂ , and s ₂ are integers of 0 or more, and q ₁ + r ₁ + s ₁ + q ₂ + r ₂ + s ₂ is an integer of 2 or more and 50 or less, and , Q ₁ + r ₁ + q ₂ + r ₂ represents an integer of 1 to 50. Further, the arrangement of the repeating units in formula (I) may be either block-like or random. ] The composition for optical components according to claim 1, wherein the hydroxyamide polymer represented by the formula (A) is a hydroxyamide polymer having a terminal group L represented by the formula (J).

[In the formula (J), X, Y and Z are the same as X, Y and Z in the formula (A).
L is the following formula (K)

[R ₃ in Formula (K) represents an alkyl group having 3 carbon atoms or a phenyl group. R ₄ and R ₅ represent a group selected from a phenyl group or an alkyl group having 1 or 2 carbon atoms, and R ₄ and R ₅ may be the same or different. v represents an integer of 1 or more and 4 or less. ]
T and u are integers of 0 or more, and t + u is an integer of 4 or more. Further, the arrangement of the repeating units in formula (J) may be either block or random. ]   The optical component according to claim 1 or 2, wherein the hydroxyamide polymer is polymerized by reacting a dicarboxylic acid compound and a diamine compound at a molar ratio in the range of 0.70 or more and 0.90 or less. Composition.   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 4. The composition for optical components according to Item 3.   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 composition for optical components according to claim 3 or 4, wherein the solution viscosity at 25 ° C when the content of the hydroxyamide polymer is adjusted is 7 mPas or more and 11 mPas or less.   It forms into a film using the composition for optical components of any one of Claims 1-5, and hydrolyzes the hydroxyamide part and alkoxysilane polymer of the hydroxyamide polymer in the said composition for optical components. Optical parts obtained by condensation reaction of silanol groups generated by the reaction.   The optical component according to claim 6, wherein an attenuation coefficient of light at a wavelength of 380 nm is 0 or more and 0.01 or less.

Images