JP4968153B2 - Composition for optical component and optical component - Google Patents

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 problems such as the need for high-temperature heating in the optical component manufacturing process, and further improvements in properties are desired 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 manufacturing process becomes complicated due to application.

  In addition, fluorinated polyimide and fluorinated polybenzoxazole have been widely studied (for example, see Patent Documents 1 and 2) and applied as an optical material. However, fluorine is introduced into the resin structure. Therefore, it may be limited to the application used, 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 3). This is because the light transmittance is improved by introducing a bulky specific structure such as a norbornane skeleton into the resin structure, but on the other hand, the introduction of an aliphatic structure and a hydrophobic structure reduces the heat resistance, and its application When the film is formed on the base substrate, the use of the resin on the substrate is low, so there is a problem that the use is limited or the uniformity of the coating film is lowered. Has the problem that the margin is narrow or 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. In addition, it is known that a composite material of polyimide or polybenzoxazole and inorganic particles is used for an optical waveguide (see, for example, Patent Documents 5 and 6). These materials disperse inorganic particles in a polymer solution. It is necessary to control dispersibility. From the viewpoint of the uniformity of the composition, control of characteristic distribution, haze, and the like are likely to occur, and there arises a problem that the margin during use is narrow and cannot be used.

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

  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 inventors of the present invention have succeeded in closing a hydroxyamide polymer having a nitrogen-containing heterocyclic group having a carbon-carbon double bond by heat and / or active energy rays. -By carrying out a crosslinking reaction, it was found that a resin having high optical properties, heat resistance, and physical properties can be obtained and can be adapted to 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 (6).

(1) An optical system comprising a hydroxyamide polymer represented by formula (A) having a nitrogen-containing heterocyclic group alkenyl group having a carbon-carbon double bond capable of undergoing a crosslinking reaction by heat or active energy rays, and a solvent Composition for parts.

[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 group represented by the following formula (C). Z represents a group selected from the groups represented by formula (D). m and n each represents an integer of 1 or more, n is an integer of 0 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 (D) represents Formula (E)

Represents a group selected from the group represented by: 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), and Formula (E) is at least 1 selected from alkyl groups having 1 to 4 carbon atoms. It may be substituted with groups. ]

(2) The composition for optical components according to item (1), wherein the hydroxyamide polymer has a weight average molecular weight of 5000 or more and 15000 or less in terms of standard polystyrene.
(3) In the composition for optical parts, a coating film was formed at an atmosphere of 23 ° C./humidity of 45% at a spin coater rotation speed of 1400 rpm, and the average thickness of the film heated at 380 ° C./250 seconds was The composition for optical components according to item (2), wherein 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.
(4) A film is formed using the composition for optical parts according to any one of items (1) to (3), and the hydroxyamide polymer in the composition for optical parts is subjected to a condensation reaction and Optical components obtained by crosslinking reaction.
(5) The optical component according to (4), wherein the optical component has a light attenuation coefficient of 0 or more and 0.01 or less at a wavelength of 380 nm.
(6) The optical component according to (4) or (5), wherein a residual ratio of carbon-carbon double bonds of the hydroxyamide polymer by Raman spectrum measurement is 0% or more and 50% or less. The optical component described.

  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.

  The present invention relates to an optical system comprising a hydroxyamide polymer represented by formula (A) having a nitrogen-containing heterocyclic group alkenyl group having a carbon-carbon double bond capable of undergoing a crosslinking reaction by heat or active energy rays, and a solvent. It is a composition for parts. Thereby, the composition for optical components which is excellent in an optical characteristic, heat resistance, contact | adherence characteristic, workability, etc. can be provided.

  Examples of the group having a nitrogen-containing heterocyclic group alkenyl group having a carbon-carbon double bond that can undergo a crosslinking reaction by heat or active energy rays in the present invention include a maleimide group, a norbornene dicarboxydo group, and a cyclohexene dicarboximide group. Is mentioned.

  In the crosslinking reaction, carbon-carbon double bonds react with each other between molecules or within a molecule to form a crosslinked structure. At the same time, the hydroxyamide polymer undergoes dehydration and cyclization by heating to form a benzoxazole polymer. Therefore, the polymer in which the dehydration cyclization and the crosslinking reaction have progressed becomes a benzoxazole polymer having a crosslinked structure, and is extremely excellent in heat resistance.

  The hydroxyamide polymer represented by the formula (A) is represented by the formula (C) and at least one bisaminophenol compound having a group selected from the groups represented by the formula (B). In the presence of a conventional acid chloride method, activated ester method, polyphosphoric acid, dicyclohexylcarbodiimide or other dehydrating condensing agent using one or more dicarboxylic acid compounds having a group selected from It can be made to react by a method such as a condensation reaction. Further, as the dicarboxylic acid compound, a dicarboxylic acid compound having a group selected from the groups represented by the formula (C) and a group selected from the groups represented by the formula (D). Can also be used in combination.

  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) and the formula (D) have two bonds that can bond to a carboxyl group.

  Alternatively, the hydroxyamide polymer represented by the formula (A) may be combined with another hydroxyamide polymer of a type having no crosslinkable group (not having a crosslinking reaction) to form an interpenetrating network structure. Similarly, it is possible to obtain a highly heat-resistant resin. In this case, the hydroxyamide polymer having no crosslinkable group includes at least one bisaminophenol compound having a group selected from the groups represented by the formula (B) and the formula (D). It can be obtained by the same method as described above using at least one dicarboxylic acid compound having a group selected from the groups represented.

  Examples of the bisaminophenol compound having a group represented by the formula (B) used in the present invention include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxy). Phenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxy Diphenylsulfone, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 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, 3, Examples thereof include 3′-diamino-4,4′-dihydroxydiphenyl ether and 4,4′-diamino-3,3′-dihydroxyphenyl ether. Among these, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene and 3,3′-diamino-4, 4′-dihydroxydiphenyl ether and the like are preferable. These may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid compound having a group represented by the formula (C) used in the present invention include 3-maleimidophthalic acid, 4-maleimidophthalic acid, 2-maleimidoisophthalic acid, 4-maleimidoisophthalic acid, 5- Maleimide isophthalic acid, 2-maleimidoterephthalic acid, 3-maleimidoterephthalic acid, 3- (5-norbornene dicarboximide) phthalic acid, 4- (5-norbornene dicarboxymido) phthalic acid, 2- (5-norbornene dicarboxyl) Mido) isophthalic acid, 4- (5-norbornene dicarboximide) isophthalic acid, 5- (5-norbornene dicarboximide) isophthalic acid, 2- (5-norbornene dicarboximide) terephthalic acid, 3- (5-norbornene) Dicarboximide) terephthalic acid, 3- (4-cyclohexenedicarbo) Simido) phthalic acid, 4- (4-cyclohexenedicarboximido) phthalic acid, 2- (4-cyclohexenedicarboximido) isophthalic acid, 4- (4-cyclohexenedicarboximido) isophthalic acid, 5- (4-cyclohexene) Dicarboxymido) isophthalic acid, 2- (4-cyclohexenedicarboximido) terephthalic acid, 3- (4-cyclohexenedicarboximido) terephthalic acid, 3- (3-cyclohexenedicarboximido) phthalic acid, 4- (3 -Cyclohexene dicarboximide) phthalic acid, 2- (3-cyclohexene dicarboximide) isophthalic acid, 4- (3-cyclohexene dicarboximide) isophthalic acid, 5- (3-cyclohexene dicarboximide) isophthalic acid, 2- (3-Cyclohexene dicarboximide) Refutaru acid and 3- (3-cyclohexene carboximidamide de) terephthalic acid, and the like, but not limited thereto. These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound having a group represented by the formula (D) used in the present invention include 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, 2,2-bis (4-carboxyphenyl) propane 2,2-bis (3-carboxyphenyl) propane, 2,2′-dimethyl-4,4′-biphenyldicarboxylic acid, 3,3′-dimethyl-4,4′-biphenyl Dicarboxylic acid, 2,2′-dimethyl-3,3′-biphenyldicarboxylic acid, 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-carboxyphenoxy) ) -P-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,4'-bis (4-carbox) Phenoxy) -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-ter Phenyl, 3,3′-bis (3-carboxyphenoxy) -m-terphenyl, 9,9-bis- (2-carboxy-phenyl) fluorene, 9,9-bis- (3-carboxy-phenyl) Enyl) 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, 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 and 2,5- (1 , 1′-biadamantane) -dicarboxylic acid and the like, but is not limited thereto. Among these, isophthalic acid and 4,4′-oxybisbenzoic acid are preferable.
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 the formula (B), the formula (C), and the formula (D) is substituted with at least one group selected from alkyl groups having 1 to 4 carbon atoms. May be. 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 used in the present invention, for example, in the acid chloride method, the acid chloride to be used is first an excess of the dicarboxylic acid compound in the presence of a catalyst such as N, N′-dimethylformamide. It can be obtained by reacting an amount of thionyl chloride with a temperature of room temperature to about 130 ° C., distilling off excess thionyl chloride by heating and reduced pressure, and then recrystallizing the residue with a solvent such as hexane. The dicarboxylic acid chloride compound thus prepared is 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 is present. A hydroxyamide polymer can be obtained by reacting 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 are represented by the formula (C). 1 type, or 2 or more types of dicarboxylic acids having a group selected from the following groups. The arrangement of the repeating units of the hydroxyamide polymer thus obtained may be block-like or random.

  Further, in the hydroxyamide polymer represented by the formula (A), the nitrogen-containing heterocyclic group having a carbon-carbon double bond obtained by using a dicarboxylic acid compound having a group represented by the formula (C) It is a copolymer having a repeating unit obtained by using a dicarboxylic acid compound having a repeating unit having an alkenyl group and a group represented by the formula (D) not having the carbon-carbon double bond group. In this case, the arrangement of the repeating unit having a nitrogen-containing cyclic group having a carbon-carbon double bond group and the repeating unit not having the same 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 (D) 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 with a dicarboxylic acid chloride compound having a group selected from the group represented by (C).

  Conversely, a bisaminophenol compound having a group selected from the groups represented by formula (B), and a dicarboxylic acid chloride compound having a group selected from groups represented by formula (C); Are reacted in advance to increase the molecular weight of the polymer, and further, a bisaminophenol compound having a group selected from groups represented by formula (B) and a group represented by formula (D) A dicarboxylic acid chloride compound having a group selected from:

  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 (D) It can be obtained by reacting a compound and a dicarboxylic acid chloride compound having a group selected from the groups represented by formula (C) at the same time.

M and n in the structure represented by the formula (A) are m is an integer of 1 or more, n is an integer of 0 or more, and m + n is an integer of 4 or more, and the bisaminophenol compound and dicarboxylic acid compound used In general, m + n is in the range of 4 to 100, although it varies depending on the type of. M and n are integers satisfying the relationship of the following formula,
0.05 ≦ (m / (m + n)) ≦ 1
Preferably, it is an integer that satisfies the relationship of the following formula.
0.5 ≦ (m / (m + n)) ≦ 1
here,
(M / (m + n)) <0.05
In this case, it means that the number of repeating units having a nitrogen-containing heterocyclic group having a carbon-carbon double bond is small, and the number of crosslinking reaction sites is small. Further, the arrangement of the repeating unit having a nitrogen-containing heterocyclic group having a carbon-carbon double bond and the repeating unit having no carbon-carbon double bond may be a block shape or a random shape.

  The hydroxyamide polymer used in the present invention causes a condensation reaction and a crosslinking reaction by heating to obtain a benzoxazole polymer.

  The hydroxyamide polymer represented by the formula (A) preferably has a standard polystyrene equivalent weight average molecular weight of 5000 or more and 15000 or less, more preferably 7000 or more and 15000 or less, and further preferably 8000 or more and 12000 or less. It is. If the weight molecular weight is smaller than the lower limit, heat resistance may deteriorate during the process after film formation, which may cause a problem of gas generation. If the weight molecular weight is larger than the upper limit, the solubility in a solvent may decrease. Yes, the viscosity of the composition for optical components of the present invention increases, so that the wettability to the base substrate decreases during coating film formation and is affected by the properties of the substrate surface. There is a possibility that the range becomes narrow and the film thickness uniformity is lowered.

  The weight average molecular weight can be determined in terms of polystyrene by preparing 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.

  In addition, 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, the molecular weight is controlled by adjusting the reaction molar ratio of the dicarboxylic acid compound and the bisaminophenol compound. And a method of using the carboxylic acid chloride compound or the aminophenol compound for the dicarboxylic acid chloride compound and the bisaminophenol compound to stop the reaction and adjusting to an arbitrary molecular weight. The carboxylic acid chloride compound and the aminophenol compound are used to terminate the reaction as an end-capping material 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 composition for optical components of the present invention can be obtained by mixing the hydroxyamide polymer obtained above and a solvent. 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 to 20 times. be able to.

  Examples of the solvent used in the present invention include a ketone solvent, an ether solvent, an ester solvent, and an aprotic polar solvent, depending on the structure of the hydroxyamide polymer. For example, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-cyclohexanone, 3,3,5-trimethylcyclohexanone, propylene carbonate, diacetone alcohol and γ-butyrolactone as ketone solvents; diethylene glycol as ether solvent 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, dipropylene glycol monomethyl ether and 1,3-butylene glycol-3-monomethyl ether; As ester solvents, propylene glycol monomethyl ether acetate, propylene Recall diacetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc .; N- Examples thereof include methyl-2-pyrrolidone, N, N-dimethylacetamide and dimethyl sulfoxide. 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 heats a surfactant, a coupling agent typified by a silane, an oxygen radical or a sulfur radical as various additives as necessary to the hydroxyamide polymer and the solvent. A radical initiator generated by the above 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.

  An optical component can be obtained using the composition for optical components of the present invention. As a manufacturing method when the optical component is in the form of a film, for example, using the hydroxyamide polymer obtained above and a solvent such as cyclohexanone, an optical component composition is prepared, and this optical component composition is Then, it is applied to a suitable 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 350 ° C. The hydroxyamide polymer in the composition for optical components is subjected to condensation reaction and crosslinking by heating at a temperature of 425 ° C. or lower and / or irradiation with active energy rays at a temperature of 300 ° C. or higher and 425 ° C. or lower. It can be reacted to form a film as a benzoxazole polymer, which can be 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, and the like can be used.

  Thus, the composition for an optical component that can be used for an optical film 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. It is preferable that the attenuation coefficient of light inside is 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 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.

  The composition for optical components is calculated from the Raman spectrum of the hydroxyamide polymer in the film as a film obtained by heating a coating film formed by coating in the same manner as described above at 380 ° C./250 seconds. The carbon-carbon double bond residual ratio is preferably 0% or more and 50% or less in view of the thermal stability of the film. In the above range, it is preferably close to 0%, more preferably 40% or less. More preferably, the content is 30% or less. The residual ratio of carbon-carbon double bonds in the hydroxyamide polymer can be used outside the above range, but if it exceeds the upper limit, the reaction may proceed due to subsequent heat treatment or the like, causing a change in physical properties.

The Raman spectrum can be measured using, for example, a three-dimensional microscopic laser Raman spectrometer Nanofinder manufactured by Tokyo Instruments Co., Ltd. The measurement of the carbon-carbon double bond residual ratio by Raman spectrum is, for example, a coating film obtained by drying a coating film prepared by spin coating on a silicon substrate by heat treatment at 200 ° C./90 seconds in an N ² gas atmosphere. , And 380 ° C./250 seconds of each heat-treated coating film, and the Raman spectrum of these coating films was measured. From the peak height derived from the carbon-carbon double bond in the Raman spectrum result, It can be calculated by an equation.
Carbon-carbon double bond residual ratio (%) = P1 ÷ P2 × 100
In the above formula, P1 is a peak height derived from a carbon-carbon double bond in a coating film subjected to heat treatment at 380 ° C./250 seconds, and P2 is carbon-carbon in a coating film subjected to heat treatment at 200 ° C./90 seconds. The peak height derived from a double bond is shown.

  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-maleimidoisophthalic acid dichloride (1) 98.1 g (1.0 mol) of maleic anhydride was added to a 4-neck 2 L flask equipped with a thermometer, a Dimro condenser, a calcium chloride tube and a stirrer. -181.1 g (1.0 mol) of aminoisophthalic acid was dissolved in 700 mL of dried N-methyl-2-pyrrolidone, 111.3 g (1.1 mol) of triethylamine was added, and the mixture was stirred at 120 ° C for 10 hours. did. Thereafter, the reaction solution was added dropwise to 7 L of 50% aqueous methanol solution, and the precipitate was collected. Further, the precipitate was stirred in 7 L of 50% aqueous methanol solution for 2 hours and then collected by filtration twice. Thereafter, the precipitate was dried to obtain 243 g (yield 93%) of 5-maleimidoisophthalic acid, which was used for the next reaction.

(2) To a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 200 g (0.77 mol) of 5-maleimidoisophthalic acid obtained above and 0.5 g of benzyltriethylammonium chloride (0 0.002 mol) and 1.8 L of 1,2-dichloroethane were charged and cooled to 0 ° C. To this, 220 mL (3.1 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Then, it stirred at 100 degreeC for 6 hours. After cooling the reaction liquid, the crystals were removed by filtration, and the crystals were washed with 500 mL of 1,2-dichloroethane. 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 600 mL of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a solid crude product. This was washed with dry n-hexane and subsequently recrystallized with diethyl ether to obtain 57 g of 5-maleimidoisophthalic acid dichloride (yield 25%).
Further, 5-maleimidoisophthalic acid dichloride was produced according to the above method.

Production Example 2
5- (5-norbornene dicarboximide) isophthalic acid dichloride (1) In Production Example 1 (1), 98.1 g (1.0 mol) of maleic anhydride and 700 mL of N-methyl-2-pyrrolidone were mixed with 5-norbornene. 281 g of 5- (5-norbornene) in the same manner as in Production Example 1 (1) except that 164.2 g (1.0 mol) of 2,3-dicarboxylic acid anhydride and 1 L of N-methyl-2-pyrrolidone were used. Dicarboxymido) isophthalic acid was obtained (yield 86%).

(2) In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 200 g (0.61 mol) of 5- (5-norbornenedicarboximide) isophthalic acid obtained above, benzyltriethyl 0.4 g (0.002 mol) of ammonium chloride and 1.4 L of 1,2-dichloroethane were charged and cooled to 0 ° C. To this, 180 mL (2.4 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Then, it stirred at 100 degreeC for 8 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 500 mL of 1,2-dichloroethane. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted and filtered twice with 600 mL of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a solid crude product. This was washed with dry n-hexane and then recrystallized with diethyl ether to obtain 91 g of 5- (5-norbornene dicarboximide) isophthalic acid dichloride (yield 41%).
In addition, 5- (5-norbornene dicarboximide) isophthalic acid dichloride was produced according to the above method.

Example 1
[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 of pyridine ( 0.22 mol) was added, then cooled to -15 ° C, and 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride were added little by little. did. After completion of the addition, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 5 hours. Then, the reaction liquid was dripped at 4 liters of 50% methanol aqueous solution by a small droplet, and the precipitate was collected. Further, the operation of stirring in 4 liters of 50% methanol aqueous solution and collecting by filtration was repeated three times. Thereafter, the precipitate was dried to obtain 36 g (yield 93%) of a hydroxyamide polymer.

Using the hydroxyamide polymer obtained above, solubility, weight average molecular weight (Mw) and solution viscosity were evaluated by the following methods.
(1) Solubility The solubility of the hydroxyamide polymer in the solvent N-methyl-2-pyrrolidone was evaluated. 1 g of hydroxyamide polymer and 2 g of N-methyl-2-pyrrolidone are put into a glass sample container with a lid, mixed manually for 30 seconds, left to stand for 30 minutes, and visually inspected for the presence of insoluble matter. Solubility was judged. 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 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).
(3) Solution Viscosity As a composition at a ratio of 1 g of hydroxyamide polymer and 9 g of N-methyl-2-pyrrolidone, this was supported by a spin coater (rotation speed 1400 rpm) in an atmosphere of 23 ° C./45% humidity. A coating film was formed thereon, 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.

[Production of composition and film]
1 g of the hydroxyamide polymer obtained above and 9 g of N-methyl-2-pyrrolidone were dissolved and mixed in a glass sample bottle, and then filtered through a Teflon (registered trademark) filter having a pore size of 0.1 μm. Got. 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, crosslinkable group residual rate and film quality uniformity were evaluated by the measurement methods shown below. Each characteristic is shown in Table 1.

(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 after dropping onto the substrate with the SiOx film, the contact angle after 5 seconds 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) 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).

(7) Crosslinking group residual ratio (carbon-carbon double bond residual ratio)
In the film production step, a coating film produced by spin-coating the composition obtained above on a silicon substrate was subjected to a heat treatment sample of 200 ° C./90 seconds and a temperature of 380 ° C./250 seconds in an N ² gas atmosphere. Each heat-treated coating film was produced. With respect to these coating films, the peak height of the crosslinking group was measured with a ruler in units of 1 mm using a three-dimensional microscopic laser Raman spectrometer Nanofinder manufactured by Tokyo Instruments Co., Ltd., and the crosslinking group residual rate was determined from the following formula.
Crosslinking group residual ratio (%) = P1 ÷ P2 × 100
P1: Peak height of crosslinking group of heat-treated sample at 380 ° C./250 seconds P2: Peak height of crosslinking group of heat-treated sample at 200 ° C./90 seconds

(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 method 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 Example 1, 11.2 g (0.0375) of 5-maleimidoisophthalic acid dichloride was used instead of 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride. Mol) and 7.6 g (0.0375 mol) of isophthalic acid dichloride were used in the same manner as in Example 1 to obtain 33 g of hydroxyamide polymer (yield 89%). Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw) and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Example 3
In Example 1, instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 11.6 g of 3,3′-diamino-4,4′-dihydroxydiphenyl ether ( 0.05 mol) and 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene 28.3 g (0.05 mol) were used in the same manner as in Example 1 except that 42 g (yield 92%) of an amide polymer 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 Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Example 4
In Example 1, instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 10.8 g of 3,3′-diamino-4,4′-dihydroxydiphenyl ( 0.05 mol) and 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene 28.3 g (0.05 mol) were used in the same manner as in Example 1 except that 42 g (yield 93%) of an amide polymer 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 Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Example 5
In Example 1, 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride was used instead of 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride. Mol) and 4,4′-oxybisbenzoic acid chloride 12.6 g (0.0425 mol) were used in the same manner as in Example 1 to obtain 38 g of hydroxyamide polymer (yield 90%). . Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Example 6
In Example 1, instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 11.6 g of 3,3′-diamino-4,4′-dihydroxydiphenyl ether ( 0.05 mol) and 9,9-bis ((3-amino-4-hydroxy) phenyl)) fluorene (28.3 g, 0.05 mol) and 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride. Mol) and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 15.5 g (0.0425 mol) of 5- (5-norbornene dicarboximide) isophthalic acid dichloride and 8.6 g (0,425 mol) of isophthalic acid dichloride. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that 0.0425 mol) was used. Using the obtained hydroxyamide polymer 39g (yield 94%), the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Example 7
In Example 1, 28.0 g of 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone was used instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether. Except for using (0.1 mol), everything was carried out in the same manner as in Example 1 to obtain 38 g of hydroxyamide polymer (yield 88%). Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Example 8
In Example 1, instead of 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 23.8 g (0.08) of 5-maleimidoisophthalic acid dichloride was used. Except for using (Mol), 36 g of hydroxyamide polymer (yield 87%) was obtained in the same manner as in Example 1. Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw) and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Comparative Example 1
In Example 1, instead of 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 17.2 g (0.0085 mol) of isophthalic acid dichloride was used. Except for the use, the same procedure as in Example 1 was carried out to obtain 32 g (yield 94%) 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 Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Comparative Example 2
In Example 1, 2,2-bis (3-amino-4hydroxyphenyl) hexafluoro instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether Except for using 36.6 g (0.1 mol) of propane, the same procedure as in Example 1 was carried out to obtain 48 g of a hydroxyamide polymer (yield 92%). Using the obtained hydroxyamide polymer, the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

Comparative Example 3
In Example 1, instead of 23.2 g (0.1 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 21.6 g of 3,3′-diamino-4,4′-dihydroxydiphenyl ( 0.1 mol), instead of 12.7 g (0.0425 mol) of 5-maleimidoisophthalic acid dichloride and 8.6 g (0.0425 mol) of isophthalic acid dichloride, 819.3 g (0.095 mol) of isophthalic acid dichloride was used. A hydroxyamide polymer was obtained in the same manner as in Example 1 except that (mol) was used. Using 32 g of the obtained hydroxyamide polymer (yield 95%), the solubility, weight average molecular weight (Mw), and solution viscosity were evaluated in the same manner as in Example 1.
After 0.1 g of this hydroxyamide polymer and 1 g of N-methyl-2-pyrrolidone were 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. Obtained. Thereafter, a film was prepared and evaluated in the same manner as in Example 1. Each characteristic is shown in Table 1.

  As is clear from the results summarized in Tables 1 and 2, the Examples are superior in solubility to cyclohexanone and good in wettability compared to the Comparative Examples, and also have good adhesion and heat resistance. The properties and the like were also excellent. It is clear that the hydroxyamide polymers of Comparative Examples 1 and 3 do not have a carbon-carbon double bond, so there is no cross-linked structure, a low glass transition temperature, and low heat resistance. In particular, the hydroxyamide body of Comparative Example 3 does not satisfy various properties due to low solubility in cyclohexanone and poor wettability. Since the hydroxyamide body of Comparative Example 2 contains fluorine, the wettability is poor and the adhesiveness is lowered, and it is clear that all the various characteristics cannot be satisfied.

  Next, when the examples were simply evaluated as optical components, the attenuation coefficient was small, and light absorption in the film was small, indicating good transparency, indicating that the optical components were good. Further, the refractive index and the like were excellent, and various characteristics could be satisfied, and the object of the present invention was sufficiently 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 (6)

Composition for optical component comprising hydroxyamide polymer represented by formula (A) having nitrogen-containing heterocyclic group alkenyl group having carbon-carbon double bond capable of crosslinking reaction by heat or active energy ray and solvent object.

[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 group represented by the following formula (C). Z represents a group selected from the groups represented by formula (D). m and n each represents an integer of 1 or more, n is an integer of 0 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 (D) represents Formula (E)

Represents a group selected from the group represented by: 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), and Formula (E) is at least 1 selected from alkyl groups having 1 to 4 carbon atoms. It may be substituted with groups. ]   The composition for optical components according to claim 1, wherein the hydroxyamide polymer has a weight average molecular weight of 5000 or more and 15000 or less in terms of standard polystyrene.   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 parts according to claim 2, 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.   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 optical component composition to a condensation reaction and a crosslinking reaction.   The optical component according to claim 4, wherein the optical component has a light attenuation coefficient of 0 or more and 0.01 or less at a wavelength of 380 nm.   The optical component according to claim 4 or 5, wherein a carbon-carbon double bond residual ratio of the hydroxyamide polymer as measured by Raman spectrum is 0% or more and 50% or less.

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