JP2012247637A - Method for manufacturing optical waveguide, and dry film resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an optical waveguide with less optical loss.SOLUTION: The method for manufacturing an optical waveguide includes the following steps (I) to (III). They are: (I) a step of forming a photocurable resin composition layer 4 containing a photo-radical initiator and a polymerizable compound, and a water-soluble non-photocurable resin composition layer 3, in this order from below, on a lower clad 1 formed on a substrate 2; (II) an exposure step of exposing the photocurable resin composition layer 4 by use of a photomask 6 to form a core part 8; and (III) an alkali development step of removing an unexposed part of the photocurable resin composition layer 4 and the water-soluble non-photocurable resin composition layer 3 with an alkali developing solution.

Description

  The present invention particularly relates to a method for producing an optical waveguide using a negative photoresist and a dry film resist that can be suitably used for the optical waveguide.

  In recent years, research on optical waveguides and optical integrated circuits and optical modules using the same has been activated with the aim of reducing the size and cost of optical components. In particular, an optical waveguide using a polymer material has been attracting attention in recent years because it can be easily produced on a substrate by a method such as coating, and can be expected to reduce mass production and cost reduction. It has also been proposed to use a resist. Examples of the polymer material used for the optical waveguide include highly transparent resins such as polymethacrylate, polycarbonate, polyimide, and polysiloxane. In particular, polysiloxane is a polymer material having excellent transparency and heat resistance, and an optical waveguide using polysiloxane (see, for example, Patent Document 1) is used for applications requiring heat resistance, such as an optical waveguide. Application to the surface mounting of the optical element on the formed substrate can be expected.

  The optical waveguide is formed using a positive photoresist or a negative photoresist. In the case of using a negative photoresist, irradiation with patterned light reduces the solubility of the exposed portion of the negative photoresist in the developer, and the unexposed portion is dissolved and dispersed in the developer after development. By doing so, a pattern of an exposed portion is formed.

  Known polysiloxane negative photoresists include blends of acrylic polymers and epoxy polysiloxanes (see, for example, Patent Document 2), and siloxane modified products of acrylic polymers (see, for example, Patent Document 3). It has been.

  However, the negative photoresist using the resins described in Patent Documents 1 to 3 has high transparency of the cured product itself, but pattern exposure is performed on a substrate coated with a photocurable resin composition that is a raw material for the negative photoresist. However, if an optical waveguide is manufactured by a method in which an unnecessary portion is removed by development and a necessary pattern is formed, there is a problem that optical loss increases.

  Conventionally, for the purpose of improving adhesion and blocking oxygen, a dry film resist in which a polyvinyl alcohol layer is provided as a non-photocurable resin composition layer between a photocurable resin composition layer and a support film layer (for example, a patent However, the application of such a dry film resist to a polymer type optical waveguide is not known.

JP 2006-195175 A Japanese Patent Laid-Open No. 8-320564 JP 2008-209739 A JP-A-2-213849 JP-A-5-72724

  Accordingly, an object of the present invention is to provide a method for manufacturing an optical waveguide with little optical loss and to provide a dry film resist for an optical waveguide useful for the manufacturing method.

As a result of intensive studies in view of the above, the present inventors have reached the present invention.
That is, the present invention provides an optical waveguide manufacturing method including the following steps (I) to (III).
(I) A photocurable resin composition layer containing a photoradical initiator and a polymerizable compound, and a water-soluble non-photocurable resin composition layer are formed on the lower clad formed on the substrate in order from the bottom. Step (II) An exposure step (III) of exposing the photocurable resin composition layer using a photomask to form a core part (III) An unexposed portion of the photocurable resin composition layer and the above Alkali development process for removing water-soluble non-photocurable resin composition layer with alkali developer

  In the present invention, a water-soluble non-photocurable resin composition layer, a photocurable resin composition layer containing a photoradical initiator and a polymerizable compound, and a protective film as necessary in this order on a support film. The present invention provides a dry film resist characterized by being formed.

  The effect of the present invention is to provide an optical waveguide manufacturing method with little optical loss and an optical waveguide dry film resist useful for the manufacturing method.

FIG. 1 is a process diagram schematically showing an example of a method of manufacturing an optical waveguide according to the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the dry film resist of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of a dry film resist for forming an upper or lower clad.

Hereinafter, the manufacturing method and dry film resist of the optical waveguide of the present invention will be described in detail based on preferred embodiments.
The optical waveguide manufacturing method of the present invention is a manufacturing method including the following steps (I) to (III):
An optical waveguide with little optical loss can be provided.
(I) A photocurable resin composition layer containing a photoradical initiator and a polymerizable compound, and a water-soluble non-photocurable resin composition layer are formed on the lower clad formed on the substrate in order from the bottom. Step (II) An exposure step (III) of exposing the photocurable resin composition layer using a photomask to form a core part (III) An unexposed portion of the photocurable resin composition layer and the above Alkaline development process for removing the water-soluble non-photocurable resin composition layer with an alkaline developer Hereinafter, the method for producing an optical waveguide of the present invention will be described in the order of each process with reference to FIGS.
FIG. 1 is a process diagram schematically showing an example of a method for manufacturing an optical waveguide according to the present invention. In FIG. 1, 1 is a lower clad, 2 is a substrate, 3 is a water-soluble non-photocurable resin composition layer, 4 is a photocurable resin composition layer, 5 is an active energy ray, 6 is a photomask, and 7 is not yet used. An exposed portion, 8 is a core portion, and 9 is an upper clad. FIG. 2 is a schematic sectional view showing an example of the dry film resist of the present invention. In FIG. 2, 3 is a water-soluble non-photocurable resin composition layer, 4 is a photocurable resin composition layer, 10 is a support film, 11 is a protective film, and 12 is a dry film resist.
FIG. 3 is a schematic cross-sectional view mainly showing an example of a dry film resist used for forming the upper clad 9 or the lower clad 1. In FIG. 3, 4 is a photocurable resin composition layer, 10 is a support film, 11 is a protective film, and 13 is a dry film resist.

  In the method for producing an optical waveguide of the present invention, first, as a step before entering the step (I), a photocurable resin composition layer for forming a lower clad is formed on a substrate 2 as shown in FIG. Then, the photocurable resin composition layer is cured to form the lower cladding 1 having a desired thickness.

  The formation of the lower clad 1 using the photocurable resin composition may be performed by applying the photocurable resin composition on the substrate 2 and then curing by a conventional method, or the photocurable resin composition shown in FIG. You may use the dry film resist 13 which laminated the physical layer 4 with the protective film 11 and the support film 10. FIG.

  When the dry film resist 13 is used, the protective film 11 of the dry film resist 13 is peeled off and the surface of the photocurable resin composition layer 4 is bonded to the substrate 2 and then cured by a conventional method.

  The photocurable resin composition for forming the lower clad is not particularly limited as long as it has a lower refractive index than that of the core part 8, but a resin having a linear expansion coefficient close to that of the core part 8 after curing may be used. Preferably, it is more preferable to use the same resin as that of the core part 8 described later.

  The substrate 2 on which the lower cladding 1 is formed is not particularly limited as long as it is used as a substrate, and a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. The thickness of the substrate is not particularly limited.

<Process (I)>
In this step, as shown in FIG. 1B, a photocurable resin composition layer 4 and a water-soluble non-photocurable resin composition are sequentially formed on the lower clad 1 formed on the substrate 2 from the bottom. Layer 3 is formed.

The photocurable resin composition layer 4 and the water-soluble photocurable resin composition layer 3 may be formed in two stages by a method such as coating, or by using the dry film resist 12 of the present invention shown in FIG. You may form in one step.
When the two layers are formed by coating, as shown in FIG. 1 (b), a photocurable resin composition layer 4 is formed on the lower cladding 1, and a water-soluble non-photocurable resin composition is formed thereon. The material layer 3 may be formed.
Further, when the two layers are formed by using the dry film resist 12 of the present invention, the protective film 11 is peeled off from the dry film resist 12 produced for forming the core portion shown in FIG. The photocurable resin composition layer 4 and the water-soluble non-photocurable resin composition layer 3 may be formed by bonding the surfaces of the photocurable resin composition layer 4 together.
As the method for forming the two layers, it is preferable to use the dry film resist 12 of the present invention because the operation is simplified and suitable for mass production.

  The coating method in the case of forming a layer by the above-mentioned coating is not particularly limited, and examples thereof include dip coating, flow coating, brush coating, spray coating, extrusion coating, spin coating, roll coating, bar coating, and the like. Coating or the like can be used, and a patterned film can be formed by a method such as screen coating or roll transfer.

  The solvent that can be used when the water-soluble non-photocurable resin composition 3 is applied is not particularly limited as long as the water-soluble non-photocurable resin composition dissolves, but is soluble in water such as methanol and ethanol. It is preferable to use alcohol or water, and water is more preferable.

  The film thickness of the water-soluble non-photocurable resin composition layer 3 is not particularly limited, but is usually in the range of 2 to 50 μm, and preferably in the range of 3 to 10 μm. If the film thickness is less than 2 μm, it may be difficult to produce a uniform film. If the film thickness exceeds 50 μm, the amount of alkali developer used may increase, or development may take time. is there.

The water-soluble non-photocurable resin used for the water-soluble non-photocurable resin composition layer 3 is soluble in an alkaline aqueous solution, and the polymerization compound used in the photocurable resin composition layer 4 has a polymerization. It is a resin that does not have a functional group (polymerizable acrylic group, methacrylic group, etc.). As such a water-soluble non-photocurable resin, a known resin may be used, and examples thereof include resins described in JP-A-2-213849 and JP-A-5-72724.
Specifically, polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble salt of carboxyalkyl starch, water-soluble cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble Water-soluble salt of polyacrylic acid, water-soluble salt of polyacrylic acid, gelatin, ethylene oxide polymer, water-soluble salt of the group consisting of various starches and the like, styrene / maleic acid copolymer, maleate resin, etc. .
Among these, since it has high permeability and excellent solvent solubility, it is preferable to use polyvinyl alcohol or polyvinyl pyrrolidone, and it is more preferable to use polyvinyl alcohol. The water-soluble non-photocurable resin composition may be used alone or in combination of two or more.

  When forming the photocurable resin composition layer 4 by coating, a solvent may be used. When using a solvent, after forming the photocurable resin composition layer 4, it heat-processes in order to remove the solvent in a layer. The conditions for the heat treatment are appropriately selected according to the boiling point and vapor pressure of the solvent used, the thickness of the photocurable resin composition layer 4, and the heat resistance temperature of the object on which the layer is formed. Heat treatment for 30 seconds to 10 minutes is a standard.

  Examples of the solvent that can be used include aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene, and tetrahydronaphthalene; pentane, isopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, and nonane. , Isononane, decane, isodecane, isododecane, cyclohexane, methylcyclohexane, menthane, decahydronaphthalene and the like saturated hydrocarbon compounds; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1, Ether solvents such as 4-dioxane; acetone, methyl ethyl ketone, methyl Ketone solvents such as sobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclohexanone; ester solvents such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate; propylene glycol monomethyl ether acetate, ethylene glycol monoethyl Examples include glycol ester solvents such as ether acetate, dipropylene glycol methyl ether acetate, and diethylene glycol monoethyl ether acetate. These solvents can be used alone or in combination of two or more.

  Although the film thickness of the photocurable resin composition layer 4 is not specifically limited, the film thickness according to the light source and fiber used is preferable, and it is preferable that it is 3-100 micrometers in order to maintain the performance as an optical waveguide.

  The photocurable resin composition used for the photocurable resin composition layer 4 contains a photo radical initiator and a polymerizable compound. A photoradical initiator is a compound that generates radicals by light of a specific wavelength, and is a compound that is used as an initiator for photoradical polymerization by generating radicals. The polymerizable compound is a radical polymerizable compound having a substituent such as a polymerizable acrylic group or methacryl group.

<Polymerizable compound>
Examples of the polymerizable compound used in the photocurable resin composition include a monofunctional acrylic compound, a polyfunctional acrylic compound, and a polymerizable siloxane compound.
In the present invention, the polyfunctional acrylic compound refers to an acrylic compound having at least two acrylic groups or methacrylic groups not containing silicon, such as a polyfunctional acrylate compound, a polyfunctional epoxy acrylate compound, a polyfunctional urethane acrylate compound, and the like. Is mentioned.

Examples of the monofunctional acrylate compound include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) Acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl , (Meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid Dodecyl, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) a 2-methoxyethyl toluate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, (Meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl Ethyl, 2-perfluoroethyl (meth) acrylate, (meth) a Perfluoromethyl laurate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate, (meth) And (meth) acrylic acid monomers such as 2-perfluorodecylethyl acrylate and 2-perfluorohexadecylethyl (meth) acrylate.
Among these monofunctional acrylate compounds, a compound having an acrylic group is preferable because the curing time is fast.

  Examples of the polyfunctional acrylate compound that is one of the polyfunctional acrylic compounds include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Methylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide Modified pentaerythritol tetra (meth) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate Poly (meth) such as rate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A diacrylate, ethylene oxide modified bisphenol A diacrylate, urethane (meth) acrylate, polyester (meth) acrylate, etc. Examples include acrylic acid esters.

  The polyfunctional epoxy acrylate compound, which is one of the polyfunctional acrylic compounds, is a compound obtained by adding (meth) acrylic acid to an epoxy compound having an epoxy ring such as a glycidyl group or an alicyclic epoxy group. Examples of the epoxy compound used for the epoxy acrylate compound include aromatic epoxy compounds such as phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether; trimethylolpropane polyglycidyl ether, Aliphatic epoxy compounds such as neopentyl diglycidyl ether, hexanediol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) tetramethylene glycol diglycidyl ether; triglycidyl isocyanurate , Having a heterocyclic structure such as triglycidyltris (2-hydroxyethyl) isocyanurate Epoxy compounds; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane Carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl- 3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, methylene bis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane), dicyclopentadiene Epoxides, ethylenebis (3,4-epoxycyclohexane carboxylate), alicyclic epoxy compounds such as 1,2-epoxy-2-epoxy ethyl cyclohexane. The epoxy acrylate compound can be obtained by adding (meth) acrylic acid or the like to the above-described epoxy compound.

  The polyfunctional urethane acrylate compound, which is one of the polyfunctional acrylic compounds, has a hydroxyl group such as hydroxymethyl (meth) acrylate or hydroxyethyl (meth) acrylate in an isocyanate group of an isocyanate compound having at least two isocyanate groups. A compound obtained by reacting a hydroxyl group of an acrylic compound. Examples of the urethane compound used in the urethane acrylate compound include aromatic isocyanate compounds such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate; hexamethylene diisocyanate. Aliphatic isocyanate compounds such as lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate; alicyclic isocyanate compounds such as isophorone diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate) It is done.

  Among these polyfunctional acrylic compounds, a compound having an acrylic group is preferable because the curing time is fast.

The polymerizable siloxane compound is a siloxane compound having one or more siloxane structures and radical polymerizable reactive functional groups ((meth) acryl group, etc.) in the molecule, and the molecular weight and production method thereof are particularly It is not limited.
As the polymerizable siloxane compound, a compound having a carboxyl group is preferable because it is excellent in alkali developability, and in particular, because it is excellent in patterning property after photocuring of the core portion 8, it is represented by the following general formula (1). A polymerizable siloxane compound obtained by hydrolytic condensation reaction of a silane compound, a silane compound represented by the following general formula (2) and a cyclic siloxane compound represented by the following general formula (3) is more preferable.

（式中、Ｒ¹は水素原子又はメチル基を表わし、Ｒ²は炭素原子数２〜６の２価の飽和炭化水素基を表わし、Ｒ³は炭素原子数１〜４のアルキル基を表わし、Ｘ¹は炭素原子数１〜４のアルコキシ基又は塩素原子を表わし、ａは２又は３の数を表わす。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and a represents a number of 2 or 3.)

（式中、Ｒ⁴は同一でも異なってもよい炭素原子数１〜４のアルキル基又は炭素原子数６〜１０のアリール基を表わし、Ｘ²は炭素原子数１〜４のアルコキシ基又は塩素原子を表わし、ｂは１又は２の数を表わす。）

Wherein R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and X ² is an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. And b represents a number of 1 or 2.)

（式中、Ｒ⁵は炭素原子数１〜４のアルキル基又は炭素原子数６〜１０のアリール基を表わし、Ｘ³は下記一般式（４）で表わされる基又は下記一般式（５）で表わされる基を表わし、ｃは１分子あたりの下記一般式（４）で表わされる基の数である１〜５の数を表わし、ｄは１分子あたりの下記一般式（５）で表わされる基の数である１〜５の数を表わす。但し、ｃ＋ｄは３〜６の数である。）

(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X ³ represents a group represented by the following general formula (4) or the following general formula (5). C represents a number of 1 to 5 which is the number of groups represented by the following general formula (4) per molecule, and d represents a group represented by the following general formula (5) per molecule. Represents the number of 1 to 5 which is the number of (where c + d is the number of 3 to 6).

（式中、Ｒ⁶は炭素原子数２〜８の２価の炭化水素基を表わす。）

(In the formula, R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms.)

（式中、Ｒ⁷は炭素原子数２〜８の２価の脂肪族炭化水素基を表わし、Ｒ⁸及びＲ⁹は同一でも異なってもよい炭素原子数１〜４のアルキル基を表わし、ｅは２又は３の数を表わす。）

(In the formula, R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, R ⁸ and R ⁹ represent an alkyl group having 1 to 4 carbon atoms which may be the same or different, and e Represents a number of 2 or 3.)

  Hereinafter, polymerization obtained by hydrolytic condensation reaction of the unsaturated silane compound represented by the general formula (1), the silane compound represented by the general formula (2), and the cyclic siloxane compound represented by the general formula (3). The polymerizable siloxane compound (hereinafter sometimes referred to as the polymerizable siloxane compound of the present invention) will be described.

In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, and is preferably a methyl group because of good storage stability.
R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms. Examples of the divalent saturated hydrocarbon group having 2 to 6 carbon atoms include ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methylethylene, 2-methylethylene, 2-methylpropylene, Examples include 2-methylbutylene, 3-methylbutylene, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl and the like.
R ² is preferably ethylene, propylene and butylene, more preferably ethylene and propylene, from the viewpoint of the heat resistance of the cured product obtained from the photocurable resin composition and the industrial availability of the raw material monomer. Propylene is preferred and most preferred.

R ³ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, t-butyl and the like. R ³ is preferably methyl, ethyl and propyl, more preferably methyl and ethyl, and most preferably methyl because hydrolysis reaction is easy and heat resistance is improved.
X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, secondary butoxy, isobutoxy, t-butoxy and the like.
X ¹ is preferably a methoxy, ethoxy and chlorine atom, more preferably methoxy and ethoxy, and most preferably methoxy because hydrolysis reaction is easy. a represents the number of 2 or 3, and the number of 3 is preferable since the heat resistance of the cured product is improved.

  Of the unsaturated silane compounds represented by the general formula (1) in which a is a number 2, preferred compounds include (3-acryloxypropyl) methyldimethoxysilane and (3-acryloxypropyl) methyldiethoxysilane. , 3-acryloxypropyl) methyldichlorosilane, (3-acryloxypropyl) ethyldimethoxysilane, (3-acryloxypropyl) ethyldiethoxysilane, (3-acryloxypropyl) ethyldichlorosilane, (3-methacryloxy) Propyl) methyldimethoxysilane, (3-methacryloxypropyl) methyldiethoxysilane, (3-methacryloxypropyl) methyldichlorosilane, (3-methacryloxypropyl) ethyldimethoxysilane, (3-methacryloxypropyl) ethyldiethoxy Silane (3-methacryloxypropyl) ethyl dimethoxy silane, and (3-methacryloxypropyl) ethyldichlorosilane, and the like.

  Among the unsaturated silane compounds represented by the general formula (1) in which a is a number of 3, preferred compounds include (3-acryloxypropyl) trimethoxysilane, (3-acryloxypropyl) triethoxysilane, (3-acryloxypropyl) trichlorosilane, (3-methacryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) triethoxysilane, (3-methacryloxypropyl) trichlorosilane and the like.

In the general formula (2), R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{3 in} the general formula (1). Examples of the aryl group having 6 to 10 carbon atoms include phenyl and ethyl. Examples include phenyl, toluyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl, phenethyl and the like. R ⁴ is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably phenyl, because of improved heat resistance.
X ² represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include the alkoxy groups exemplified in the description of X ^{1 in} the general formula (1).
X ² is preferably methoxy, ethoxy and a chlorine atom, more preferably methoxy and ethoxy, and most preferably methoxy because hydrolysis reaction is easy. b represents the number of 1 or 2, and the number of 2 is preferable because crack resistance is improved.

The silane compound represented by the general formula (2) may be used alone, but since the heat resistance of the cured product is improved, the silane compound in which b is 1 and the number in which b is 2 It is preferable to use in combination with a silane compound which is When a silane compound in which b is the number 1 and a silane compound in which b is the number 2 are used in combination, the silane compound in which b is the number 1 is compared with the silane compound in which b is the number 2. The molar ratio is preferably 0 to 10, more preferably 0.5 to 5, and most preferably 1 to 3.
Further, silane compounds having different R ⁴ may be used in combination, but at least one of them is preferably a silane compound in which R ⁴ is phenyl. When silane compounds having different R ⁴ are used in combination, the proportion of phenyl groups in R ⁴ is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more. Is most preferred.

Preferred examples of the silane compound represented by the general formula (2) in which b is the number 1 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrichlorosilane, ethyl Examples include trimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, and phenyltrichlorosilane.
Among the silane compounds represented by the above general formula (2) in which b is the number 2, preferred examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, diethyldimethoxysilane, and diethyl. Dietoxysilane, Diethyldichlorosilane, Methylphenyldimethoxysilane, Methylphenyldiethoxysilane, Methylphenyldichlorosilane, Ethylphenyldimethoxysilane, Ethylphenyldiethoxysilane, Ethylphenyldichlorosilane, Diphenyldimethoxy Examples include silane, diphenyldiethoxysilane, and diphenyldichlorosilane.

In the general formula (3), R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{3 in} the general formula (1), and examples of the aryl group having 6 to 10 carbon atoms include the general formula (2 And the aryl group exemplified in the description of R ⁴ in FIG.
R ⁵ is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl, because of improved heat resistance.

X ³ represents a group represented by the general formula (4) or a group represented by the general formula (5). In the above general formula (4), R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. Examples of the divalent hydrocarbon group having 2 to 8 carbon atoms include ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methylethylene, 2-methylethylene, 2-methylpropylene, 2 A divalent aliphatic hydrocarbon group such as methylbutylene or 3-methylbutylene; 2 such as cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, 2-cyclohexylethane-1,4′-diyl, etc. Valent alicyclic hydrocarbon group; divalent aromatic hydrocarbon group such as 2-phenylethane-1,4′-diyl and the like.
As R ⁶ , ethylene, 2-methylethylene, and 2-phenylethane—from the viewpoint of heat resistance of a cured product obtained from the photocurable resin composition and industrial availability of the raw material monomer. 1,4′-diyl is preferred, 2-methylethylene and 2-phenylethane-1,4′-diyl are more preferred, and 2-methylethylene is most preferred.

In the general formula (5), R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms. Examples of the divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms include the divalent aliphatic hydrocarbon groups exemplified in the description of R ^{6 in} the general formula (4).
R ⁸ and R ⁹ represent an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{3 in} the general formula (1).
R ⁸ and R ⁹ are preferably methyl and ethyl, and more preferably methyl, because the hydrolysis reaction is easy.
e represents a number of 2 or 3, and since the linear expansion coefficient after curing is small, a number of 3 is preferable. c represents the number of 1 to 5 which is the number of groups represented by the above general formula (4) per molecule, and d is the number of the group represented by the above general formula (5) per molecule. Represents the number 5. However, c + d is a number of 3-6.
As c + d, the number of 3-5 is preferable, the number of 3-4 is more preferable, and the number of 4 is the most preferable from the industrial availability of a raw material.

  The cyclic siloxane compound represented by the general formula (3) includes a compound represented by the following general formula (4a) and a compound represented by the following general formula (5a) on the SiH group of the compound represented by the following general formula (3a). Can be obtained by a hydrosilylation reaction.

（式中、Ｒ⁵、ｃ及びｄは上記一般式（３）と同義である。）

(In the formula, R ⁵ , c and d have the same meaning as in the general formula (3).)

（式中、Ｒ¹⁰はＳｉＨ基の水素原子と反応してＲ⁶となる不飽和基を表わす。）

(In the formula, R ¹⁰ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^6. )

（式中、Ｒ¹¹はＳｉＨ基の水素原子と反応してＲ⁷となる不飽和基を表わし、Ｒ⁸、Ｒ⁹及びｅは上記一般式（５）と同義である。）

(In the formula, R ¹¹ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^7, and R ⁸ , R ^9, and e have the same meaning as in the general formula (5).)

In the general formula (3a), R ⁵ , c and d have the same meaning as in the general formula (3). Preferred examples of the cyclic siloxane compound represented by the general formula (3a) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4, 6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, and 2,4,6,8,10, Examples thereof include 12-hexamethylcyclohexasiloxane.

In the general formula (4a), R ¹⁰ represents an unsaturated group that reacts with a hydrogen atom of a SiH group to become R ⁶ . Preferred examples of the compound represented by the general formula (5a) include acrylic acid, methacrylic acid, 3-methyl-3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7 -Octenoic acid, 2-vinylcyclohexanecarboxylic acid, 3-vinylcyclohexanecarboxylic acid, 4-vinylcyclohexanecarboxylic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid and the like.

In the general formula (5a), R ¹¹ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^7, and R ⁸ , R ^9, and e have the same meaning as in the general formula (5). Preferred examples of the unsaturated silane compound represented by the general formula (5a) include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

  In the reaction of the polymerizable siloxane compound of the present invention, when the reaction ratio of the unsaturated silane compound represented by the general formula (1) is too small, curing is insufficient, and when it is too large, crack resistance is reduced. Therefore, the reaction ratio of the unsaturated silane compound represented by the general formula (1) is preferably 10 to 90 mol%, more preferably 20 to 75 mol%, and more preferably 25 to 65 mol%. Most preferably.

  In the reaction of the polymerizable siloxane compound of the present invention, when the reaction ratio of the silane compound represented by the general formula (2) is too small, curing is insufficient, and when it is too large, crack resistance is reduced. Therefore, the reaction ratio of the silane compound represented by the general formula (2) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and 15 to 60 mol%. Most preferred.

  In the reaction of the polymerizable siloxane compound of the present invention, if the reaction ratio of the cyclic siloxane compound represented by the general formula (3) is too small, the alkali developability becomes insufficient, and if it is too large, the film at the time of development is insufficient. Since the reduction increases, the reaction ratio of the cyclic siloxane compound represented by the general formula (3) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and more preferably 15 to 70. Most preferably, it is mol%.

As mentioned above, although the polymerizable compound used for a photocurable resin composition was demonstrated, since heat resistance is requested | required for core part formation in these polymerizable compounds, a polymerizable siloxane compound is preferable.
When a polymerizable siloxane compound is used as the polymerizable compound, it is preferable to use a monofunctional acrylic compound or a polyfunctional acrylic compound, more preferably a polyfunctional acrylic compound, because the mechanical strength of the cured product is improved. .
The content of the monofunctional acrylic compound or polyfunctional acrylic compound is preferably 5 to 250 parts by mass, more preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the polymerizable siloxane compound. More preferably, it is -150 mass parts.

  Furthermore, when a polymerizable siloxane compound is used as the polymerizable compound, it is preferable to use a polyfunctional epoxy compound in combination because adhesion to the substrate is improved.

The polyfunctional epoxy compound is a polyfunctional epoxy compound that does not contain a silicon structure in the central structure. For example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol Diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1 Tri (glycidyloxymethyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) Aliphatic epoxy compounds of methane; aromatic epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolak type epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate And alicyclic epoxy compounds such as 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; tetraglycidyl diaminodiphenylmethane, tri Glycidylamines such as glycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dicyclopentadiene dioxide and the like A diphthalene type epoxy compound, a triphenylmethane type epoxy compound, a dicyclopentadiene type epoxy compound, and the like.
Among these polyfunctional epoxy compounds, an aromatic epoxy resin is preferable because adhesion to the substrate is further improved.

  The content of the polyfunctional epoxy compound is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and 5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable siloxane compound. More preferably.

  Next, the photo radical initiator will be described. In the present invention, the photo radical initiator means a compound capable of initiating a polymerization reaction of radical polymerization by irradiation with active energy rays, and the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies, and the like. Can be mentioned. As the photoradical generator, ketone compounds such as acetophenone compounds, diketone compounds, benzophenone compounds, and thioxanthone compounds are preferable.

  The content of the photo radical initiator is preferably 1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and 2 to 7 parts by mass with respect to 100 parts by mass of the polymerizable compound. More preferably.

  In addition to the above, the photocurable resin composition layer, if necessary, a photosensitizer, a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, an antifoaming agent, a pigment, Dye etc. can be mix | blended.

<Process (II)>
In this step, the photocurable resin composition layer 4 formed in the step (I) is exposed using the photomask 6 to form the core portion 8.
Specifically, as shown in FIG. 1C, the photocurable resin composition layer 4 is irradiated (exposed) with the active energy ray 5 through the photomask 6, thereby exposing the photocurable resin composition. As for the layer 4, only the part used as the core part 8 is hardened | cured as shown in FIG.1 (d). Through such an exposure process, the core portion 8 is formed.

  In this step, the photocurable resin composition layer 4 is cured by irradiating the active energy ray 5, but heat treatment may be performed to improve the adhesion between the cured product layer and the substrate 2. . Such heat treatment is preferably performed at a temperature of 100 to 260 ° C. for 15 minutes to 2 hours in an inert gas atmosphere such as nitrogen, helium, or argon.

As the light source for irradiating the active energy ray 5, ultra high pressure mercury lamp, deep UV lamp, high pressure mercury lamp, low pressure mercury lamp, metal halide lamp, excimer laser, fluorescent lamp, light emitting diode, tungsten lamp, xenon lamp, carbon arc lamp, semiconductor laser, etc. These light sources are appropriately selected according to the photosensitive wavelength of the photo radical initiator used.
The irradiation energy of the active energy ray 5 is appropriately selected depending on the thickness of the photocurable resin composition layer 4 and the water-soluble non-photocurable resin composition layer 3, the type and amount of the photoradical initiator.

<Process (III)>
In this step, as shown in FIG. 1 (e), the unexposed portion 7 and the water-soluble non-photocurable resin composition layer 3 of the photocurable resin composition layer 4 are removed with an alkali developer to obtain an optical waveguide. The core part 8 is left.

  The alkali developer is not particularly limited, and examples thereof include inorganic alkalis such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium silicate, and ammonia; primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonene, etc. Cyclic tertiary amines; An aqueous solution of an alkali such as an aromatic tertiary amine such as chloroquine, collidine, lutidine and quinoline; an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used. The alkali concentration of the developing solution used for the removal of the conventional negative type photocurable resin composition layer may be sufficient. These alkaline aqueous solutions may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant.

  As the contact method with the alkali developer, for example, any method such as a liquid piling method, a dipping method, a shower method, or a spray method can be used, and the contact time is determined by the photocurable resin composition to be used. Although it varies depending on the molecular weight, the temperature of the developer, etc., it is usually 30 to 180 seconds. After removing the portion having improved alkali solubility with an alkaline developer, it is preferably rinsed with running water or shower, and may be dehydrated and dried in the range of 50 to 120 ° C. if necessary.

  After the step (III) according to the present invention, heat treatment may be performed to improve the adhesion between the core portion 8 and the object such as the substrate 2. Such heat treatment is preferably performed at a temperature of 100 to 260 ° C. for 15 minutes to 2 hours in an inert gas atmosphere such as nitrogen, helium, or argon.

  After the step (III) according to the present invention, when the above heat treatment is performed, the photocurable resin used for forming the lower clad so as to embed the core portion 8 as shown in FIG. An optical waveguide with little optical loss can be produced by covering with a composition and curing by a conventional method to form the upper clad 9.

  In the formation of the upper clad 9 using the photocurable resin composition, as with the formation of the lower clad 1, the photocurable resin composition may be applied and then cured by a conventional method, as shown in FIG. You may use the dry film resist 13 which laminated the photocurable resin composition layer 4 with the protective film 11 and the support film 10. FIG.

  When the dry film resist 13 is used, the protective film 11 of the dry film resist 13 is peeled off, and the surface of the photocurable resin composition layer 4 is bonded to the surface on which the core portion 8 is formed. It only has to be cured.

  The optical waveguide obtained by the optical waveguide manufacturing method of the present invention described above can be suitably used for optical devices such as optical waveguide devices, optical integrated circuits, and optical wiring boards, in particular, optical devices using a surface emitting laser as a light source. .

  Further, in the optical waveguide obtained by the method for manufacturing an optical waveguide of the present invention, the resin used for the photocurable resin composition layer 4 is excellent in transparency, insulation, heat resistance, chemical resistance, and the like. As an active matrix substrate having a photocurable resin composition layer 4 as an interlayer insulating film and used in a liquid crystal display device, an organic EL display device, etc., among others, an active matrix substrate having a TFT having a polycrystalline silicon thin film as an active layer Very useful.

  In addition, the optical waveguide obtained by the method of manufacturing an optical waveguide of the present invention includes a photocurable resin composition layer 4 and a wafer coating material (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film). , Junction coating) or a package material (sealing material, die bonding material), which is also useful as a semiconductor element, a multilayer wiring board, or the like. As semiconductor elements, individual semiconductor elements such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAM (dynamic random access memory), SRAM (static random access memory), EPROM (erasable programmable)・ Read-only memory (ROM), mask ROM (mask read-only memory), EEPROM (electrically erasable programmable read-only memory), storage elements such as flash memory, microprocessors, DSP, ASIC, etc. Theoretical circuit elements, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), light emitting diodes Such a photoelectric conversion element such as a charge coupled device and the like. Examples of the multilayer wiring board include a high-density wiring board such as MCM.

  Next, the dry film resist of the present invention will be described with reference to FIG.

  As shown in FIG. 2, in the dry film resist 12 of the present invention, a water-soluble non-photocurable resin composition layer 3 and a photocurable resin composition layer 4 are formed on a support film 10 in this order. The protective film 11 is formed on the photocurable resin composition layer 4 as necessary.

  As the water-soluble non-photocurable resin composition layer 3 and the photocurable resin composition layer 4 constituting the dry film resist 12 of the present invention, preferred conditions of the respective layers described in the method for producing an optical waveguide are the same. Applied.

  As the support film 10, for example, a PET film, a polyethylene film, a polypropylene film, and the like can be used, but a PET film is preferable because of excellent thermal characteristics and mechanical characteristics as the support film 10. The film thickness of the support film 10 is usually in the range of 1 to 5 μm, and it is preferable to be in the range of 10 to 100 μm because it is easy to form the clad and core portion of the optical waveguide.

  As the protective film 11 formed as necessary, for example, a polyethylene terephthalate (hereinafter abbreviated as PET) film, a polyethylene film, an ethylene-vinyl acetate copolymer (EVA) film, or the like can be used, but it is inexpensive. A polyethylene film is preferable because of excellent surface slipperiness. The film thickness of the protective film 11 is usually in the range of 1 to 500 μm, and is preferably in the range of 5 to 100 μm because peeling is easy.

Next, an example of the preferable manufacturing method of the dry film resist of this invention is demonstrated.
First, as shown in FIG. 2, a water-soluble non-photocurable resin composition layer 3 and a photocurable resin composition layer 4 having a desired thickness are formed on the support film 10 in this order.

  The method for forming the water-soluble non-photocurable resin composition layer 3 on the support film 10 and the method for forming the photocurable resin composition layer 4 on the water-soluble non-photocurable resin composition layer 3 are the above-mentioned optical The method may be the same as the method for manufacturing the waveguide, and preferred solvents and film thicknesses are also the same.

  After the above two layers are formed on the support film 10, pre-baking is performed to remove the solvent in the layers, and a protective film 11 is formed on the photocurable resin composition layer 4 to produce a dry film resist 12. The

  Although the method to form the protective film 11 on the photocurable resin composition layer 4 is not specifically limited, For example, what is necessary is just to stick using a coating machine.

  When using the dry film resist 12 of this invention, after peeling off the protective film 11 from the dry film resist 12, it thermocompression-bonded to the target object, affixed on the target object, and the support film 10 was peeled off as needed. Thereafter, exposure, development, and the like may be performed under the above conditions.

  The dry film resist of the present invention described above is suitable for forming an optical waveguide, particularly a core portion of the optical waveguide. The water-soluble non-photocurable resin used for the water-soluble non-photocurable resin composition layer is the above-described dry film resist. , Polyvinyl alcohol or polyvinylpyrrolidone, and the polymerizable compound used in the photocurable resin composition layer is an unsaturated silane compound represented by the general formula (1) and a silane represented by the general formula (2). The dry film resist, which is a polymerizable siloxane compound obtained by hydrolytic condensation reaction of the compound and the cyclic siloxane compound represented by the general formula (3), is excellent in heat resistance and the like. Is preferred

  EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these. In the examples, “parts” and “%” are based on mass.

○ Manufacture of photocurable resin composition for forming core part [Production Example 1-1: Production of polymerizable siloxane compound A-1 of the present invention]
<Step 1: Production of cyclic siloxane compound a-1>
In a reaction vessel having a stirrer, a thermometer and a refluxer, 300 g of toluene as a solvent and 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a compound represented by the above general formula (3a) , And 0.0001 g of a platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) was charged as a catalyst. While stirring, 213 g (1.5 mol) of methacrylic acid t-butyl ester was added over 1 hour at 60 ° C., and the mixture was further aged by stirring for 4 hours. Next, 77 g (0.52 mol) of vinyltrimethoxysilane was added as a compound represented by the general formula (5a) over 1 hour, and the mixture was further aged by stirring at 70 ° C. for 5 hours. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C., and the cyclic siloxane compound a (represented by the above general formula (3) in which the carboxyl group in the above general formula (4) was capped (protected) with a t-butyl group. Cyclic siloxane compound a-1) was obtained.

<Step 2: Production of polymerizable siloxane compound A-1 of the present invention>
In a reaction vessel having a stirrer, a thermometer and a refluxer, 122.5 g (0.50 mol) of 3-methacryloxypropyltrimethoxysilane as a compound represented by the above general formula (1), and the above general formula (3) 246.7 g (0.3 mol) of cyclic siloxane compound a-1 as the compound represented, 90 g (0.45 mol) of phenyltrimethoxysilane and 46.23 g of diphenyldimethoxysilane as the compound represented by the general formula (2) (0.2 mol) and 100 g of toluene as a solvent were added, 30 g of a 5% oxalic acid aqueous solution was added dropwise at 5 to 10 ° C. over 1 hour with ice cooling, and the mixture was further stirred at 10 ° C. for 15 hours.
Reflux dehydration and dealcoholization treatment was performed at 50 ° C. under reduced pressure, and the solvent toluene was changed to propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) at 50 ° C. under reduced pressure to obtain a 25% PGMEA solution. In order to remove the t-butyl group, 5 g of boron trifluoride diethyl ether complex was added, and the mixture was stirred at 80 ° C. for 3 hours, and then an acidic substance adsorbent (trade name: Kyoward 500SH, manufactured by Kyowa Chemical Industry). 30 g was added and further stirred at 80 ° C. for 1 hour.
About the obtained slurry liquid, after removing a solid substance by filtration, it concentrated under reduced pressure and the 50% PGMEA solution of polymeric siloxane compound A-1 of this invention was obtained. The mass average molecular weight of the obtained polymerizable siloxane compound A-1 of the present invention was determined by GPC analysis. The results are shown in [Table 1] below.

[Production Examples 1-2 to 1-4: Production of polymerizable siloxane compounds A-2 to A-4 of the present invention]
Production Example 1 except that the amount of the compound represented by the general formulas (1) to (3) was changed to the number of moles shown in the following [Table 1] (number in () in [Table 1]). The same operation as 1 was performed to obtain a 50% PGMEA solution of the polymerizable siloxane compounds A-2 to A-4 of the present invention. The mass average molecular weights of the obtained polymerizable siloxane compounds A-2 to A-4 of the present invention were determined by GPC analysis. The results are shown in [Table 1] below.
In [Table 1] below, the amount of the compound represented by the general formulas (1) to (3) used in Production Example 1-1 and the terminal structure of the resulting polymerizable siloxane compound are also shown. Show.

[Production Example 1-5: Production of polymerizable siloxane compound A-5]
In Production Example 1-1, the amount of 3-methacryloxypropyltrimethoxysilane used was reduced from 122.5 g (0.50 mol) to 56.4 g (0.23 mol), and 246.7 g of cyclic siloxane compound a ( 2- (t-butoxycarbonyl) propyltrimethoxysilane 118.8 g (0.45 mol) is used instead of 0.3 mol), and the amount of phenyltrimethoxysilane used is 90 g (0.45 mol) to 60 g. (0.3 mol) and the same operation as in Production Example 1-1 except that the amount of diphenyldimethoxysilane used was reduced from 46.2 g (0.2 mol) to 36.5 g (0.15 mol). And a 50 mass% PGMEA solution of polymerizable siloxane compound A-5 was obtained. The obtained polymerizable siloxane compound A-5 had a mass average molecular weight of 3,200 as determined by GPC analysis.

[Production Example 1-6: Production of polymerizable siloxane compound A-6]
A 50 mass% PGMEA solution of polymerizable siloxane compound A-6 was obtained according to Synthesis Example 1-1 of JP-A-2008-201881. The obtained polymerizable siloxane compound A-6 had a mass average molecular weight of 12,000 as determined by GPC analysis.

[Preparation of photocurable resin composition for core formation]
A-1 to A-6 as a polymerizable siloxane compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (B-1) as a photo radical initiator, and PEGMEA ( C-1), using tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate (D-1) as a polyfunctional acrylic compound, after blending to have the composition shown in Table 2 below, Filtration was performed to prepare photocurable resin compositions X-1 to X-6.

○ Manufacture of photocurable resin composition Y-1 for forming lower and upper clads [Production Example 2-1: Production of silicon-containing polymer A]
In accordance with the examples of JP 2007-238868 A, a silicon-containing polymer A for forming lower and upper clads was obtained by the following method.

In the reaction vessel 1, 119.0 g (0.6 mol) of phenyltrimethoxysilane, 48.1 g (0.4 mol) of dimethyldimethoxysilane, and 108.0 g of 0.032% phosphoric acid aqueous solution as a catalyst were mixed and heated to 10 ° C. After stirring for 2 hours, 6.06 g of 0.5 mol / L sodium hydroxide aqueous solution was added.
In the reaction vessel 2, 246.4 g (1.00 mol) of 3,4-epoxycyclohexylethyltrimethoxysilane and 108.0 g of ethanol were mixed, and 108.0 g of 0.032% phosphoric acid aqueous solution was mixed. The reaction solution was added dropwise over 5 minutes while being careful not to exceed 10 ° C, and stirred at 10 ° C or lower for 2 hours. Then, 6.06 g of 0.5 mol / L sodium hydroxide aqueous solution was added.

The reaction liquid in the reaction tank 2 was added to the reaction tank 1 and mixed, and then 1200 ml of toluene and 1200 ml of ethanol were added, and the outer bath was heated to 130 ° C. While removing water by azeotropic distillation, polycondensation was performed until the weight-average molecular weight of the silicon-containing polymer reached 9000 or more. 1780 g (12 mol) of triethyl orthoformate was added and heated to 130 ° C. After reaching 130 ° C., the mixture was heated and stirred for 1 hour. 90 g of adsorbent was added, and the mixture was heated and stirred at 100 ° C. for 1 hour. After removing the adsorbent by filtration, volatile components were removed at 60 ° C. and 20 mmHg, and 45 g of toluene and 1000 g of methanol were added to separate the two layers. Volatile components were removed from the lower layer at 60 ° C. and 3 mmHg to obtain a silicon-containing polymer A.
The mass average molecular weight of the silicon-containing polymer A was 12000, the epoxy equivalent measured by the potentiometric method was 307, and no silanol group (Si—OH) was detected by analysis by ¹ H-NMR.

  For silicon polymer A, bis- [4- (bis (4-butoxyphenyl) sulfonio) phenyl] sulfide hexafluoroantimonate (B-2) as a photo radical initiator, PGMEA (C-1) as a solvent, 2,2-bis (3,4-epoxycyclohexyl) propane (E-1) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (E-2) are used as polyfunctional epoxy compounds. Then, after blending so as to have the composition shown in [Table 3] below, the resin composition for forming lower and upper clads was prepared by filtration.

Preparation of dry film resist The following dry film resists were prepared according to Japanese Patent Application Laid-Open No. 2007-238868.

[Preparation of dry film resist for core formation]
Preparation of a dry film resist for forming a core part was performed according to the following Preparation Example 3-1 and Comparative Preparation Example 3-1. In addition, the following were used for the support film (protective film) and the water-soluble non-photocurable resin composition.

<Support film, protective film>
PET (product name: TN-200, manufactured by Toyobo Co., Ltd.)

<Water-soluble non-photocurable resin composition>
Polyvinyl alcohol (hereinafter abbreviated as PVA, manufactured by Wako Pure Chemical Industries, Ltd., trade name: polyvinyl alcohol polymerization degree 500)

[Production Method 3-1]
Using an applicator on the PET film as the support film, a polyvinyl alcohol (PVA) aqueous solution for forming a water-soluble non-photocurable resin composition layer is coated to a thickness of about 10 μm and heated in an oven at 100 ° C. for 10 minutes. And dried.
Next, the thickness after drying the photocurable resin compositions X-1 to X-6 described in [Table 2] above using the applicator for the water-soluble non-photocurable resin composition layer (PVA layer) formed. The film was coated to a thickness of about 30 μm, and dried by heating in an oven set at 100 ° C. for 10 minutes. After taking out from the oven and air-cooling, a PET film was attached as a protective film on the photocurable resin composition layer to prepare a dry film resist for forming a core part of the present invention.
In addition, when the dry film resist is produced by the production method 3-1 using the photocurable resin composition X-3, the resin after being coated on the support film (PET film) and dried is fluid and flows. Therefore, it was difficult to store after production.

[Comparative Manufacturing Method 3-1]
Using an applicator on the PET film to be the support film, the photocurable resin compositions X-1 to X-6 described in [Table 2] are coated so that the thickness after drying is about 30 μm. It was dried by heating for 10 minutes in an oven set at ° C. After taking out from the oven and air-cooling, a PET film was attached as a protective film on the photocurable resin composition layer, and a comparative dry film resist for forming a core part was produced.

[Production of dry film resist for forming lower clad]
Using an applicator on the PET film to be the support film, the photocurable resin composition Y-1 was coated so that the thickness after drying was about 30 μm, and heated in an oven set at 100 ° C. for 10 minutes. Dried. After taking out from the oven and air-cooling, a PET film was attached as a protective film on the photocurable resin composition layer to prepare a dry film resist for forming a lower clad.

[Production of dry film resist for upper clad formation]
Using an applicator on the PET film to be the support film, the photocurable resin composition Y-1 was coated so that the thickness after drying was about 70 μm, and heated in an oven set at 100 ° C. for 10 minutes. Dried. After taking out from the oven and air-cooling, a PET film was attached as a protective film on the photocurable resin composition layer to prepare a dry film resist for forming an upper clad.

Production of Optical Waveguide Using the dry film resist for forming the lower clad, the upper clad and the core formed as described above, and the Si wafer substrate, an optical waveguide was produced by the following procedure.

[Formation of lower cladding]
The protective film of the dry clad forming dry film resist is peeled off, the surface of the photocurable resin composition layer is placed on the Si wafer substrate, and set in a diaphragm type vacuum laminator (manufactured by Nichigo Morton, model: V-130). did. After reducing the pressure for 60 seconds at a temperature of 60 ° C. and a degree of vacuum of 1 Pa or less, the dry film was bonded to the substrate under the conditions of a temperature of 60 ° C., a pressure of 0.5 MPa, and a pressurization time of 60 seconds to form a lower clad material layer. After taking out from the vacuum laminator device and air-cooling and peeling off the support film, the surface of the lower clad material layer made of the photocurable resin composition layer was flattened by heating in an oven at 90 ° C. for 1 minute. Thereafter, the lower clad material layer was irradiated with 2000 mJ / cm ² (converted to a wavelength of 365 nm exposure) with an ultra-high pressure mercury lamp, and further heated and cured in an oven at 180 ° C. for 15 minutes to form the lower clad.

[Formation of core part]
[Production Method 4-1: Formation of Core Using Dry Film Resist of the Present Invention, Exposure Step under Air]
The protective film of the dry film resist for forming a core part of the present invention produced by the production method 3-1 is peeled off, the surface of the photocurable resin composition layer is placed on the lower clad obtained above, and the diaphragm type Set to vacuum laminator. After reducing the pressure for 60 seconds at a temperature of 60 ° C. and a degree of vacuum of 1 Pa or less, the core film-forming dry film resist was bonded to the lower cladding under the conditions of a temperature of 60 ° C., a pressure of 0.6 MPa, and a pressurization time of 60 seconds. In this order, a substrate, a lower clad, a photocurable resin composition layer, a water-soluble non-photocurable resin composition layer, and a core material layer as a support film were formed. After taking out from the vacuum laminator apparatus and air-cooling and peeling off the support film, the surface of the core material layer was flattened by heating in an oven at 90 ° C. for 1 minute. After air cooling, the core material layer was irradiated with 2000 mJ / cm ² (converted to a wavelength of 365 nm exposure) under an air atmosphere with a super high pressure mercury lamp through a photomask (mask width 40 μm, mask-to-mask distance 100 μm). After ultraviolet irradiation, development was performed with 0.3 wt% -NaOH aqueous solution for 15 seconds, and washing was performed with ultrapure water rinse for 60 seconds. Then, as post-baking, it heated for 30 minutes in 180 degreeC oven, and the core part was formed.

[Production Method 4-2: Formation of Core Part by Application, Exposure Step in Air Atmosphere]
Using an applicator on the lower clad obtained above, the photocurable resin composition described in [Table 2] was coated so that the thickness after drying was about 30 μm, and the oven was set at 120 ° C. Heated for 10 minutes and dried to obtain a photocurable resin composition layer. Next, a PVA aqueous solution was applied to a thickness of about 10 μm, heated in an oven at 120 ° C. for 10 minutes and dried, and in order from the bottom, the substrate, the lower cladding, the photocurable resin composition layer, the water-soluble non-light A core material layer to be a curable resin composition layer was formed. The core material layer was irradiated with ultraviolet rays of 2000 mJ / cm ² (wavelength 365 nm exposure conversion) in an air atmosphere by a super high pressure mercury lamp through a photomask (mask width 40 μm, mask distance 100 μm). After ultraviolet irradiation, development was performed with 0.3 wt% -NaOH aqueous solution for 15 seconds, and washing was performed with ultrapure water rinse for 60 seconds. Then, as post-baking, it heated for 30 minutes in 180 degreeC oven, and the core part was formed.

[Comparative production method 4-1: Step of not forming a water-soluble non-photocurable resin composition resin layer in production method 4-1]
In the production method 4-1, except that the core part forming dry film resist produced by the method of comparative production method 3-1 was used instead of the core part forming dry film resist 12 produced by the production method 3-1. Manufactured in the same manner as in Production method 4-1, and a core part was formed.

[Comparative production method 4-2: Step of forming a water-insoluble non-photocurable resin composition layer (PET layer) instead of the water-soluble non-photocurable resin composition layer in Production method 4-1]
The protective film of the dry film resist for forming a core part produced by the method of Comparative production method 3-1 is peeled off, the surface of the photocurable resin composition layer is placed on the lower clad obtained above, and a diaphragm type vacuum Set in the laminator. After reducing the pressure for 60 seconds at a temperature of 60 ° C. and a degree of vacuum of 1 Pa or less, the core film-forming dry film resist was bonded to the lower cladding under the conditions of a temperature of 60 ° C., a pressure of 0.6 MPa, and a pressurization time of 60 seconds. In this order, a substrate, a lower clad, a photocurable resin composition layer, and a core material layer serving as a support film were formed. After air cooling, the core material layer was irradiated with ultraviolet rays of 2000 mJ / cm ² (wavelength 365 nm exposure conversion) with an ultrahigh pressure mercury lamp through a photomask (mask width 40 μm, distance between masks 100 μm) in an air atmosphere. After the ultraviolet irradiation, the support film was peeled off, developed with a 0.3 wt% -NaOH aqueous solution for 15 seconds, and washed with ultrapure water rinse for 60 seconds. The core portion was formed by heating in an oven at 180 ° C. for 30 minutes.

[Comparative manufacturing method 4-3: Step of performing exposure in a nitrogen atmosphere in manufacturing method 4-1]
In the comparative manufacturing method 4-1, the core portion was formed by the same method as the comparative manufacturing method 4-1, except that the ultraviolet irradiation was performed in a nitrogen atmosphere instead of an air atmosphere.

[Comparative production method 4-4: Step of not forming a water-soluble non-photocurable resin composition resin layer in production method 4-2]
Using an applicator on the lower clad obtained above, the photocurable resin composition described in [Table 2] was coated so that the thickness after drying was about 30 μm, and the oven was set at 120 ° C. The mixture was heated for 10 minutes and dried to obtain a photocurable resin composition layer, and a core material layer serving as a substrate, a lower clad, and a photocurable resin composition layer was formed in this order from the bottom. The core material layer was irradiated with an active energy ray of 2000 mJ / cm ² (converted to a wavelength of 365 nm exposure) with an ultrahigh pressure mercury lamp through a photomask (mask width 40 μm, distance between masks 100 μm) in an air atmosphere. After ultraviolet irradiation, development was performed with 0.3 wt% -NaOH aqueous solution for 15 seconds, and washing was performed with ultrapure water rinse for 60 seconds. Then, as post-baking, it heated for 30 minutes in 180 degreeC oven, and the core part was formed.

[Formation of upper cladding: Fabrication of optical waveguide]
The protective film of the upper clad forming dry film resist was peeled off, and the surface of the photocurable resin composition layer was placed on the core part obtained above and set in a diaphragm type vacuum laminator. After reducing the pressure for 60 seconds at a temperature of 60 ° C. and a vacuum of 1 Pa or less, the dry film was bonded to the substrate under the conditions of a temperature of 60 ° C., a pressure of 0.6 MPa, and a pressurization time of 60 seconds to form an upper clad material layer. After taking out from the vacuum laminator apparatus and air-cooling and peeling off the support film, the surface of the upper clad material layer made of the photocurable resin composition was flattened by heating in an oven at 90 ° C. for 1 minute. After that, the upper clad material layer is irradiated with ultraviolet rays of 4000 mJ / cm ² (wavelength 365 nm exposure conversion) with an ultra-high pressure mercury lamp, and further heated and cured in an oven at 180 ° C. for 15 minutes to form the upper clad. The optical waveguides described in [Table 4] below were produced.

[Production of optical waveguide test piece for evaluation]
The optical waveguide with a substrate obtained above was diced to obtain an end face to obtain an optical waveguide having an optical path length of 5 cm. Thereafter, the optical waveguide was peeled from the substrate, and an optical waveguide test piece having a length in the optical path direction of 5 cm, a width of 40 μm, and a thickness of 40 μm was produced.

(Insertion loss measurement method)
The insertion loss was measured in accordance with the method for measuring insertion loss of “Test method for polymer optical waveguide (JPCA-4PE02-05-1S-2008)” of the JPCA standard. In addition, an aligning machine manufactured by Suruga Seiki Co., Ltd. was used, and a 0.85 μm ASE light source (manufactured by Fiber Lab, model: ASE0850-05) was used as a measurement light source. Light is incident from one end face (incident end) of the test piece with a single mode fiber, light emitted from the other end face (exit end) of the test piece is received by the 200 PCF fiber, and the light received by the fiber is a photodetector. (Measured by Anritsu, model MU931422A). In the measurement, a refractive index matching agent was used for each of the incident end and the exit end.

  From the above results, the optical waveguide produced by the production method of the present invention is less susceptible to oxygen inhibition due to the use of the water-soluble non-photocurable resin composition, and the optical loss is obtained because a pattern with the shape as designed is obtained. It was confirmed that there were few. Further, it can be seen that the production method of the present invention does not adversely affect the alkali development process, does not require an inert gas, and the production process is simple.

DESCRIPTION OF SYMBOLS 1 Lower clad 2 Board | substrate 3 Water-soluble non-photocurable resin composition layer 4 Photocurable resin composition layer 5 Active energy ray 6 Photomask 7 Unexposed part 8 Core part 9 Upper clad 10 Support film 11 Protective film 12 This invention Dry film resist 13 Dry film resist

Claims (11)

An optical waveguide manufacturing method including the following steps (I) to (III):
(I) A photocurable resin composition layer containing a photoradical initiator and a polymerizable compound, and a water-soluble non-photocurable resin composition layer are formed on the lower clad formed on the substrate in order from the bottom. Step (II) An exposure step (III) of exposing the photocurable resin composition layer using a photomask to form a core part (III) An unexposed portion of the photocurable resin composition layer and the above Alkali development process for removing water-soluble non-photocurable resin composition layer with alkali developer   The method for producing an optical waveguide according to claim 1, wherein the polymerizable compound is at least one selected from a monofunctional acrylic compound, a polyfunctional acrylic compound, and a polymerizable siloxane compound. The polymerizable siloxane compound is a hydrolytic condensation reaction of an unsaturated silane compound represented by the following general formula (1), a silane compound represented by the following general formula (2), and a cyclic siloxane compound represented by the following general formula (3). The method for producing an optical waveguide according to claim 2, wherein the polymerizable siloxane compound is obtained as described above.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and a represents a number of 2 or 3.)

Wherein R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and X ² is an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. And b represents a number of 1 or 2.)

(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X ³ represents a group represented by the following general formula (4) or the following general formula (5). C represents a number of 1 to 5 which is the number of groups represented by the general formula (4) per molecule, and d represents the number of groups represented by the general formula (5) per molecule. Represents a number of 1 to 5 where c + d is a number of 3 to 6.)

(In the formula, R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms.)

(Wherein R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, R ⁸ and R ⁹ independently represent an alkyl group having 1 to 4 carbon atoms, and e is 2 or Represents the number 3)   The said photocurable resin composition contains 5-250 mass parts of said monofunctional acrylic compounds or polyfunctional acrylic compounds with respect to 100 mass parts of said polymerizable siloxane compounds. The manufacturing method of the optical waveguide as described in 1 ..   5. The light according to claim 1, wherein the water-soluble non-photo-curable resin used in the water-soluble non-photo-curable resin composition layer is polyvinyl alcohol or polyvinyl pyrrolidone. A method for manufacturing a waveguide.   A dry film resist in which a water-soluble non-photocurable resin composition layer and a photocurable resin composition layer containing a photoradical initiator and a polymerizable compound are formed in this order on a support film, It uses for formation of the photocurable resin composition layer in step I), and a water-soluble non-photocurable resin composition layer, The manufacturing method of the optical waveguide of any one of Claims 1-5 characterized by the above-mentioned. .   The said dry film resist is a manufacturing method of the optical waveguide of Claim 6 by which the protective film is formed on the said photocurable resin composition layer.   A dry film characterized in that a water-soluble non-photocurable resin composition layer and a photocurable resin composition layer containing a photoradical initiator and a polymerizable compound are formed in this order on a support film. Resist.   The dry film resist according to claim 8, wherein a protective film is formed on the photocurable resin composition layer.   10. The dry film resist according to claim 8, wherein the dry film resist is used for forming a core portion of an optical waveguide. The water-soluble non-photo-curable resin used for the water-soluble non-photo-curable resin composition layer is polyvinyl alcohol or polyvinyl pyrrolidone, and the polymerizable compound is an unsaturated silane represented by the following general formula (1) A polymerizable siloxane compound obtained by hydrolytic condensation reaction of a compound, a silane compound represented by the following general formula (2) and a cyclic siloxane compound represented by the following general formula (3): 10. The dry film resist according to any one of 10 above.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and a represents a number of 2 or 3.)

Wherein R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and X ² is an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. And b represents a number of 1 or 2.)

(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X ³ represents a group represented by the following general formula (4) or the following general formula (5). C represents a number of 1 to 5 which is the number of groups represented by the general formula (4) per molecule, and d represents the number of groups represented by the general formula (5) per molecule. Represents a number of 1 to 5 where c + d is a number of 3 to 6.)

(In the formula, R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms.)

(In the formula, R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, R ⁸ and R ⁹ represent an alkyl group having 1 to 4 carbon atoms which may be the same or different, and e Represents a number of 2 or 3.)

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