JP2009175244A - Resin composition for optical material, resin film for optical material, and optical waveguide using them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for optical material which is excellent in transparency, curing property and heat resistance, to provide a resin film for optical material which uses the resin composition for optical material, and to provide an optical waveguide which uses the composition and the film, and is excellent in transparency, reliability and heat resistance. <P>SOLUTION: The resin composition for optical material contains: (A) an acrylic polymer and/or methacrylic polymer having a specified (meth)acrylic group as a repeating unit, and a repeating unit having an ethylenically unsaturated group bonded through an urethane bond in a side chain and/or a repeating unit having an ethylenically unsaturated group bonded through an amide bond in a side chain; (B) a polymerizable compound; and (C) a polymerization initiator. The resin film for an optical material is obtained by using the above resin composition for an optical material, and the optical waveguide is obtained by using the above composition or the film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition for an optical material, a resin film for an optical material, and an optical waveguide using these, and in particular, a resin composition for an optical material excellent in transparency, curability, and heat resistance, and the resin composition The present invention relates to a resin composition for forming an optical waveguide containing a product, a resin film for an optical material using the resin composition for an optical material, and an optical waveguide excellent in transparency, reliability, and heat resistance using the same.

In recent years, in high-speed and high-density signal transmission between electronic devices and between wiring boards, signal transmission interference and attenuation become barriers in conventional transmission using electric wiring, and the limits of high-speed and high-density are beginning to appear. In order to overcome this problem, a technique for optically connecting electronic elements and wiring boards, so-called optical interconnection, has been studied. As an optical transmission line, polymer optical waveguides are attracting attention because of their ease of processing, low cost, high flexibility in wiring, and high density.
As a form of the polymer optical waveguide, a type prepared on a glass epoxy resin substrate assumed to be applied to an opto-electric hybrid board, or a flexible type not having a hard support substrate assuming connection between boards is considered suitable.

Polymer optical waveguides require transparency (low light propagation loss) as well as heat resistance from the viewpoints of the usage environment of equipment and component mounting, but as such optical waveguide materials, (meth) acrylic Polymers (for example, see Patent Documents 1 to 3) are known.
However, although the (meth) acrylic polymers described in Patent Documents 1 to 3 have transparency at a wavelength of 850 nm, reliability evaluation such as light propagation loss after a high-temperature and high-humidity test or a temperature cycle test is specific. There is no description of the actual test results and it is not clear. Similarly, there is no description regarding specific test results such as evaluation of heat resistance, for example, light propagation loss after a solder reflow test, and it is not clear.

JP-A-63-81301 Japanese Patent Laid-Open No. 06-258537 JP 2003-195079 A

  The present invention has been made to solve the above-mentioned problems, and is a resin composition for optical materials excellent in transparency, curability and heat resistance, and a resin for optical materials using the resin composition for optical materials. It is an object of the present invention to provide a film and an optical waveguide excellent in transparency, reliability, and heat resistance using the film.

As a result of extensive studies, the present inventors have (A) a (meth) acrylic polymer having a specific repeating unit, (B) a polymerizable compound, and (C) a resin composition for an optical material containing a polymerization initiator, Or it discovered that the said problem could be solved by manufacturing an optical waveguide using the resin film for optical materials using this resin composition for optical materials.
That is, the present invention provides (A) ethylene having at least a repeating unit represented by the following general formula (1) and bonded to a side chain represented by the following general formula (2) via a urethane bond. A (meth) acrylic polymer containing a repeating unit having an ethylenically unsaturated group and / or a repeating unit having an ethylenically unsaturated group bonded to a side chain represented by the following general formula (3) via an amide bond, (B) Polymerizable compound, and (C) Optical material resin composition containing polymerization initiator

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 20 carbon atoms.)

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. X ¹ and X ² are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms. Is shown.)

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. X ³ and X ⁴ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms. And at least one of a resin film for optical material, a lower clad layer, a core portion, and an upper clad layer using the resin composition for optical material, or the optical material resin composition or optical material An optical waveguide formed using a resin film is provided.

  The resin composition for optical materials of the present invention and the resin film for optical materials using the resin composition for optical materials are excellent in transparency, curability, and heat resistance, and an optical waveguide produced using these Is excellent in transparency, reliability, and heat resistance.

  The resin composition for an optical material of the present invention includes (A) a (meth) acrylic polymer having a specific repeating unit, (B) a polymerizable compound, and (C) a polymerization initiator, and is irradiated with actinic rays or A resin composition that is cured by heating is preferred.

Hereinafter, the component (A) used in the present invention will be described.
The (meth) acrylic polymer in the component (A) of the present invention refers to a polymer obtained by polymerizing acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, and derivatives thereof as monomers. The (meth) acrylic polymer may be a homopolymer of the above monomer, or may be a copolymer obtained by polymerizing two or more of these monomers. Furthermore, the copolymer containing said monomer and monomers other than the above may be used in the range which does not inhibit the effect of this invention. Further, it may be a mixture of a plurality of (meth) acrylic polymers.
The component (A) of the present invention has at least a repeating unit represented by the following general formula (1).

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include monovalent organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, an ester group, and a carbamoyl group. Hydroxyl group, halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, carbonyl group, formyl group, ester group, carbamoyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, silyl group, silyloxy It may be substituted with a group or the like.

In the (meth) acrylic polymer of the component (A), the compound that is a raw material of the repeating unit represented by the general formula (1) is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, pentyl (meth ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl heptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) a Relate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, methoxypolyethylene glycol (meth) Aliphatic (meth) acrylic esters such as acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate And cycloaliphatic (meth) acrylates such as isobornyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (Meth) acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxyethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxy Aromatic (meth) acrylates such as polyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and phenoxypolypropylene glycol (meth) acrylate Ter; 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, heterocyclic (meth) acrylic acid esters such as 2- (meth) acryloyloxyethyl-N-carbazole, these Examples include modified caprolactone.
Among these, from the viewpoint of transparency and heat resistance, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate It is preferable that they are aliphatic (meth) acrylic esters such as: the above alicyclic (meth) acrylic esters; the above aromatic (meth) acrylic esters; and the above heterocyclic (meth) acrylic esters.
These compounds can be used alone or in combination of two or more.

  In the (meth) acrylic polymer of component (A), the content of the repeating unit represented by the general formula (1) is preferably 20 to 99 mol%. When it is 20 mol% or more, the obtained cured product does not become brittle, and when it is 99 mol% or less, the curability, the strength of the obtained cured product, and the heat resistance are sufficient. From the above viewpoint, the content of the repeating unit represented by the general formula (1) is more preferably 25 to 90 mol%, and particularly preferably 30 to 80 mol%.

  In addition, the (meth) acrylic polymer of the component (A) is composed of a repeating unit having an ethylenically unsaturated group bonded via a urethane bond to a side chain represented by the following general formula (2), and the following general formula ( 3) It has at least one repeating unit having an ethylenically unsaturated group bonded to the side chain represented by 3) via an amide bond. That is, it has one or both of the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3).

In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ and X ² each independently represent a single bond or a divalent organic group having 1 to 20 carbon atoms. Show.

In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ³ and X ⁴ each independently represent a single bond or a divalent organic group having 1 to 20 carbon atoms. Show.
In addition, since the repeating unit represented by the general formula (3) requires that an ethylenically unsaturated group is bonded via an amide bond, the organic group X ⁴ bonded to the amide group is bonded via carbon. Limited to what you do.

The organic group (R ^{3 to} R ⁶ ) in the general formulas (2) and (3) is the same as the organic group having 1 to 20 carbon atoms shown in the description of R ² described above.

  In the (meth) acrylic polymer of the component (A), the method for introducing the repeating unit having an ethylenically unsaturated group bonded to the side chain represented by the general formula (2) via a urethane bond is not particularly limited. For example, there may be mentioned a method in which an ethylenically unsaturated isocyanate, an ethylenically unsaturated phenol or the like is subjected to an addition reaction after copolymerizing an ethylenically unsaturated isocyanate or the like.

There is no restriction | limiting in particular as ethylenically unsaturated isocyanate, For example, N- (meth) acryloyl isocyanate, (meth) acryloyloxymethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxyethoxyethyl An isocyanate etc. are mentioned.
These compounds can be used alone or in combination of two or more.

The ethylenically unsaturated alcohol is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. Examples include (meth) acrylate.
These compounds can be used alone or in combination of two or more.

There is no restriction | limiting in particular as ethylenically unsaturated phenol, For example, o-vinylphenol, m-vinylphenol, p-vinylphenol, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p- Examples thereof include hydroxyphenyl (meth) acrylate, o-hydroxybenzyl (meth) acrylate, m-hydroxybenzyl (meth) acrylate, p-hydroxybenzyl (meth) acrylate and the like.
These compounds can be used alone or in combination of two or more.

  When the (meth) acrylic polymer of component (A) contains a repeating unit having an ethylenically unsaturated group bonded to the side chain represented by the general formula (2) via a urethane bond, the content is It is preferable that it is 1-80 mol%. When it is 1 mol% or more, the curability and the strength of the obtained cured product are sufficient, and when it is 80 mol% or less, the obtained cured product does not become brittle. From the above viewpoint, the content of the repeating unit represented by the general formula (2) is more preferably 3 to 60 mol%, and particularly preferably 5 to 40 mol%.

  In the (meth) acrylic polymer of component (A), the method for introducing the repeating unit having an ethylenically unsaturated group bonded to the side chain represented by the general formula (3) via an amide bond is not particularly limited. For example, there may be mentioned a method in which the ethylenically unsaturated isocyanate or the like is copolymerized and then an ethylenically unsaturated carboxylic acid or the like is subjected to an addition reaction.

The ethylenically unsaturated carboxylic acid is not particularly limited. For example, ((meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, mono (2- ( (Meth) acryloyloxyethyl) succinate, mono (2- (meth) acryloyloxyethyl) phthalate, mono (2- (meth) acryloyloxyethyl) isophthalate, mono (2- (meth) acryloyloxyethyl) terephthalate, mono ( 2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydroisophthalate, mono (2- (meth) (Acryloyloxyethyl) hexahydrotere Tallates, .omega.-carboxy - polycaprolactone mono (meth) acrylate, o- vinyl benzoate, m- vinylbenzoic acid, p- vinylbenzoic acid.
Among these, (meth) acrylic acid, crotonic acid, and mono (2- (meth) acryloyloxyethyl) hexahydrophthalate are preferable from the viewpoints of transparency, heat resistance, and reactivity.
These compounds can be used alone or in combination of two or more.

  When the (meth) acrylic polymer of component (A) has a repeating unit having an ethylenically unsaturated group bonded to the side chain represented by the general formula (3) via an amide bond, the content is 1 It is preferably ˜80 mol%. When it is 1 mol% or more, the curability and the strength of the obtained cured product are sufficient, and when it is 80 mol% or less, the obtained cured product does not become brittle. From the above viewpoint, the content of the repeating unit represented by the general formula (3) is more preferably 3 to 60 mol%, and particularly preferably 5 to 40 mol%.

  The (meth) acrylic polymer of the component (A) may further have a structural unit having a maleimide skeleton represented by the following general formula (4) as necessary from the viewpoint of heat resistance.

Wherein, R ⁷ represents an organic group of a hydrogen atom or a C 1-20. As the organic group represented by R ^7, the same as the organic group having 1 to 20 carbon atoms indicated in the foregoing description of R ^2.

In the (meth) acrylic polymer of component (A), the compound that is a raw material of the repeating unit having a maleimide skeleton represented by the general formula (4) is not particularly limited, and examples thereof include N-methylmaleimide and N-ethyl. Maleimide, N-propylmaleimide, N-isopropylmaleimide, N-2,2-dimethylpropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, N-2- Methyl-2-butylmaleimide, N-pentylmaleimide, N-2-pentylmaleimide, N-3-pentylmaleimide, N-hexylmaleimide, N-2-hexylmaleimide, N-3-hexylmaleimide, N-2-ethylhexyl Maleimide, N-heptylmaleimide, N-octyl Alkylmaleimides such as maleimide, N-nonylmaleimide, N-decylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-2-methylcyclohexylmaleimide, N-2- Cycloalkylmaleimides such as ethylcyclohexylmaleimide and N-2-chlorocyclohexylmaleimide; arylmaleimides such as N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide and N-2-chlorophenylmaleimide Can be mentioned.
Among these, from the viewpoints of transparency and heat resistance, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, Alkyl maleimides such as N-tert-butylmaleimide; cycloalkylmaleimides; arylarylimides are preferably used, and N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-2-methylcyclohexylmaleimide, N-phenylmaleimide Is more preferable.
These compounds can be used alone or in combination of two or more.

  When the (meth) acrylic polymer of the component (A) has a repeating unit having a maleimide skeleton represented by the general formula (4), the content is preferably 1 to 70 mol%. When it is 1 mol% or more, heat resistance derived from the maleimide skeleton is obtained, and when it is 70 mol% or less, transparency is sufficient and the obtained cured product does not become brittle. From the above viewpoint, the content of the repeating unit represented by the general formula (4) is more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%.

  The (meth) acrylic polymer of the component (A) may have a structural unit represented by the following general formula (5) as necessary from the viewpoint of developability with an alkaline developer.

In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ⁵ represents a single bond or a divalent organic group having 1 to 20 carbon atoms.

In the (meth) acrylic polymer of component (A), the method for introducing the repeating unit represented by the general formula (5) is not particularly limited. For example, a compound in which a carboxyl group such as an ethylenically unsaturated carboxylic acid is protected. A method for introducing a repeating unit having an ethylenically unsaturated group into the side chain represented by the general formula (2) and / or (3) and then deprotecting the protecting group of the carboxyl group after copolymerizing Etc.
The ethylenically unsaturated carboxylic acid is not particularly limited. For example, (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, mono (2- ( (Meth) acryloyloxyethyl) succinate, mono (2- (meth) acryloyloxyethyl) phthalate, mono (2- (meth) acryloyloxyethyl) isophthalate, mono (2- (meth) acryloyloxyethyl) terephthalate, mono ( 2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydroisophthalate, mono (2- (meth) (Acryloyloxyethyl) hexahydrotere Tallates, .omega.-carboxy - polycaprolactone mono (meth) acrylate, 3-vinylbenzoic acid, 4-vinylbenzoic acid.

  Among these, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, mono (2- (meth) acryloyloxyethyl) succinate, mono (2- (meta) from the viewpoint of transparency and developability with an alkaline developer. ) Acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydroisophthalate, mono (2- (meth) acryloyloxyethyl) Hexahydroterephthalate is preferred.

Further, the protective group for the carboxyl group is not particularly limited, and examples thereof include a t-butyl group and a silyl group.
In addition, repeating units having an ethylenically unsaturated group in the side chain represented by the general formula (2) and / or (3) are copolymerized using maleic anhydride, citraconic anhydride, and itaconic anhydride as raw materials. May be converted to a structural unit represented by the general formula (5) by opening with a suitable alcohol such as methanol, ethanol or propanol.
These compounds can be used alone or in combination of two or more.

  When the (meth) acrylic polymer of the component (A) has a repeating unit represented by the general formula (5), the content is preferably 3 to 60 mol%. When it is 3 mol% or more, development with an alkaline developer is easy. On the other hand, when it is 60 mol% or less, the developer is resistant to developing solution (the portion that becomes a pattern without being removed by development is not affected by the developer). Good properties). From the above viewpoint, the content of the repeating unit represented by the general formula (5) is more preferably 5 to 50 mol%, and particularly preferably 7 to 40 mol%.

The (meth) acrylic polymer of the component (A) may further have a repeating unit other than the repeating units represented by the general formulas (1) to (5) as necessary.
There is no restriction | limiting in particular as a compound which has an ethylenically unsaturated group used as the raw material of such a repeating unit, For example, styrene, alpha-methylstyrene, beta-methylstyrene, 3-methylstyrene, 4-methylstyrene, alpha , 2-dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, (meth) acrylonitrile, vinyl cyclohexyl ether, vinyl phenyl ether, vinyl benzyl ether, vinyl acetate, N-vinyl pyrrolidone, N-vinyl carbazole, Examples include vinyl pyridine, vinyl chloride, vinylidene chloride.
Among these, from the viewpoints of transparency and heat resistance, styrene, α-methylstyrene, β-methylstyrene, 3-methylstyrene, 4-methylstyrene, α, 2-dimethylstyrene, 2,4-dimethylstyrene, 2, 5-Dimethylstyrene, (meth) acrylonitrile, vinyl acetate, and N-vinylcarbazole are preferable.
These compounds can be used alone or in combination of two or more.

  The (meth) acrylic polymer of the component (A) is not particularly limited in its synthesis method. For example, the compound used as a raw material for the repeating unit represented by the general formulas (1) to (3), and if necessary, more general A compound that is a raw material of the repeating unit represented by formulas (4) and (5), a compound that is a raw material of a repeating unit other than the repeating units represented by general formulas (1) to (5), and an appropriate heat It can be obtained by copolymerization while heating using a radical polymerization initiator. At this time, if necessary, an organic solvent can be used as a reaction solvent. Moreover, it can also be used in combination with an appropriate chain transfer agent as required.

  The thermal radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1 -Bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane Peroxyketals such as 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; α, α′-bis (t-butyl Peroxy) diisopropylbenzene, dicumyl peroxide, t- Dialkyl peroxides such as butylcumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide and benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxide Peroxycarbonates such as oxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate; t-butyl peroxypivalate, t- Hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t -Hexilpa Oxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-3,5 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, Peroxyesters such as 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane and t-butylperoxyacetate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-Dimethylvaleronitrile), 2,2′- Zobisu (4-methoxy-2'-dimethylvaleronitrile) azo compounds and the like.

The organic solvent used as the reaction solvent is not particularly limited as long as it can dissolve the (meth) acrylic polymer of the component (A). For example, aromatics such as toluene, xylene, mesitylene, cumene, p-cymene, etc. Group hydrocarbons; chain ethers such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and dibutyl ether; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy Ketones such as -4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; ethylene glycol dimethyl ether Polyhydric alcohol alkyl ethers such as ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol Polyhydric alcohol alkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N, N-dimethylacetate Examples include amides such as toamide and N-methylpyrrolidone.
These organic solvents can be used alone or in combination of two or more.

The weight average molecular weight of the component (A) (meth) acrylic polymer is preferably 1,000 to 3,000,000. When it is 1,000 or more, the molecular weight is large, and the strength of the cured product when the resin composition is sufficient is sufficient. The compatibility of is good. From the above viewpoint, the (meth) acrylic polymer (A) component preferably has a weight average molecular weight of 3,000 to 2,000,000, more preferably 5,000 to 1,000,000. Particularly preferred.
The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

When the (meth) acrylic polymer of the component (A) has a repeating unit represented by the general formula (5), the acid value can be defined so that development is possible with an alkaline developer. For example, when an alkaline aqueous solution is used as the developer, the acid value is preferably 20 to 300 mgKOH / g. When it is 20 mgKOH / g or more, development is easy, while when it is 300 mgKOH / g or less, the developer resistance is not lowered. From the above viewpoint, the acid value is more preferably 30 to 250 mgKOH / g, and particularly preferably 40 to 200 mgKOH / g.
When an alkaline aqueous developer composed of an alkaline aqueous solution and one or more organic solvents is used as the developer, the acid value is preferably 10 to 260 mgKOH / g. When the acid value is 10 mgKOH / g or more, development is easy, and when it is 260 mgKOH / g or less, the developer resistance is not lowered. From the above viewpoint, the acid value is more preferably 20 to 250 mgKOH / g, and particularly preferably 30 to 200 mgKOH / g.

  (A) It is preferable that the compounding quantity of the (meth) acrylic polymer of a component is 10-85 mass% with respect to the total amount of (A) component and (B) component. When it is 10% by mass or more, the strength and flexibility of the cured product of the resin composition for optical materials is sufficient, and when it is 85% by mass or less, it is easily entangled by the component (B) during curing. The developer resistance is not insufficient. From the above viewpoint, the blending amount of the (meth) acrylic polymer is more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass.

Hereinafter, the component (B) used in the present invention will be described.
There is no restriction | limiting in particular as a polymeric compound of (B) component, For example, ethylenic unsaturated, such as (meth) acrylate, vinyl ether, vinyl ester, vinyl amide, arylated vinyl, vinyl pyridine, vinyl halide, vinylidene halide And compounds having a polymerizable substituent such as a group.
Among these, (meth) acrylate and arylated vinyl are preferably mentioned from the viewpoint of transparency and heat resistance.
As the (meth) acrylate, any of monofunctional, bifunctional, or trifunctional or higher polyfunctional ones can be used.

As monofunctional (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (Meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl heptyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl ( Acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro- 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, Aliphatic (meth) acrylates such as mono (2- (meth) acryloyloxyethyl) succinate; cyclopentyl (meth) acrylate Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, Alicyclic (meth) acrylates such as mono (2- (meth) acryloyloxyethyl) hexahydrophthalate; phenyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) Acrylate, 2-naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxy Siethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl ( Aromatic (meth) acrylates such as meth) acrylate; 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) Acryloyl heterocyclic (meth) acrylates such as oxyethyl -N- carbazole, and these caprolactone modified products thereof.
Among these, from the viewpoints of transparency and heat resistance, the alicyclic (meth) acrylate; the aromatic (meth) acrylate; and the heterocyclic (meth) acrylate are preferable.

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated polypropylene glycol di (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopent Glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated 2- Aliphatic (meth) acrylates such as methyl-1,3-propanediol di (meth) acrylate; cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, propoxylated cyclohexanedimethanol (meth) acrylate, Et Silylated propoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated tricyclodecane dimethanol (meth) acrylate, propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated propoxylation Tricyclodecane dimethanol (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated Fats such as hydrogenated bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, and ethoxylated propoxylated hydrogenated bisphenol F di (meth) acrylate Cyclic (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, propoxy Bisphenol F di (meth) acrylate, ethoxylated propoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol AF di (meth) acrylate, propoxylated bisphenol AF di (meth) acrylate, ethoxylated propoxylated bisphenol AF di (meth) ) Acrylate, ethoxylated fluorene type di (meth) acrylate, propoxylated fluorene type di (meth) acrylate, ethoxylated propoxylated fluorene type di (meth) acrylate Aromatic (meth) acrylates such as acrylates; heterocyclic (meth) acrylates such as ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, and ethoxylated propoxylated isocyanuric acid di (meth) acrylate These modified caprolactones; aliphatic (meth) acrylates such as neopentyl glycol type epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol F Type alicyclic (meth) acrylate such as epoxy (meth) acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy ( Data) acrylate, bisphenol AF type epoxy (meth) acrylates, and aromatic epoxy (meth) acrylates such as fluorene epoxy (meth) acrylate.
Among these, from the viewpoint of transparency and heat resistance, the alicyclic (meth) acrylate; the aromatic (meth) acrylate; the heterocyclic (meth) acrylate; the alicyclic epoxy (meth) acrylate; Aromatic epoxy (meth) acrylate is preferred.

Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxylated trimethylol. Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) Aliphatic (meth) acrylates such as acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate; ethoxylated isocyanuric acid tri (meth) acrylate, propoxylated isocyanuric Heterocyclic (meth) acrylates such as acid tri (meth) acrylate and ethoxylated propoxylated isocyanuric acid tri (meth) acrylate; modified caprolactone thereof; phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) Aromatic epoxy (meth) acrylates such as acrylate may be mentioned.
Among these, from the viewpoints of transparency and heat resistance, heterocyclic (meth) acrylates; aromatic epoxy (meth) acrylates are preferable.
These compounds can be used individually or in combination of 2 or more types, and also can be used in combination with other polymerizable compounds.

In addition to the (meth) acrylate, the polymerizable compound of the component (B) is preferably a compound having a cyclic ether group in the molecule from the viewpoint of compatibility with the (meth) acrylic copolymer of the component (A). .
Although there is no restriction | limiting in particular as a cyclic ether group, For example, an epoxy group, an oxetanyl group, etc. are mentioned.

The compound having an epoxy group in the molecule is not particularly limited. For example, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type Bifunctional phenol glycidyl ether type such as epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F Type epoxy resin, hydrogenated 2,2′-biphenol type epoxy resin, hydrogenated bifunctional phenol glycidyl ether type such as hydrogenated 4,4′-biphenol type epoxy resin; phenol novolac Polyfunctional glycol glycidyl ether type with 3 or more functions such as epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene-phenol type epoxy resin, dicyclopentadiene-cresol type epoxy resin, tetraphenylolethane type epoxy resin, etc .; polyethylene glycol type Bifunctional aliphatic alcohol glycidyl ether type such as epoxy resin, polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, 1,6-hexanediol type epoxy resin; cyclohexanediol type epoxy resin, cyclohexanedimethanol type epoxy resin, tri Bifunctional cycloaliphatic alcohol glycidyl ether type such as cyclodecane dimethanol type epoxy resin; trimethylolpropane type epoxy resin, sorbitol Type polyfunctional aliphatic alcohol glycidyl ether type such as glyceryl type epoxy resin, glycerin type epoxy resin; bifunctional aromatic glycidyl ester such as diglycidyl phthalate; tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl Bifunctional alicyclic glycidyl esters such as esters; bifunctional aromatic glycidyl amines such as N, N-diglycidylaniline and N, N-diglycidyltrifluoromethylaniline; N, N, N ′, N′-tetraglycidyl Trifunctional or more polyfunctional aromatic glycidylamines such as -4,4-diaminodiphenylmethane, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, o-triglycidyl-p-aminophenol; Alicyclic diepoxy acetal, Bifunctional cycloaliphatic epoxy resins such as cyclic diepoxy adipate, alicyclic diepoxycarboxylate, vinylcyclohexene dioxide; 1,2-epoxy-4- of 2,2-bis (hydroxymethyl) -1-butanol Trifunctional or higher polyfunctional alicyclic epoxy resin such as (2-oxiranyl) cyclohexane adduct; Trifunctional or higher functional heterocyclic epoxy resin such as triglycidyl isocyanurate; Silicon-containing organopolysiloxane type epoxy resin A bifunctional or trifunctional or higher polyfunctional epoxy resin is exemplified.
Among these, from the viewpoint of transparency and heat resistance, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy Resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, etc. bifunctional phenol glycidyl ether type epoxy resin; the above various hydrogenated bifunctional phenol glycidyl ether type epoxy resins; the above various polyfunctional phenol glycidyl ether type Epoxy resin; various bifunctional alicyclic alcohol glycidyl ether type epoxy resins; bifunctional aromatic glycidyl ester; bifunctional alicyclic glycidyl ester; bifunctional fat It is preferable that the above-mentioned silicon-containing bifunctional or trifunctional or higher polyfunctional epoxy resin; Formula epoxy resin; the trifunctional or higher polyfunctional alicyclic epoxy resin; the trifunctional or higher polyfunctional heterocyclic epoxy resins.

The compound having an oxetanyl group in the molecule is not particularly limited. For example, hydroquinone type oxetane resin, resorcinol type oxetane resin, catechol type oxetane resin, bisphenol A type oxetane resin, tetrabromobisphenol A type oxetane resin, bisphenol F type Bifunctional phenol oxetanyl ether type such as oxetane resin, bisphenol AF type oxetane resin, bisphenol AD type oxetane resin, biphenyl type oxetane resin, naphthalene type oxetane resin, fluorene type oxetane resin; hydrogenated bisphenol A type oxetane resin, hydrogenated bisphenol F Bifunctional phenol oxet such as hydrogenated oxetane resin, hydrogenated 2,2'-biphenol type oxetane resin, hydrogenated 4,4'-biphenol type oxetane resin Nyl ether type; polyfunctional phenol oxetanyl having three or more functionalities such as phenol novolac type oxetane resin, cresol novolac type oxetane resin, dicyclopentadiene-phenol type oxetane resin, dicyclopentadiene-cresol type oxetane resin, tetraphenylolethane type oxetane resin Ether type; polyethylene glycol type oxetane resin, polypropylene glycol type oxetane resin, neopentyl glycol type oxetane resin, bifunctional aliphatic alcohol oxetanyl ether type such as 1,6-hexanediol type oxetane resin; cyclohexanediol type oxetane resin, cyclohexanedi Bifunctional alicyclic alcohol oxet such as methanol type oxetane resin and tricyclodecane dimethanol type oxetane resin Tanyl ether type; trifunctional or higher polyfunctional aliphatic alcohol oxetanyl ether type such as trimethylolpropane type oxetane resin, sorbitol type oxetane resin, glycerin type oxetane resin; bifunctional aromatic oxetanyl ester such as dioxetanyl phthalate; tetrahydro Bifunctional alicyclic oxetanyl esters such as dioxetanyl phthalate and dioxetanyl hexahydrophthalate; bifunctional aromatic oxetanylamines such as N, N-dioxetanylaniline and N, N-dioxetanyltrifluoromethylaniline; N, N, N ′, N′-tetraoxetanyl-4,4-diaminodiphenylmethane, 1,3-bis (N, N-oxetanylaminomethyl) cyclohexane, N, N, o-triglycidyl-p-amino Trifunctional or higher polyfunctional aromatic oxetanylamine such as enol; Trifunctional or higher functional heterocyclic oxetane resin such as trioxetanyl isocyanurate; Silicon-containing bifunctional or trifunctional or higher polyfunctional polyfunctional heterocyclic oxetane resin such as organopolysiloxane type oxetanyl resin Examples thereof include functional oxetane resins.
Among these, from the viewpoint of transparency and heat resistance, hydroquinone type oxetane resin, resorcinol type oxetane resin, catechol type oxetane resin, bisphenol A type oxetane resin, bisphenol F type oxetane resin, bisphenol AF type oxetane resin, bisphenol AD type oxetane Resin, biphenyl type oxetane resin, naphthalene type oxetane resin, fluorene type oxetane resin and other bifunctional phenol oxetanyl ether type oxetane resins; the above various hydrogenated bifunctional phenol oxetanyl ether type oxetane resins; the above various polyfunctional phenol oxetanyl ether types Oxetane resin; various bifunctional alicyclic alcohol oxetanyl ether type oxetane resins; bifunctional aromatic oxetanyl ester; bifunctional It is preferable that the above-mentioned silicon-containing bifunctional or trifunctional or higher polyfunctional oxetane resin; cyclic oxetanyl ester; the trifunctional or higher polyfunctional heterocyclic oxetane resin.
These compounds can be used alone or in combination of two or more, and can also be used in combination with other polymerizable compounds.

  It is preferable that the compounding quantity of the polymeric compound of (B) component is 15-90 mass% with respect to the total amount of (A) component and (B) component. When it is 15% by mass or more, the (meth) acrylic copolymer of the component (A) can be easily entangled and cured, and the developer resistance is not insufficient. On the other hand, if it is 90% by mass or less, the film strength and flexibility of the cured film are sufficient. From the above viewpoint, the blending amount of the component (B) is more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass.

Hereinafter, the component (C) used in the present invention will be described.
The polymerization initiator of component (C) is not particularly limited as long as it initiates polymerization by heating or irradiation with actinic rays such as ultraviolet rays and visible rays. For example, ethylene as a polymerizable compound of component (B) In the case of using a compound having a polymerizable unsaturated group, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc. may be mentioned, and a compound having a cyclic ether group in the molecule as the polymerizable compound of component (B) Examples thereof include a thermal cationic polymerization initiator and a photo cationic polymerization initiator.

There is no restriction | limiting in particular as a thermal radical polymerization initiator, The thing similar to the thermal radical polymerization initiator used when synthesize | combining the (meth) acrylic polymer of the above-mentioned (A) component can be used.
Among them, diacyl peroxide, peroxy ester, and azo compound are preferable from the viewpoints of curability, transparency, and heat resistance.

There is no restriction | limiting in particular as radical photopolymerization initiator, For example, benzoinketals, such as 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl -1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4 [4 Α-hydroxy ketones such as-(2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2- (2-hydroxyoxyphenylacetate) Ethoxy) ethyl, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyate) G) Glyoxyesters such as ethyl; 2-benzyl-2-dimethylamino-1- (4-morpholin-4-ylphenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-Morpholin-4-ylphenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl]-(4-morpholin) -2-ylpropane Α-amino ketones such as -1-one; 1,2-octanedione, 1- [4- (phenylthio), 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Oxime esters such as methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime); bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis Phosphine oxides such as 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxy) 2,4,5-triarylimidazole dimers such as phenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4 ′ Benzophenone compounds such as diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2, Quinone compounds such as 3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethylben Benzoin compounds such as indium; benzyl compounds such as benzyldimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis (9,9′-acridinylheptane): N-phenylglycine, coumarin and the like .
In the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole sites may give the same and symmetric compounds, but give differently asymmetric compounds. May be.
Among these, from the viewpoint of curability and transparency, the α-hydroxyketone; the glyoxyester; the oxime ester; and the phosphine oxide are preferable.
The above heat and photo radical polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

The thermal cationic polymerization initiator is not particularly limited, and examples thereof include benzylsulfonium salts such as p-alkoxyphenylbenzylmethylsulfonium hexafluoroantimonate; benzyl-p-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-o- Examples thereof include pyridinium salts such as cyanopyridinium hexafluoroantimonate and cinnamyl-o-cyanopyridinium hexafluoroantimonate; and benzylammonium salts such as benzyldimethylphenylammonium hexafluoroantimonate.
Among these, the benzylsulfonium salt is preferable from the viewpoints of curability, transparency, and heat resistance.

Although there is no restriction | limiting in particular as a photocationic polymerization initiator, For example, diaryl iodonium salts, such as aryl diazonium salts, such as p-methoxybenzenediazonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and diphenyliodonium hexafluoroantimonate; Fluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate, etc. Triarylsulfonium salts of Triselselenonium salts such as ruselenonium hexafluorophosphate, triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroantimonate; dimethylphenacylsulfonium hexafluoroantimonate, diethylphenacylsulfonium hexafluoroantimonate, etc. Dialkylphenacylsulfonium salts; dialkyl-4-hydroxy salts such as 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate; α-hydroxymethylbenzoin sulfonate, N-hydroxyimide Sulfonate, α-sulfonyloxyketone, β-sulfonyloxyketone, etc. An acid ester.
Among these, from the viewpoint of curability, transparency, and heat resistance, the triarylsulfonium salt is preferable.
These thermal and photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

  (C) It is preferable that the compounding quantity of the polymerization initiator of a component is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. When it is 0.01 parts by mass or more, curing is sufficient, and when it is 10 parts by mass or less, sufficient light transmittance is obtained. From the above viewpoint, the amount of component (C) is more preferably 0.05 to 7 parts by mass, and particularly preferably 0.1 to 5 parts by mass.

  Further, in the resin composition for an optical material of the present invention, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, a filler, etc., as necessary. You may add what is called an additive in the range which does not have a bad influence on the effect of this invention.

  A wavelength of 830 nm at a temperature of 25 ° C. of a cured film obtained by polymerizing and curing a resin composition for an optical material comprising (A) (meth) acrylic polymer, (B) polymerizable compound, and (C) polymerization initiator of the present invention. The refractive index at is preferably 1.400 to 1.700. When the refractive index is 1.400 to 1.700, the refractive index is not significantly different from that of a normal optical resin, so that versatility as an optical material is not impaired. From the above viewpoint, the refractive index is more preferably 1.425 to 1.675 or less, and particularly preferably 1.450 to 1.650.

  Further, the wavelength of a cured film having a thickness of 50 μm obtained by polymerizing and curing the resin composition for an optical material comprising (A) (meth) acrylic polymer, (B) polymerizable compound, and (C) polymerization initiator of the present invention. The transmittance at 400 nm is preferably 80% or more. When the transmittance is 80% or more, the amount of transmitted light is sufficient. From the above viewpoint, the transmittance is more preferably 85% or more. Note that the upper limit of the transmittance is not particularly limited.

The resin composition for an optical material of the present invention may be diluted using a suitable organic solvent. The organic solvent used here is not particularly limited as long as it can dissolve the resin composition, and is the same as the organic solvent used as a reaction solvent capable of dissolving the (meth) acrylic polymer of component (A) described above. Can be used.
These organic solvents can be used alone or in combination of two or more.
Moreover, it is preferable that solid content concentration is 10-80 mass% normally.

When preparing the resin composition for optical materials, it is preferable to mix by stirring. Although there is no restriction | limiting in particular in the stirring method, From the viewpoint of stirring efficiency, stirring using a propeller is preferable. Although there is no restriction | limiting in particular in the rotational speed of the propeller at the time of stirring, It is preferable that it is 10-1,000 rpm. When it is 10 rpm or more, each component is sufficiently mixed, and when it is 1,000 rpm or less, entrainment of bubbles due to rotation of the propeller is reduced. From the above viewpoint, the rotation speed of the propeller is more preferably 50 to 800 rpm, and particularly preferably 100 to 500 rpm.
The stirring time is not particularly limited, but is preferably 1 to 24 hours. When the stirring time is 1 hour or longer, the respective components are sufficiently mixed, and when it is 24 hours or shorter, the preparation time can be shortened, and the productivity is improved.

  The prepared resin composition for an optical material is preferably filtered using a filter having a pore diameter of 50 μm or less. By using a filter having a pore diameter of 50 μm or less, large foreign matters are not removed, and repellency is not caused at the time of application, and light scattering is suppressed and transparency is not impaired. From the above viewpoint, it is more preferable to filter using a filter having a pore diameter of 30 μm or less, and it is particularly preferable to filter using a filter having a pore diameter of 10 μm or less.

  The prepared resin composition for an optical material is preferably degassed under reduced pressure. There is no restriction | limiting in particular in the defoaming method, For example, the method of using a vacuum pump, a bell jar, and the defoaming apparatus with a vacuum apparatus is mentioned. Although there is no restriction | limiting in particular in the pressure at the time of pressure reduction, The pressure in which the low boiling point component contained in a resin composition does not boil is preferable. Moreover, although there is no restriction | limiting in particular in vacuum degassing time, It is preferable that it is 3 to 60 minutes. If it is 3 minutes or longer, bubbles dissolved in the resin composition can be removed, and if it is 60 minutes or less, the defoaming time contained in the resin composition can be shortened, and the productivity is improved.

  The resin composition for an optical material of the present invention is excellent in transparency and heat resistance, and is suitable as a resin composition for forming an optical waveguide.

Hereinafter, the resin film for optical materials of the present invention will be described.
The resin film for optical materials of the present invention comprises the above resin composition for optical materials, and the resin composition for optical materials containing the components (A) to (C) is applied to a suitable support film. It can be easily manufactured. Moreover, when the said resin composition for optical materials is diluted with the said organic solvent, it can manufacture by apply | coating a resin composition to a support film and removing an organic solvent.

The support film is not particularly limited. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polycarbonates, polyamides, polyimides, polyamideimides, polyetherimides, polyether sulfides, Examples include polyethersulfone, polyetherketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and liquid crystal polymer. Among these, from the viewpoint of flexibility and toughness, it may be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone. preferable.
In addition, from the viewpoint of improving releasability from the resin layer, a film that has been subjected to release treatment with a silicone compound, a fluorine-containing compound, or the like may be used as necessary.

  The thickness of the support film may be appropriately changed depending on the intended flexibility, but is preferably 3 to 250 μm. When it is 3 μm or more, the film strength is sufficient, and when it is 250 μm or less, sufficient flexibility is obtained. From the above viewpoint, the thickness of the support film is more preferably 5 to 200 μm, and particularly preferably 7 to 150 μm.

  A resin film for an optical material produced by applying a resin composition for an optical material on a support film, a protective film is attached on the resin layer as necessary, and the three layers comprising the support film, the resin layer, and the protective film It is good also as a structure.

  The protective film is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene. Among these, polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene are preferable from the viewpoints of flexibility and toughness. In addition, you may use the film in which the mold release process was given with the silicone type compound, the fluorine-containing compound, etc. from a viewpoint of peelability improvement with a resin layer as needed.

  The thickness of the protective film may be appropriately changed depending on the intended flexibility, but is preferably 10 to 250 μm. When it is 10 μm or more, the film strength is sufficient, and when it is 250 μm or less, sufficient flexibility is obtained. From the above viewpoint, the thickness of the protective film is more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

  Also about the thickness of the resin layer of the resin film for optical materials of this invention, it is not specifically limited, It is preferable that it is 5-500 micrometers normally by the thickness after drying. If the thickness is 5 μm or more, the strength of the resin film or the cured product of the resin film is sufficient because the thickness is sufficient. On the other hand, if the thickness is 500 μm or less, the drying can be performed sufficiently and the amount of residual solvent in the resin film increases. Without foaming when the cured product of the resin film is heated.

  The resin film for optical material thus obtained can be easily stored, for example, by winding it into a roll. Moreover, a roll-shaped film can be cut out into a suitable size and stored in a sheet shape.

  The resin film for optical materials of the present invention is excellent in transparency and heat resistance, and is suitable as a resin film for forming an optical waveguide.

Hereinafter, application examples when the resin film for an optical material of the present invention is used as a resin film for forming an optical waveguide, which is the most suitable application, will be described.
The resin film for forming an optical waveguide can also be produced by the same method as the resin film for optical material.
The support film used in the production process of the core portion forming resin film is not particularly limited as long as it can transmit the actinic ray for exposure used for core pattern formation. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. Polyester such as phthalate; Polyolefin such as polyethylene and polypropylene; Polycarbonate, Polyamide, Polyimide, Polyamideimide, Polyetherimide, Polyethersulfide, Polyethersulfone, Polyetherketone, Polyphenylenesulfide, Polyarylate, Polysulfone, Liquid crystal polymer Etc.
Among these, from the viewpoints of the transmittance of actinic rays for exposure, flexibility, and toughness, the above polyesters and the above polyolefins are preferable. Furthermore, it is more preferable to use a highly transparent support film from the viewpoint of improving the transmittance of exposure actinic rays and reducing the side wall roughness of the core pattern. Examples of such highly transparent support films include Cosmo Shine A1517 and Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.
In addition, from the viewpoint of improving releasability from the resin layer, a film that has been subjected to release treatment with a silicone compound, a fluorine-containing compound, or the like may be used as necessary.

  The thickness of the support film of the core portion forming resin film is preferably 5 to 50 μm. When it is 5 μm or more, the strength as a support is sufficient, and when it is 50 μm or less, the gap between the photomask and the core portion forming resin layer is not increased when the core pattern is formed, and the pattern resolution is good. From the above viewpoint, the thickness of the support film is more preferably 10 to 40 μm, and particularly preferably 15 to 30 μm.

Hereinafter, the optical waveguide of the present invention will be described.
A sectional view of the optical waveguide is shown in FIG. The optical waveguide 1 is formed on a substrate 5 and has a core part 2 made of a core part-forming resin composition having a high refractive index, a lower clad layer 4 made of a resin composition for forming a clad layer having a low refractive index, and An upper cladding layer 3 is used.
The composition for forming an optical waveguide and the resin film for forming an optical waveguide of the present invention are preferably used for at least one of the lower cladding layer 4, the core portion 2, and the upper cladding layer 3 of the optical waveguide 1.

  By using the optical waveguide forming resin film, the flatness of each layer, the interlayer adhesion between the clad and the core, and the resolution (correspondence between thin lines or narrow lines) at the time of forming the optical waveguide core pattern can be further improved. It is excellent in flatness, and it is possible to form a fine pattern with a small line width and line spacing.

  In the optical waveguide 1, the base material 5 is not particularly limited. For example, a glass epoxy resin substrate, a ceramic substrate, a glass substrate, a silicon substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, a substrate with a metal layer, a plastic film And a plastic film with a resin layer and a plastic film with a metal layer.

The optical waveguide 1 may be a flexible optical waveguide when a substrate having flexibility and toughness is used as the substrate 5, for example, a support film of the resin film for forming an optical waveguide is used as the substrate. May function as a protective film for the optical waveguide 1. By disposing the protective film 5, the flexibility and toughness of the protective film 5 can be imparted to the optical waveguide 1. Furthermore, since the optical waveguide 1 is not damaged or scratched, the ease of handling is improved.
From the above viewpoint, the base material 5 is disposed as a protective film outside the upper clad layer 3 as shown in FIG. 1B, or the lower clad layer 4 and the upper clad layer as shown in FIG. The base material 5 may be arrange | positioned as a protective film on both the outer sides of 3.
If the optical waveguide 1 has sufficient flexibility and toughness, the protective film 5 may not be disposed as shown in FIG.

The thickness of the lower clad layer 4 is not particularly limited, but is preferably 2 to 200 μm. If it is 2 μm or more, it becomes easy to confine the propagating light inside the core, and if it is 200 μm or less, the entire thickness of the optical waveguide 1 is not too large. The thickness of the lower cladding layer 4 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the lower surface of the lower cladding layer 4.
There is no restriction | limiting in particular about the thickness of the resin film for lower clad layer formation, and thickness is adjusted so that the thickness of the lower clad layer 4 after hardening may become said range.

  The height of the core part 2 is not particularly limited, but is preferably 10 to 150 μm. When the height of the core is 10 μm or more, the alignment tolerance is not reduced in coupling with the light emitting / receiving element or the optical fiber after the optical waveguide is formed, and when the core portion is 150 μm or less, the light is received and emitted after the optical waveguide is formed. In coupling with an element or an optical fiber, coupling efficiency is not reduced. From the above viewpoint, the height of the core part is more preferably 15 to 130 μm, and particularly preferably 20 to 120 μm. In addition, there is no restriction | limiting in particular about the thickness of the resin film for core part formation, but thickness is adjusted so that the height of the core part after hardening may become said range.

  The thickness of the upper clad layer 3 is not particularly limited as long as the core portion 2 can be embedded, but the thickness after drying is preferably 12 to 500 μm. The thickness of the upper clad layer 3 may be the same as or different from the thickness of the lower clad layer 4 formed first, but is thicker than the thickness of the lower clad layer 4 from the viewpoint of embedding the core portion 2. It is preferable. The thickness of the upper cladding layer 3 is a value from the boundary between the core portion 2 and the lower cladding layer 4 to the upper surface of the upper cladding layer 3.

  In the optical waveguide of the present invention, the light propagation loss is preferably 0.3 dB / cm or less. When it is 0.3 dB / cm or less, the loss of light becomes small and the strength of the transmission signal is sufficient. From the above viewpoint, the light propagation loss is more preferably 0.2 dB / cm or less.

In the optical waveguide of the present invention, it is preferable that the light propagation loss after conducting a high-temperature and high-humidity test at a temperature of 85 ° C. and a humidity of 85% for 1000 hours is 0.3 dB / cm or less. When it is 0.3 dB / cm or less, the loss of light becomes small and the strength of the transmission signal is sufficient. From the above viewpoint, the light propagation loss is more preferably 0.2 dB / cm or less.
The high-temperature and high-humidity storage test at a temperature of 85 ° C. and a humidity of 85% means a high-temperature and high-humidity storage test performed under conditions in accordance with the JPCA standard (JPCA-PE02-05-01S).

In the optical waveguide of the present invention, the light propagation loss after 1000 cycles of the temperature cycle test between −55 ° C. and 125 ° C. is preferably 0.3 dB / cm or less. When it is 0.3 dB / cm or less, the loss of light becomes small and the strength of the transmission signal is sufficient. From the above viewpoint, the light propagation loss is more preferably 0.2 dB / cm or less.
In addition, the temperature cycle test between temperature -55 degreeC and 125 degreeC means the temperature cycle test implemented on the conditions according to a JPCA standard (JPCA-PE02-05-01S).

In the optical waveguide of the present invention, it is preferable that the light propagation loss after performing the reflow test at the maximum temperature of 265 ° C. three times is 0.3 dB / cm or less. If it is 0.3 dB / cm or less, the loss of light becomes small, and if the intensity of the transmission signal is sufficient, component mounting by the reflow process can be performed at the same time, so the applicable range is widened. From the above viewpoint, the light propagation loss is more preferably 0.2 dB / cm or less.
The reflow test at the maximum temperature of 265 ° C. means a lead-free solder reflow test that is performed under conditions in accordance with the JEDEC standard (JEDEC JESD22A113E).

The optical waveguide of the present invention is excellent in transparency, reliability, and heat resistance, and may be used as an optical transmission path of an optical module. Examples of the optical module include an optical waveguide with an optical fiber in which optical fibers are connected to both ends of the optical waveguide, an optical waveguide with a connector in which connectors are connected to both ends of the optical waveguide, and an opto-electrical device in which the optical waveguide and the printed wiring board are combined. Examples include a composite substrate, an optical / electrical conversion module that combines an optical waveguide and an optical / electrical conversion element that mutually converts an optical signal and an electrical signal, and a wavelength multiplexer / demultiplexer that combines an optical waveguide and a wavelength division filter.
In the photoelectric composite substrate, the printed wiring board to be combined is not particularly limited, and examples thereof include a rigid substrate such as a glass epoxy substrate and a ceramic substrate, a flexible substrate such as a polyimide substrate and a polyethylene terephthalate substrate.

Hereinafter, the manufacturing method for forming the optical waveguide 1 using the resin composition for forming an optical waveguide and / or the resin composition for forming an optical waveguide of the present invention will be described.
There is no restriction | limiting in particular as a method of manufacturing the optical waveguide 1 of this invention, For example, the resin layer for optical waveguide formation is formed on a base material using the resin composition for optical waveguide formation and / or the resin film for optical waveguide formation. The method of forming and manufacturing is mentioned.

  The base material used in the present invention is not particularly limited, and is a glass epoxy resin substrate, a ceramic substrate, a glass substrate, a silicon substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, a substrate with a metal layer, a plastic film, a resin layer. And a plastic film with a metal layer and a plastic film with a metal layer.

The method for forming the optical waveguide forming resin layer is not particularly limited. For example, using the optical waveguide forming resin composition, spin coating, dip coating, spraying, bar coating, roll coating, curtain Examples thereof include a coating method, a gravure coating method, a screen coating method, an inkjet coating method, and the like.
When the photosensitive composition for forming an optical waveguide is diluted with a suitable organic solvent, a drying step may be added after forming the resin layer as necessary. Examples of the drying method include heat drying and reduced pressure drying. Moreover, you may use these together as needed.

As another method of forming the optical waveguide forming resin layer, there is a method of forming by an lamination method using an optical waveguide forming resin film using the optical waveguide forming resin composition.
Among these, from the viewpoint of excellent ability to form an optical waveguide having excellent flatness and a line width and a small fine pattern between the lines, a method of manufacturing by an optical waveguide forming resin film is preferable.

Hereinafter, although the manufacturing method for forming the optical waveguide 1 using the resin film for optical waveguide formation for a lower clad layer, a core part, and an upper clad layer is demonstrated, this invention is not restrict | limited at all to this. .
First, as a first step, a resin film for forming a lower cladding layer is laminated on the substrate 5. Although there is no restriction | limiting in particular as a lamination | stacking method in a 1st process, For example, the method of laminating | stacking by crimping, heating using a roll laminator or a flat plate laminator, etc. are mentioned. The flat plate laminator in the present invention refers to a laminator in which a laminated material is sandwiched between a pair of flat plates and pressed by pressing the flat plate. For example, a vacuum pressurizing laminator can be suitably used. The heating temperature here is preferably 20 to 130 ° C., and the pressure bonding pressure is preferably 0.1 to 1.0 MPa, but these conditions are not particularly limited. When a protective film exists in the resin film for lower clad layer formation, it laminates | stacks, after removing a protective film.

  When laminating using a vacuum pressurizing laminator, a lower clad layer forming resin film may be temporarily pasted onto the substrate 5 in advance using a roll laminator. Here, from the viewpoint of improving adhesion and followability, it is preferable to perform temporary bonding while pressure bonding. When pressure bonding, it may be performed while heating using a laminator having a heat roll. The laminating temperature is preferably 20 to 130 ° C. If it is 20 degreeC or more, the adhesiveness of the resin film for lower clad layer formation and the base material 5 will improve, and if it is 130 degrees C or less, the resin layer does not flow too much at the time of roll lamination, and the required film thickness is can get. From the above viewpoint, it is more preferable that it is 40-100 degreeC. The pressure is preferably 0.2 to 0.9 MPa and the laminating speed is preferably 0.1 to 3 m / min, but these conditions are not particularly limited.

The lower clad layer forming resin layer laminated on the substrate 5 is cured by light and / or heat to form the lower clad layer 4. The removal of the support film of the lower clad layer forming resin film may be performed either before or after curing.
The irradiation amount of actinic rays when the lower clad layer-forming resin layer is cured with light is preferably 0.1 to 5 J / cm ² , but there is no particular limitation on this condition. Moreover, when actinic rays permeate | transmit a base material, in order to make it harden | cure efficiently, the double-sided exposure machine which can irradiate actinic rays simultaneously from both surfaces can be used. Moreover, you may irradiate actinic light, heating. In addition, as a process after photocuring, you may perform a 50-200 degreeC heat processing as needed.
The heating temperature when the lower clad layer forming resin layer is cured by heat is preferably 50 to 200 ° C., but this condition is not particularly limited.

When the support film for the resin film for forming the lower clad layer functions as the protective film 5 for the optical waveguide 1, it is cured under the same conditions as described above by light and / or heat without laminating the resin film for forming the lower clad layer. Then, the lower cladding layer 4 may be formed.
The protective film for the resin film for forming the lower cladding layer may be removed before curing or after curing.

  As the second step, a core part-forming resin film is laminated on the lower cladding layer 4 by the same method as in the first step. Here, the core part forming resin layer is preferably made of a photosensitive resin composition that is designed to have a higher refractive index than the lower clad layer forming resin layer and can form a core pattern with actinic rays.

As a third step, the core portion 2 (core pattern) is exposed. The method for exposing the core 2 is not particularly limited. For example, a method of irradiating actinic rays in an image form through a negative mask pattern called artwork, a direct actinic ray without passing through a photomask using laser direct drawing And the like.
Examples of the active light source include a light source that effectively emits ultraviolet light, such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a mercury vapor arc lamp, a metal halide lamp, a xenon lamp, and a carbon arc lamp. Other examples include light sources that effectively emit visible light, such as photographic flood bulbs and solar lamps.

It is preferable that the irradiation amount of the actinic ray at the time of exposing the core part 2 is 0.01-10 J / cm < ² >. When it is 0.01 J / cm ² or more, the curing reaction proceeds sufficiently, and the core 2 is not washed away by development. On the other hand, if it is 10 J / cm ² or less, the core part 2 does not become thick due to excessive exposure, and a fine pattern can be formed. From these viewpoints, the dose of active ray is more preferably from 0.03~5J / cm ^2, and particularly preferably 0.05~3J / cm ^2.
The core part 2 may be exposed through the support film of the core part forming resin film or after the support film is removed.

  Moreover, you may perform post-exposure heating as needed from a viewpoint of the resolution of the core part 2 and adhesive improvement after exposure. The time from ultraviolet irradiation to post-exposure heating is preferably within 10 minutes, but this condition is not particularly limited. The post-exposure heating temperature is preferably 40 to 160 ° C., and the time is preferably 30 seconds to 10 minutes, but these conditions are not particularly limited.

As a 4th process, when exposed through the support film of the resin film for core part formation, this is removed and it develops using the developing solution suitable for the composition of the resin layer for core part formation.
The development method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these image development methods together as needed.
Although there is no restriction | limiting in particular as a developing solution, For example, organic-solvent type developers, such as an organic solvent, a semi-aqueous type developing solution which consists of an organic solvent, and water; Examples include alkaline developers such as developers.
The development temperature is adjusted according to the developability of the core layer forming resin layer.

The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; chain ethers such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and dibutyl ether. Cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; ethylene carbonate, propylene carbonate Which carbonic acid ester; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol Polyhydric alcohol alkyl ethers such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Polyether alcohol acetate such as ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N, Examples include amides such as N-dimethylacetamide and N-methylpyrrolidone.
These organic solvents can be used alone or in combination of two or more. Further, a surface active agent, an antifoaming agent or the like may be mixed in the organic solvent.

The semi-aqueous developer is not particularly limited as long as it is composed of one or more organic solvents and water.
The concentration of the organic solvent is usually preferably 2 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the semi-aqueous developer.

The base of the alkaline aqueous solution is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; hydrogen carbonate Alkali metal bicarbonates such as lithium, sodium bicarbonate and potassium bicarbonate; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; tetraboric acid Sodium salts such as sodium and sodium metasilicate; ammonium salts such as ammonium carbonate and ammonium hydrogen carbonate; tetramethylammonium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, - propanediol, and organic bases such as 1,3-diamino-propanol-2-morpholine.
These bases can be used alone or in combination of two or more.
The pH of the alkaline aqueous solution used for development is preferably 9 to 14, more preferably pH 10 to 13. Moreover, you may mix surfactant, an antifoamer, etc. in alkaline aqueous solution.

The alkaline quasi-aqueous developer is not particularly limited as long as it is composed of an alkaline aqueous solution and one or more organic solvents. The pH of the alkaline quasi-aqueous developer is preferably as small as possible within a range where development can be sufficiently performed, preferably pH 8 to 13, and more preferably pH 9 to 12.
The concentration of the organic solvent is usually preferably 2 to 90% by mass. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the alkaline quasi-aqueous developer.

As a treatment after development, the organic solvent, a semi-aqueous cleaning solution composed of the organic solvent and water, or water may be used as necessary.
The cleaning method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these washing | cleaning methods together as needed.
The said organic solvent can be used individually or in combination of 2 or more types. In the semi-aqueous cleaning liquid, the concentration of the organic solvent is usually preferably 2 to 90% by mass. The washing temperature is adjusted in accordance with the developability of the core portion forming resin layer.

As processing after development or washing, exposure and / or heating may be performed as necessary from the viewpoint of improving curability and adhesion of the core portion 2. The heating temperature is preferably 40 to 200 ° C., and the irradiation amount of active light is preferably 0.01 to 10 J / cm ² , but these conditions are not particularly limited.

  As a fifth step, an upper clad layer forming resin film is laminated on the lower clad layer 4 and the core portion 2 by the same method as the first and second steps. Here, the upper clad layer forming resin layer is designed to have a lower refractive index than the core portion forming resin layer. The thickness of the upper clad forming resin layer is preferably larger than the height of the core portion 2.

Next, the upper clad layer forming resin layer is cured by light and / or heat to form the upper clad layer 3 in the same manner as in the first step.
The irradiation amount of actinic rays when the upper clad layer-forming resin layer is cured by light is preferably 0.1 to 30 J / cm ² , but this condition is not particularly limited. Moreover, when actinic rays permeate | transmit a base material, in order to make it harden | cure efficiently, the double-sided exposure machine which can irradiate actinic rays simultaneously from both surfaces can be used. Moreover, you may irradiate actinic light, heating as needed, and you may heat-process as a process after photocuring. The heating temperature during and / or after irradiation with actinic rays is preferably 50 to 200 ° C., but these conditions are not particularly limited.
The heating temperature when the upper clad layer forming resin layer is cured by heat is preferably 50 to 200 ° C., but this condition is not particularly limited.
In addition, when the removal of the support film of the resin film for upper clad layer formation is required, you may remove before hardening or after hardening.
The optical waveguide 1 can be manufactured through the above steps.

  Examples of the present invention will be described more specifically below, but the present invention is not limited to these examples.

Production Example 1
[Production of (Meth) acrylic polymer A-1]
In a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, 83 parts by mass of methyl ethyl ketone was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 55 ° C., 20 parts by mass of N-cyclohexylmaleimide, 44 parts by mass of dicyclopentanyl methacrylate, 42 parts by mass of methyl methacrylate, 32 parts by mass of 2-methacryloyloxyethyl isocyanate, 2,2′-azobis (2 , 4-dimethylvaleronitrile) and a mixture of 56 parts by weight of methyl ethyl ketone were added dropwise over 3 hours, followed by stirring at 55 ° C. for 5 hours, and further stirring at 80 ° C. for 2 hours to cool to room temperature.
Subsequently, the liquid temperature was raised to 50 ° C., and a mixture of 18 parts by weight of methacrylic acid, 0.07 parts by weight of dibutyltin dilaurate and 18 parts by weight of methyl ethyl ketone was added dropwise over 30 minutes, and then stirred at 50 ° C. for 3 hours. Then, the (meth) acrylic polymer A-1 solution (solid content 50 mass%) was obtained.

[Measurement of weight average molecular weight]
It was 62,000 as a result of measuring the weight average molecular weight (standard polystyrene conversion) of A-1 using GPC (Tosoh Corporation SD-8022 / DP-8020 / RI-8020). In addition, Hitachi Chemical Co., Ltd. Gelpack GL-A150-S / GL-A160-S was used for the column.

Production Example 2
[Production of (Meth) acrylic polymer A-2]
In a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, 83 parts by mass of methyl ethyl ketone was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 55 ° C., 20 parts by mass of N-cyclohexylmaleimide, 82 parts by mass of benzyl methacrylate, 17 parts by mass of methyl methacrylate, 19 parts by mass of 2-methacryloyloxyethyl isocyanate, 2,2′-azobis (2,4- A mixture of 1 part by weight of dimethylvaleronitrile) and 56 parts by weight of methyl ethyl ketone was added dropwise over 3 hours, followed by stirring at 55 ° C. for 5 hours, further stirring at 80 ° C. for 2 hours, and cooling to room temperature.
Subsequently, the liquid temperature was raised to 50 ° C., and a mixture of 11 parts by weight of methacrylic acid, 0.07 parts by weight of dibutyltin dilaurate and 11 parts by weight of methyl ethyl ketone was added dropwise over 30 minutes, followed by stirring at 50 ° C. for 3 hours. Then, the (meth) acrylic polymer A-2 solution (solid content 50 mass%) was obtained.
As a result of measuring the weight average molecular weight by the same method as in Production Example 1, it was 56,000.

Production Example 3
[Production of (Meth) acrylic polymer A-3]
In a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, 83 parts by mass of methyl ethyl ketone was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 55 ° C., 20 parts by mass of N-cyclohexylmaleimide, 82 parts by mass of benzyl methacrylate, 17 parts by mass of methyl methacrylate, 19 parts by mass of 2-methacryloyloxyethyl isocyanate, 2,2′-azobis (2,4- A mixture of 1 part by weight of dimethylvaleronitrile) and 56 parts by weight of methyl ethyl ketone was added dropwise over 3 hours, followed by stirring at 55 ° C. for 5 hours, further stirring at 80 ° C. for 2 hours, and cooling to room temperature.
Subsequently, the liquid temperature was raised to 50 ° C., and a mixture of 5 parts by mass of methacrylic acid, 8 parts by mass of 2-hydroxyethyl methacrylate, 0.07 parts by mass of dibutyltin dilaurate and 13 parts by mass of methyl ethyl ketone was dropped over 30 minutes. Then, stirring was continued at 50 degreeC for 3 hours, and the (meth) acrylic polymer A-3 solution (50 mass% of solid content) was obtained.
As a result of measuring the weight average molecular weight by the same method as in Production Example 1, it was 54,000.

Production Example 4
[Production of (Meth) acrylic polymer A-4]
In a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, 83 parts by mass of methyl ethyl ketone was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 55 ° C., 20 parts by mass of N-cyclohexylmaleimide, 44 parts by mass of dicyclopentanyl methacrylate, 42 parts by mass of methyl methacrylate, 32 parts by mass of 2-methacryloyloxyethyl isocyanate, 2,2′-azobis (2 , 4-dimethylvaleronitrile) and a mixture of 56 parts by weight of methyl ethyl ketone were added dropwise over 3 hours, followed by stirring at 55 ° C. for 5 hours, and further stirring at 80 ° C. for 2 hours to cool to room temperature.
Subsequently, the liquid temperature was raised to 50 ° C., and a mixture of 9 parts by mass of methacrylic acid, 13 parts by mass of 2-hydroxyethyl methacrylate, 0.07 parts by mass of dibutyltin dilaurate, and 22 parts by mass of methyl ethyl ketone was dropped over 30 minutes. Then, stirring was continued at 50 degreeC for 3 hours, and the (meth) acrylic polymer A-4 solution (50 mass% of solid content) was obtained.
As a result of measuring the weight average molecular weight by the same method as in Production Example 1, it was 65,000.

Production Example 5
[Production of (Meth) acrylic polymer A-5]
In a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, 83 parts by mass of methyl ethyl ketone was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 55 ° C., 20 parts by weight of cyclohexyl methacrylate, 82 parts by weight of benzyl methacrylate, 17 parts by weight of methyl methacrylate, 19 parts by weight of 2-hydroxyethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile ) A mixture of 1 part by mass and 56 parts by mass of methyl ethyl ketone was added dropwise over 3 hours, followed by stirring at 55 ° C. for 5 hours, and further stirring at 80 ° C. for 2 hours to obtain a (meth) acrylic polymer A-5 solution (solid 50% by mass).
As a result of measuring the weight average molecular weight by the same method as in Production Example 1, it was 61,000.

Production Example 6
[Production of (Meth) acrylic polymer A-6]
In a flask equipped with a stirrer, a cooling pipe, a gas introduction pipe, a dropping funnel and a thermometer, 83 parts by mass of methyl ethyl ketone was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 55 ° C., 20 parts by mass of cyclohexyl methacrylate, 44 parts by mass of dicyclopentanyl methacrylate, 42 parts by mass of methyl methacrylate, 32 parts by mass of 2-hydroxyethyl methacrylate, 2,2′-azobis (2,4- A mixture of 1 part by weight of dimethylvaleronitrile) and 56 parts by weight of methyl ethyl ketone was added dropwise over 3 hours, followed by stirring at 55 ° C. for 5 hours and further stirring at 80 ° C. for 2 hours to obtain (meth) acrylic polymer A-6. A solution (solid content 50 mass%) was obtained.
As a result of measuring the weight average molecular weight by the same method as in Production Example 1, it was 67,000.

Example 1
[Preparation of resin varnish COV-1 for core formation]
(A) (meth) acrylic polymer as the A-1 solution (solid content 50% by mass) 120 parts by mass (solid content 60 parts by mass), (B) as the polymerizable compound, ethoxylated bisphenol A diacrylate (Shin Nakamura) As chemical initiator A-BPE-6) 20 parts by mass, p-cumylphenoxyethyl acrylate (Shin-Nakamura Chemical Co., Ltd. A-CMP-1E) 20 parts by mass and (C) a polymerization initiator, [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959, manufactured by Ciba Specialty Chemicals Co., Ltd.), 1 part by weight, bis (2,4,6 -Trimethylbenzoyl) phenylphosphine oxide (Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd.) Was weighed into a re bottle, using a stirrer, temperature 25 ° C., at a rotation speed 400rpm conditions, and stirred for 6 hours to prepare a resin varnish for forming a core part. Then, pressure filtration was performed using a polyfluorone filter with a pore size of 2 μm (PF020 manufactured by Advantech Toyo Co., Ltd.) and a membrane filter with a pore size of 0.5 μm (J050A manufactured by Advantech Toyo Co., Ltd.) at a temperature of 25 ° C. and a pressure of 0.4 MPa. did. Subsequently, using a vacuum pump and a bell jar, vacuum degassing was performed for 15 minutes under the condition of a degree of vacuum of 200 mmHg to obtain a resin varnish COV-1 for forming a core part.

[Preparation of Core Part Forming Resin Film COF-1]
The core part-forming resin varnish COV-1 is applied on a non-treated surface of a PET film (A1517 manufactured by Toyobo Co., Ltd., thickness 16 μm) using a coating machine (Multicoater TM-MC manufactured by Hirano Techseed Co., Ltd.). , Dried at 80 ° C. for 10 minutes and 100 ° C. for 10 minutes, and then a release PET film (A31 manufactured by Teijin DuPont Films Co., Ltd., thickness 25 μm) was pasted as a protective film to obtain a core part-forming resin film COF-1. . At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine, but in this example, the thickness after curing was adjusted to 50 μm.

[Preparation of Clad Layer Forming Resin Varnish CLV-1]
(A) As a (meth) acrylic polymer containing a maleimide skeleton in the main chain, the A-1 solution (solid content 50% by mass) 120 parts by mass (solid content 60 parts by mass), and (B) a polymerizable compound ethoxylated. 20 parts by mass of bisphenol A diacrylate (A-BPE-6, Shin-Nakamura Chemical Co., Ltd.), 20 parts by mass of ethoxylated isocyanuric acid triacrylate (A-9300, Shin-Nakamura Chemical Co., Ltd.), ethoxylated cyclohexanedimethanol di 20 parts by mass of acrylate (A-CHD-4E manufactured by Shin-Nakamura Chemical Co., Ltd.) and (C) 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1 as a polymerization initiator -Propan-1-one (Irgacure 2959 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 part by mass, screw (2, 4, 6 1 part by weight of trimethylbenzoyl) phenylphosphine oxide (Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd.) is weighed in a wide-mouthed plastic bottle, and stirred for 6 hours using a stirrer at a temperature of 25 ° C. and a rotation speed of 400 rpm. And the resin varnish for core part formation was prepared. Then, pressure filtration was performed using a polyfluorone filter with a pore size of 2 μm (PF020 manufactured by Advantech Toyo Co., Ltd.) and a membrane filter with a pore size of 0.5 μm (J050A manufactured by Advantech Toyo Co., Ltd.) at a temperature of 25 ° C. and a pressure of 0.4 MPa. did. Subsequently, defoaming was performed under reduced pressure for 15 minutes using a vacuum pump and a bell jar under conditions of a reduced pressure of 200 mmHg to obtain a clad layer forming resin varnish CLV-1.

[Preparation of Clad Layer Forming Resin Film CLF-1]
The clad layer forming resin varnish CLV-1 is coated and dried on the non-treated surface of a PET film (A4100 manufactured by Toyobo Co., Ltd., thickness 50 μm) in the same manner as the core layer forming resin film. Resin film CLF-1 was obtained. At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine. In this example, the thickness after curing is 25 μm for the resin film for forming the lower cladding layer, and the upper cladding is formed. The resin film was adjusted to 75 μm, and the cured film for refractive index and transmittance measurement was adjusted to 50 μm.

[Preparation of cured film for measuring refractive index and transmittance]
An ultraviolet exposure machine (MAP-1200-L manufactured by Dainippon Screen Co., Ltd.) is used for the core portion forming resin film COF-1 and the cladding layer forming resin film CLF-1, and ultraviolet rays (wavelength 365 nm) are 2000 mJ / cm. ² irradiated. Subsequently, after removing the protective film (A31) and drying at 130 ° C. for 1 hour, the support film (A1517 or A4100) was removed to obtain a cured film having a thickness of 50 μm.

[Measurement of refractive index]
The refractive index at a wavelength of 830 nm at a temperature of 25 ° C. of the obtained cured film was measured using a prism coupler (manufactured by SAIRON TECHNOLOGY, SPA-4000).

[Measurement of transmittance]
The transmittance of the obtained cured film at a wavelength of 400 nm at a temperature of 25 ° C. was measured using a spectrophotometer (U-3410 Spectrophotometer manufactured by Hitachi, Ltd.). Evaluation was made according to the following criteria.
○: 80% or more ×: less than 80%

[Fabrication of optical waveguide]
Using a roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.), the lower clad layer forming resin film CLF-1 from which the protective film (A31) has been removed is used as a glass epoxy resin substrate (E-, manufactured by Hitachi Chemical Co., Ltd.). 679FB) was laminated under conditions of a pressure of 0.4 MPa, a temperature of 80 ° C., and a speed of 0.4 m / min. Furthermore, using a vacuum pressurization type laminator (MVLP-500 / 600 manufactured by Meiki Seisakusho Co., Ltd.), pressure bonding was performed under the conditions of a pressure of 0.4 MPa, a temperature of 80 ° C., and a pressurization time of 30 seconds.
Next, the lower cladding layer 4 is removed by removing the support film (A4100) after irradiating the ultraviolet ray (wavelength 365 nm) with 2000 mJ / cm ² using an ultraviolet exposure machine (Dai Nippon Screen Co., Ltd. MAP-1200-L). Formed.

Subsequently, using the roll laminator, the core portion-forming resin film COF-1 from which the protective film (A31) has been removed is placed on the lower cladding layer 4 at a pressure of 0.4 MPa, a temperature of 80 ° C., and a speed of 0.4 m / min. It laminated | stacked on the conditions of. Further, the above-described vacuum pressure laminator was used for pressure bonding under conditions of a pressure of 0.4 MPa, a temperature of 80 ° C., and a pressurization time of 30 seconds.
Next, the film was irradiated with ultraviolet rays (wavelength 365 nm) of 500 mJ / cm ² through the negative photomask having a width of 50 μm with the above-described ultraviolet exposure machine, and then heated after exposure at 80 ° C. for 5 minutes. After removing the supporting film (A1517) and developing the core part 2 using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 80/20 mass ratio), propylene glycol monomethyl ether and then isopropanol were added. And then dried by heating at 100 ° C. for 1 hour.

Next, the upper clad layer-forming resin film CLF-1 from which the protective film (A31) has been removed using the vacuum pressure laminator is applied to the core 2 and the lower clad layer 4 at a pressure of 0.4 MPa and a temperature of 80 ° C. And it laminated | stacked on the conditions of pressurization time 30 second. After irradiating ultraviolet rays (wavelength 365 nm) at 2000 mJ / cm ² and removing the support film (A4100), the upper cladding layer 3 is formed by heat treatment at 130 ° C. for 1 hour, and the light shown in FIG. A waveguide 1 was obtained. Thereafter, an optical waveguide having a waveguide length of 10 cm was cut out using a dicing saw (DAD-341 manufactured by DISCO Corporation).

Examples 2 to 5 and Comparative Example 1
According to the blending ratio shown in Table 1, core-forming photosensitive resin varnish COV-2 to 4 were prepared. Similarly, the photosensitive resin varnish CLV-2-4 for clad layer formation were prepared according to the compounding ratio shown in Table 2. In the same manner as in Example 1, core-forming photosensitive resin films COF-2 to 4 and clad layer-forming photosensitive resin films CLF-2 to 4 were produced. The results of measuring the refractive index and transmittance of these cured films are shown in Tables 1 and 2.
Then, the optical waveguide was produced by the method similar to Example 1 using these resin films for optical waveguide formation. Table 3 shows combinations of the resin film for forming the core part and the resin film for forming the cladding layer used for the production of the optical waveguide.

* 1: (Meth) acrylic polymer solution produced in Production Example 1 * 2: (Meth) acrylic polymer solution produced in Production Example 2 * 3: (Meth) acrylic polymer solution produced in Production Example 3 * 4: Production Example (Meth) acrylic polymer solution prepared in 5 * 5: Ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 6: p-cumylphenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 7: 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals)
* 8: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Ciba Specialty Chemicals)
* 9: Measured under the conditions of a wavelength of 830 nm, 25 ° C., and a film thickness of 50 μm. * 10: ○: Measured under conditions of 80% or more, x ... less than 80%, wavelength of 400 nm, 25 ° C., and film thickness of 50 μm.

* 1: (Meth) acrylic polymer solution produced in Production Example 1 * 11: (Meth) acrylic polymer solution produced in Production Example 4 * 12: (Meth) acrylic polymer solution produced in Production Example 6 * 13: Ethoxylation Isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 14: Ethoxylated cyclohexanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 15: Hydrogenated bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 7: 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals)
* 8: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Ciba Specialty Chemicals)
* 9: Measured under the conditions of a wavelength of 830 nm, 25 ° C., and a film thickness of 50 μm. * 10: ○: Measured under conditions of 80% or more, x ... less than 80%, wavelength of 400 nm, 25 ° C., and film thickness of 50 μm.

[Measurement of optical propagation loss]
The optical propagation loss of the optical waveguide (waveguide length 10 cm) obtained in Examples 1 to 5 and Comparative Example 1 is a VCSEL (FLS-300-01-VCL manufactured by EXFO) having a light source having a wavelength of 850 nm as a central wavelength. ), A light receiving sensor (Q82214 manufactured by Advantest Corporation), an incident fiber (GI-50 / 125 multimode fiber, NA = 0.20) and an outgoing fiber (SI-114 / 125, NA = 0.22), Measurements were made by the cutback method (measurement waveguide lengths 10, 5, 3, 2 cm) and evaluated according to the following criteria. .
○: 0.3 dB / cm or less ×: larger than 0.3 dB / cm

[High temperature and high humidity test]
The optical waveguides (waveguide length 10 cm) obtained in Examples 1 to 5 and Comparative Example 1 were subjected to the JPCA standard (JPCA-PE02-05-) using a high-temperature and high-humidity tester (PL-2KT manufactured by ESPEC Corporation). 01S), a high-temperature and high-humidity test at a temperature of 85 ° C. and a humidity of 85% was conducted for 1000 hours.
The light propagation loss of the optical waveguide after the high-temperature and high-humidity leaving test was measured using the same light source, light receiving element, incident fiber and outgoing fiber as described above, and evaluated according to the following criteria. .
○: 0.3 dB / cm or less ×: larger than 0.3 dB / cm

[Temperature cycle test]
The optical waveguides (waveguide length 10 cm) obtained in Examples 1 to 5 and Comparative Example 1 were subjected to the JPCA standard (JPCA-PE02-05-) using a temperature cycle tester (ETAC WINTECH NT1010 manufactured by Enomoto Kasei Co., Ltd.). The temperature cycle test between −55 ° C. and 125 ° C. was performed 1000 cycles under the conditions in accordance with 01S). Detailed temperature cycle test conditions are shown in Table 4.

The light propagation loss of the optical waveguide after the temperature cycle test was measured using the same light source, light receiving element, incident fiber and output fiber as described above, and evaluated according to the following criteria.
○: 0.3 dB / cm or less ×: larger than 0.3 dB / cm

[Reflow test]
The optical waveguides (waveguide length 10 cm) obtained in Examples 1 to 5 and Comparative Example 1 were subjected to IPC / JEDEC J-STD-020B using a reflow tester (Furukawa Electric Co., Ltd. Salamanda XNA-645PC). The reflow test at the maximum temperature of 265 ° C. was performed three times under the conditions according to the above. Detailed reflow conditions are shown in Table 5, and the temperature profile in the reflow furnace is shown in FIG.

The light propagation loss of the optical waveguide after the reflow test was measured using the same light source, light receiving element, incident fiber and output fiber as described above, and evaluated according to the following criteria.
○: 0.3 dB / cm or less x: Greater than 0.3 dB / cm Table 6 shows the measurement results of the above optical propagation loss.

* 16: ○ ... 0.3 dB / cm or less, x ... greater than 0.3 dB / cm

  From Table 1, Table 2, and Table 6, the resin composition for optical materials of the present invention is excellent in transparency and heat resistance, and an optical waveguide produced using these has transparency, reliability, and heat resistance. It turns out that it is excellent. On the other hand, it turns out that the optical waveguide manufactured using the resin composition for optical materials which does not belong to this invention is inferior to reliability and heat resistance.

  The resin composition for optical materials and the resin film for optical materials using the resin composition for optical materials of the present invention are extremely excellent in transparency and heat resistance. Therefore, the optical waveguide manufactured using these optical material resin compositions or optical material resin films is excellent in transparency, reliability, and heat resistance.

It is sectional drawing explaining the form of the optical waveguide of this invention. It is a graph which shows the temperature profile in the reflow furnace in the reflow test implemented by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical waveguide 2 Core part 3 Upper clad layer 4 Lower clad layer 5 Base material

Claims (15)

(A) having at least a repeating unit represented by the following general formula (1) and having an ethylenically unsaturated group bonded to a side chain represented by the following general formula (2) via a urethane bond (Meth) acrylic polymer containing a repeating unit and / or a repeating unit having an ethylenically unsaturated group bonded to a side chain represented by the following general formula (3) via an amide bond, (B) polymerizable compound And (C) a resin composition for optical materials containing a polymerization initiator.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 20 carbon atoms.)

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. X ¹ and X ² are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms. Is shown.)

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. X ³ and X ⁴ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms. Is shown.) The resin composition for optical materials according to claim 1, wherein the (A) (meth) acrylic polymer further comprises a repeating unit having a maleimide skeleton represented by the following general formula (4).

(In the formula, R ⁷ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.) (A) The resin composition for optical materials according to claim 1 or 2, wherein the (meth) acrylic polymer further has a repeating unit represented by the following general formula (5).

(In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. X ⁵ represents a single bond or a divalent organic group having 1 to 20 carbon atoms.)   (B) The resin composition for optical materials in any one of Claims 1-3 in which a polymeric compound contains the compound which has an ethylenically unsaturated group in the molecule | numerator.   (A) The compounding quantity of (meth) acrylic polymer is 10-85 mass% with respect to the total amount of (A) component and (B) component, and the compounding quantity of (B) polymeric compound is (A) component and ( It is 15-90 mass% with respect to the total amount of B) component, and the compounding quantity of (C) polymerization initiator is 0.01-10 mass with respect to 100 mass parts of total amounts of (A) component and (B) component. The resin composition for an optical material according to any one of claims 1 to 4, wherein the resin composition is an optical part.   6. The refractive index at a wavelength of 830 nm at a temperature of 25 ° C. of a cured film obtained by polymerizing and curing the resin composition for an optical material is 1.400 to 1.700. 6. A resin composition for optical materials.   The optical property according to any one of claims 1 to 6, wherein a cured film having a thickness of 50 µm obtained by polymerizing and curing the resin composition for an optical material has a transmittance at a wavelength of 400 nm at a temperature of 25 ° C of 80% or more. Resin composition for materials.   The resin composition for optical materials according to any one of claims 1 to 7, which is used for forming an optical waveguide.   The resin film for optical materials using the resin composition for optical materials in any one of Claims 1-8.   An optical waveguide in which at least one of the lower cladding layer, the core portion, and the upper cladding layer is formed using the resin composition for forming an optical waveguide according to claim 8.   An optical waveguide in which at least one of the lower cladding layer, the core portion, and the upper cladding layer is formed using the resin film for optical material according to claim 9.   The optical waveguide according to claim 10 or 11, wherein the optical propagation loss is 0.3 dB / cm or less.   The optical waveguide according to any one of claims 10 to 12, wherein a light propagation loss after conducting a high-temperature and high-humidity standing test at a temperature of 85 ° C and a humidity of 85% for 1000 hours is 0.3 dB / cm or less.   The optical waveguide according to any one of claims 10 to 13, wherein a light propagation loss after 1000 cycles of a temperature cycle test between temperatures -55 ° C and 125 ° C is 0.3 dB / cm or less.   The optical waveguide according to any one of claims 10 to 14, wherein a light propagation loss after performing a reflow test at a maximum temperature of 265 ° C three times is 0.3 dB / cm or less.

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