JP5904362B2 - Resin composition for optical material, resin film for optical material, and optical waveguide - Google Patents

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 the same, and in particular, an optical resin composition excellent in heat resistance and transparency and soluble in an alkaline aqueous solution, and the resin composition The present invention relates to a resin film for optical materials made of a material and an optical waveguide using them.

In recent years, in high-speed and high-density signal transmission between electronic devices and between wiring boards, signal transmission interference and attenuation are barriers in conventional transmission using electric wiring, and the limits of high-speed and high-density have begun 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, a polymer optical waveguide has attracted attention because of its ease of processing, low cost, high flexibility in wiring, and high density.
As a form of the polymer optical waveguide, a type that is prepared on a glass epoxy resin substrate that is assumed to be applied to an opto-electric hybrid board or a flexible type that does not have a rigid support substrate that is assumed to be connected between boards is considered suitable.

Polymer optical waveguides are required to have high transparency (low optical propagation loss) and high heat resistance from the viewpoint of the usage environment and component mounting of the equipment to be applied. ) Acrylic polymers (see, for example, Patent Documents 1 and 2) are known.
However, although the (meth) acrylic polymers described in these patent documents have a high transparency of 0.3 dB / cm at a wavelength of 850 nm, the evaluation of heat resistance, for example, light propagation loss after a solder reflow test, etc. There is no specific description of the actual test results and it is not clear.

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 excellent in heat resistance and transparency, and soluble in an alkaline aqueous solution, a resin film for optical materials comprising the same, and a resin film for optical materials comprising the same. An object of the present invention is to provide an optical waveguide.

The present inventors have result of intensive studies, comprising a (A) a main chain of the alkali-soluble having a urethane skeleton epoxy (meth) acrylate bets, (B) a polymerizable compound and (C) a polymerization initiator It has been found that the above problem can be solved by producing an optical waveguide using a resin composition for an optical material and a resin film for an optical material comprising the same.

That is, the present invention relates to [1] (A) an optical material resin comprising an alkali-soluble epoxy (meth) acrylate having a urethane skeleton in the main chain , (B) a polymerizable compound, and (C) a polymerization initiator. Relates to the composition.
Moreover, this invention is [10] the compounding quantity of (2) (A) component with respect to the total amount of (A) component and (B) component, and the compounding quantity of (B) component is (A ) Component and the total amount of component (B) are 15 to 90% by mass, and the blending amount of component (C) is 0.1 to 100 parts by mass of the total amount of component (A) and component (B). It is related with the resin composition for optical materials of said [1] description which is 10 mass parts.
Moreover, this invention is described in said [1] or [2] whose [3] (B) polymeric compound is at least one of the compounds represented by the following general formula (1)-(2). It relates to the resin composition for optical materials.

（一般式（１）中、Ｘ^１及びＸ^２は、各々独立にＯ、Ｓ、Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｅ、Ｏ［ＣＨ_２ＣＨ（ＣＨ_３）Ｏ］_ａのいずれかの２価の基を示し、ａ及びｅは各々独立して１〜２０の整数を示す。式中、Ｙ^１は、

(In General Formula (1), X ¹ and X ² are each independently divalent one of O, S, O (CH ₂ CH ₂ O) _e , and O [CH ₂ CH (CH ₃ ) O] _a. A and e each independently represent an integer of 1 to 20. In the formula, Y ¹ is

のいずれかで示される２価の基を、ｃは２〜１０の整数を示す。
Ｒ^１及びＲ^６は、各々独立して水素原子、メチル基のいずれかを示す。Ｒ^２〜Ｒ^４は、各々独立して水素原子、フッ素原子、炭素数１〜２０の有機基、炭素数１〜２０の含フッ素有機基のいずれかを示す。）

And c represents an integer of 2 to 10.
R ¹ and R ⁶ each independently represent a hydrogen atom or a methyl group. R ^{2 to} R ⁴ each independently represent a hydrogen atom, a fluorine atom, an organic group having 1 to 20 carbon atoms, or a fluorine-containing organic group having 1 to 20 carbon atoms. )

（一般式（２）中、Ｙ^２は、

(In General Formula (2), Y ² is

のいずれかで示される２価の基を示す。Ｒ^１１及びＲ^１６は、各々独立して水素原子、メチル基のいずれかを示す。Ｒ^１２〜Ｒ^１５は、各々独立して水素原子、フッ素原子、炭素数１〜２０の有機基、炭素数１〜２０の含フッ素有機基のいずれかを示す。ｄは１〜５の整数、ｅは２〜１０の整数を示す。）
また、本発明は、［４］ （Ｂ）重合性化合物として、さらに２つ以上のエポキシ基を有する化合物を含有する上記［１］〜［３］のいずれかに記載の光学材料用樹脂組成物に関する。
また、本発明は、［５］ （Ｃ）重合開始剤が、光ラジカル重合開始剤である上記［１］〜［４］のいずれかに記載の光学材料用樹脂組成物に関する。
また、本発明は、［６］ 上記［１］〜［５］のいずれかに記載の光学材料用樹脂組成物からなる光学材料用樹脂フィルムに関する。
また、本発明は、［７］ 基材フィルム、上記［１］〜［５］のいずれかに記載の光学材料用樹脂組成物からなる光学材料用樹脂組成物層、及び保護フィルムからなる３層構造の上記［６］に記載の光学材料用樹脂フィルムに関する。
また、本発明は、［８］ 下部クラッド層、コア部、上部クラッド層の少なくとも１つを上記［１］〜［５］のいずれかに記載の光学材料用樹脂組成物を用いて形成した光導波路に関する。
また、本発明は、［９］ 下部クラッド層、コア部、上部クラッド層の少なくとも１つを上記［６］に記載の光学材料用樹脂フィルムを用いて形成した光導波路に関する。
なお、本発明で用いる（メタ）アクリレートは、アクリレート及び／又はメタクリレートを意味する。

Or a divalent group represented by any of the above. R ¹¹ and R ¹⁶ each independently represent a hydrogen atom or a methyl group. R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, an organic group having 1 to 20 carbon atoms, or a fluorine-containing organic group having 1 to 20 carbon atoms. d represents an integer of 1 to 5, and e represents an integer of 2 to 10. )
Moreover, this invention is [4] (B) The resin composition for optical materials in any one of said [1]-[3] containing the compound which has a 2 or more epoxy group as a polymeric compound further. About.
Moreover, this invention relates to the resin composition for optical materials in any one of said [1]-[4] whose [5] (C) polymerization initiator is a radical photopolymerization initiator.
Moreover, this invention relates to the resin film for optical materials which consists of a resin composition for optical materials in any one of [6] said [1]-[5].
The present invention also provides [7] a base film, a resin composition layer for an optical material comprising the resin composition for an optical material according to any one of the above [1] to [5], and a three-layer comprising a protective film. It is related with the resin film for optical materials as described in said [6] of a structure.
Moreover, this invention is [8] the optical light which formed at least 1 of the lower clad layer, the core part, and the upper clad layer using the resin composition for optical materials in any one of said [1]-[5]. Related to waveguides.
The present invention also relates to [9] an optical waveguide in which at least one of the lower clad layer, the core portion, and the upper clad layer is formed using the resin film for optical materials according to the above [6].
In addition, (meth) acrylate used by this invention means an acrylate and / or a methacrylate.

  The resin composition for optical materials of the present invention and the resin film for optical materials comprising the same are soluble in an alkaline aqueous solution, and an optical waveguide produced using these is excellent in heat resistance and transparency.

It is sectional drawing explaining the form of the optical waveguide of this invention.

The resin composition for optical material of the present invention, an optical comprising a (A) a main chain of the alkali-soluble having a urethane skeleton epoxy (meth) acrylate bets, (B) a polymerizable compound and (C) a polymerization initiator An alkali-soluble epoxy (meth) acrylate having a urethane skeleton in the main chain of (A) is an epoxy (meth) having two or more hydroxyl groups and ethylenically unsaturated groups in the molecule. An epoxy (meth) acrylate compound, which is a polyurethane compound obtained by reacting an acrylate compound, a diisocyanate compound, and a diol compound having a carboxyl group, having two or more hydroxyl groups and ethylenically unsaturated groups in the molecule, , Bisphenol A type epoxy compound, bisphenol F type epoxy compound, novolac type epoxy compound And Ri compounds der obtained by reacting an epoxy compound (meth) acrylic acid having a fluorene skeleton, a resin composition which is cured by irradiation of heat or actinic light.
Hereinafter will be described the main chain as the component (A) used in the present invention with the epoxy (meth) acrylate bets alkali-soluble having a urethane skeleton.

Is an epoxy (meth) acrylate bets alkali-soluble having a urethane skeleton in the main chain of the component (A), was dissolved in a developing solution comprising an alkaline aqueous solution, the solubility to the extent that the development process of interest is performed There is no particular limitation as long as it has, but from the viewpoint of transparency, heat resistance, solubility in alkaline aqueous solution, epoxy (meth) acrylate compound having two or more hydroxyl groups and ethylenically unsaturated groups in the molecule; It is preferable to use a polyurethane compound obtained by reacting a diisocyanate compound with a diol compound having a carboxyl group.

  As described above, the polyurethane compound includes an epoxy (meth) acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group (hereinafter referred to as “raw material epoxy (meth) acrylate”), a diisocyanate compound (hereinafter referred to as “raw material diisocyanate”). And a diol compound having a carboxyl group (hereinafter referred to as “raw diol”) as a raw material component. First, these raw material components will be described.

  Examples of the raw material epoxy (meth) acrylate include compounds obtained by reacting (meth) acrylic acid with bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, novolac type epoxy compounds, epoxy compounds having a fluorene skeleton, and the like. It is done.

  As the raw material diisocyanate, any compound having two isocyanato groups can be used without particular limitation. For example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, norbornane-diisocyanate methyl and the like can be mentioned. These may be used alone or in combination of two or more.

  The raw material diol is a compound having two hydroxyl groups such as an alcoholic hydroxyl group and / or a phenolic hydroxyl group in the molecule and a carboxyl group. The hydroxyl group preferably has an alcoholic hydroxyl group from the viewpoint of improving the developability of the resin composition for optical materials with an alkaline aqueous solution. Examples of such diol compounds include dimethylolpropionic acid and dimethylolbutanoic acid.

The example of the process of manufacturing an epoxy (meth) acrylate using the raw material component mentioned above is demonstrated .

  In the production process of the polyurethane compound, first, the raw material epoxy (meth) acrylate and the raw material diol are reacted with the raw material diisocyanate. In such a reaction, a so-called urethanization reaction occurs mainly between the hydroxyl group in the raw material epoxy (meth) acrylate and the isocyanate group in the raw material diisocyanate and between the hydroxyl group in the raw material diol and the isocyanate group in the raw material diisocyanate. By this reaction, for example, a polyurethane compound in which a structural unit derived from a raw material epoxy (meth) acrylate and a structural unit derived from a raw material diol are alternately or block-polymerized via a structural unit derived from a raw material diisocyanate. Occurs.

  An example of such a polyurethane compound is a compound represented by the following general formula (3).

ここで、一般式（３）中、Ｒ^２１はエポキシ（メタ）アクリレートの残基、Ｒ^２２はジイソシアネートの残基、Ｒ^２３は原料ジオールに由来する炭素数１〜５のアルキル基、Ｒ^２４は水素原子又はメチル基を示す。なお残基とは、原料成分から結合に供された官能基を除いた部分の構造をいう。また、式中に複数ある基は、それぞれ同一でも異なってもいてもよい。また、上記ウレタン化合物が有する末端の水酸基は、飽和若しくは不飽和多塩基酸無水物で処理されていてもよい。

Here, in the general formula (3), R ²¹ is a residue of epoxy (meth) acrylate, R ²² is a residue of diisocyanate, R ²³ is an alkyl group having 1 to 5 carbon atoms derived from the raw material diol, and R ²⁴ is A hydrogen atom or a methyl group is shown. In addition, a residue means the structure of the part remove | excluding the functional group used for the coupling | bonding from the raw material component. In addition, a plurality of groups in the formula may be the same or different. The terminal hydroxyl group of the urethane compound may be treated with a saturated or unsaturated polybasic acid anhydride.

  In the production process of the polyurethane compound described above, a diol compound different from these may be further added in addition to the raw material epoxy (meth) acrylate, the raw material diol and the raw material diisocyanate. Thereby, it becomes possible to change the main chain structure of the obtained polyurethane compound, and the characteristics such as the acid value described later can be adjusted to a desired range. Moreover, in each process mentioned above, you may use a catalyst etc. suitably.

  Moreover, you may make the polyurethane compound mentioned above and raw material epoxy react further. In this reaction, a so-called epoxycarboxylation reaction occurs mainly between the carboxyl group derived from the diol compound in the polyurethane compound and the epoxy group of the raw material epoxy. Thus, the compound obtained is equipped with the principal chain formed from the polyurethane compound mentioned above, and the side chain containing the ethylenically unsaturated group derived from raw material epoxy (meth) acrylate or raw material epoxy, for example. .

As the polyurethane compound of this embodiment, among the compounds represented by the general formula (3), the hard segment part of the raw material epoxy (meth) acrylate that is one of the main skeletons of polyurethane, that is, R ²¹ has a bisphenol A type structure. Those are preferred. Such polyurethane compounds are commercially available as UXE-3011, UXE-3012, UXE-3024 (manufactured by Nippon Kayaku Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  In addition, since the resin composition for optical materials containing such a polyurethane compound can form a cured film having toughness and excellent elongation, crack resistance and HAST resistance after curing (HAST Highly Accelerated Stress Test) Can be improved.

The acid value of the epoxy (meth) acrylate bets alkali-soluble having a urethane skeleton (a) a main chain is preferably 20~180mgKOH / g, more preferably 30~150mgKOH / g, 40~120mgKOH / G is particularly preferable. Thereby, the developability by the alkaline aqueous solution of the resin composition for optical materials becomes good, and an excellent resolution can be obtained. Adjustment of an acid value can raise an acid value by increasing the compounding quantity of the diol compound which has a carboxyl group, and can make the value of an acid value small conversely.

Here, the acid value can be measured by the following method. First, after precisely weighing about 1 g of the measurement resin solution, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
A = 10 × Vf × 56.1 / (Wp × I)
In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the measurement resin solution mass (g), and I represents the measurement resin. The ratio (% by mass) of the nonvolatile content of the solution is shown.

Also, have a weight average molecular weight of the alkali-soluble epoxy (meth) acrylate bets having a urethane skeleton in (a) a main chain, from the viewpoint of coating properties, preferably 3,000 to 30,000, is 5,000 to 20,000 More preferably, it is particularly preferably 7000 to 15000.

  In addition, a weight average molecular weight (Mw) can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC).

  It is preferable that the compounding quantity 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 exposure. The developer resistance is not insufficient. From the above viewpoint, the content 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.
The polymerizable compound as the component (B) is not particularly limited as long as it is polymerized by heating or irradiation with ultraviolet rays, and examples thereof include compounds having a polymerizable substituent such as an ethylenically unsaturated group.
Specific examples include (meth) acrylates, vinylidene halides, vinyl ethers, vinyl esters, vinyl pyridines, vinyl amides, arylated vinyls, etc. Of these, from the viewpoint of transparency, (meth) acrylates and arylated vinyls. It is preferable that As the (meth) acrylate, any of monofunctional, bifunctional, or polyfunctional ones can be used.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, Isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate , Lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) 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, Aliphatics such as methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, ethoxypolypropyleneglycol (meth) acrylate, mono (2- (meth) acryloyloxyethyl) succinate ( (Meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate Cyclic (meth) acrylate; benzyl (meth) acrylate, phenyl (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, phenoxypolyethyleneglycol (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl Aromatic (meth) acrylates such as (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate; 2-tetrahydro Heterocyclic (meth) acrylates such as furfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) acryloyloxyethyl-N-carbazole, and their caprolactone modifications Body and the like.
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, neopentyl Recall 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-methyl Aliphatic (meth) acrylates such as 1,3-propanediol di (meth) acrylate; cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, propoxylated cyclohexanedimethanol (meth) acrylate, etoxy Propoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated tricyclodecane dimethanol (meth) acrylate, propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated propoxylated tri Cyclodecane 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 water Alicyclic rings such as hydrogenated bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, and ethoxylated propoxylated hydrogenated bisphenol F di (meth) acrylate Formula (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, propoxylated 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 di (meth) acrylate, propoxylated fluorene di (meth) acrylate, ethoxylated propoxy fluorene di (meth) acrylate Heterocyclic (meth) acrylates such as ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, ethoxylated propoxylated isocyanuric acid di (meth) acrylate, etc. Acrylates; these caprolactone modified products; aliphatic epoxy (meth) acrylates such as neopentyl glycol type epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated Alicyclic epoxy (meth) acrylates such as bisphenol F type epoxy (meth) acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol Type epoxy (meth) 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; It is preferably a group epoxy (meth) acrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxylated tri Methylolpropane 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 (me ) 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 Heterocyclic (meth) acrylates such as isocyanuric acid tri (meth) acrylate and ethoxylated propoxylated isocyanuric acid tri (meth) acrylate; these caprolactone modified products; phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meta) ) Aromatic epoxy (meth) acrylates such as acrylate.
Among these, from the viewpoint of transparency and heat resistance, heterocyclic (meth) acrylates; aromatic epoxy (meth) acrylates are preferable.
These compounds can be used alone or in combination of two or more, and can also be used in combination with other polymerizable compounds.

  Further, as the polymerizable compound of component (B), from the viewpoint of heat resistance, at least one selected from the group consisting of an alicyclic structure, an aryl group, an aryloxy group and an aralkyl group in the molecule, and an ethylenically unsaturated group It is preferable to use one or more kinds of compounds containing. Specific examples include (meth) acrylate or N-vinylcarbazole containing at least one selected from the group consisting of an alicyclic structure, an aryl group, an aryloxy group, and an aralkyl group. In addition, an aryl group represents aromatic heterocyclic groups, such as aromatic carbon hydrogen groups, such as a phenyl group and a naphthyl group, and a carbazole group, for example.

  More specifically, as the polymerizable compound of component (B), at least one of compounds containing an aryl group and an ethylenically unsaturated group represented by the following general formulas (1) to (2) is used. Is more preferable.

（一般式（１）中、Ｘ^１及びＸ^２は、各々独立にＯ、Ｓ、Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｅ、Ｏ［ＣＨ_２ＣＨ（ＣＨ_３）Ｏ］_ａのいずれかの２価の基を示し、ａ及びｅは各々独立して１〜２０の整数を示す。式中、Ｙ^１は、

(In General Formula (1), X ¹ and X ² are each independently divalent one of O, S, O (CH ₂ CH ₂ O) _e , and O [CH ₂ CH (CH ₃ ) O] _a. A and e each independently represent an integer of 1 to 20. In the formula, Y ¹ is

のいずれかで示される２価の基を、ｃは２〜１０の整数を示す。
Ｒ^１及びＲ^６は、各々独立して水素原子、メチル基のいずれかを示す。Ｒ^２〜Ｒ^４は、各々独立して水素原子、フッ素原子、炭素数１〜２０の有機基、炭素数１〜２０の含フッ素有機基のいずれかを示す。）

And c represents an integer of 2 to 10.
R ¹ and R ⁶ each independently represent a hydrogen atom or a methyl group. R ^{2 to} R ⁴ each independently represent a hydrogen atom, a fluorine atom, an organic group having 1 to 20 carbon atoms, or a fluorine-containing organic group having 1 to 20 carbon atoms. )

（一般式（２）中、Ｙ^２は、

(In General Formula (2), Y ² is

のいずれかで示される２価の基を示す。Ｒ^１１及びＲ^１６は、各々独立して水素原子、メチル基のいずれかを示す。Ｒ^１２〜Ｒ^１５は、各々独立して水素原子、フッ素原子、炭素数１〜２０の有機基、炭素数１〜２０の含フッ素有機基のいずれかを示す。ｄは１〜５の整数、ｅは２〜１０の整数を示す。）

Or a divalent group represented by any of the above. R ¹¹ and R ¹⁶ each independently represent a hydrogen atom or a methyl group. R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, an organic group having 1 to 20 carbon atoms, or a fluorine-containing organic group having 1 to 20 carbon atoms. d represents an integer of 1 to 5, and e represents an integer of 2 to 10. )

  Examples of the organic group in the general formulas (1) to (2) include monovalent or 2 such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group. Valent groups such as hydroxyl group, halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group. Group, alkylthio group, arylthio group, amino group, silyl group and the like.

  Moreover, as a preferable (B) polymeric compound other than (meth) acrylate, what contains the compound which has a 2 or more epoxy group in a molecule | numerator is mentioned. By using this, a so-called epoxycarboxylation reaction occurs with the carboxyl group derived from the diol compound in the polyurethane compound of the component (A), and improvement in heat resistance and strength can be expected.

  Specifically, bisphenol A type epoxy resin, tetrabromobisphenol 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 Bifunctional phenol glycidyl ether such as resin; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated 2,2′-biphenol type epoxy resin, hydrogenated 4,4′-biphenol type epoxy resin, etc. Hydrogenated bifunctional phenol glycidyl ether; phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene-phenol type epoxy resin, tetraphenylolethane type epoxy resin, etc. Polyfunctional phenol glycidyl ether; polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, bifunctional aliphatic alcohol glycidyl ether such as 1,6-hexanediol type epoxy resin; cyclohexanedimethanol type epoxy Resin, bifunctional alicyclic alcohol glycidyl ether such as tricyclodecane dimethanol type epoxy resin; polyfunctional aliphatic alcohol glycidyl ether such as trimethylolpropane type epoxy resin, sorbitol type epoxy resin, glycerin type epoxy resin; diphthalic acid 2 functional aromatic glycidyl esters such as glycidyl ester; 2 such as tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester Noble alicyclic glycidyl ester; bifunctional aromatic glycidylamine such as N, N-diglycidylaniline, N, N-diglycidyltrifluoromethylaniline; N, N, N ′, N′-tetraglycidyl-4,4 Polyfunctional aromatic glycidylamines such as diaminodiphenylmethane, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, O-triglycidyl-p-aminophenol; alicyclic diepoxy acetals, ants Bifunctional alicyclic epoxy resins such as cyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinylcyclohexene dioxide; 1,2-epoxy-4- of 2,2-bis (hydroxymethyl) -1-butanol Polyfunctional fats such as (2-oxiranyl) cyclohexane adducts Polyfunctional heterocyclic epoxy resins such as triglycidyl isocyanurate; wherein epoxy resins such as difunctional or polyfunctional silicon-containing epoxy resins such as organopolysiloxane type epoxy resins.

Among these, from the viewpoint of transparency and heat resistance, 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 Bifunctional phenol glycidyl ether such as epoxy resin; Hydrogenated bifunctional phenol glycidyl ether; Polyfunctional phenol glycidyl ether; Bifunctional alicyclic alcohol glycidyl ether; Bifunctional aromatic glycidyl ester; Bifunctional alicyclic Preferably, the glycidyl ester; the bifunctional alicyclic epoxy resin; the polyfunctional alicyclic epoxy resin; the polyfunctional heterocyclic epoxy resin; and the bifunctional or polyfunctional silicon-containing epoxy 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, it is easy to cure together with (A) an alkali-soluble epoxy (meth) acrylate having a urethane skeleton in the main chain (an acid-modified vinyl group-containing epoxy resin having a urethane structure), and resistance to developer. There is no shortage. Moreover, if it is 90 mass% or less, the film strength and flexibility of a cured film are enough. From the above viewpoint, the content 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 for component (C) is not particularly limited as long as it initiates polymerization by heating or irradiation with ultraviolet rays, for example, a compound having an ethylenically unsaturated group as the polymerizable compound for component (B). When used, a thermal radical polymerization initiator, a photo radical polymerization initiator, and the like can be mentioned, but a photo radical polymerization initiator is preferable because it has a high curing rate and can be cured at room temperature.

Examples of the thermal radical polymerization initiator 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, 1,1- Peroxyketals such as bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; α, α′-bis (t-butylperoxy) diisopropylbenzene , Dicumyl peroxide, t-butyl cumylper Dialkyl peroxides such as oxide and di-t-butyl peroxide; Diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide and benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxydicarbonate Peroxycarbonates such as di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate; t-butyl peroxypivalate, t-hexyl peroxy Pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylper Oxy-2-e Ruhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, 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, 2,5-dimethyl-2 , 5-bis (benzoylperoxy) hexane, peroxyesters such as t-butylperoxyacetate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (4-methoxy And azo compounds such as cis-2′-dimethylvaleronitrile).
Among these, from the viewpoints of curability, transparency, and heat resistance, the diacyl peroxide; the peroxy ester; and the azo compound are preferable.

  Examples of the radical photopolymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- Α-hydroxy ketones such as 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one; 2-benzyl-2-dimethylamino-1 Α-amino ketones such as-(4-morpholinophenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Oxime esters such as (4-phenylthio) phenyl] -1,2-octadion-2- (benzoyl) oxime; bis (2,4,6 Phosphine oxides such as -trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole 2,4,5-tria such as dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Reel imidazole dimer; benzophenone, N, N′-tetramethyl-4, Benzophenone compounds such as' -diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 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- Quinone compounds such as phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; benzyl compounds such as benzyldimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis (9,9'-acridinylheptane): N- Examples include phenylglycine and coumarin.

  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. Also. A thioxanthone compound and a tertiary amine may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid.

  Among these, from the viewpoints of curability, transparency, and heat resistance, the α-hydroxy ketone and the phosphine oxide are preferable. These thermal 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.

  Moreover, when using the epoxy resin which is a compound which has a 2 or more epoxy group as a polymeric compound of (B) component, as a polymerization initiator of (C) component, a thermal cation polymerization initiator and a photocationic polymerization initiator However, a photocationic polymerization initiator is preferred because the curing rate is high and room temperature curing is possible.

Examples of the thermal cationic polymerization initiator include benzylsulfonium salts such as p-alkoxyphenylbenzylmethylsulfonium hexafluoroantimonate; benzyl-p-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-o-cyanopyridinium hexafluoroantimonate. And pyridinium salts such as cinnamyl-o-cyanopyridinium hexafluoroantimonate; and benzylammonium salts such as benzyldimethylphenylammonium hexafluoroantimonate.
Among these, from the viewpoint of curability, transparency, and heat resistance, the benzylsulfonium salt is preferable.

Examples of the photocationic polymerization initiator include aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenyl Triarylsulfonium salts such as sulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate ; Triphenylselenonium Triarylselenonium salts such as oxafluorophosphate, triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroantimonate; dialkylphenacyl such as dimethylphenacylsulfonium hexafluoroantimonate, diethylphenacylsulfonium hexafluoroantimonate Sulfonium salts; dialkyl-4-hydroxy salts such as 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate; α-hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate, α -Sulfonate esters such as sulfonyloxyketone and β-sulfoniloxyketone And the like.
Among these, the above triarylsulfonium salts are preferable from the viewpoints of curability, transparency, and heat resistance. 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 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. When it is 0.1 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, it is more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

  In addition to the above, in the resin composition for an optical material of the present invention, an antioxidant, a yellowing inhibitor, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, You may add what is called additives, such as a filler, in the ratio which does not have a bad influence on the effect of this invention.

Hereinafter, the resin composition for optical materials of the present invention will be described.
The resin composition for optical materials of the present invention may be diluted with a suitable organic solvent and used as a resin varnish for optical materials. The organic solvent used here is not particularly limited as long as it can dissolve the resin composition. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, p-cymene; tetrahydrofuran, 1, 4 -Cyclic ethers such as dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; acetic acid Esters such as methyl, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; ethylene glycol monomethyl ether, ethylene glycol Cole 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 monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Polyhydric alcohol alkyl ethers such as butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Polyhydric alcohol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Examples include amides such as pyrrolidone.
Among these, from the viewpoint of solubility and boiling point, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and N, N-dimethylacetamide.
These organic solvents can be used alone or in combination of two or more.
Moreover, it is preferable that the solid content density | concentration in a resin varnish is 20-80 mass% normally.

  When preparing the resin varnish for optical material, 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, the components (A) to (C) and the organic solvent are 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, it is more preferably 50 to 800 rpm, and particularly preferably 100 to 500 rpm. Although there is no restriction | limiting in particular in stirring time, It is preferable that it is 1 to 24 hours. When it is 1 hour, the components (A) to (C) and the organic solvent are sufficiently mixed, and when it is 24 hours or less, the varnish preparation time can be shortened.

  The prepared resin varnish for an optical material is preferably filtered using a filter having a pore size of 50 μm or less. When the pore diameter is 50 μm or less, large foreign matters and the like are removed, and no “repelling” or the like occurs during varnish application, and scattering of light propagating through the core portion is suppressed. 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 varnish for optical material is preferably degassed under reduced pressure. There is no restriction | limiting in particular in the defoaming method, As a specific example, a degassing apparatus with a vacuum pump and a bell jar and a vacuum apparatus can be used. Although there is no restriction | limiting in particular in the pressure at the time of pressure reduction, The pressure which the organic solvent contained in a resin varnish does not boil is preferable. 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 varnish can be removed. If it is 60 minutes or less, the organic solvent contained in the resin varnish will not volatilize.

Alkali-soluble (meth) epoxy acrylated bets in (A) the main chain of the present invention comprises a urethane skeleton, and (B) a polymerizable compound and (C) consisting of a polymerization initiator to the resin compound for optical material polymerized, cured to The refractive index of the cured film at a temperature of 25 ° C. at a wavelength of 830 nm is preferably 1.400 to 1.700. If 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, it is more preferably 1.425 to 1.675, and particularly preferably 1.450 to 1.650.

Alkali-soluble (meth) epoxy acrylated bets in (A) the main chain of the present invention comprises a urethane skeleton, and (B) a polymerizable compound and (C) consisting of a polymerization initiator to the resin compound for optical material polymerized, cured to The transmittance of the cured film having a thickness of 50 μm at a wavelength of 400 nm is preferably 80% or more. If it is 80% or more, the amount of transmitted light is sufficient. From the above viewpoint, it is more preferably 85% or more. Note that the upper limit of the transmittance is not particularly limited. The transmittance can be measured using a spectrophotometer.

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 resin composition for optical materials, and the resin varnish for optical materials containing the components (A) to (C) is applied to a suitable base film, and the solvent is removed. By doing so, it can be easily manufactured. Moreover, you may manufacture by apply | coating the resin composition for optical materials directly to a base film.

  There is no restriction | limiting in particular as a base film, For example, Polyester, such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyolefin, such as polyethylene and a polypropylene; Polycarbonate, polyamide, polyimide, polyamideimide, polyetherimide, polyether sulfide , Polyethersulfone, polyetherketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, liquid crystal polymer, and the like. 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.

  The thickness of the base 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 is more preferably 5 to 200 μm, and particularly preferably 7 to 150 μm. In addition, from the viewpoint of improving releasability from the resin layer, a film that has been subjected to a release treatment with a release agent such as a silicone compound or a fluorine-containing compound may be used as necessary.

  A resin film for an optical material produced by applying a resin varnish for an optical material or a resin composition for an optical material on a base film, and a protective film is attached on the resin layer as necessary. It is good also as a 3 layer structure which consists of a resin layer and a protective film.

  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, from the viewpoint of improving releasability from the resin layer, a film that has been subjected to a release treatment with a release agent such as a silicone compound or a fluorine-containing compound may be used as necessary. 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 is more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

  Although it does not specifically limit about the thickness of the resin composition layer of the resin film for optical materials of this invention, It is preferable that it is 5-500 micrometers normally by the thickness after drying. If the thickness is 5 μm or more, the resin film or the cured product of the film has sufficient strength because the thickness is sufficient, and if it is 500 μm or less, the drying can be sufficiently performed without increasing the amount of residual solvent in the resin film. When the cured product of the film is heated, it does not foam.

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

  The resin composition for an optical material of the present invention is suitable as a resin composition for forming an optical waveguide. Similarly, the resin film for an optical material of the present invention is suitable as a resin film for forming an optical waveguide.

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, and a lower cladding layer 4 made of a resin composition for forming a cladding layer having a low refractive index. And the upper clad layer 3.
The resin composition for an optical material and the resin film for an optical material 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. Among these, it is more preferable to use it for at least the core part 2 from the viewpoint that a pattern can be formed with a developer composed of an alkaline aqueous solution.

  By using a resin film for optical materials, it is possible to further improve the interlayer adhesion between the clad and the core and the pattern formability (correspondence between fine lines or narrow lines) when forming the optical waveguide core pattern. Can be formed. In addition, it is possible to provide a process with excellent productivity in which a large-area optical waveguide can be manufactured at one time.

  In the optical waveguide 1, a hard base material such as a silicon substrate, a glass substrate, or a glass epoxy resin substrate such as FR-4 can be used as the base material 5. The optical waveguide 1 may be a flexible optical waveguide using the base film having flexibility and toughness instead of the base material.

When a base film having flexibility and toughness is used as the base 5, the base 5 may function as a cover film for the optical waveguide 1. By disposing the cover film, the flexibility and toughness of the cover film can be imparted to the optical waveguide 1. Further, since the optical waveguide 1 is not damaged or scratched, the ease of handling is improved.
From the above viewpoint, the cover film 5 is disposed outside the upper cladding layer 3 as shown in FIG. 1B, or both the lower cladding layer 4 and the upper cladding layer 3 are used as shown in FIG. The cover film 5 may be arrange | positioned on the outer side.
If the optical waveguide 1 has sufficient flexibility and toughness, the cover film 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 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 100 μm. When the height of the core is 10 μm or more, the alignment tolerance is not reduced in the coupling with the light emitting / receiving element or the optical fiber 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 80 μm, and particularly preferably 20 to 70 μm. In addition, there is no restriction | limiting in particular about the thickness of the resin film for core part formation, 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 to do. 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, it is more preferably 0.2 dB / cm or less.

Hereinafter, application examples when the resin film for 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 base film used in the process of producing the resin film for optical material for forming the core part is not particularly limited as long as it can transmit the actinic ray for exposure used for core pattern formation described later. For example, polyethylene terephthalate And polyesters such as polybutylene terephthalate and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polycarbonates, polyphenylene ethers and polyarylates.
Among these, polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene are preferable from the viewpoints of the transmittance of exposure actinic rays, flexibility and toughness. Furthermore, it is more preferable to use a highly transparent base 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 base film 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 a release treatment with a release agent such as a silicone compound or a fluorine-containing compound may be used as necessary.

  The thickness of the base film of the core portion forming resin film is preferably 5 to 50 μm. If it is 5 μm or more, the strength as a support is sufficient, and if it is 50 μm or less, the gap between the photomask and the resin composition layer for forming the core part does not increase when the core pattern is formed, and the pattern formability is good. is there. From the above viewpoint, the thickness of the base film is more preferably 10 to 40 μm, and particularly preferably 15 to 30 μm.

  An optical waveguide-forming resin film produced by applying an optical waveguide-forming resin varnish or an optical waveguide-forming resin composition on the base film is prepared by applying the protective film on the resin layer as necessary. It is good also as a 3 layer structure which consists of a material film, the resin layer for optical waveguide formation (resin composition for optical materials), and a protective film.

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

Hereinafter, the manufacturing method for forming the optical waveguide 1 using the resin varnish for optical waveguide formation and / or the resin film for optical waveguide formation is demonstrated.
A method for producing the optical waveguide 1 of the present invention is not particularly limited, but a method for producing the core portion forming resin varnish and a clad layer forming resin varnish by a spin coating method or the like, or a core portion forming resin. Examples thereof include a production method using a film and a resin film for forming a clad layer by a lamination method. Moreover, it can also manufacture combining these methods. Among these, from the viewpoint that an optical waveguide manufacturing process with excellent productivity can be provided, a method of manufacturing by a lamination method using a resin film for forming an optical waveguide is preferable.

Hereinafter, a manufacturing method for forming the optical waveguide 1 using the resin film for forming an optical waveguide for the lower clad layer, the core portion, and the upper clad layer will be described.
First, as a first step, a lower clad layer forming resin film is laminated on the base material 5 to form the lower clad layer 4. The laminating method in the first step includes a method of laminating by pressure bonding while heating using a roll laminator or a flat plate laminator, but from the viewpoint of adhesion and followability, using a flat plate laminator. It is preferable to laminate the resin film for lower clad layer formation under reduced pressure. In the present invention, the flat plate type laminator 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 40 to 130 ° C., and the pressing 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 forming the lower cladding layer, the protective film is laminated after removing the protective film.
In addition, before lamination | stacking by a vacuum pressurization-type laminator, you may temporarily stick the resin film for lower clad layer formation on the base material 5 beforehand 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. When it is 20 ° C. or higher, the adhesion between the resin film for forming the lower clad layer and the substrate 5 is improved, and when it is 130 ° C. or lower, the resin layer does not flow too much during 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.

Subsequently, the lower clad layer forming resin film laminated on the base material 5 is cured by light and / or heating, and the lower clad layer forming resin film is removed to form the lower clad layer 4. .
The irradiation amount of actinic rays when forming the lower cladding layer 4 is preferably 0.1 to 5 J / cm ² and the heating temperature is preferably 50 to 200 ° C. There is no limit.

  Next, as a second step, the core portion forming resin film is laminated by the same method as in the first step. Here, the core part-forming resin film is designed to have a higher refractive index than that of the lower clad layer-forming resin film, and preferably comprises a photosensitive resin composition capable of forming a core pattern with actinic rays. The resin composition for optical materials has photosensitivity.

Next, a core part is exposed as a 3rd process, and the core pattern (core part 2) of an optical waveguide is formed. Specifically, actinic rays are irradiated in an image form through a negative or positive mask pattern called an artwork. In addition, an active light beam may be directly irradiated on an image without passing through a photomask using laser direct drawing. Examples of the active light source include known light sources that effectively emit ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp. In addition, there are those that effectively emit visible light, such as a photographic flood light bulb and a solar lamp.
The actinic ray irradiation amount here is preferably 0.01 to 10 J / cm ² . When it is 0.01 J / cm ² or more, the curing reaction proceeds sufficiently, and the core portion 2 is not washed away by the development process described later, and when it is 10 J / cm ² or less, the core portion 2 is caused by excessive exposure. It is suitable for forming a fine pattern without being fat. From the viewpoints described above, more preferably 0.05~5J / cm ^2, and particularly preferably 0.1~3J / cm ^2.
In addition, after exposure, you may perform post-exposure heating from a viewpoint of the resolution of the core part 2, and adhesive improvement. The time from ultraviolet irradiation to post-exposure heating is preferably within 10 minutes. Within 10 minutes, the active species generated by ultraviolet irradiation will not be deactivated. The post-exposure heating temperature is preferably 40 to 160 ° C., and the time is preferably 30 seconds to 10 minutes.

  After exposure, the base film of the resin film for forming the core part is removed, and using a developer corresponding to the composition of the resin film for forming the core part, such as an alkaline aqueous solution or an aqueous developer, for example, spraying, rocking immersion Development is performed by a known method such as brushing, scraping, dipping or paddle. Moreover, you may use together 2 or more types of image development methods as needed.

  The base of the alkaline aqueous solution is not particularly limited. For example, alkali hydroxide such as lithium, sodium or potassium hydroxide; alkali carbonate such as lithium, sodium, potassium or ammonium carbonate or bicarbonate; Alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; sodium salts such as borax and sodium metasilicate; tetramethylammonium hydroxide and triethanolamine And organic bases such as ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol and 1,3-diaminopropanol-2-morpholine. The pH of the alkaline aqueous solution used for development is preferably 9 to 11, and the temperature is adjusted in accordance with the developability of the core portion-forming resin composition layer. Further, in the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

The aqueous developer is not particularly limited as long as it is composed of water or an alkaline aqueous solution and one or more organic solvents. The pH of the aqueous developer is preferably as low as possible within the range where the development of the resin film for forming a core part can be sufficiently performed, preferably pH 8-12, and particularly preferably pH 9-10.
Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol and propylene glycol; ketones such as acetone and 4-hydroxy-4-methyl-2-pentanone; ethylene glycol monomethyl ether and ethylene glycol mono Examples thereof include polyhydric alcohol alkyl ethers such as ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
These can be used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by mass, and the temperature is adjusted according to the developability of the resin composition for forming a core part. Further, a small amount of a surfactant, an antifoaming agent or the like may be mixed in the aqueous developer.

  As the processing after development, the core portion 2 of the optical waveguide may be cleaned using a cleaning liquid composed of water and the organic solvent as necessary. An organic solvent can be used individually or in combination of 2 or more types. In general, the concentration of the organic solvent is preferably 2 to 90% by mass, and the temperature is adjusted in accordance with the developability of the core portion-forming resin composition.

As processing after development or washing, if necessary, the core portion 2 may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.1 to 10 J / cm ² .

Subsequently, as a fourth step, the upper clad layer forming resin film is laminated by the same method as in the first and second steps to form the upper clad layer 3. Here, the upper clad layer forming resin film is designed to have a lower refractive index than the core portion forming resin film. Further, the thickness of the upper cladding layer 3 is preferably larger than the height of the core portion 2.
Next, the upper clad layer-forming resin film is cured by light and / or heat in the same manner as in the first step to form the upper clad layer 3.
When the base film of the resin film for forming a clad layer is PET, the irradiation amount of actinic rays is preferably 0.1 to 5 J / cm ² . On the other hand, when the base film is polyethylene naphthalate, polyamide, polyimide, polyamideimide, polyetherimide, polyphenylene ether, polyether sulfide, polyethersulfone, polysulfone, etc., actinic rays having a short wavelength such as ultraviolet rays are used compared to PET. Since it is difficult to pass through, the irradiation amount of actinic rays is preferably 0.5 to 30 J / cm ² . When it is 0.5 J / cm ² or more, the curing reaction proceeds sufficiently, and when it is 30 J / cm ² or less, the time of light irradiation does not take too long. From the viewpoints described above, more preferably 3~27J / cm ^2, and particularly preferably 5~25J / cm ^2.
In addition, in order to make it harden | cure, the double-sided exposure machine which can irradiate actinic light simultaneously from both surfaces can be used. Moreover, you may irradiate actinic light, heating. The heating temperature during and / or after irradiation with actinic rays is preferably 50 to 200 ° C., but these conditions are not particularly limited.
After forming the upper cladding layer 3, the base film can be removed if necessary to produce the optical waveguide 1.

  Since the optical waveguide of the present invention is excellent in heat resistance and transparency, it may be used as an optical transmission line 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 either a rigid substrate such as a glass epoxy substrate or a flexible substrate such as a polyimide substrate may be used.

  The following examples further illustrate the present invention, but the present invention is not limited to these examples.

(Synthesis 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, 42 parts by mass of propylene glycol monomethyl ether acetate and 21 parts by mass of methyl lactate were weighed and stirred while introducing nitrogen gas. . The liquid temperature was raised to 65 ° C., 15 parts by mass of N-cyclohexylmaleimide, 30 parts by mass of benzyl methacrylate, 29 parts by mass of t-butyl methacrylate, 14 parts by mass of 2-hydroxyethyl methacrylate, 13 parts by mass of methacrylic acid, 2,2 ′ -A mixture of 4 parts by mass of azobis (2,4-dimethylvaleronitrile), 37 parts by mass of propylene glycol monomethyl ether acetate and 21 parts by mass of methyl lactate was added dropwise over 3 hours, followed by stirring at 65 ° C for 3 hours, and further 95 Stirring was continued at 1 ° C. for 1 hour to obtain a (meth) acrylic polymer A-1 solution (solid content: 45% by mass).

[Measurement of weight average molecular weight]
As a result of measuring the weight average molecular weight (in terms of standard polystyrene) of A-1 using GPC (“SD-8022”, “DP-8020”, and “RI-8020” manufactured by Tosoh Corporation), 3.5 × 10 ⁴ . As the column, “Gelpack GL-A150-S” and “Gelpack GL-A160-S” manufactured by Hitachi Chemical Co., Ltd. were used. Tetrahydrofuran was used as the eluent, the sample concentration was 0.5 mg / ml, and the elution rate was 1 ml / min.

[Measurement of acid value]
As a result of measuring the acid value of A-1, it was 80 mgKOH / g. In addition, the acid value was computed from the amount of 0.1 mol / L potassium hydroxide aqueous solution required for neutralizing A-1 solution. At this time, the point at which the phenolphthalein added as an indicator changed color from colorless to pink was defined as the neutralization point.

[Preparation of Clad Layer Forming Resin Varnish CLV-1]
120 parts by mass (solid content: 54 parts by mass) of the A-1 solution (solid content: 45% by mass), which is the (meth) acrylic polymer synthesized above, and ethoxylated isocyanuric acid triacrylate (Hitachi Chemical Industries) as the component (B) 18 parts by mass of “Fancryl FA-731A” manufactured by Co., Ltd. and 18 parts by mass of “NK Ester A-TMTP-9EO” manufactured by Shin-Nakamura Chemical Co., Ltd. , 10 parts by mass of hydrogenated bisphenol A type epoxy resin (“Epicoat YX8034” (epoxy equivalent 290 g / eq) manufactured by Japan Epoxy Resin Co., Ltd.), 1- [4- (2-hydroxyethoxy) phenyl] as component (C) -2-Hydroxy-2-methyl-1-propan-1-one (Ciba Japan Co., Ltd.) "Irgacure 2959") 1 part by mass, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Ciba Japan "Irgacure 819") 1 part by mass, and 10 parts of propylene glycol monomethyl ether acetate as a diluent solvent The parts were mixed with stirring. After pressure filtration using a polyflon filter having a pore diameter of 2 μm (“PF020” manufactured by Advantech Toyo Co., Ltd.), degassing was performed under reduced pressure to obtain a resin varnish CLV-1 for forming a cladding layer.

[Preparation of Cladding Layer Forming Resin Film CLF-1]
Clad layer forming resin composition CLV-1 was coated on a non-treated surface of a PET film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 50 μm) (“Multicoater TM-MC manufactured by Hirano Techseed Co., Ltd.). ”), And after drying at 80 ° C. for 10 minutes and 100 ° C. for 10 minutes, a surface release treatment PET film (“ Purex A31 ”manufactured by Teijin DuPont Films Ltd., thickness 25 μm) is applied as a protective film, A resin film CLF-1 for forming a cladding layer 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 embodiment, the thickness after curing is 20 μm for the lower clad layer forming resin film, and the upper clad layer. The forming resin film was adjusted to 60 μm.
The refractive index of the clad layer forming resin film CLF-1 was 1.518 as measured by the method described below.

(Example 1)
[Preparation of resin varnish COV-1 for core formation]
As an acid-modified vinyl group-containing epoxy resin having a urethane skeleton in the main chain of the component (A), an acid-modified BPA / urethane type epoxy acrylate (“KAYARAD UXE-3024” manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 1.0 × 10 ⁴ , acid value 60 mgKOH / g) 60 parts by mass, as component (B), 15 parts by mass of ethoxylated bisphenol A diacrylate (“Funkryl FA-324A” manufactured by Hitachi Chemical Co., Ltd.) and ethoxylated bisphenol A di 15 parts by mass of acrylate (Hitachi Chemical Co., Ltd. “Fancryl FA-321A”), as component (B), phenol biphenylene type epoxy resin (Nippon Kayaku Co., Ltd. “NC-3000”, epoxy equivalent 275 g / eq) ) 10 parts by mass, as component (C), 1- [4- (2-hydroxy) Toxi) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“Irgacure 2959” manufactured by Ciba Japan KK), 1 part by mass, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ("Irgacure 819" manufactured by Ciba Japan Co., Ltd.) 1 part by mass and 20 parts by mass of propylene glycol monomethyl ether acetate as a diluent solvent were mixed with stirring. After pressure filtration using a polyflon filter having a pore size of 2 μm (“PF020” manufactured by Advantech Toyo Co., Ltd.), degassing was performed under reduced pressure to obtain a resin varnish COV-1 for core formation.

[Preparation of Core Part Forming Resin Film COF-1]
The core part-forming resin varnish COV-1 was applied onto the non-treated surface of a PET film (“Cosmo Shine A1517” manufactured by Toyobo Co., Ltd., thickness 16 μm) using the above-mentioned coating machine, and at 80 ° C. for 10 minutes. After drying at 100 ° C. for 10 minutes, a surface release-treated PET film (“Purex A31” manufactured by Teijin DuPont Films 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.

(Examples 2-3) and (Comparative Examples 1-6)
According to the blending ratio shown in Table 1, core part-forming resin varnishes COV-2 to 9 were prepared, and core part-forming resin films COF-2 to 9 were prepared in the same manner as in Example 1.

[Measurement of light transmittance at a wavelength of 850 nm]
The core part-forming resin film from which the protective film (Purex A31) has been removed is placed on a slide glass (size: 76 mm × 26 mm, thickness: 1 mm) using the vacuum laminator, pressure 0.4 MPa, temperature 50 ° C. And it laminated | stacked on the conditions of pressurization time 30 second. Next, ultraviolet rays (wavelength 365 nm) were irradiated with 1000 mJ / cm ² with the ultraviolet exposure machine, and further heated at 160 ° C. for 1 hour to prepare a sample for measuring light transmittance. The light transmittance of this sample at a wavelength of 850 nm was measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-3310”).

[Measurement of total light transmittance, YI, haze]
With the sample for measuring light transmittance, total light transmittance, YI (Yellowness Index), and haze were measured. A chromaticity meter (manufactured by Nippon Denshoku Industries Co., Ltd., “COH-300A”) was used for the measurement.

[Measurement of refractive index]
A core portion-forming resin film is laminated and cured on a silicon substrate (size: 60 × 20 mm, thickness: 0.6 mm) in the same manner as the sample for light transmittance measurement, and a sample for refractive index measurement is produced. did. The refractive index of the sample at a wavelength of 830 nm was measured using a prism-coupled refractometer (“Model 2020” manufactured by Metricon).

[Evaluation of film formability]
When a resin film for forming a core part was produced using the coating machine, it was evaluated according to the following criteria whether a coating film having a thickness of 50 μm could be wound around a core having a diameter of 3 inches.
○: Winding possible △: Wrinkling occurs within 3 hours of room temperature storage after winding: ×: Wrinkling occurs during winding

[Evaluation of protective film peelability]
The peelability when the protective film was peeled off from the core portion forming resin film was evaluated according to the following criteria.
A: No adhesion of the resin to the protective film (Purex A31 non-release treated surface can be used as the protective film)
○: Resin does not adhere to the protective film (Purex A31 release treatment surface is used as the protective film)
Δ: Resin does not adhere to the protective film, but peeling marks appear (Purex A31 release treatment surface is used as the protective film)
X: Resin adheres to protective film

[Measurement of elastic modulus, strength, elongation]
The core layer forming resin film was irradiated with 1000 mJ / cm ^{2 of} ultraviolet rays (wavelength 365 nm) with an ultraviolet exposure machine, and then the substrate film (Cosmo Shine A1517) was removed, followed by heating at 160 ° C. for 1 hour. Thereafter, the protective film (Purex A31) was removed and cut into a length of 70 mm and a width of 10 mm to prepare a measurement sample. The elastic modulus, strength, and elongation of this sample were measured using a tensile test apparatus (manufactured by TS Engineering Co., Ltd., “RTM-100”) under conditions of a distance between chucks of 50 mm and a pulling speed of 5 mm / min.

[Measurement of Glass Transition Temperature ( _Tg )]
The core layer forming resin film was irradiated with 1000 mJ / cm ^{2 of} ultraviolet rays (wavelength 365 nm) with an ultraviolet exposure machine, the substrate film (Cosmo Shine A1517) was removed, and then heated at 160 ° C. for 1 hour. Thereafter, the protective film (Purex A31) was removed and cut into a length of 35 mm and a width of 5 mm to prepare a sample for measurement. The T _g of this sample was measured using a dynamic viscoelasticity measuring device (Rheometrics, “RSAII”) under the conditions of a distance between chucks of 20 mm, a heating rate of 5 ° C./min, and a temperature range of 25 ° C. to 250 ° C. . Note that T _g was a temperature at which the dielectric loss tangent (tan δ) obtained by the measurement showed a maximum value.

[Measurement of thermal decomposition temperature]
The T _g sample and in the same manner to prepare a sample for measurement, comminuted this thermogravimetric analyzer (Seiko Instruments Co., Ltd., TG / DTA6300) atmosphere using a heating rate 10 ° C. / The thermal decomposition temperature was measured under the conditions of min and a temperature range of 25 ° C to 400 ° C. For the evaluation, a temperature (T _d5 ) at which mass was reduced by 5% from the initial stage was used.

[Measurement of thermal expansion coefficient]
The core layer forming resin film was irradiated with 1000 mJ / cm ^{2 of} ultraviolet rays (wavelength 365 nm) with an ultraviolet exposure machine, the substrate film (Cosmo Shine A1517) was removed, and then heated at 160 ° C. for 1 hour. Thereafter, the protective film (Purex A31) was removed and cut into a length of 30 mm and a width of 3 mm to prepare a sample for measurement. The thermal expansion coefficient of this sample was measured using a thermomechanical analyzer (“TMA / SS6000” manufactured by Seiko Instruments Inc.) with a chuck distance of 20 mm, a heating rate of 5 ° C./min, and a temperature range of 25 ° C. to 250 ° C. Measured under conditions. In the measurement results, the thermal expansion coefficient in a temperature region lower than Tg is expressed as α ₁ , and the thermal expansion coefficient in a high temperature region is expressed as α ₂ .

[Fabrication of optical waveguide]
Using a vacuum pressure laminator (“MVLP-500 / 600” manufactured by Meiki Seisakusho Co., Ltd.), the protective film (Purex A31) was removed under the conditions of a pressure of 0.4 MPa, a temperature of 80 ° C., and a pressurization time of 30 seconds. The lower clad layer-forming resin film CLF-1 is placed on a glass epoxy resin substrate (“MCL-E-679FB” manufactured by Hitachi Chemical Co., Ltd., thickness 0.6 mm, copper foil is removed by etching) under a pressure of 0. Lamination was performed under the conditions of 4 MPa, a temperature of 90 ° C., and a pressing time of 30 seconds. Next, by using a UV exposure machine (“MAP-1200-L” manufactured by Dainippon Screen Mfg. Co., Ltd.), the support film (Cosmo Shine A4100) is removed after irradiation with UV light (wavelength 365 nm) at 1000 mJ / cm ² . The lower cladding layer 4 was formed.

Subsequently, the core part-forming resin film COF-1 from which the protective film (Purex A31) has been removed using a roll laminator (“HLM-1500” manufactured by Hitachi Chemical Technoplant Co., Ltd.) is formed on the lower clad layer 4. And a pressure of 0.5 MPa, a temperature of 50 ° C., and a speed of 0.2 m / min. Subsequently, the core part 2 (core pattern) was exposed by irradiating 700 mJ / cm < ² > of ultraviolet rays (wavelength 365 nm) with the said ultraviolet exposure machine through the negative photomask which has a 50 micrometers wide optical waveguide formation pattern. After removing the support film (Cosmo Shine A1517), using a spray developing device (“RX-40D” manufactured by Yamagata Kikai Co., Ltd.), a 1% by weight aqueous sodium carbonate solution at a temperature of 30 ° C., a spray pressure of 0.15 MPa, development Development was performed under conditions of a time of 100 seconds. Then, it wash | cleaned with the pure water and heat-dried at 80 degreeC for 1 hour.

Next, using the vacuum pressurizing laminator, the upper clad layer forming resin film CLF-1 from which the protective film (Purex A31) has been removed is applied to the core portion 2 and the lower clad layer 4 with a pressure of 0.4 MPa, Lamination was performed under the conditions of a temperature of 80 ° C. and a pressurization time of 30 seconds. After irradiating ultraviolet rays (wavelength 365 nm) at 2000 mJ / cm ² and removing the support film (Cosmo Shine A4100), the upper clad layer 3 is formed by heating and curing at 160 ° C. for 1 hour. The optical waveguide 1 shown was obtained. Thereafter, a rigid optical waveguide having a length of 10 cm was cut out using a dicing saw (“DAD-341” manufactured by DISCO Corporation).

[Measurement of optical loss]
The optical propagation loss of the obtained optical waveguide is a VCSEL ("FLS-300-01-VCL" manufactured by EXFO) having a wavelength of 850 nm as a light source, a light receiving sensor ("Q82214" manufactured by Advantest Corporation), an incident fiber. (GI-50 / 125 multimode fiber, NA = 0.20), and output fiber (SI-114 / 125, NA = 0.22). The optical propagation loss was calculated by dividing the measured optical loss (dB) by the optical waveguide length (10 cm).

  The evaluation results of Examples 1 to 3 and Comparative Examples 1 to 6 are collectively shown in Tables 1 and 2.

１）酸変性ビニル基含有エポキシ樹脂；酸変性ビスフェノールＡ／ウレタン型エポキシアクリレート（日本化薬株式会社製「ＫＡＹＡＲＡＤ ＵＸＥ−３０２４」、重量平均分子量：１．０×１０^４、酸価：６０ｍｇＫＯＨ／ｇ）
２）酸変性ビスフェノールＦ型エポキシアクリレート（日本化薬株式会社製「ＫＡＹＡＲＡＤ ＺＦＲ−１４９１Ｈ」、重量平均分子量：１．２×１０^４、酸価：９８ｍｇＫＯＨ／ｇ）
３）酸変性ビフェニル型エポキシアクリレート（日本化薬株式会社製「ＫＡＹＡＲＡＤ ＺＣＲ−１５６９Ｈ」、重量平均分子量：４．５×１０^３、酸価：９８ｍｇＫＯＨ／ｇ）
４）酸変性ビフェニル型エポキシアクリレート（日本化薬株式会社製「ＫＡＹＡＲＡＤ ＺＣＲ−１６４２Ｈ」、重量平均分子量：６．５×１０^３、酸価：９８ｍｇＫＯＨ／ｇ）
５）酸変性フェノールノボラック型エポキシアクリレート（新中村化学工業株式会社製「ＮＫエステル ＥＡ−６３４０」、重量平均分子量：１．１×１０^３、酸価：８０ｍｇＫＯＨ／ｇ）
６）酸変性クレゾールノボラック型エポキシアクリレート（新中村化学工業株式会社製「ＮＫエステル ＥＡ−７１４０」、重量平均分子量：１．６×１０^３、酸価：６９ｍｇＫＯＨ／ｇ）
７）酸変性クレゾールノボラック型エポキシアクリレート（新中村化学工業（株）製「ＮＫエステル ＥＡ−７４４０」、重量平均分子量：３．２×１０^３、酸価：７６ｍｇＫＯＨ／ｇ）
８）エトキシ化ビスフェノールＡジアクリレート（日立化成工業株式会社製「ファンクリルＦＡ−３２４Ａ」）（一般式(１)）
９）エトキシ化ビスフェノールＡジアクリレート（日立化成工業株式会社製「ファンクリルＦＡ−３２１Ａ」）（一般式(１)）
１０）ビスフェノールＡ型エポキシアクリレート（新中村化学工業株式会社製「ＮＫエステル ＥＡ−１０２０」）（一般式(２)）
１１）フルオレン型ジアクリレート（新中村化学工業株式会社製「ＮＫエステル Ａ−ＢＰＥＦ」）（一般式(１)）
１２）エトキシ化フルオレン型ジアクリレート（大阪ガスケミカル株式会社製「オグソールＥＡ−０５００」）（一般式(１)）
１３）フェノールビフェニレン型エポキシ樹脂（日本化薬株式会社製「ＮＣ−３０００」、エポキシ当量２７５ｇ／ｅｑ）
１４）１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン（チバ・ジャパン株式会社製「イルガキュア２９５９」）
１５）ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド（チバ・ジャパン株式会社製「イルガキュア８１９」）

1) Acid-modified vinyl group-containing epoxy resin; acid-modified bisphenol A / urethane type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd. “KAYARAD UXE-3024”, weight average molecular weight: 1.0 × 10 ⁴ , acid value: 60 mgKOH / g )
2) Acid-modified bisphenol F type epoxy acrylate (“KAYARAD ZFR-1491H” manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 1.2 × 10 ⁴ , acid value: 98 mgKOH / g)
3) Acid-modified biphenyl type epoxy acrylate (“KAYARAD ZCR-1569H” manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 4.5 × 10 ³ , acid value: 98 mgKOH / g)
4) Acid-modified biphenyl type epoxy acrylate (“KAYARAD ZCR-1642H” manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 6.5 × 10 ³ , acid value: 98 mgKOH / g)
5) Acid-modified phenol novolac type epoxy acrylate (“NK Ester EA-6340” manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 1.1 × 10 ³ , acid value: 80 mgKOH / g)
6) Acid-modified cresol novolac type epoxy acrylate (“Nakester EA-7140” manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 1.6 × 10 ³ , acid value: 69 mgKOH / g)
7) Acid-modified cresol novolak type epoxy acrylate (“Nak Ester EA-7440” manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 3.2 × 10 ³ , acid value: 76 mgKOH / g)
8) Ethoxylated bisphenol A diacrylate (“Fancryl FA-324A” manufactured by Hitachi Chemical Co., Ltd.) (general formula (1))
9) Ethoxylated bisphenol A diacrylate (“Fancryl FA-321A” manufactured by Hitachi Chemical Co., Ltd.) (general formula (1))
10) Bisphenol A type epoxy acrylate (“NK Ester EA-1020” manufactured by Shin-Nakamura Chemical Co., Ltd.) (general formula (2))
11) Fluorene type diacrylate (“NK Ester A-BPEF” manufactured by Shin-Nakamura Chemical Co., Ltd.) (general formula (1))
12) Ethoxylated fluorene type diacrylate (“Ogsol EA-0500” manufactured by Osaka Gas Chemical Co., Ltd.) (general formula (1))
13) Phenol biphenylene type epoxy resin (“NC-3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275 g / eq)
14) 1- [4- (2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“Irgacure 2959” manufactured by Ciba Japan KK)
15) Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (“Irgacure 819” manufactured by Ciba Japan Co., Ltd.)

Example 4
An optical waveguide was prepared in the same manner as the optical waveguide manufacturing method except that COF-2 was used as the core portion forming resin film and COF-1 was used as the cladding forming resin film, and the optical propagation loss was measured. As a result, the light propagation loss was 0.1 dB / cm.

As shown in Examples 1 to 4, the resin composition for an optical material using the acid-modified vinyl group-containing epoxy resin having a urethane structure of the present invention is excellent in transparency and heat resistance. It can be seen that the manufactured optical waveguide is also excellent in transparency. In particular, the resin composition using the acrylate having a fluorene structure shown in Examples 2 to 4 has a relatively high refractive index and a particularly low optical loss of 0.1 dB / cm. Can be suitably used. Moreover, since fluorene acrylate has a high viscosity, it turns out that the optical resin film excellent in film formation property and protective film peelability can be produced.
On the other hand, acid-modified bisphenol F type epoxy acrylate (ZFR-1491H), acid-modified biphenyl type epoxy acrylate (ZCR-1569H), acid-modified phenol novolac type epoxy acrylate (EA-6340) shown in Comparative Examples 1, 2, 4, and 5 ), A resin composition for optical materials that does not belong to the present invention using the acid-modified cresol novolac epoxy acrylate (EA-7140) is excellent in transparency, but the resin adheres to the protective film when the protective film is peeled off. It can be seen that it is difficult to use in film form. Moreover, although the resin composition for optics which does not belong to this invention using the acid modification biphenyl type epoxy acrylate (ZCR-1642H) shown in the comparative example 3 is a level which can produce an optical waveguide, it is a film formation compared with an Example. It can be seen that the heat resistance and the protective film peelability are inferior, and that the Tg is low, the heat resistance is poor. Moreover, it turns out that the optical resin composition which does not belong to this invention using the acid modification | denaturation cresol novolak-type epoxy acrylate (EA-7440) shown in the comparative example 6 is inferior to protective film peelability and light propagation loss.

  The resin composition for an optical material of the present invention is excellent in transparency and heat resistance, and an optical waveguide produced using these is also excellent in transparency. Moreover, the resin film for optical materials using this resin composition for optical materials is excellent in film formation property and protective film peelability, and can be used suitably in manufacture of an optical waveguide.

DESCRIPTION OF SYMBOLS 1 Optical waveguide 2 Core part 3 Upper clad layer 4 Lower clad layer 5 Base material (or cover film)

Claims (9)

(A) A resin composition for optical materials comprising an alkali-soluble epoxy (meth) acrylate having a urethane structure in the main chain , (B) a polymerizable compound, and (C) a polymerization initiator ,
The alkali-soluble epoxy (meth) acrylate having a urethane skeleton in the main chain of (A) is composed of an epoxy (meth) acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group in the molecule, a diisocyanate compound, and a carboxyl. A polyurethane compound obtained by reacting a diol compound having a group,
The epoxy (meth) acrylate compound having two or more hydroxyl groups and ethylenically unsaturated groups in the molecule is a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a novolac type epoxy compound, and an epoxy compound having a fluorene skeleton. The resin composition for optical materials which is a compound obtained by making (meth) acrylic acid react .
  The blending amount of component (A) is 10 to 85% by mass with respect to the total amount of component (A) and component (B), and the blending amount of component (B) is the total amount of component (A) and component (B). The blending amount of the component (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). A resin composition for optical materials. (B) The resin composition for optical materials according to claim 1, wherein the polymerizable compound is at least one of compounds represented by the following general formulas (1) to (2).

(In General Formula (1), X ¹ and X ² are each independently divalent one of O, S, O (CH ₂ CH ₂ O) _e , and O [CH ₂ CH (CH ₃ ) O] _a. A and e each independently represent an integer of 1 to 20. In the formula, Y ¹ is

And c represents an integer of 2 to 10.
R ¹ and R ⁶ each independently represent a hydrogen atom or a methyl group. R ^{2 to} R ⁴ each independently represent a hydrogen atom, a fluorine atom, an organic group having 1 to 20 carbon atoms, or a fluorine-containing organic group having 1 to 20 carbon atoms. )

(In General Formula (2), Y ² is

Or a divalent group represented by any of the above. R ¹¹ and R ¹⁶ each independently represent a hydrogen atom or a methyl group. R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, an organic group having 1 to 20 carbon atoms, or a fluorine-containing organic group having 1 to 20 carbon atoms. d represents an integer of 1 to 5, and e represents an integer of 2 to 10. )   (B) The resin composition for optical materials in any one of Claims 1-3 which contains the compound which has a 2 or more epoxy group as a polymeric compound further.   (C) Polymerization initiator is radical photopolymerization initiator, The resin composition for optical materials in any one of Claims 1-4.   The resin film for optical materials which consists of a resin composition for optical materials in any one of Claims 1-5.   The resin for optical materials according to claim 6, having a three-layer structure comprising a base film, a resin composition layer for optical materials comprising the resin composition for optical materials according to any one of claims 1 to 5, and a protective film. the film.   An optical waveguide in which at least one of a lower cladding layer, a core portion, and an upper cladding layer is formed using the resin composition for optical materials according to any one of claims 1 to 5.   An optical waveguide in which at least one of a lower clad layer, a core portion, and an upper clad layer is formed using the resin film for optical materials according to claim 6.

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