JP5226224B2 - Curable resin composition and optical waveguide - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention uses an active energy ray-curable resin composition suitable for an optical waveguide, which is excellent in bending resistance, heat resistance, and moisture resistance, and has little curing shrinkage and light propagation loss, and the resin composition. Related to the optical waveguide.

  In recent years, with a marked increase in the amount of information accompanying the spread and development of computers and the Internet, further increase in capacity and speed of information communication has been demanded. As a means for high-speed and large-capacity communication, optical communication using light as an information transmission medium, in particular, optical fibers and optical waveguides are used in a wide range of fields, and in particular, light using film- or sheet-shaped resin compositions. Waveguides are expected to be used in various fields in the future from the viewpoints of low cost, impact stability, large area, and flexibility. In addition, optical waveguides are required to have high heat resistance to withstand high-temperature processes such as lead-free solder reflow, but they are also expected to be used for optical / electrical hybrid boards with electrical wiring and optical waveguide wiring on the same substrate. . As a resin composition used for an optical waveguide, a resin that is cured by active energy rays such as light is often used from the viewpoint of processability.

  One of the active energy ray-curable resins used for the optical waveguide is an epoxy resin because it is highly transparent and has a small light propagation loss and a small shrinkage in curing when the resin is cured. As described above, the epoxy resin has advantages such as high transparency and low cure shrinkage, but has disadvantages such as poor flexibility and easy cracking against deformation. Therefore, improvements such as blending a polyol compound and imparting flexibility have been made. For example, a photosensitive resin composition for an optical waveguide containing an epoxy resin blended with a polyol compound is known (for example, Patent Documents). 1). Moreover, although it is a field completely different from an optical waveguide, an active energy ray-curable resin comprising a compound having an epoxy group, a specific carbonate diol, and an active energy ray active catalyst is known (for example, Patent Document 2).

JP 2005-126497 A JP-A-9-71636

  The present inventors examined using the active energy ray-curable resin shown above for the core and clad of the optical waveguide. However, Patent Document 1 discloses a resin composition comprising an alicyclic epoxy resin having an ester bond and a polyol. However, when an alicyclic epoxy resin having an ester bond is used, It was found that decomposition and hydrolysis are likely to occur, and there is a problem in environmental resistance (moisture heat resistance). Further, in the case of forming a mixed substrate with an optical wiring, particularly with an optical waveguide, heat resistance that can withstand lead-free solder reflow is necessary. However, any existing invention can be applied to a combined optical / electric substrate. It was found that a resin composition for an optical waveguide could not be obtained and still had problems.

  When the polycarbonate polyol is in the form of a solid, wax, or paste, as in the composition described in Patent Document 2, the dispersibility is poor, the transparency is lowered, or a certain thickness such as an optical waveguide is used. It was found that when a molded body having a thickness was cured, a difference in the degree of curing occurred between the surface layer and the inner layer, and “wrinkles” were caused by curing. That is, it has been found that any existing invention has a problem as a resin composition for an optical waveguide.

  That is, the object of the present invention is a resin composition that is cured by an active energy ray composed of an epoxy resin and a polyol, and has transparency, flexibility, heat and humidity resistance, and excellent curability, workability, and environmental resistance. In addition, an optical waveguide having a small light propagation loss, particularly a curable resin composition useful for manufacturing an optical / electrical hybrid substrate requiring high heat resistance, and an optical waveguide made of the curable resin are provided. There is.

  As a result of extensive studies, the present inventor has found that the curable resin comprises an alicyclic diepoxy compound in which the structure of the compound and its isomer ratio are specified, a polyol having a number average molecular weight of a specific value or more, and an active energy ray-sensitive catalyst. The inventors have found that the above object can be achieved by a composition, and completed the present invention.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、同一又は異なって、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を有していてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す）
で表される３，４，３′，４′−ジエポキシビシクロヘキシル化合物であって、該３，４，３′，４′−ジエポキシビシクロヘキシル化合物の異性体の含有量が、３，４，３′，４′−ジエポキシビシクロヘキシル化合物とその異性体の総和に対して、ガスクロマトグラフィーによるピーク面積の割合として１８％以下である化合物であることを特徴とする硬化性樹脂組成物を提供する。 That is, the present invention is a resin composition comprising an alicyclic diepoxy compound (A), a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C), the alicyclic diepoxy compound (A) is represented by the following formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
Wherein the isomer content of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound is 3,4,3 ′, 4′-diepoxybicyclohexyl compound. , 3 ', 4'-diepoxybicyclohexyl compound and its isomer, a curable resin composition characterized by being a compound having a peak area ratio of 18 % or less by gas chromatography. provide.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、同一又は異なって、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を有していてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す）
で表される４，４′−ジヒドロキシビシクロヘキシル化合物を、有機溶媒中、脱水触媒の存在下、副生する水を留去しながら脱水反応を行うことにより得られる下記式（２）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、前記に同じ）
で表されるビシクロヘキシル−３，３′−ジエン化合物であって、該ビシクロヘキシル−３，３′−ジエン化合物の異性体の含有量が、ビシクロヘキシル−３，３′−ジエン化合物とその異性体の総和に対して、ガスクロマトグラフィーによるピーク面積の割合として１５％以下である脂環式ジエン化合物をエポキシ化することにより得られる３，４，３′，４′−ジエポキシビシクロヘキシル化合物であることを特徴とする硬化性樹脂組成物。 The present invention also provides a resin composition comprising an alicyclic diepoxy compound (A), a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C), wherein the alicyclic diepoxy compound (A) is represented by the following formula (3)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
The following formula (2) obtained by conducting a dehydration reaction of the 4,4′-dihydroxybicyclohexyl compound represented by the following formula in an organic solvent while distilling off by-product water in the presence of a dehydration catalyst:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as above)
A bicyclohexyl-3,3′-diene compound represented by the formula: wherein the isomer content of the bicyclohexyl-3,3′-diene compound is such that the bicyclohexyl-3,3′-diene compound and its isomer It is a 3,4,3 ′, 4′-diepoxybicyclohexyl compound obtained by epoxidizing an alicyclic diene compound having a peak area ratio of 15% or less with respect to the total body. A curable resin composition characterized by being.

  In each of the above curable resin compositions, the polyol (B) may be a polyol (B1) having a main chain composed of a carbon-carbon bond. The polyol (B1) having a main chain composed of carbon-carbon bonds may be a polydiene polyol or polyolefin polyol having hydroxyl groups at both ends of the molecular chain. The polydiene-based polyol includes polybutadiene polyol. The polydiene polyol may be a polydiene polyol in which a part of the double bond of the main chain is epoxidized. The polydiene-based polyol in which a part of the double bond in the main chain is epoxidized includes a polybutadiene polyol in which a part of the double bond in the main chain is epoxidized. Examples of the polyolefin-based polyol include polyolefin-based polyols obtained by hydrogenating a polydiene-based polyol having hydroxyl groups at both ends of the molecular chain. The polydiene-based polyol having hydroxyl groups at both ends of the molecular chain includes polyisoprene having hydroxyl groups at both ends of the molecular chain.

（式中、Ｒ¹⁹は水素原子、アルキル基又はアリール基を示し、ｎは１〜５０の整数である） The polyol (B1) having a main chain composed of carbon-carbon bonds may be a vinyl ether oligomer having hydroxyl groups at both ends. The vinyl ether oligomer having hydroxyl groups at both ends includes an oligomer represented by the following chemical formula (4).

(In the formula, R ¹⁹ represents a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 1 to 50)

  In each of the curable resin compositions, the polyol (B) may be a liquid polycarbonate polyol (B2). The polycarbonate polyol (B2) is composed of a 1,6-hexanediol component, another diol component, and a carbonate component, and the molar ratio of the 1,6-hexanediol component to the other diol component is 9: 1 to 1. : The compound which is 9 is included.

  In each of the curable resin compositions, the polyol (B) may be a liquid polyester polyol (B3). The polyester polyol (B3) includes a caprolactone copolymer.

  In each of the above curable resin compositions, the polyol (B) may be a liquid polyether polyol (B4). The polyether polyol (B4) includes a ring-opening copolymer of a cyclic ether.

  The blending amount of the alicyclic diepoxy compound (A) is 30 to 90 parts by weight of the polyol (B) with respect to the total amount (100 parts by weight) of the alicyclic diepoxy compound (A) and the polyol (B). It is preferable that the amount is 10 to 70 parts by weight and the amount of the catalyst (C) is 0.05 to 10 parts by weight.

Each of the above curable resin compositions may further contain a linear or branched alcohol having 3 to 15 carbon atoms and 1 to 23 fluorine atoms. Moreover, the epoxy resin which has an aromatic ring or a bromine and an aromatic ring may be included.
Each curable resin composition may have a glass transition temperature of 250 ° C. or higher.

  The present invention further provides an optical waveguide comprising a core and a clad, wherein at least one of the core and the clad is made of a cured product of the curable resin composition.

  In this optical waveguide, the difference in refractive index between the core and the clad is preferably 0.01 or more.

  The curable resin composition of the present invention uses an alicyclic diepoxy compound in which the structure of the compound and its isomer ratio are specified, and a polyol having a number average molecular weight of a specific value or more, so that it is difficult to cause thermal decomposition and hydrolysis. In addition, it does not easily cause “wrinkles” due to the difference in the degree of curing between the surface layer and the inner layer during curing, and is excellent in productivity, workability, and stability against environmental changes. Reflecting the above characteristics, the optical waveguide using the curable resin composition has good handleability and high reliability even under severe environmental changes, especially through a severe processing process such as lead-free solder reflow. Have

  The curable resin composition of the present invention is a resin composition comprising an alicyclic diepoxy compound (A), a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C). The cyclic diepoxy compound (A) is (i) a 3,4,3 ′, 4′-diepoxybicyclohexyl compound represented by the formula (1), wherein the 3,4,3 ′, 4 ′ -The content of the isomer of the diepoxybicyclohexyl compound is 20% as a ratio of the peak area by gas chromatography with respect to the sum of the 3,4,3 ', 4'-diepoxybicyclohexyl compound and its isomer. Or (ii) the 4,4′-dihydroxybicyclohexyl compound represented by the above formula (3) is distilled off in the presence of a dehydration catalyst in an organic solvent. While anti-dehydration The bicyclohexyl-3,3'-diene compound represented by the above formula (2) obtained by carrying out the step, wherein the content of the isomer of the bicyclohexyl-3,3'-diene compound is bicyclohexyl. 3,4,3 obtained by epoxidizing an alicyclic diene compound having a peak area ratio of less than 20% by gas chromatography with respect to the sum of the -3,3'-diene compound and its isomers It is a curable resin composition characterized by being a ', 4'-diepoxybicyclohexyl compound. This curable resin composition may contain fluorine or sulfur for adjusting the refractive index, an aromatic ring, a halogen-containing additive, or inorganic particles as necessary. In addition, the antifoaming agent, the acid diffusion controller, the reactive diluent, the flexible epoxy resin, the photosensitizer, the dehydrating agent, the surfactant, and the charging are within the range not inhibiting the effect of the present invention. Various additives such as organic fine particles such as inhibitors, plasticizers and lubricants, crosslinked rubber particles, and inorganic fine particles such as titanium oxide, silica, and zirconia oxide may be included.

[Alicyclic diepoxy compound (A)]
In the formula (1), the halogen atoms in R ^{1 to} R ¹⁸ include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group in the “hydrocarbon group optionally having an oxygen atom or halogen atom” include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Is mentioned. Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl and decyl groups (for example, carbon number An alkyl group having 1 to 10 carbon atoms, preferably about 1 to 5 carbon atoms; an alkenyl group such as vinyl or an allyl group (for example, an alkenyl group having 2 to 10 carbon atoms, preferably about 2 to 5 carbon atoms); Alkynyl groups (for example, alkynyl groups having 2 to 10 carbon atoms, preferably about 2 to 5 carbon atoms). Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups; bridged cyclic groups and the like. Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups. Examples of the hydrocarbon group having an oxygen atom include a group in which an oxygen atom is interposed in the carbon chain of the hydrocarbon group (for example, an alkoxyalkyl group such as a methoxymethyl group or an ethoxymethyl group). . As the hydrocarbon group having a halogen atom, for example, one or more hydrogen atoms of the hydrocarbon group such as chloromethyl group, trifluoromethyl group, chlorophenyl group are halogen atoms (fluorine, chlorine, bromine or iodine atoms). ). The alkoxy group in the “optionally substituted alkoxy group” is an alkoxy group having about 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy group or the like. Group and the like. As a substituent of an alkoxy group, the said halogen atom etc. are mentioned, for example.

Among the 3,4,3 ′, 4′-diepoxybicyclohexyl compounds represented by the formula (1), 3,4,3 ′, 4′-diepoxy in which R ^{1 to} R ¹⁸ are all hydrogen atoms Bicyclohexyl is particularly preferred.

Since 3,4,3 ′, 4′-diepoxybicyclohexyl compounds and their isomers have similar physical properties such as boiling point, they cannot often be separated by a general gas chromatography apparatus. Therefore, it is desirable to perform quantitative analysis of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound and its isomers by gas chromatography using a capillary column having higher resolution. Quantitative analysis of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound and its isomer by gas chromatography can be performed under the following measurement conditions. The structure of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound and its isomer can be confirmed by, for example, NMR, GC-MS, GC-IR and the like.
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 30 m, film thickness 0.25 μm, inner diameter 0.32 mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 1.0 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 300 ° C
Temperature rise pattern (column): Hold at 100 ° C. for 2 minutes, heat up to 300 ° C. at 5 ° C./minute, hold at 300 ° C. for 10 minutes Split ratio: 100
Sample: 1 μl (epoxy compound: acetone = 1: 40)

  In the 3,4,3 ′, 4′-diepoxybicyclohexyl compound represented by the formula (1), the isomer of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound contained as an impurity The content is 20% or less as a ratio of the peak area by gas chromatography with respect to the sum of 3,4,3 ′, 4′-diepoxybicyclohexyl compound (main compound) and its isomers, preferably It is 18% or less, more preferably 16% or less. Such an alicyclic diepoxy compound has a markedly faster curing reaction rate than that having a content of the isomer exceeding 20%, and the glass transition temperature of the cured product after curing is significantly increased. Physical properties such as heat resistance are remarkably improved.

Such an alicyclic diepoxy compound is, for example, a bicyclohexyl-3,3′-diene compound represented by the formula (2), which is an isomer of the bicyclohexyl-3,3′-diene compound ( The content of isomers having different positions of double bonds) is less than 20% (for example, 19%) as a ratio of the peak area by gas chromatography with respect to the sum of the bicyclohexyl-3,3′-diene compound and its isomers. 0.5% or less, preferably 15% or less) can be produced by epoxidizing a cycloaliphatic diene compound. In formula (2), R ^{1 to} R ¹⁸ are the same as described above.

Here, the bicyclohexyl-3,3′-diene compound represented by the formula (2) having a low isomer content used as a raw material is, for example, a 4,4′-dihydroxybiphenyl compound represented by the formula (3). The cyclohexyl compound can be obtained by performing a dehydration reaction in an organic solvent in the presence of a dehydration catalyst while distilling off by-produced water. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ^{15 in the} formula (3) , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as described above.

  More specifically, for example, in the presence of a dehydration catalyst that dissolves the 4,4′-dihydroxybicyclohexyl compound represented by the formula (3) in a liquid or reaction solution under the reaction conditions in an organic solvent (i). Heating to a temperature of 130 to 200 ° C. under a pressure exceeding 20 Torr (2.67 kPa), and performing a dehydration reaction while distilling off by-product water, and (ii) following the step (i), The reaction mixture is heated to a temperature of 100 to 220 ° C. under a pressure of 200 Torr (26.7 kPa) or less to distill the produced bicyclohexyl-3,3′-diene compound represented by the formula (2). It can manufacture by passing through a process. This method will be described below.

  A typical example of the compound represented by the formula (3) is 4,4′-dihydroxybicyclohexyl (hydrogenated biphenol).

  The organic solvent used in the step (i) is not particularly limited as long as it is an inert solvent under the reaction conditions, but is preferably a liquid at 25 ° C. and having a boiling point of about 120 to 200 ° C. Typical examples of preferable organic solvents include aromatic hydrocarbons such as xylene, cumene, and pseudocumene; and aliphatic hydrocarbons such as dodecane and undecane. As an organic solvent, in order to easily separate and remove by-product water, an organic solvent that is azeotropic with water and can be separated from water may be used. A solvent that reacts in the presence of an acid such as a ketone or an ester is not preferable even if the boiling point is in the above range. Alcohol is not preferred because it may cause a dehydration reaction.

  The amount of the organic solvent used can be appropriately selected in consideration of operability, reaction rate and the like, but is usually about 50 to 1000 parts by weight with respect to 100 parts by weight of the substrate 4,4′-dihydroxybicyclohexyl compound. Yes, preferably about 80 to 800 parts by weight, more preferably about 100 to 500 parts by weight.

  The dehydration catalyst used in the step (i) is not particularly limited as long as it has a dehydration activity and is liquid under the reaction conditions or can be dissolved in the reaction liquid (completely dissolved in the use amount described later). Those having no activity or as low as possible with respect to the reaction solvent are preferable. The dehydration catalyst that is liquid under the reaction conditions is preferably one that is finely dispersed in the reaction solution. As the dehydration catalyst, usually, inorganic acids such as phosphoric acid and sulfuric acid, acids such as sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid, or salts thereof, in particular, complete with an organic base of the acid. Neutralized or partially neutralized salts are used. A dehydration catalyst can be used individually or in combination of 2 or more types.

  When using a neutralized salt of an acid with an organic base, a neutralized salt (fully or partially neutralized salt) may be isolated and purified from a reaction mixture obtained by reacting an acid with an organic base. However, a reaction mixture obtained by reacting an acid with an organic base (containing a completely neutralized salt and / or a partially neutralized salt) can be used as it is. In the latter case, the reaction mixture may contain free acid. In the latter case, the mixing ratio of the acid and the organic base is, for example, about 0.01 to 1 equivalent, preferably about 0.05 to 0.5 equivalent, more preferably about 1 to 1 equivalent of the acid. Is about 0.1 to 0.47 equivalent. In particular, when a reaction mixture of sulfuric acid and organic base is used, the mixing ratio of sulfuric acid and organic base is preferably 0.02 to 2 mol, more preferably 0.1 to 1 mol of sulfuric acid. The amount is about 1.0 to 1.0 mol, particularly preferably about 0.2 to 0.95 mol. Moreover, when using the neutralized salt by the organic base of an acid, an acid and an organic base may be added separately and the neutralized salt may be formed in a system.

  The organic base may be any organic compound that exhibits basicity. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene. -5 (DBN), 1,4-diazabicyclo [2.2.2] octane, piperidine, N-methylpiperidine, pyrrolidine, N-methylpyrrolidine, triethylamine, tributylamine, trioctylamine, benzyldimethylamine, 4-dimethyl Examples include amines such as aminopyridine and N, N-dimethylaniline (particularly tertiary amines); nitrogen-containing aromatic heterocyclic compounds such as pyridine, collidine, quinoline and imidazole; guanidines; hydrazines and the like. Among these, third compounds such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), triethylenediamine, triethylamine and the like. Secondary amines (particularly cyclic amines), guanidines and hydrazines are preferred, and DBU, DBN, triethylenediamine and triethylamine are particularly preferred. Moreover, as an organic base, the thing of pKa11 or more is preferable and the thing whose boiling point is 150 degreeC or more is preferable.

  When an alkali metal salt of sulfuric acid such as potassium hydrogen sulfate is used as a dehydration catalyst, the content of the isomer of the bicyclohexyl-3,3'-diene compound is reduced to that of the bicyclohexyl-3,3'-diene compound and its isomer. An area ratio by gas chromatography of less than 20% is not obtained with respect to the sum. When ammonium bisulfate is used as the dehydration catalyst, the content of isomers of the bicyclohexyl-3,3'-diene compound is the sum of the bicyclohexyl-3,3'-diene compound and its isomer. On the other hand, a peak area ratio by gas chromatography of about 19% is obtained.

  Therefore, as a dehydration catalyst, a completely neutralized salt or a partially neutralized salt of an organic base such as sulfonic acids (p-toluenesulfonic acid, etc.), phosphoric acid, sulfuric acid, sulfonic acids (p-toluenesulfonic acid, etc.), phosphoric acid A completely neutralized salt or partially neutralized salt with an organic base, and a completely neutralized salt or partially neutralized salt with an organic base of sulfuric acid are preferred. Of these, sulfonic acids (particularly p-toluenesulfonic acid), completely neutralized salts or partially neutralized salts of organic acids with sulfonic acids, and completely neutralized salts or partially neutralized salts of sulfuric acid with organic bases are particularly preferable. A completely neutralized salt or a partially neutralized salt (particularly a partially neutralized salt) of sulfuric acid with an organic base is preferred.

  The amount of the dehydration catalyst used is, for example, 0.001 to 0.5 mol, preferably 0.001 to 0, per 1 mol of the 4,4′-dihydroxybicyclohexyl compound represented by the formula (3) as the raw material. 0.3 mol, more preferably 0.005 to 0.2 mol.

  The pressure is different between the step (i) and the step (ii). In the reaction solution of step (i), only one of the unreacted 4,4′-dihydroxybicyclohexyl compound and the two cyclohexane rings to which the hydroxyl group in the 4,4′-dihydroxybicyclohexyl compound is bonded. A reaction intermediate converted into a cyclohexene ring by intramolecular dehydration, the target bicyclohexyl-3,3′-diene compound, by-product water, a dehydration catalyst, and a reaction solvent coexist. In this step (i), by-product water is distilled, but at this time, it is not desirable to distill the reaction intermediate from the following points. That is, (1) the reaction intermediate can be converted into the target compound by further intramolecular dehydration, and thus distilling it causes a decrease in the yield of the target compound. (2) The reaction intermediate is generally Since it is a sublimable solid, when using a distillation column, the solid precipitates in the distillation path of by-product water, so that the distillation path is blocked and the pressure inside the reactor is increased, and the reaction vessel Cause troubles such as rupture, breakage, and splashing of the reaction solution. Therefore, in the step (i), the dehydration reaction is performed while distilling off by-product water under a pressure exceeding 20 Torr (2.67 kPa) so that the reaction intermediate is not distilled. The pressure is preferably higher than 20 Torr and lower than normal pressure (higher than 2.67 kPa and lower than 0.1 MPa), more preferably higher than 100 Torr and lower than normal pressure (higher than 13.3 kPa and lower than 0.1 MPa), more preferably higher than 200 Torr. Normal pressure or lower (higher than 26.7 kPa and 0.1 MPa or lower), and normal pressure is particularly preferable from the viewpoint of operability. The temperature (reaction temperature) in the step (i) is 130 to 200 ° C, preferably 140 to 195 ° C, more preferably 150 to 195 ° C. If the temperature is too high, side reactions occur and the yield decreases. If the temperature is too low, the reaction rate becomes slow. The reaction time is, for example, about 1 to 10 hours, preferably about 2 to 6 hours for a synthetic scale of about 3 L.

  On the other hand, in step (ii), the target bicyclohexyl-3,3'-diene compound is distilled from the reaction mixture after distilling by-product water. The reaction mixture obtained in step (i) may be directly used in step (ii), but if necessary, the reaction mixture may be appropriately extracted, washed, adjusted in liquidity, etc. You may use for process (ii) after giving a process. When the boiling point of the organic solvent used in the reaction is lower than the boiling point of the target bicyclohexyl-3,3′-diene compound, the organic solvent is usually distilled off and then bicyclohexyl-3,3′-diene. The compound is distilled off.

  In this step (ii), since the reaction intermediate is hardly present, problems such as clogging of the distillation path do not occur even when the pressure is lowered, and when the pressure is high, it takes time to distill the target compound. Operate at a pressure of 200 Torr (26.7 kPa) or less. The pressure in step (ii) is preferably lower than the pressure in step (i). For example, the difference between the pressure in step (i) and the pressure in step (ii) (the former-the latter) is, for example, 100 Torr or more (13.3 kPa or more), preferably 200 Torr or more (26.7 kPa or more), more preferably 500 Torr or more. (66.7 kPa or more). The pressure in step (ii) is preferably 3 to 200 Torr (0.40 to 26.7 kPa), more preferably 3 to 100 Torr (0.40 to 13.3 kPa), and still more preferably 3 to 20 Torr (0.40 to 0.40). 2.67 kPa). The temperature of process (ii) is 100-220 degreeC, Preferably it is 120-180 degreeC, More preferably, it is about 130-150 degreeC grade. If the temperature is too high, side reactions are liable to occur and the recovery rate of the bicyclohexyl-3,3'-diene compound decreases. On the other hand, if the temperature is too low, the distilling rate becomes slow.

  In order to distill a bicyclohexyl-3,3'-diene compound, etc., for example, when a distillation apparatus is attached to a reactor, etc., a distillation column, an Oldershaw type distillation apparatus, etc. are generally used as the distillation apparatus. Any distillation apparatus having a reflux ratio can be used without particular limitation.

  The bicyclohexyl-3,3′-diene compound distilled in step (ii) can be further purified as necessary. As a purification method, when a small amount of water is contained, separation can be performed using a difference in specific gravity, but purification by distillation is generally preferable.

  According to such a method, by-product water is produced under specific reaction conditions in the presence of a dehydration catalyst that dissolves the raw 4,4'-dihydroxybicyclohexyl compound in an organic solvent in a liquid state or reaction solution under the reaction conditions. After the reaction while distilling off, the produced bicyclohexyl-3,3'-diene compound is distilled off under specific conditions, so that the reaction can be carried out at a relatively low temperature and in a relatively short time. Can prevent side reactions such as conversion, and can prevent loss due to distillation of reaction intermediates and blockage due to sublimation, etc., so that high purity bicyclohexyl-3,3'-diene compound with low impurity content can be easily and high It can be efficiently obtained in a yield. That is, the content of the isomer of the bicyclohexyl-3,3′-diene compound represented by the formula (2) is determined by gas chromatography with respect to the sum of the bicyclohexyl-3,3′-diene compound and its isomer. An alicyclic diene compound having a peak area ratio of less than 20% (for example, 19.5% or less, preferably 15% or less) can be obtained.

  In addition, in the conventional method, for example, the method described in JP-A No. 2000-169399, a long reaction time is required. Therefore, a large amount of undesirable by-products are generated due to side reactions such as isomerization. By-product isomers have physical properties such as boiling point and solvent solubility that are close to those of the target compound, so that once produced, separation becomes extremely difficult. When such a cyclic olefin compound containing a large amount of by-products is epoxidized and used as a curable resin, a cured product having low physical properties such as heat resistance cannot be obtained during curing. Bicyclohexyl-3,3'-diene compounds and their isomers are very similar in physical properties such as boiling point, and therefore cannot be separated by a general gas chromatography apparatus. The yield and purity of the cyclohexyl-3,3'-diene compound are described in a higher manner. The analysis of the bicyclohexyl-3,3'-diene compound and its isomer is preferably carried out by gas chromatography using a capillary column having a high resolution.

The quantitative analysis of the bicyclohexyl-3,3′-diene compound and its isomer by gas chromatography can be carried out under the following measurement conditions. The structure of the bicyclohexyl-3,3′-diene compound and its isomer can be confirmed by, for example, NMR, GC-MS, GC-IR and the like.
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 60m, inner diameter 0.32mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 2.6 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Temperature rise pattern (column): Hold at 60 ° C. for 5 minutes, temperature rise to 300 ° C. at 10 ° C./minute Split ratio: 100
Sample: 1 μl

  The epoxidation method of the bicyclohexyl-3,3′-diene compound is not particularly limited. For example, a method using an organic percarboxylic acid as an oxidizing agent (epoxidizing agent), a hydroperoxide such as t-butyl hydroperoxide, and the like. Although any method using a metal compound such as a molybdenum compound may be used, a method using an organic percarboxylic acid is preferable from the viewpoint of safety, economy, yield, and the like. Hereinafter, this method will be described.

  As the organic percarboxylic acid, for example, performic acid, peracetic acid, perbenzoic acid, perisobutyric acid, trifluoroperacetic acid and the like can be used. Among organic percarboxylic acids, peracetic acid is a preferred epoxidizing agent because of its high reactivity and high stability. Among them, the use of an organic percarboxylic acid substantially free of moisture, specifically, having a moisture content of 0.8% by weight or less, preferably 0.6% by weight or less has a high epoxidation rate. This is preferable in that a compound is obtained. The organic percarboxylic acid substantially free of water is produced by air oxidation of aldehydes, for example, acetaldehyde. For example, peracetic acid is disclosed in German Patent Publication No. 1418465 and JP-A 54-30006. Manufactured by the described method. According to this method, it is possible to synthesize organic percarboxylic acid in a large amount continuously, compared with the case where organic percarboxylic acid is synthesized from hydrogen peroxide and extracted with a solvent to produce organic percarboxylic acid. Therefore, it can be obtained substantially inexpensively.

  The amount of the epoxidizing agent is not strictly limited, and the optimum amount in each case depends on the individual epoxidizing agent used, the reactivity of the bicyclohexyl-3,3'-diene compound, and the like. The amount of the epoxidizing agent is, for example, about 1.0 to 3.0 mol, preferably about 1.05 to 1.5 mol with respect to 1 mol of the unsaturated group. From the viewpoint of economy and side reaction, it is usually disadvantageous to exceed 3.0 times mole.

  The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the apparatus and the physical properties of the raw material. As the solvent, it can be used for the purpose of lowering the viscosity of the raw material, stabilizing by diluting the epoxidizing agent, and in the case of peracetic acid, esters, aromatic compounds, ethers and the like can be used. Particularly preferred solvents are ethyl acetate, hexane, cyclohexane, toluene, benzene and the like, and ethyl acetate is particularly preferred. The reaction temperature is determined by the reactivity of the epoxidizing agent used and the bicyclohexyl-3,3'-diene compound. For example, the reaction temperature when peracetic acid is used is preferably 20 to 70 ° C. If it is less than 20 ° C., the reaction is slow, and if it exceeds 70 ° C., peracetic acid decomposes with heat generation, which is not preferable.

  No special operation is required for the crude liquid obtained by the reaction. For example, the crude liquid may be aged by stirring for 1 to 5 hours. Isolation of the epoxy compound from the obtained crude liquid is an appropriate method, such as a method of precipitating with a poor solvent, a method of pouring the epoxy compound into hot water with stirring and distilling off the solvent, a method of directly removing the solvent, It can be carried out by a method such as isolation by distillation purification.

  Thus, the isomer content (isomer ratio) of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound represented by the formula (1) is represented by the formula (1) 3. , 4,3 ', 4'-diepoxybicyclohexyl compound and its isomers, the peak area ratio by gas chromatography is 20% or less (preferably 18% or less, more preferably 16% or less) An alicyclic diepoxy compound can be obtained.

  In this invention, the compounding quantity of an alicyclic diepoxy compound (A) is 30-90 weight part with respect to the total amount (100 weight part) of an alicyclic diepoxy compound (A) and a polyol (B). Preferably, it is 50-80 weight part. When the blending amount of the alicyclic diepoxy compound (A) exceeds 90 parts by weight, the effect of adding the polyol is small, and “wrinkles” are likely to occur during curing, or the flexibility of the cured product may be reduced. Yes, when the blending amount of the alicyclic diepoxy compound (A) is less than 30 parts by weight, heat resistance and transparency may be lowered.

[Polyol (B)]
The polyol (B) used in the curable resin composition of the present invention is a compound having two or more hydroxyl groups in one molecule, and preferably has 2 to 3 hydroxyl groups per molecule. In the present invention, the polyol (B) is a polyol (B1) having a main chain composed of carbon-carbon bonds, a liquid polycarbonate polyol (B2), a liquid polyester polyol (B3), or a liquid polyether polyol (B4). ) Is preferred.

  When the curable resin composition of the present invention is cured, the alicyclic diepoxy compound (A) and the polyol (B) form a copolymer (cured product) by cationic polymerization. Here, for example, when an ether bond is included in the main chain of the polyol component of the copolymer, the cured product is likely to be thermally decomposed, and when an ester bond is included, hydrolysis is likely to occur. Therefore, stability tends to decrease when the cured product is used in a high-temperature and high-humidity environment. For this reason, it is more desirable that the polyol (B) has a structure that does not contain an ether bond, an ester bond, or the like in the main chain. As such a polyol (B), a polyol (B1) whose main chain is composed mainly of a carbon-carbon bond, or a polycarbonate polyol (which is not susceptible to hydrolysis even if it has an oxygen atom in the main chain) B2) can be used.

  The number average molecular weight of the polyol (B) in this invention is 400 or more (for example, 400-10000), Preferably it is 480-10000, More preferably, it is 1000-10000, More preferably, it is 1500-5000. When the molecular weight of the polyol (B) is less than 400, the amount of the hydroxyl group relative to the epoxy group of the alicyclic diepoxy compound (A) is relatively large, so that it becomes hydrophilic and easily takes in moisture. Since this moisture causes curing inhibition, the degree of curing decreases. For this reason, it becomes a cause of wrinkles at the time of curing, adhesiveness remains after curing, productivity decreases, heat resistance, elastic modulus, and bending strength decrease, so that it cannot be used depending on applications. On the other hand, when the molecular weight exceeds 10,000, the liquid may not be liquid, or the viscosity may be high and the handleability may be lowered. Moreover, the quantity of the hydroxyl group with respect to the epoxy group of an alicyclic diepoxy compound (A) becomes relatively small, and the speed | rate of the curing reaction at the time of energy ray irradiation of an epoxy resin becomes slow. For this reason, the curing reaction does not sufficiently proceed to the inner layer in the curing step, and a difference in the degree of curing occurs between the surface layer and the inner layer, which may cause “wrinkles” in the resin composition.

  When the polyol (B) of the present invention is a polyol (B1) having a main chain composed of carbon-carbon bonds, 60% or more of the main chain (however, excluding terminal groups) are carbon atoms, preferably 65 % Or more is a carbon atom, and more preferably, the main chain consists only of carbon atoms. The polyol (B1) is preferably exemplified by a saturated or unsaturated linear or branched diol having 25 to 700 carbon atoms from the viewpoint of molecular weight control. The position of the hydroxyl group is not particularly limited at the end of the main chain and the side chain, but is preferably located at both ends of the main chain from the viewpoint of softening and toughening. Among these, polydiene polyols or polyolefin polyols having hydroxyl groups at both ends of the molecular chain are preferable.

  As the polydiene polyol having hydroxyl groups at both ends of the molecular chain, polybutadiene or polyisoprene having hydroxyl groups at both ends of the molecular chain, or having hydroxyl groups at both ends of the molecular chain, and a double bond of the main chain A polydiene-based polyol partially epoxidized (for example, hydroxyl-terminated polybutadiene) is preferred.

  Examples of the polyolefin-based polyol having hydroxyl groups at both ends of the molecular chain include polyethylene and polypropylene having hydroxyl groups at both ends of the molecular chain. Preferably, the polydiene having hydroxyl groups at both ends of the molecular chain described above. What was manufactured by hydrogenating a system polyol is preferable. For example, hydrogenated polybutadiene or polyisoprene having hydroxyl groups at both ends of the molecular chain is preferable.

As the polyol (B1) in the present invention, in addition to the above, vinyl ether oligomers having hydroxyl groups at both ends are also preferable. For example, vinyl ether oligomers represented by the above formula (4) can be used. In the formula (4), R ¹⁹ represents hydrogen or an alkyl or aryl group, n is an integer of 1 to 50. Examples of the alkyl group herein include linear or branched alkyl groups having about 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and hexyl groups. Be mentioned. Examples of the aryl group include phenyl and naphthyl groups. The aromatic ring of the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, but are not limited thereto.

  Examples of the polyol listed above include “Epolide PB3600” manufactured by Daicel Chemical Industries, Ltd., and “TOE-2000H” manufactured by Kyowa Hakko Chemical Co., Ltd. as commercially available products. These can be used alone or in combination of two or more.

  The polyol (B) in the present invention is also preferably a liquid polycarbonate polyol (B2). Here, “liquid” means that the viscosity measured at 25 ° C. is less than 100 Pa · s. When the polyol (B) is in a solid state (wax, paste, etc.), the miscibility with the alicyclic diepoxy compound (A) is poor, and the effect of adding the polyol is reduced. That is, when the hydroxyl group concentration is biased, the degree of curing becomes non-uniform during curing, and “wrinkles” are generated, which tends to reduce productivity. Moreover, due to poor dispersion, the transparency may be reduced and the light propagation loss may be increased.

  As the polycarbonate polyol (B2), the same phosgene method as the method for producing a normal polycarbonate polyol, or a carbonate exchange reaction using a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate or diphenyl carbonate (Japanese Patent Laid-Open No. 62-187725, JP-A-2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420 and the like.

  Examples of the polyol used in the carbonate exchange reaction together with dialkyl carbonate and the like include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol And dipropylene glycol.

  Examples of the polycarbonate polyol include “Placcel CD205PL, CD205HL, CD210PL, CD210HL, CD220PL, CD220HL” manufactured by Daicel Chemical Industries, Ltd., “UH-CARB50, UH-CARB300, UH-CARB300, UH-CARB90 (1/3), UH-CARB90 (1/1), UC-CARB100 ". “PCDL T4671, T4672, T5650J, T5651 and T5652” manufactured by Asahi Kasei Chemicals Corporation are available as commercial products. These can be used alone or in combination of two or more.

Among the above, the polycarbonate polyol is composed of a 1,6-hexanediol component, another diol component represented by the chemical formula HO—R ²⁰ —OH, and a carbonate component from the viewpoints of softening effect and production cost. In the case of the oligomer to be used, it is particularly preferable from the viewpoint of compatibility with the alicyclic diepoxy compound (A). In the above case, the molar ratio of the 1,6-hexanediol component to the other diol component is preferably 9: 1 to 1: 9, more preferably 7: 3 to 3: 7. R ²⁰ represents a divalent organic group. R ²⁰ has, for example, 2 to 14 carbon atoms and may contain oxygen, nitrogen and sulfur atoms, and may be linear or branched. Furthermore, it may have 1 to 3 cyclic structures, and may contain oxygen, nitrogen, and sulfur atoms in the ring. Of these, a divalent hydrocarbon group having 2 to 14 carbon atoms (in particular, an alkylene group, a cycloalkylene group, or a group in which these are bonded) in which an oxygen atom may be interposed is preferable as R ²⁰ .

  The polyol (B) in the present invention is also preferably a liquid polyester polyol (B3). In this case, the polyester polyol is composed of a polyol component and a carboxylic acid component, and can be synthesized by dehydration esterification reaction, transesterification reaction, ring-opening polymerization of lactone, or a combination thereof. Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, 2,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, Examples include propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, and pentaerythritol. As the carboxylic acid component, oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, Citralaconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, lactic acid, malic acid Glycolic acid, dimethylolpropionic acid, dimethylolbutanoic acid and the like. Examples of lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

  Among the above, the polyester polyol (B3) of the present invention is particularly preferably a polycaprolactone polyol (caprolactone copolymer). Examples of the polycaprolactone polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, methylpentanediol, 2, 4-diethylpentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, ethylene oxide or propylene oxide adduct of bisphenol A, glycerin, etc. Examples include polycaprolactone polyols obtained by ring-opening addition polymerization of ε-caprolactone in the presence of a known polyhydric alcohol. These can be used alone or in admixture of two or more. The polyester polyol (B3) is particularly preferably a polycaprolactone polyol (caprolactone copolymer) obtained by ring-opening addition polymerization of two or more polyhydric alcohols and caprolactone.

  Examples of the polyester polyol (B3) include “Placcel 205, 205H, 205U, 205BA, 208, 210, 210CP, 210BA, 212, 212CP, 220, 220CPB, 220NP1, 220BA, 220ED, manufactured by Daicel Chemical Industries, Ltd. 220EB, 220EC, 230, 230CP, 240, 240CP, 210N, 220N, L205AL, L208AL, L212AL, L220AL, L230AL, 220ED, 220EB, 220EC, 205BA, 210BA, 220BA, 305, 308, 312, L312AL, 320, L320AL , L330AL, 410, 410D, 610, P3403, CDE9P, P3403, E227, etc. are commercially available.

  When the polyol (B) of the present invention is a liquid polyether polyol (B4), examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. These are produced by ring-opening polymerization of cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran. These can be used alone or in admixture of two or more. As the polyether polyol (B4), a ring-opening copolymer of a cyclic ether is particularly preferable.

  As the polyether polyol, “P-400, P-700, P-1000, P-2000, P-3000, G-300, G-400, G-700, G-1500, manufactured by Asahi Denka Kogyo Co., Ltd. G-3000, G-4000, EDP-450, EDP-550, DG-500, DG-575, SP-600, SP-690SC-800, SC-1000, SC-1001, Quadrol ", Nippon Oil & Fat Co., Ltd. Polyethylene glycol “PEG # 200, 400, 600, 1000, 1500, 2000, 4000, 6000”, Bishool “2EN-6, 4EN, 10EN, 2P, 2PN, 3PN” manufactured by Toho Chemical Industry Co., Ltd., Asahi Glass Co., Ltd. ) “Poly-G 420P, 720PG, 1020P, 2020P, 3020P, 630PG, 1030PG” 1530PG, 2530PG, 3030PG, 4030PG, 5030PG, 210PG, 212PG, 448PG, 412PG, 439PG, 216PG, X-213, X-301, X-302, X-303, 400P, 415P, 419P, 423P, 443P, 427P, 441P, 442P, 610PG, 357SA, 465SA, 480SA, 530SA, X-71-531, X-71-532, 375S, 531S, RF-64, RF-66 "," PTXG "manufactured by Asahi Kasei Corporation, Sanyo “PEG200, PEG300, PEG400, PEG600, PEG1000, PEG1500, PEG1540, PEG2000, PEG4000S, PEG4000N, PEG6000S, PEG6000P” manufactured by Kasei Kogyo Co., Ltd. NIX GP-200, GE-250, TP-700, TE-700, EP-400, HE-400, HE-560, HE-600, RA-530, RX-401, RX-300, RX-403, RX -500, HR-460A "," Sannik Triol GP-250, GP-400, GP-600, GP-1000, TP-400 "," Sanix Polyol RP-410A, HR-450P, HS-209 ", “Sanix Hexatriol SP-750” and the like are commercially available.

  Polyol (B1), polyol (B2), polyol (B3), polyol (B4) Any of these may be used in admixture of two or more.

  In the present invention, the blending amount of the polyol (B) is preferably 10 to 70 parts by weight, more preferably 20 to the total amount (100 parts by weight) of the alicyclic diepoxy compound (A) and the polyol (B). ~ 50 parts by weight. When the blending amount of the polyol (B) is less than 10 parts by weight, the effect of adding the polyol is small, “wrinkles” are likely to occur in the curing step, and the flexibility of the cured product may be reduced. When the blending amount of B) exceeds 70 parts by weight, heat resistance and transparency may be lowered.

[Catalyst (C)]
The catalyst (C) used in the curable resin composition of the present invention is not particularly limited as long as it is a catalyst that generates protons, anions, radicals, and the like upon irradiation with active energy rays such as ultraviolet rays, and is a cationic polymerization initiator. A radical polymerization catalyst or an anion polymerization catalyst may be used, but a cationic polymerization catalyst is preferred. The active energy rays are not particularly limited, such as ultraviolet rays and electron beams, but ultraviolet rays are preferably used from the viewpoint of reactivity and the like. Specific examples of the catalyst (C) are different depending on the combination of the alicyclic diepoxy compound (A) and the polyol (B). For example, examples of the photocationic polymerization initiator include diaryliodonium salts and triarylsulfonium salts. Be mentioned. In addition, the catalyst (C) may be used in combination with different photocationic polymerization initiators, may be used in combination with a photocationic polymerization initiator and a photoradical polymerization initiator, and may generate protons by photocationic polymerization initiator and heat. A generated thermal cationic polymerization initiator may be used in combination. As the catalyst (C), an existing commercial product can be used. “CYRACURE UVI-6922, UVI-6976” manufactured by The DOW Chemical Company, “Adekatopmer SP-” manufactured by Asahi Denka Kogyo Co., Ltd. 150, SP-152, SP-170, SP-172 "," Shin-Aid SI-60L, SI-80L, SI-100L, SI-110L, SI-180L "manufactured by Sanshin Chemical Industry Co., Ltd., GE Toshiba Silicone ( "UV9380c" manufactured by Co., Ltd., "Rhodorsil 2074" manufactured by Rhodia Japan Co., Ltd., "IRGACURE250" manufactured by Ciba Specialty Chemicals Co., Ltd., and "Uvacure 1590" manufactured by Daicel-Cytech Co., Ltd. are available on the market. .

  The compounding quantity in the curable resin composition of the catalyst (C) of this invention is 0.05-10 with respect to the total amount (100 weight part) of an alicyclic diepoxy compound (A) and a polyol (B). A weight part is preferable, More preferably, it is 1-5 weight part. When the content of the catalyst (C) is less than 0.05 parts by weight, the initiation efficiency of the polymerization reaction at the time of irradiation with active energy rays is poor, resulting in local polymerization and unevenness, or decreased productivity. When the content exceeds 10 parts by weight, heat resistance and transparency may be lowered. It becomes difficult to control the curing reaction, or the molecular weight of the cured product is reduced.

[Other ingredients]
The curable resin composition of the present invention may contain a fluorine-containing alcohol from the viewpoint of adjusting the refractive index. In that case, the fluorine-containing alcohol is preferably a linear or branched alcohol having 3 to 15 carbon atoms and 1 to 23 fluorine atoms. By containing the fluorine-containing alcohol, the refractive index of the curable resin composition can be adjusted to be low. Examples of the fluorine-containing alcohol include 1H, 1H-trifluoroethanol, 1H, 1H-pentafluoropropanol, 6- (perfluoroethyl) hexanol, 1H, 1H-heptafluorobutanol, and 2- (perfluorobutyl). Ethanol, 3- (perfluorobutyl) propanol, 6- (perfluorobutyl) hexanol, 2-perfluoropropoxy-2,3,3,3-tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 3- ( Perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 2- (perfluorooctyl) ethanol, 3- (perfluorooctyl) propanol, 6- (perfluorooctyl) hexanol, 2- (perfluorodecyl) ethane 1H, 1H-2,5-di (trifluoromethyl) -3,6-dioxaundecafluorononanol, 6- (perfluoro-1-methylethyl) hexanol, 2- (perfluoro-3) -Methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyloctyl) ethanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropen Tanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H, 9H-hexadecafluorononanol, 2H-hexafluoro-2-propanol, 1H, 1H, 3H-hexafluorobutanol, 2,2,3 3,4,4,5,5, -octafluoro-1,6-hexanediol, 2,2,3,3 , 4,5,5,6,6,7,7- dodecafluoro-1,8-octanediol, 2,2-bis (trifluoromethyl) propanol. Although content in the curable resin composition of fluorine-containing alcohol can be suitably changed according to a desired refractive index, 1 to 30 weight% is preferable, More preferably, it is 5 to 20 weight%.

  The curable resin composition of the present invention includes, in addition to the alicyclic diepoxy compound (A), in addition to the alicyclic diepoxy compound (A), an epoxy resin having an aromatic ring or bromine and aromatic ring, sulfur, or another resin having a hydroxyl group. You may contain. By containing the resin having the aromatic ring or bromine, aromatic ring and sulfur, the refractive index of the curable resin composition can be adjusted high. As the above-mentioned resin, it is also possible to use an existing commercial product. For example, as a commercially available product, as a bisphenol A type epoxy resin, “Epicoat 828, 1001, 1004,” manufactured by Japan Epoxy Resin Co., Ltd. 1009 ”,“ Epicron 850-S, 860, 1055 ”manufactured by Dainippon Ink & Chemicals, Inc., and“ Epicron 830-S ”manufactured by Dainippon Ink & Chemicals, Inc. "Epiclon EXA1514" manufactured by Dainippon Ink & Chemicals, Inc. as the resin, "Denacol EX-141" manufactured by Nagase ChemteX Corporation as the phenyl glycidyl ether, and "Japan Epoxy Resin Co., Ltd." manufactured as the polyfunctional epoxy resin. Epicoat 152, 157S65, 1031S 604 "," Epicron N-665, HP-7200 "manufactured by Dainippon Ink & Chemicals, Inc., and" Nacrolene type epoxy resin "Epicron HP-4032, EXA-4701" manufactured by Dainippon Ink & Chemicals, Inc., biphenol Type epoxy resin "Epicoat YX4000" manufactured by Japan Epoxy Resin Co., Ltd., "Epicoat 1256, 4250" manufactured by Japan Epoxy Resin Co., Ltd. as phenoxy resin, and "Epicoat" manufactured by Japan Epoxy Resin Co., Ltd. as brominated epoxy resins. 5050, 5051 "," Epiclon 152, 153 "manufactured by Dainippon Ink & Chemicals, Ltd.," Denacol EX-147 "(dibromophenylglycidyl ether) manufactured by Nagase ChemteX Corporation," Sumika "manufactured by Sumitomo Chemical Co., Ltd. Excel PES 500 P ", and the like. Although content in the curable resin composition of the said resin can be changed suitably according to a desired refractive index, 1 to 70 weight% is preferable, More preferably, it is 5 to 60 weight%.

  The aromatic ring, bromine and aromatic ring, or sulfur-containing resin is preferably used in a curable resin composition constituting the core of the optical waveguide, and the fluorine-containing alcohol is cured to constitute the cladding of the optical waveguide. It is preferably used for a functional resin composition.

  For the purpose of adjusting the reaction rate, a compound having a hydroxyl group (including a low molecular weight polyol having a number average molecular weight of less than 400) may be added to the curable resin composition of the present invention as necessary. In that case, examples of the compound having a hydroxyl group include ethylene glycol, diethylene glycol, and glycerin. As described above, the addition of a hydroxyl group can increase the curing reaction rate. However, when a large amount of the above compound is added, a chain transfer reaction is liable to occur, so that the degree of curing is lowered and the heat resistance of the resin composition is lowered.

  The viscosity (25 ° C.) of the curable resin composition is preferably 100 to 100,000 mPa · s, more preferably 200 to 50,000 mPa · s from the viewpoint of workability.

  100 degreeC or more is preferable, as for the glass transition temperature (Tg) of the hardened | cured material of the said curable resin composition, More preferably, it is 120 degreeC or more, More preferably, it is 250 degreeC or more. When Tg after curing is less than 100 ° C., deformation may occur when exposed to a high temperature environment, and the characteristics of the optical waveguide may deteriorate.

  The light transmittance of the cured product of the curable resin composition (manufactured by Shimadzu Corporation, spectrophotometer “UV-2450”, wavelength 850 nm, thickness of cured product 3 mm) is preferably 93 T% or more. When the light transmittance is less than 93 T%, when used as a material for an optical waveguide, propagation loss may increase and communication efficiency may decrease.

  When the curable resin composition of the present invention is used as a member for an optical waveguide, it goes without saying that the curable resin composition of the present invention is used for a core and a clad. It can be used as an intermediate layer between the substrate and the optical waveguide.

  The optical waveguide of the present invention includes a core and a clad. At least one of the core and the clad needs to be made of the curable resin composition of the present invention, and it is preferable that both the core and the clad are the curable resin composition of the present invention. The “core” mentioned above refers to the light guide portion of the optical waveguide, and the clad is a medium having a lower refractive index than the core and is provided in contact with the periphery of the core, and the core / cladding interface. The part provided for the purpose of causing total reflection. When the curable resin composition of the present invention is not used for either the core or the clad, or when it is used only for the base material or the intermediate layer of the base material and the optical waveguide, the shrinkage of the present invention can be reduced and the reliability when used for a long time The effect of improving the properties cannot be obtained.

  In the optical waveguide of the present invention, the refractive index of the core is preferably 0.01 or more larger than the refractive index of the cladding, and more preferably 0.02 or more. When the refractive index is smaller than 0.01, the critical angle of total reflection at the interface between the core and the clad is reduced, and the incident angle is limited. Therefore, it is sometimes necessary to reduce the aperture of the core. As described above, the refractive index can be controlled by selecting a substituent of the constituent raw material or adding an additive. For example, fluorine-containing alcohol (which decreases the refractive index), aromatic ring, Alternatively, it can be controlled by adding a resin having bromine and aromatic rings or sulfur, or zirconia oxide fine particles (increasing the refractive index).

  The width and height of the core part of the optical waveguide of the present invention is preferably 5 to 100 μm, more preferably 25 to 75 μm. When the width and height of the core part exceeds 100 μm, the incident angle of light to the optical waveguide is increased and light exceeding the critical angle is incident, so that part of the incident light is not propagated, Propagation loss may increase. If the thickness is less than 5 μm, the amount of incident light is small, which may not be suitable for large-capacity communication.

[Curing method of curable resin composition and manufacturing method of optical waveguide]
Below, the hardening method of the curable resin composition of this invention and the manufacturing method of an optical waveguide are shown. Although an example of the wet lithography method is shown here, the manufacturing method is not limited to the methods listed here.

  Clad curable resin composition (1) to which alicyclic diepoxy compound (A), polyol (B), catalyst (C) and, if necessary, fluorine-containing alcohol are added in a predetermined ratio, and alicyclic A curable resin composition (2) for the core, in which a diepoxy compound (A), a polyol (B), a catalyst (C), and, if necessary, an epoxy resin having a bromine and a benzene ring is added at a predetermined ratio, is prepared. To do.

  Subsequently, the curable resin composition (1) is applied on the substrate. As the substrate, a silicon or glass substrate is generally cited. Moreover, it does not specifically limit as a coating method, A spin coat method, a spray method, a roll coat method, an inkjet method etc. can be used. Among these, the spin coating method is most preferably used from the viewpoints of surface smoothness and thickness accuracy. Spin coating is performed by two-stage coating, a pre-process for 1 to 60 seconds at 0 to 100 ° C. and 10 to 1000 rpm, and a post-process for 30 to 300 seconds at 500 to 10,000 rpm. It is preferable from the viewpoint of improving accuracy such as coating thickness and surface smoothness. Dry or pre-bake treatment.

Then, an active energy ray is irradiated, the curable resin composition (1) is hardened, and a clad layer is formed. In this case, visible light, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron beams and the like can be used as active energy rays to be irradiated. Among these, ultraviolet rays having a wavelength of 200 to 400 nm are preferably used from the viewpoint of industrial properties such as safety and reaction efficiency. Preferred irradiation conditions, for example, illuminance 1~1000mW / cm ^2, include irradiating at an irradiation amount 0.1~10000mJ / cm ^2. As an active energy ray irradiation device, for example, a lamp light source such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp, a pulse such as an argon ion laser or a helium neon laser, or a continuous laser light source can be used. It is.

  Next, a core is formed. The curable resin composition (2) is applied onto the clad layer by the same method as described above. Subsequently, only a predetermined portion (usually a straight shape) of the coating layer is cured using a photomask having a predetermined line-shaped slit pattern. Next, the difference in solubility between the cured portion and the uncured portion is transferred, and the uncured portion is removed using a developer to produce a core shape. The developer varies depending on the type of the curable resin composition (2). For example, an aqueous alkali solution such as sodium hydroxide, ammonia, ethylamine, diethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline is used. Alternatively, an organic solvent such as methyl ethyl ketone, acetone, toluene, tetrahydrofuran, or alcohol can be used. As a developing method, a known method such as a liquid piling method, a dipping method, or a shower developing method can be used, and the developing time is preferably about 30 to 600 seconds. The developer is removed by air drying or washing with water.

  Furthermore, by the same method as described above, the curable resin composition (1) is applied and cured to form a clad layer to obtain an optical waveguide. Finally, post-baking is preferable because removal of the solvent and the like, and the hardness and heat resistance of the resin layer are improved.

[Methods for measuring physical properties and methods for evaluating effects]
Below, the measuring method used about this invention and the evaluation method of an effect are illustrated.

(1) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer.

(2) Glass transition temperature (Tg)
The applicator is used to apply the curable resin composition to a thickness of 20 μm on the steel plate. Using a UV irradiation device (trade name “ECS-301” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 1500 mJ / cm ² ) and post-cured at 150 ° C. for 4 hours. It peeled and the test piece was created.
Using a rigid pendulum type viscoelasticity measuring device ("RPT3000" manufactured by A & D Co., Ltd.), the peak temperature of the logarithmic decay rate was measured, and the glass transition temperature (Tg) was 250 ° C or higher. And less than 250 ° C. was regarded as insufficient (×).

(3) Flexibility Using an applicator, the curable resin composition is applied on a steel plate with a thickness of 100 μm. Using a UV irradiation device (trade name “ECS-301” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 1500 mmJ / cm ² ) and post-cured at 150 ° C. for 4 hours. It peeled and the test piece was created.
It measured based on JISK5400, and when it was a measurement with a mandrel diameter of 10 mm, the case where it did not break was evaluated as having good bending resistance (◯), and the case where it cracked was evaluated as insufficient bending resistance (×).

(4) Occurrence of “wrinkle” due to curing Create a test piece under the same conditions as in (3), and visually observe the cured state of the test piece, and the one that does not cause the occurrence of “wrinkle” is good. (○) was judged, and the occurrence of “wrinkle” was judged as defective (×).

(5) Adhesiveness In the same manner as in (3), a curable resin composition was applied and cured on a substrate (steel plate) to provide a cured product layer (layer thickness: 100 μm). Thereafter, the same curable resin composition was similarly applied and cured (layer thickness: 100 μm) on the cured product layer to prepare a test piece having two cured product layers.
The test piece was allowed to stand at (i) -40 ° C. for 30 minutes using a constant temperature and humidity chamber (Espec Corp. “TSE-11-A”), and (ii) at 85 ° C. and 85% RH for 30 minutes. The cycle of leaving was repeated 500 cycles. The rate of temperature increase is 3 ° C./min and the rate of temperature decrease is 1 ° C./min.
After 500 cycles, a dye penetrant flaw detection liquid (manufactured by Nippon Matec Co., Ltd., trade name “KD-CHECK RDP-1”) is applied to the interface between the two cured product layers, and cracks and peeling are visually observed (test) Number of times: n = 5), when no peeling at the interface was observed in all the test pieces, it was judged that the adhesion was good (◯), and when even one peeling was observed, the adhesion was poor (×) It was judged.

(6) Propagation loss An optical waveguide was used as a sample. In the same manner as in the example, an optical waveguide having a straight line of 150 μm thickness including a core of 50 μm × 50 μm is manufactured on a substrate of a 4-inch silicon wafer, and an optical waveguide sample having a waveguide length of 10 mm is manufactured by dicing. A test was conducted.
Measurement was performed using an optical test set (“MT9810B” manufactured by Anritsu Corporation). Light having a wavelength of 850 nm was incident from one end of the optical waveguide sample, the amount of light emitted from the other end was measured with a power meter, and the ratio to the amount of light when not passing through the sample was defined as propagation loss (dB). Using the average value of the number of tests three times, when the propagation loss is 1.0 (dB / cm) or less, the propagation loss is small (good: ○), when the propagation loss exceeds 1.0 (dB / cm) Judged to be large (defect: x).

(7) Reliability (propagation loss after thermal history)
The sample measured in (6) was heated in a hot air oven at 260 ° C. for 1 minute, and then left for 1 week in an environment of 85 ° C. and 85% RH.
In the same manner as (6), the propagation loss after the thermal history of the sample was measured, and judged according to the same standard as (6).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Analysis method]
(1) Gas chromatography (GC analysis) of bicyclohexyl-3,3'-diene and its isomers
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 60m, inner diameter 0.32mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 2.6 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Temperature rise pattern (column): Hold at 60 ° C. for 5 minutes, temperature rise to 300 ° C. at 10 ° C./minute Split ratio: 100
Sample: 1 μl
The ratio of bicyclohexyl-3,3'-diene and its isomer was determined as follows. That is, the GC analysis was performed under the above conditions, and the area of the maximum peak (bicyclohexyl-3,3′-diene) appearing around a retention time of 20.97 minutes and the peak around 20.91 minutes (isomers) appearing just before that ), The content ratio of the isomer to the bicyclohexyl-3,3′-diene was determined. That is, the isomer ratio (%) is calculated as isomer area ÷ (isomer area + bicyclohexyl-3,3′-diene area) × 100.

(2) Gas chromatography (GC analysis) of 3,4,3 ', 4'-diepoxybicyclohexyl and its isomers
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 30 m, film thickness 0.25 μm, inner diameter 0.32 mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 1.0 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 300 ° C
Temperature rise pattern (column): Hold at 100 ° C. for 2 minutes, heat up to 300 ° C. at 5 ° C./minute, hold at 300 ° C. for 10 minutes Split ratio: 100
Sample: 1 μl (epoxy compound: acetone = 1: 40)
The ratio of 3,4,3 ', 4'-diepoxybicyclohexyl and its isomer was determined as follows. That is, GC analysis was performed under the above conditions, and the maximum two peaks [3,4,3 ′, 4′-diepoxybicyclohexyl (two peaks are stereoisomeric) appearing at a retention time of about 19.8 minutes to 20.0 minutes. )], And the total area of 3 peaks (isomers) appearing immediately before that in the vicinity of 19.1 to 19.5 minutes, 3,4,3 ′, 4′-di The content ratio of isomers to epoxybicyclohexyl was determined. That is, the isomer ratio (%) is calculated by (total isomer area) / (total isomer area + 3,4,3 ′, 4′-diepoxybicyclohexyl total area) × 100.

(3) GC-MS analysis of 3,4,3 ′, 4′-diepoxybicyclohexyl and its isomers Measuring apparatus: HP 6890 (GC part), 5973 (MS part) manufactured by Hewlett-Packard Company
Column: HP-5MS, length 30 m, film thickness 0.25 μm, inner diameter 0.25 mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Temperature rising pattern (column): held at 100 ° C. for 2 minutes, heated to 300 ° C. at 5 ° C./minute, held at 300 ° C. for 18 minutes Inlet temperature: 250 ℃
MSD transfer line temperature: 280 ° C
Carrier gas: helium Carrier gas flow rate: 0.7 ml / min (constant flow)
Split ratio: Splitless Sample injection volume: 1.0 μl
Measurement mode: EI
Ion source temperature: 230 ° C
Quadrupole temperature: 106 ° C
MS range: m / z = 25-400
Sample preparation: 0.1 g of sample was dissolved in 3.0 g of acetone. The alicyclic diepoxy compound obtained in Synthesis Example 1 was subjected to GC-MS analysis. The results (gas chromatogram and MS spectrum of each component) are shown in FIGS. Retention times of 17.73 minutes, 17.91 minutes, and 18.13 minutes are the isomer peaks of 3,4,3 ', 4'-diepoxybicyclohexyl, 18.48 minutes, and 18.69 minutes. Are peaks of 3,4,3 ′, 4′-diepoxybicyclohexyl. Since the analysis conditions are slightly different from those in the case of the GC analysis, the retention time of each peak is different, but the appearance order is the same. FIG. 4 is an MS spectrum of a gas chromatogram and a peak at a retention time of 17.73 minutes, and FIG. 5 is an enlarged view thereof. FIG. 6 is a gas chromatogram and an MS spectrum of a peak having a retention time of 17.91 minutes, and FIG. 7 is an enlarged view thereof. FIG. 8 is an MS spectrum of a gas chromatogram and a peak at a retention time of 18.13 minutes, and FIG. 9 is an enlarged view thereof. FIG. 10 is a gas chromatogram and an MS spectrum of a peak having a retention time of 18.48 minutes, and FIG. 11 is an enlarged view thereof. FIG. 12 is a gas chromatogram and an MS spectrum of a peak having a retention time of 18.69 minutes, and FIG. 13 is an enlarged view thereof. According to the MS spectrum, any of the above components has a molecular ion peak of m / z = 194.

で表される水添ビフェノール（＝４，４′−ジヒドロキシビシクロヘキシル）１０００ｇ（５．０５モル）、上記で調製した脱水触媒１２５ｇ（硫酸として０．６８モル）、プソイドクメン１５００ｇを入れ、フラスコを加熱した。内温が１１５℃を超えたあたりから水の生成が確認された。さらに昇温を続けてプソイドクメンの沸点まで温度を上げ（内温１６２〜１７０℃）、常圧で脱水反応を行った。副生した水は留出させ、脱水管により系外に排出した。なお、脱水触媒は反応条件下において液体であり反応液中に微分散していた。３時間経過後、ほぼ理論量の水（１８０ｇ）が留出したため反応終了とした。反応終了液を１０段のオールダーショウ型の蒸留塔を用い、プソイドクメンを留去した後、内部圧力１０Ｔｏｒｒ（１．３３ｋＰａ）、内温１３７〜１４０℃にて蒸留し、７３１ｇのビシクロヘキシル−３，３′−ジエンを得た。ＧＣ分析の結果、得られたビシクロヘキシル−３，３′−ジエン中にはその異性体が含まれており（ＧＣ−ＭＳ分析により確認）、下記式（２ａ）

で表されるビシクロヘキシル−３，３′−ジエンとその異性体の含有比は９１：９であった（図３参照）。
得られたビシクロヘキシル−３，３′−ジエン（異性体を含む）２４３ｇ、酢酸エチル７３０ｇを反応器に仕込み、窒素を気相部に吹き込みながら、かつ、反応系内の温度を３７．５℃になるようにコントロールしながら約３時間かけて３０重量％過酢酸の酢酸エチル溶液（水分率０．４１重量％）２７４ｇを滴下した。過酢酸溶液滴下終了後、４０℃で１時間熟成し反応を終了した。さらに３０℃で反応終了時の粗液を水洗し、７０℃／２０ｍｍＨｇで低沸点化合物の除去を行い、脂環式エポキシ化合物２７０ｇを得た。このときの収率は９３％であった。粘度（２５℃）を測定したところ、８４ｍＰａ・ｓであった。得られた脂環式エポキシ化合物のオキシラン酸素濃度は１５．０重量％であった。また¹Ｈ−ＮＭＲの測定では、δ４．５〜５ｐｐｍ付近の内部二重結合に由来するピークが消失し、δ３．１ｐｐｍ付近にエポキシ基に由来するプロトンのピークの生成が確認され、下記式（１ａ）

で表される３，４，３′，４′−ジエポキシビシクロヘキシルであることが確認された。ＧＣ分析の結果、得られた脂環式エポキシ化合物中には３，４，３′，４′−ジエポキシビシクロヘキシルとその異性体が含まれており、異性体比率は９％であった（図１参照）。なお、異性体比率は次式により算出した。
異性体比率＝（２２６２＋１７１５＋５７０２）÷（２２６２＋１７１５＋５７０２ ＋２８５１４＋７４５８７）×１００＝９％ Synthesis example 1 (isomer ratio 9%)
A dehydration catalyst was prepared by stirring and mixing 70 g (0.68 mol) of 95 wt% sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
The following formula (3a) was added to a 3 liter flask equipped with a stirrer, a thermometer, and a dehydration pipe and a heated distillation pipe.

1000 g (5.05 mol) of hydrogenated biphenol (= 4,4′-dihydroxybicyclohexyl) represented by the above, 125 g of the dehydration catalyst prepared above (0.68 mol as sulfuric acid), and 1500 g of pseudocumene were added, and the flask was heated. did. The generation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised to raise the temperature to the boiling point of pseudocumene (internal temperature 162 to 170 ° C.), and dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. The dehydration catalyst was liquid under the reaction conditions and was finely dispersed in the reaction solution. After about 3 hours, almost theoretical amount of water (180 g) was distilled, and the reaction was terminated. Pseudocumene was distilled off using a 10-stage Oldershaw type distillation column, and the reaction-terminated liquid was distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 137 to 140 ° C. to obtain 731 g of bicyclohexyl-3. , 3'-diene was obtained. As a result of GC analysis, the obtained bicyclohexyl-3,3′-diene contained the isomer (confirmed by GC-MS analysis), and the following formula (2a)

The content ratio of bicyclohexyl-3,3′-diene represented by the formula (I) and its isomer was 91: 9 (see FIG. 3).
243 g of the obtained bicyclohexyl-3,3′-diene (including isomer) and 730 g of ethyl acetate were charged into the reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was 37.5 ° C. 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over a period of about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 270 g of an alicyclic epoxy compound. The yield at this time was 93%. It was 84 mPa * s when the viscosity (25 degreeC) was measured. The oxirane oxygen concentration of the obtained alicyclic epoxy compound was 15.0% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ 4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ 3.1 ppm. 1a)

It was confirmed that it was 3,4,3 ′, 4′-diepoxybicyclohexyl represented by the following formula. As a result of GC analysis, the obtained alicyclic epoxy compound contained 3,4,3 ′, 4′-diepoxybicyclohexyl and its isomer, and the isomer ratio was 9% ( (See FIG. 1). The isomer ratio was calculated by the following formula.
Isomeric ratio = (2262 + 1715 + 5702) ÷ (2262 + 1715 + 5702 + 28514 + 74587) x 100 = 9%

Comparative Synthesis Example 1 (isomer ratio 21%)
6 kg of hydrogenated biphenol and 620 g of potassium hydrogen sulfate were added to a 10-liter four-necked flask equipped with a stirrer, a 20-stage distillation column, and a thermometer. Subsequently, the flask was heated to 180 ° C., and after stirring the hydrogenated biphenol, stirring was started. The reaction was continued while distilling by-product water from the top of the distillation column, and after 3 hours, the pressure in the reaction system was reduced to 10 Torr (1.33 kPa), and water and bicyclohexyl-3,3'-diene were distilled. Distilled out of the system continuously from the top of the tower. The water and bicyclohexyl-3,3′-diene distilled off outside the system were separated into two layers with a decanter, and only the upper layer liquid was taken out. Thereafter, the reaction temperature was raised to 220 ° C. over 4 hours, and the reaction was terminated when the distillation of water and bicyclohexyl-3,3′-diene ceased. The yield of the distillate crude liquid of bicyclohexyl-3,3'-diene was 4507 g. 4500 g of the above dicyclohexyl-3,3′-diene distillate was put into a 5 liter four-necked flask equipped with a stirrer, 20-stage distillation column and thermometer, and heated to 180 ° C. with an oil bath. did. Thereafter, the pressure in the reaction system is reduced to 10 Torr (1.33 kPa), and water is distilled off, and then the temperature of the uppermost stage of the distillation column is maintained at 145 ° C., and bicyclohexyl-3, 3'-Diene was purified by distillation to obtain a colorless and transparent liquid. Yield was 4353 g. As a result of performing GC analysis on the liquid, the resulting bicyclohexyl-3,3'-diene contained isomers, and the content ratio of bicyclohexyl-3,3'-diene and isomers was 80. : 20.
243 g of the obtained bicyclohexyl-3,3′-diene (including isomer) and 730 g of ethyl acetate were charged into the reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was 37.5 ° C. 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over a period of about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 267 g of an alicyclic epoxy compound. The yield at this time was 92%. It was 63 mPa * s when the viscosity (25 degreeC) was measured. The obtained alicyclic epoxy compound had an oxirane oxygen concentration of 14.9% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ3.1 ppm. , 3 ′, 4′-diepoxybicyclohexyl was confirmed. As a result of GC analysis, the obtained alicyclic epoxy compound contained 3,4,3 ', 4'-diepoxybicyclohexyl and its isomer, and the isomer ratio was 21% (Fig. 2). The isomer ratio was calculated by the following formula.
Isomeric ratio = (5404 + 3923 + 13067) ÷ (5404 + 3923 + 130 67 + 23563 + 60859) × 100 = 21%

Example 1
As shown in Table 1, 75 parts by weight of Synthesis Example 1 as an alicyclic diepoxy resin, 25 parts by weight of hydroxyl-terminated epoxidized butadiene (manufactured by Daicel Chemical Industries, Ltd., trade name “Epolide PB3600”) as a polyol, As an ultraviolet-sensitive catalyst, triallylsulfonium hexafluorophosphate salt (manufactured by Daicel-Cytec Co., Ltd., 3 parts by weight of trade name “Uvacure 1590” and 1 part by weight of ethylene glycol was stirred at a temperature of 60 ° C. for 1 hour. The curable resin composition 1 was prepared by mixing.
As shown in Table 1, the obtained curable resin composition 1 has excellent properties for use as an optical waveguide, the cured product having good bending resistance and adhesion, small curing shrinkage, and the like. It was.

Example 2
As shown in Table 1, curable resin composition 2 was used in the same manner as in Example 1 except that hydroxyl-terminated hydrogenated polyisoprene (trade name “Epol” manufactured by Idemitsu Kosan Co., Ltd.) was used as the polyol. Was prepared.
As shown in Table 1, the obtained curable resin composition 2 had excellent characteristics.

Example 3
As shown in Table 1, as a polyol, a hydroxyl group-type vinyl ether oligomer at both ends (manufactured by Kyowa Hakko Chemical Co., Ltd., trade name “TOE-2000H”: HO (CH ₂ ) ₂ (CH (OC ₂ H ₅ ) CH ₂ ) _n A curable resin composition 3 was prepared in exactly the same manner as in Example 1 except that (CH ₂ OH) was used.
As shown in Table 1, the obtained curable resin composition 3 had excellent characteristics.

Example 4
As shown in Table 1, a curable resin composition 4 was used in the same manner as in Example 1 except that a liquid polycarbonate polyol (trade name “Placcel CD205PL” manufactured by Daicel Chemical Industries, Ltd.) was used as the polyol. Was prepared. The refractive index was 1.51.
As shown in Table 1, the obtained curable resin composition 4 had excellent characteristics.

Example 5
As shown in Table 1, curable resin composition 5 was used in the same manner as in Example 1 except that liquid polycarbonate polyol (trade name “Placcel CD220PL” manufactured by Daicel Chemical Industries, Ltd.) was used as the polyol. Was prepared.
As shown in Table 1, the obtained curable resin composition 5 had excellent characteristics. The refractive index of the cured product of the thermosetting resin was 1.50.

Example 6
As shown in Table 1, a curable resin composition 6 was prepared using the same raw materials as in Example 5 and changing the contents of the epoxy resin and the polyol to 50 parts by weight, respectively.
As shown in Table 1, the obtained curable resin composition 6 had excellent characteristics. The refractive index of the cured product of the thermosetting resin was 1.49.

Example 7
A curable resin composition 7 was prepared in the same manner as in Example 5 except that a fluorine-containing alcohol (Daikin Fine Chemical Laboratory, “A-5410”) was added and the content was changed as shown in Table 1. Prepared.
As shown in Table 1, the obtained curable resin composition 7 had excellent characteristics. The refractive index of the cured product of the thermosetting resin was 1.49.

Example 8
A curable resin composition exactly as in Example 5, except that brominated phenylglycidyl ether (manufactured by Nagase ChemteX, “Denacol EX-147”) was added and the content was changed as shown in Table 1. 8 was prepared.
As shown in Table 1, the obtained curable resin composition 8 had excellent characteristics. The refractive index of the cured product of the thermosetting resin was 1.51.

Example 9
As shown in Table 1, a curable resin composition 9 was used in the same manner as in Example 1 except that a liquid polyester polyol (trade name “Placcel L220AL” manufactured by Daicel Chemical Industries, Ltd.) was used as the polyol. Was prepared.
As shown in Table 1, the obtained curable resin composition 9 had excellent characteristics. The refractive index of the cured product of the thermosetting resin was 1.50.

Example 10
As shown in Table 1, a curable resin composition 10 was prepared in the same manner as in Example 1 except that liquid polyether polyol (manufactured by Asahi Kasei Fibers Co., Ltd., trade name “PTXG”) was used as the polyol. Prepared.
As shown in Table 1, the obtained curable resin composition 10 had excellent characteristics. The refractive index of the cured product of the thermosetting resin was 1.50.

Comparative Example 1
As shown in Table 2, a curable resin composition 11 was prepared in the same manner as in Example 5 without adding a polyol.
As shown in Table 2, the obtained curable resin composition 11 was “wrinkled” during curing, and was inferior in flex resistance and adhesion.

Comparative Example 2
As shown in Table 2, a curable resin composition 12 was prepared in exactly the same manner as in Example 5 except that Comparative Synthesis Example 1 was used as the epoxy compound (A).
As shown in Table 2, the obtained curable resin composition 12 had a low Tg of the cured product and poor heat resistance.

Comparative Example 3
As shown in Table 2, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 2021P”) was used as the epoxy compound (A). Except for the above, a curable resin composition 13 was prepared in exactly the same manner as in Example 5.
As shown in Table 2, the obtained curable resin composition 13 had a low Tg of the cured product and poor heat resistance.

  Furthermore, an optical waveguide was produced using the curable resin compositions produced in the above examples and comparative examples.

An optical waveguide was produced using the curable resin composition 1 produced in Example 1 as a core and the curable resin composition 5 produced in Example 5 as a cladding.
A curable resin composition 5 is applied onto a silicon wafer by spin coating so that the cured film thickness is 50 μm, and ultraviolet rays with an illuminance of 30 mW / cm ² are applied for 50 seconds in an air atmosphere using a mask aligner. Was applied to form a clad layer. Next, the curable resin composition 1 is applied on the clad layer by spin coating so that the cured film thickness is 50 μm, and then the ultraviolet light is passed through a mask having a core part having a width of 50 μm. Was irradiated. Next, the uncured portion was removed with a developer composed of acetone, and then heat treatment was performed at 150 ° C. for 4 hours. Further, on the upper surface, the curable resin composition 5 was applied and cured by spin coating so that the cured film thickness was 50 μm, a clad layer was formed, and heat treatment was performed at 150 ° C. for 4 hours, An optical waveguide was produced.
When the obtained optical waveguide was evaluated for propagation loss and reliability, it was an optical waveguide having excellent characteristics with low propagation loss and good reliability.

In exactly the same manner as described above, the curable resin composition 8 produced in Example 8 was used as a core, and the curable resin compositions 2 to 7 produced in Examples 2 to 7 and 9 to 10 and Comparative Examples 1 to 3 were used. , 9-13 were produced as clad waveguides.
As a result, the optical waveguide using the curable resin composition of the example was an optical waveguide having excellent characteristics with little propagation loss and good reliability. On the other hand, in the curable resin composition 11, since “wrinkles” occurred during curing, a large amount of defective products occurred, and the productivity was remarkably inferior.

2 is a GC analysis chart of the alicyclic diepoxy compound obtained in Synthesis Example 1. FIG. 2 is a GC analysis chart of an alicyclic diepoxy compound obtained in Comparative Synthesis Example 1. FIG. 2 is a GC analysis chart of bicyclohexyl-3,3′-diene obtained in Synthesis Example 1. FIG. It is a gas chromatogram (upper figure) in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 17.73 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 17.73 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 17.91 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 17.91 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 18.13 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 18.13 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 18.48 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 18.48 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 18.69 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 18.69 minutes.

Claims (22)

A resin composition comprising an alicyclic diepoxy compound (A), a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C), wherein the alicyclic diepoxy compound (A) is: Formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
Wherein the isomer content of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound is 3,4,3 ′, 4′-diepoxybicyclohexyl compound. , 3 ', 4'-diepoxybicyclohexyl compound and its isomer, a curable resin composition characterized by being a compound having a peak area ratio of 18 % or less by gas chromatography. A resin composition comprising an alicyclic diepoxy compound (A), a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C), wherein the alicyclic diepoxy compound (A) is: Formula (3)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
The following formula (2) obtained by conducting a dehydration reaction of the 4,4′-dihydroxybicyclohexyl compound represented by the following formula in an organic solvent while distilling off by-product water in the presence of a dehydration catalyst:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as above)
A bicyclohexyl-3,3′-diene compound represented by the formula: wherein the isomer content of the bicyclohexyl-3,3′-diene compound is such that the bicyclohexyl-3,3′-diene compound and its isomer It is a 3,4,3 ′, 4′-diepoxybicyclohexyl compound obtained by epoxidizing an alicyclic diene compound having a peak area ratio of 15% or less with respect to the total body. A curable resin composition characterized by being.   The curable resin composition according to claim 1 or 2, wherein the polyol (B) is a polyol (B1) having a main chain composed of a carbon-carbon bond.   The curable resin composition according to claim 3, wherein the polyol (B1) having a main chain composed of carbon-carbon bonds is a polydiene polyol or polyolefin polyol having hydroxyl groups at both ends of the molecular chain.   The curable resin composition according to claim 4, wherein the polydiene-based polyol is a polybutadiene polyol.   The curable resin composition according to claim 4, wherein the polydiene-based polyol is a polydiene-based polyol in which a part of the double bond of the main chain is epoxidized.   7. The curable resin composition according to claim 6, wherein the polydiene-based polyol in which a part of the double bond of the main chain is epoxidized is a polybutadiene polyol in which a part of the double bond of the main chain is epoxidized.   The curable resin composition according to claim 4, wherein the polyolefin-based polyol is a polyolefin-based polyol obtained by hydrogenating a polydiene-based polyol having hydroxyl groups at both ends of the molecular chain.   The curable resin composition according to claim 8, wherein the polydiene-based polyol having hydroxyl groups at both ends of the molecular chain is polyisoprene having hydroxyl groups at both ends of the molecular chain.   4. The curable resin composition according to claim 3, wherein the polyol (B1) having a main chain composed of carbon-carbon bonds is a vinyl ether oligomer having hydroxyl groups at both ends. The curable resin composition according to claim 10, wherein the vinyl ether oligomer having hydroxyl groups at both ends is an oligomer represented by the following chemical formula (4).

(In the formula, R ¹⁹ represents a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 1 to 50)   The curable resin composition according to claim 1 or 2, wherein the polyol (B) is a liquid polycarbonate polyol (B2).   The polycarbonate polyol (B2) is composed of a 1,6-hexanediol component, another diol component, and a carbonate component, and the molar ratio of the 1,6-hexanediol component to the other diol component is 9: 1 to 1: The curable resin composition according to claim 12, which is 9.   The curable resin composition according to claim 1 or 2, wherein the polyol (B) is a liquid polyester polyol (B3).   The curable resin composition according to claim 14, wherein the polyester polyol (B3) is a caprolactone copolymer.   The curable resin composition according to claim 1 or 2, wherein the polyol (B) is a liquid polyether polyol (B4).   The blending amount of the alicyclic diepoxy compound (A) is 30 to 90 parts by weight of the polyol (B) with respect to the total amount (100 parts by weight) of the alicyclic diepoxy compound (A) and the polyol (B). The compounding amount is 10 to 70 parts by weight, and the compounding amount of the catalyst (C) is 0.05 to 10 parts by weight. The curable resin composition according to any one of claims 1 to 16.   The curable resin composition according to any one of claims 1 to 17, further comprising a linear or branched alcohol having 3 to 15 carbon atoms and 1 to 23 fluorine atoms.   Furthermore, the curable resin composition of any one of Claims 1-18 containing the epoxy resin which has an aromatic ring or a bromine and an aromatic ring.   The glass transition temperature (Tg) of hardened | cured material is 250 degreeC or more, The curable resin composition in any one of Claims 1-19.   An optical waveguide comprising a core and a clad, wherein at least one of the core and the clad is made of a cured product of the curable resin composition according to any one of claims 1 to 20. .   The optical waveguide according to claim 21, wherein the difference in refractive index between the core and the clad is 0.01 or more.

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