JP5248787B2 - Photocurable resin composition and painted product - Google Patents

Description

  The present invention is a photocurable resin composition that exhibits excellent curability by irradiation with active energy rays such as ultraviolet rays and can form a coating film having excellent coating performance such as heat resistance, adhesion, hardness, and dimensional stability. And a cured product of the composition, and a coated product such as a coated metal can, a coated metal plate, and a coated resin film obtained by applying the composition to the surface of the object to be coated and curing.

  Conventionally, as a photocurable resin composition, it has a cationically polymerizable paint containing a cationically polymerizable compound having an epoxy group or a vinyl group and a cationic polymerization initiator that generates a cation by ultraviolet irradiation, and has a radically polymerizable unsaturated group. A radical polymerization type paint containing a radical polymerizable compound and a radical polymerization initiator that generates radicals upon irradiation with ultraviolet rays is known (for example, JP-A-2003-231860).

  However, the radical polymerization type paint has a characteristic that the curing speed is relatively fast. However, since the adhesion to the material is insufficient and the curing is inhibited by oxygen, the surface curability is inferior. There is a problem that a facility such as nitrogen filling is necessary for use in 2-8μ). On the other hand, cationic polymerization paints have advantages such as better adhesion to the material and no need for nitrogen sealing and other facilities compared to radical polymerization paints, but they have a slow curing rate. There is a problem that the coating film performance, particularly the coating film appearance, heat resistance and dimensional stability are insufficient.

JP 2003-231860 A

  The purpose of the present invention is that it does not require equipment such as nitrogen sealing, and exhibits excellent curability by irradiation with ultraviolet rays or the like at a low irradiation amount, and the coating film performance such as heat resistance, adhesion, hardness, dimensional stability, etc. To provide a photocurable resin composition capable of forming an excellent coating film, a cured product of the composition, and a coated product obtained by applying the composition to the surface of the object to be coated and curing the composition. is there.

  As a result of intensive studies to achieve the above object, the present inventors have found that a photocurable resin composition containing a curable compound containing a specific alicyclic diepoxy compound and a photocationic polymerization initiator has an activity such as ultraviolet rays. The inventors have found that when irradiated with energy rays, they can be cured at a high speed and can form a coating film excellent in coating film appearance, heat resistance, adhesion, hardness, dimensional stability, and the like, thereby completing 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％以下である脂環式ジエポキシ化合物（Ａ）（前記異性体を含む）１０〜９０重量％と、分子中に脂環エポキシ基又はグリシジル基を有する、前記脂環式ジエポキシ化合物（Ａ）以外のエポキシ化合物（Ｂ１）［下記（Ｂ４）に含まれるものを除く］、オキセタン化合物（Ｂ２）、ビニルエーテル化合物（Ｂ３）、エポキシ基及び水酸基のうち少なくとも何れかの基を１つ以上有するアクリル系共重合体（Ｂ４）及び分子中に水酸基を２〜６個有する重合体である２〜６官能ポリオール化合物（Ｂ５）［上記（Ｂ４）に含まれるものを除く］から選択された少なくとも１種の化合物（Ｂ）９０〜１０重量％とからなる硬化性化合物（Ｃ）［（Ａ）と（Ｂ）との合計は１００重量％］１００重量部に対して、光カチオン重合開始剤（Ｄ）０．０１〜２０重量部を配合した光硬化性樹脂組成物を提供する。 That is, the present invention provides 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 isomers thereof, alicyclic diepoxy compound (A) having a peak area ratio of 18% or less by gas chromatography (including the isomers ) ) Epoxy compound (B1) other than the alicyclic diepoxy compound (A) having 10 to 90% by weight and an alicyclic epoxy group or glycidyl group in the molecule [excluding those contained in the following (B4)] , Oxetane compound (B2), vinyl ether compound (B3), acrylic copolymer (B4) having at least one of an epoxy group and a hydroxyl group, and water in the molecule 2 to 6 functional polyol compound (B5), which is a polymer having 2 to 6 acid groups [ 90 to 10% by weight of at least one compound (B) selected from [excluding those contained in (B4) above] The photocationic polymerization initiator (D) 0.01 to 20 parts by weight was blended with 100 parts by weight of the curable compound (C) consisting of [the total of (A) and (B) is 100% by weight]. A photocurable resin composition is provided.

  This photocurable resin composition may further contain 0.01 to 10 parts by weight of a leveling agent with respect to 100 parts by weight of the curable compound (C).

（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脂環式ジエポキシ化合物（Ａ′）（前記異性体がエポキシ化されたものを含む）１０〜９０重量％と、分子中に脂環エポキシ基又はグリシジル基を有する、前記脂環式ジエポキシ化合物（Ａ′）以外のエポキシ化合物（Ｂ１）［下記（Ｂ４）に含まれるものを除く］、オキセタン化合物（Ｂ２）、ビニルエーテル化合物（Ｂ３）、エポキシ基及び水酸基のうち少なくとも何れかの基を１つ以上有するアクリル系共重合体（Ｂ４）及び分子中に水酸基を２〜６個有する重合体である２〜６官能ポリオール化合物（Ｂ５）［上記（Ｂ４）に含まれるものを除く］から選択された少なくとも１種の化合物（Ｂ）９０〜１０重量％とからなる硬化性化合物（Ｃ′）［（Ａ′）と（Ｂ）との合計は１００重量％］１００重量部に対して、光カチオン重合開始剤（Ｄ）０．０１〜２０重量部を配合した光硬化性樹脂組成物を提供する。
The present invention also provides the following formula (2):

(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. )
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 An alicyclic diepoxy compound (A ′) obtained by epoxidizing an alicyclic diene compound having a peak area ratio of 15% or less based on the total sum of the isomers (the isomer is epoxidized) ) and 10 to 90 wt%, including those having an alicyclic epoxy group or a glycidyl group in the molecule, contained in the alicyclic diepoxy compound (a ') other than the epoxy compound (B1) [the following (B4) are excluding, oxetane compound (B2), a vinyl ether compound (B3), 1 or more have at least one of groups of the epoxy group and a hydroxyl group That the acrylic copolymer (B4) and 2-6 functional polyol compound is a polymer having 2 to 6 hydroxyl groups in the molecule (B5) at least selected from the excluding those contained in the (B4)] Photocationic polymerization starts with respect to 100 parts by weight of a curable compound (C ′) consisting of 90 to 10% by weight of one compound (B) [total of (A ′) and (B) is 100% by weight]. The photocurable resin composition which mix | blended 0.01-20 weight part of agent (D) is provided.

  This photocurable resin composition may further contain 0.01 to 10 parts by weight of a leveling agent with respect to 100 parts by weight of the curable compound (C ′).

Each of the above-mentioned photocurable resin compositions can be used, for example, as an automotive clear paint, a topcoat agent for plastic films, a coating agent for protecting plastic parts, a coating agent for protecting metal materials, a coating agent for forming a color filter protective film, etc. . Moreover, said photocurable resin composition may become a glass transition temperature of 124 degreeC or more of the hardened | cured material obtained by irradiating an active energy ray.

  The present invention further provides a cured product obtained by irradiating each photocurable resin composition with active energy rays.

  The present invention further provides a coated product obtained by applying the above-mentioned photo-curable resin composition to the surface of an object to be coated and irradiating with active energy rays. Examples of the painted material include a painted metal can, a painted metal plate, and a painted resin film.

  The photocurable resin composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays at a low dose, and the cured film is a coating film appearance, heat resistance, adhesion, Excellent coating performance such as hardness and dimensional stability. Therefore, it can be suitably used as an automotive clear paint, a top coating agent for plastic films, a coating agent for protecting plastic parts, a coating agent for forming a color filter protective film, and the like.

  The photocurable resin composition of the present invention is a composition that can be cured by cationic polymerization by irradiation with active energy rays such as ultraviolet rays. Below, each component in this composition is demonstrated.

[Alicyclic diepoxy compounds (A) and (A ′)]
The alicyclic diepoxy compound (A) in the present invention is a 3,4,3 ′, 4′-diepoxybicyclohexyl compound represented by the formula (1), which is contained as an impurity. The content of isomers of 4,3 ', 4'-diepoxybicyclohexyl compound is determined by gas chromatography with respect to the sum of 3,4,3', 4'-diepoxybicyclohexyl compound and its isomer. The ratio of the peak area is 20% or less.

In 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 alicyclic diepoxy compound (A), the isomer content of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound contained as an impurity is 3,4,3 ′, 4′-diene. The ratio of the peak area by gas chromatography is 20% or less (preferably 18% or less, more preferably 16% or less) with respect to the sum of the epoxybicyclohexyl compound (main compound) and its isomers. Such an alicyclic diepoxy compound has a markedly faster curing rate when irradiated with ultraviolet rays or the like than those having an isomer content of more than 20%, and a cured product (coating film, etc.) after curing. ) Significantly increases the glass transition temperature and remarkably improves physical properties such as heat resistance, hardness and dimensional stability. In addition to heat resistance, hardness, and dimensional stability, it is remarkably superior to other alicyclic epoxy compounds in terms of adhesion to metal and plastic surfaces.

Such an alicyclic diepoxy compound (A) is, for example, a bicyclohexyl-3,3′-diene compound represented by the above formula (2), and the bicyclohexyl-3,3′-diene compound. The content of isomers (isomers with different double bond positions) is less than 20% as a proportion of peak area by gas chromatography with respect to the sum of the bicyclohexyl-3,3'-diene compound and its isomers. It can be produced by epoxidizing an alicyclic diene compound (for example, 19.5% or less, preferably 15% or less). The alicyclic diepoxy compound obtained by this production method is referred to as “alicyclic diepoxy compound (A ′)”. In formula (2), R ^{1 to} R ¹⁸ are the same as described above.

（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。 Here, the bicyclohexyl-3,3′-diene compound represented by the formula (2) having a small isomer content used as a raw material is, for example, 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 as above)
Is obtained by performing a dehydration reaction in an organic solvent while distilling off by-product water in the presence of a dehydration catalyst.

  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 the conventional method for producing bicyclohexyl-3,3′-diene (see, for example, Japanese Patent Application Laid-Open Nos. 2000-169399 and 2005-97274), the isomerization reaction easily proceeds, and bicyclohexyl-3. The ratio of 3,3'-diene and its isomer does not exceed 80:20. 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 a cyclic olefin compound containing a large amount of such by-products is epoxidized and used as a curable resin, a cured product (coating film) having excellent physical properties such as heat resistance and low reactivity during curing can be obtained. Absent. 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

  As an epoxidizing agent that can be used for the epoxidation of the double bond of the bicyclohexyl-3,3′-diene compound (alicyclic diene compound) represented by the formula (2), an aliphatic substantially free of moisture is used. Preference is given to using percarboxylic acids. This is because when the epoxidation reaction is carried out in the presence of moisture, the ring-opening reaction of the epoxy group proceeds and the yield of the epoxy compound decreases. For this reason, it is preferable to use an aliphatic percarboxylic acid that does not substantially contain moisture. Specifically, the moisture contained in the aliphatic percarboxylic acid is 0.8% by weight or less, preferably 0.6% by weight or less. As the aliphatic percarboxylic acid substantially free of water, peracetic acid produced by air oxidation such as acetaldehyde can be used. For example, peracetic acid is produced by the methods described in German Published Patent No. 1418465 and Japanese Patent Laid-Open No. 54-30006. According to this method, compared with the case where aliphatic percarboxylic acid is synthesized from hydrogen peroxide and extracted with a solvent to produce aliphatic percarboxylic acid, a large amount of aliphatic percarboxylic acid is continuously produced in a large amount. Can be obtained substantially inexpensively.

  As the aliphatic percarboxylic acids, formic acid, peracetic acid, perisobutyric acid, pertrifluoroacetic acid and the like can be used. Of these, peracetic acid is a preferred epoxidizing agent that is industrially available at low cost and has high stability. There is no strict limitation on the amount of the aliphatic percarboxylic acid which is an epoxidizing agent, and the optimum amount in each case is the individual epoxidizing agent used, the alicyclic diepoxy compound represented by the formula (1) obtained. Depends on variable factors such as the desired degree of epoxidation. Usually, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the double bond. However, it is usually disadvantageous to exceed 2 times mol due to economic problems and side reactions described below. In the case of peracetic acid, 1 to 1.5 times mol is preferable.

  The epoxidation reaction is carried out by adjusting the presence or absence of an inert solvent and the reaction temperature in accordance with the equipment and physical properties of the raw materials. The inert solvent can be used for the purpose of reducing the viscosity of the alicyclic diene compound represented by the formula (2) as a raw material, stabilizing by diluting the epoxidizing agent, etc. For example, aromatic compounds and esters can be used. Particularly preferred solvents are hexane, cyclohexane, toluene, ethyl acetate and methyl acetate.

  The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. Generally, it is 0 degreeC or more and 100 degrees C or less. Speaking of peracetic acid which is a preferred epoxidizing agent, 20 to 70 ° C. is preferable. The reaction is slow at 20 ° C. or lower, and peracetic acid is decomposed at 70 ° C. The molar ratio of the epoxidizing agent to the double bond in the alicyclic diene compound represented by the formula (2) is usually 2.0 to 1.0, preferably 1.5 to 1.05. When the charged molar ratio of the epoxidizing agent is less than 1.0, the production ratio of the compound in which one double bond is not epoxidized is increased, or the alicyclic diene represented by the formula (2) as a starting material. Since a compound may remain, it is not preferable. It is also uneconomical to use an epoxidizing agent in an amount exceeding 2.0.

  No special operation of the reaction mixture is necessary. For example, the mixture may be stirred for 1 to 5 hours. Isolation of the alicyclic diepoxy compound represented by the formula (1) from the obtained reaction mixture is carried out by an appropriate method, for example, precipitation with a poor solvent, and the reaction mixture is poured into hot water under stirring. Can be removed by distillation, direct desolvation, or the like. However, it is usually only necessary to separate the solvent, etc., without separating a compound in which one double bond is not epoxidized or a compound in which one or two epoxy groups are opened as described above. The mixture containing the alicyclic diepoxy compound represented by the formula (1) can be used as the component (A) or (A ′) of the photocurable resin composition of the present invention.

  As described above, the resin component in the reaction mixture is mainly composed of an alicyclic diepoxy compound represented by the formula (1), a compound in which one double bond is not epoxidized, and one or two epoxy groups. It is composed of a ring-opened compound and contains 20% by weight or more, preferably 80% or more, and more preferably 90% or more of the alicyclic epoxy compound represented by the formula (1). When the content of the alicyclic epoxy compound represented by the formula (1) is less than 20% by weight, when the photocurable resin composition of the present invention is cured, the mechanical properties and adhesion of the cured product are lowered. To do.

[Compound (B)]
In the photocurable resin composition of the present invention, an epoxy other than the alicyclic diepoxy compound (A) having an alicyclic epoxy group or a glycidyl group in the molecule together with the component (A) [or (A ′)]. A compound (B1), an oxetane compound (B2), a vinyl ether compound (B3), an acrylic polymer (B4) having at least one of an epoxy group and a hydroxyl group, and a 2-6 functional polyol compound (B5) At least one compound (B) selected from:

  As the epoxy compound (B1), any compound having one or more (preferably 1 to 2) alicyclic epoxy groups or glycidyl groups in the molecule can be used without particular limitation. The “alicyclic epoxy group” is a group (for example, 3,4-epoxycyclohexyl group, 3, 4) in which an epoxy group (oxirane ring) is formed containing two carbon atoms constituting the cycloaliphatic skeleton. -Epoxy-6-methylcyclohexyl group and the like.

  Specific examples of the compound having one or more alicyclic epoxy groups include bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, (3,4-epoxy -6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester, 3,4-epoxycyclohexylmethyl alcohol, 3 , 4-epoxycyclohexylethyltrimethoxysilane, compounds represented by the following formula (4) or (5), and the like. In addition, m in Formula (4) shows the integer of 1-30. These compounds can be used alone or in combination of two or more.

  Among the above, as a particularly suitable compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexylethyltrimethoxysilane, the above formula ( The compound represented by 4) and the compound represented by Formula (5) are mentioned.

  Specific examples of the compound having one or more glycidyl groups include bisphenol A type, F type, S type epoxy resin, hydrogenated bisphenol A type epoxy resin, triglycidyl isocyanurate, cresol novolac polyglycidyl ether, and the like. . Among these, bisphenol A type epoxy resins and hydrogenated bisphenol A type epoxy resins are preferable.

  The epoxy compound (B1) can also be obtained on the market. For example, “Celoxide 2021P”, “Celoxide 2081”, “Epolide GT401”, “Epolide PB3600”, “Epolide PB4700”, “EHPE3150”, “Epolide GT301” ”,“ Celoxide 3000 ”[manufactured by Daicel Chemical Industries, Ltd.],“ ERL-4221 ”,“ UVR-6128 ”,“ UVR-6105 ”[manufactured by Dow Chemical Co., Ltd.], etc. The

  The oxetane compound (B2) is not particularly limited as long as it is a compound having an oxetane ring in the molecule. For example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl- 3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) Oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane and the like. These compounds can also be obtained on the market, for example, “OXT-101, 121, 211, 221, 212, 610” manufactured by Toagosei Co., Ltd., “OXE” manufactured by Ube Industries, Ltd. Is done.

  The vinyl ether compound (B3) is not particularly limited as long as it has one or more (for example, 1 to 4) vinyl ether groups in the molecule. Examples of commercially available vinyl ether compounds (B3) include n-butyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol divinyl ether, cyclohexanediol divinyl ether, and cyclohexanedimethanol. Examples thereof include divinyl ether, trimethylolpropane trivinyl ether, and pentaerythritol tetravinyl ether. These can be obtained from Nippon Carbide Industries Co., Ltd., Maruzen Petrochemical Co., Ltd., Merck Ltd., etc.

  Acrylic copolymer (B4) having at least one of at least one of an epoxy group and a hydroxyl group (hereinafter referred to as “epoxy group and / or hydroxyl group-containing acrylic copolymer (B4)”) or simply an acrylic polymer. The “combination (B4)” is not particularly limited as long as it is an acrylic copolymer having at least one epoxy group and / or hydroxyl group in the molecule.

  The epoxy group and / or hydroxyl group-containing acrylic copolymer (B4) includes at least one of the epoxy group-containing monomer and the hydroxyl group-containing monomer and, if necessary, another monomer copolymerizable with the monomer. Can be obtained by copolymerization. The epoxy group-containing monomer can be used without particular limitation as long as it is a polymerizable unsaturated monomer containing an epoxy group. Typical examples include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, and allyl glycidyl. Examples thereof include ether and vinyl glycidyl ether. Of these, glycidyl acrylate and glycidyl methacrylate are preferably used. As the hydroxyl group-containing monomer, any polymerizable unsaturated monomer containing a hydroxyl group can be used without particular limitation. Typical examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy. Examples thereof include hydroxyalkyl esters having 1 to 8 carbon atoms of acrylic acid or methacrylic acid such as propyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.

  The other monomer copolymerizable with the epoxy group-containing monomer and / or the hydroxyl group-containing monomer is a monomer that is appropriately used depending on the intended performance of the resulting acrylic copolymer (B4). Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-, i- or t-butyl acrylate, n-, i- or t-butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, C1-C24 alkyl or cyclo of acrylic acid or methacrylic acid such as lauryl methacrylate, stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc. Alkyl ester; α, β-ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid; acrylamide, methacrylamide, N-methylacrylamide, N-ethylmethacrylamide, diacetoneacrylamide, Acrylamide or methacrylamide such as N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide or derivatives thereof; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene Vinyl propionate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl pivalate, Veova monomer (manufactured by Shell Chemical Co., Ltd., vinyl ester of branched fatty acid), Silaplane FM07 1, the FM0721, the FM0725 (all being polydimethylsiloxane macromonomer made by Chisso Corporation, having a terminal methacryloyl group) can be exemplified other vinyl monomers, such as. As the other copolymerizable monomer, among these, acrylic acid or methacrylic acid alkyl having 1 to 24 carbon atoms (particularly having 1 to 12 carbon atoms) is preferred. In addition, in the polymerization of the acrylic copolymer (B4), by using a polydimethylsiloxane macromonomer such as Silaplane FM0721 as another monomer, the leveling property of the obtained coating film, and the coating film after retorting The slipperiness can be improved.

  The acrylic copolymer (B4) contains a monomer component composed of the above-mentioned epoxy group-containing monomer and / or hydroxyl group-containing monomer, and other monomers that can be copolymerized as required, for example, in the presence or absence of a radical polymerization initiator. In the presence, it can be obtained by polymerization by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like. When synthesizing the acrylic copolymer (B4) by solution polymerization, the solvent is a low radically polymerizable compound such as an epoxy compound, an oxetane compound or a vinyl ether compound (hereinafter referred to as “epoxy compound etc.”). It may be preferable to use. The monomer may be dissolved in an organic solvent such as toluene and added to the polymerization system. When an epoxy compound or the like is used as a solvent, a mixture of an acrylic copolymer obtained by polymerization and the epoxy compound or the like (when an organic solvent such as toluene is used, the organic solvent is distilled off) The concentrate can be used as it is for the preparation of the photocurable resin composition of the present invention. In this case, the ratio (weight ratio) between the acrylic copolymer and the epoxy compound or the like (total amount) is not particularly limited, but is preferably about 10/90 to 50/50, for example. If the ratio is too small, the effect of improving the strength due to the blending of the acrylic copolymer tends to be low, and conversely if the ratio is too large, the viscosity of the composition increases and workability tends to deteriorate.

  The acrylic copolymer (B4) has a number average molecular weight of 1,000 to 100,000, preferably 1500 to 30,000.

The blending ratio of each monomer component in the polymerization of the acrylic copolymer (B4) is preferably within the following range with respect to 100 parts by weight of the total amount of monomer components.
Epoxy group-containing monomer: 3 to 45 parts by weight (preferably 5 to 40 parts by weight)
Hydroxyl group-containing monomer: 3 to 45 parts by weight (preferably 5 to 40 parts by weight)
Other monomer: 94 to 10 parts by weight (preferably 90 to 20 parts by weight)

  In the acrylic copolymer (B4), the concentration (total concentration) of the epoxy group and the hydroxyl group is 0.1 to 7 equivalent / kg, preferably 2 to 5 equivalent / kg.

  A 2-6 functional polyol compound (B5) is a polymer which has 2-6 hydroxyl groups in a molecule | numerator. Examples of such polyol compounds include polyester polyols, polyether polyols, polycarbonate polyols, and polyols containing two or more types of ester bonds, ether bonds, and carbonate bonds in the molecule.

  The polyester polyol is a liquid oligomer having an ester skeleton in the molecule and having two or more terminal hydroxyl groups, and is the same as the method for producing a normal polyester polyol, dehydration esterification reaction, transesterification reaction, lactone ring-opening polymerization It is synthesized by a method combining these and these.

  Polyols used in the synthesis of polyester polyol include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, and 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, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, pentaerythritol Which will be described later Poly Ether polyols, and polycarbonate polyols, and the like.

  Carboxylic acids include 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, citralacone Acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, lactic acid, malic acid, Examples include glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

  As a commercially available polyester polyol, for example, “Placcel series; 205U, L205AL, L208AL, L212AL, L220AL, L230AL, 220ED, 220EC, 220EB, 303, 305, 308, 312, L312AL, 320, L320AL, 410, 410D , P3403, E227, DC2009, DC2016, DC2209 ”(manufactured by Daicel Chemical Industries, Ltd.),“ Kurapol ”(manufactured by Kuraray Co., Ltd.), and the like.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. The polyether is produced by ring-opening polymerization of a cyclic ether such as ethylene oxide, propylene oxide, and tetrahydrofuran.

  Examples of commercially available polyether polyols include "P-400, P-700, P-1000, P-2000, P-3000, G-300, G-400, G-700, G-1500, G-". 3000, G-4000, EDP-450, EDP-550, DG-500, DG-575, SP-600, SP-690SC-800, SC-1000, SC-1001, Quadrol ”(above, Asahi Denka Kogyo Co., Ltd. )), "Polyethylene glycol 200, 400, 600, 1000, 1500, 2000, 4000, 6000" (above, manufactured by NOF Corporation), "Bisol 2EN-6, 4EN, 10EN, 2P, 2PN, 3PN" (Above, manufactured by Toho Chemical Industry Co., Ltd.), “Poly-G 420P, 720PG, 1020P, 2020P, 3020 , 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 "(above, Asahi Glass Co., Ltd.) PEG 200, PEG 300, PEG 400, PEG 600, PEG 1000, PEG 1500, PEG 1540, PEG 2000, PEG 4000S, PEG 4000N, PEG 6000S, PEG 6 00P, SANNICS 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, Sanniks Triol GP-250, GP-400, GP-600, GP-1000, TP-400, Sanniks polyol RP-410A, HR-450P, HS-209 Sanniks hexa Triol SP-750 "(manufactured by Sanyo Chemical Industries, Ltd.).

  As the polycarbonate polyol, a liquid oligomer having a carbonate skeleton in the molecule and having two or more terminal hydroxyl groups is a carbonate polyol, and the phosgene method, or dimethyl carbonate, diethyl carbonate Synthesis by a carbonate exchange reaction using such dialkyl carbonate or diphenyl carbonate (JP-A-62-187725, JP-A-2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420, etc.) Is done.

  Examples of the polyol used in the carbonate exchange reaction together with the dialkyl carbonate 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, Dipropylene glycol glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, trimethylolethane, trimethyl Roll octane, and pentaerythritol. Further, ester glycol (manufactured by Mitsubishi Gas Chemical Co., Inc.) and the above-described polyester polyol and polyether polyol can also be used.

  Commercially available polycarbonate polyols include “UH-CARB50, UH-CARB100, UH-CARB300, UH-CARB90 (1/3), UH-CARB90 (1/1), UC-CARB100” (above, Ube Industries, Ltd. )), "Placcel CD 205, CD 210, CD 220, CD 205PL, CD 205HL, CD 210PL, CD 210HL, CD 220PL, CD 220HL, CD 220EC, CD 221T" (above, manufactured by Daicel Chemical Industries, Ltd.) Etc.

  In the photocurable resin composition of the present invention, the blending ratio of the alicyclic diepoxy compound (A) [or (A ′)] and the compound (B) is selected in consideration of the performance and cost of the cured coating film. it can.

  The compounding ratio of the alicyclic diepoxy compound (A) [or (A ′)] and the compound (B) is usually the former / the latter (weight ratio) = 10/90 to 90/10, preferably The former / the latter (weight ratio) = 30/70 to 90/10, particularly preferably the former / the latter (weight ratio) = 40/60 to 88/12. The higher the former amount, the faster the curing speed, the heat resistance of the cured product (coating film), the hardness, the adhesion to metals and plastics, and the dimensional stability. It tends to decrease and the cost tends to increase.

[Photocationic polymerization initiator (D)]
The cationic photopolymerization initiator (D) used in the present invention generates a cation by irradiation with an active energy ray such as ultraviolet rays to form the alicyclic diepoxy compound (A) [or (A ′)] and the compound (B). Compounds that initiate polymerization, such as hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts and other cationic polymerizations represented by the following formulas (I) to (XV) Mention may be made of initiators.

Ar ₂ I ⁺ · X ⁻ (I)
(In the formula, Ar represents an aryl group such as a phenyl group, and X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ ).
Ar ₃ S ⁺ · X ⁻ (II)
(Wherein Ar and X ⁻ have the same meaning as above)

（式中、Ｒ¹⁹は炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表わし、ｒは０〜３の整数を表わし、Ｘ^-は上記と同じ意味を有する）

(In the formula, R ¹⁹ represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, r represents an integer of 0 to 3, and X ⁻ has the same meaning as described above).

［式中、Ｙ^-はＰＦ₆ ^-、ＳｂＦ₆ ^-、ＡｓＦ₆ ^-又はＳｂＦ₅（ＯＨ）を表わす］

[Wherein Y ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ or SbF ₅ (OH)]

（式中、Ｘ^-は上記と同じ意味を有する）

(Where X ^- has the same meaning as above)

（式中、Ｘ^-は上記と同じ意味を有する）

(Where X ^- has the same meaning as above)

（式中、Ｘ^-は上記と同じ意味を有する）

(Where X ^- has the same meaning as above)

（式中、Ｒ²⁰は炭素数７〜１５のアラルキル基又は炭素数３〜９のアルケニル基を表わし、Ｒ²¹は炭素数１〜７の炭化水素基又はヒドロキシフェニル基を表わし、Ｒ²²は酸素原子又は硫黄原子を含有していてもよい炭素数１〜５のアルキル基を表わし、Ｘ^-は上記の意味を有する）

(In the formula, R ²⁰ represents an aralkyl group having 7 to 15 carbon atoms or an alkenyl group having 3 to 9 carbon atoms, R ²¹ represents a hydrocarbon group or hydroxyphenyl group having 1 to 7 carbon atoms, and R ²² represents oxygen. Represents an alkyl group having 1 to 5 carbon atoms which may contain an atom or a sulfur atom, and X ⁻ has the above-mentioned meaning)

（式中、Ｒ²³及びＲ²⁴はそれぞれ独立に炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表わす）

(Wherein R ²³ and R ²⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms)

（式中、Ｒ²³及びＲ²⁴は上記と同じ意味を有する）

(Wherein R ²³ and R ²⁴ have the same meaning as above)

  Commercially available products can also be used as the photocationic polymerization initiator (D). Examples of commercially available products include UVACURE 1590 (manufactured by Daicel Cytec Co., Ltd.), CD-1010, CD-1011, CD-1012 (and above). , Manufactured by Sartomer, USA), Irgacure 264 (manufactured by Ciba Geigy), CIT-1682 [manufactured by Nippon Soda Co., Ltd.], and the like.

Among the photocationic polymerization initiators described above, compounds having a hexafluorophosphate anion (PF ₆ ⁻ ) are preferable from the viewpoints of toxicity, versatility and the like.

  In the photocurable resin composition of the present invention, the content of the photocationic polymerization initiator (D) is 10 to 90% by weight of the alicyclic diepoxy compound (A) or (A ′) and the compound (B) 90 to 10%. % By weight of curable compound (C) or (C ′) [total of (A) or (A ′) and (B) is 100% by weight] per 100 parts by weight. Part, preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight. If the usage-amount of a photocationic polymerization initiator (D) is less than 0.01 weight part, sclerosis | hardenability will deteriorate easily, and if it uses exceeding 20 weight part, the physical property in hardened | cured material will fall easily.

  In addition to the above-mentioned (A) [or (A ′)], (B), and essential (D) component that is a film-forming resin component, the photocurable resin composition of the present invention, if necessary, Leveling agents; sensitizers; pigments such as colored pigments and extender pigments, dyes, dyes; polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, component (A) [or (A ' )] And modified resins such as epoxy resins other than (C1) and epoxidized polybutadiene resins; organic resin fine particles; solvents and the like.

  The leveling agent is blended for the purpose of improving the lubricity of the resulting coating film. For example, a fatty acid ester wax, which is an esterified product of a polyol compound and a fatty acid, a silicon wax, a fluorine wax, an acrylic Mention may be made of waxes such as waxes, polyolefin waxes, animal waxes and plant waxes.

  Examples of the polyol compound used as a raw material for the fatty acid ester wax include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and glycerin. , Di- or higher polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Among these, a polyol compound having three or more hydroxyl groups in one molecule is preferable, and among them, polyglycerol, trimethylolpropane, and pentaerythritol are preferable.

  Examples of the fatty acid that is the other raw material of the fatty acid ester wax include saturated or unsaturated fatty acids, preferably fatty acids having 6 to 32 carbon atoms. Specific examples of suitable fatty acids include saturated fatty acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, serotic acid, montanic acid and melicic acid; Mention may be made of unsaturated fatty acids such as acids, undecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, cetoleic acid, erucic acid, ricanoic acid, ricinoleic acid, arachidonic acid.

  The fatty acid ester wax is preferably one in which at least 1/3 of the number of hydroxyl groups of the polyol compound is esterified with a fatty acid.

  Examples of the silicon-based wax include BYK-300, BYK-320, BYK-330 [above, manufactured by BYK Chemie), Silwet L-77, Silwet L-720, and Silwet L-7602 [above, Nippon Unicar Co., Ltd.], Paintad 29, Paintad 32, Paintad M [above, manufactured by Dow Corning], Shin-Etsu Silicone KF-96 (manufactured by Shin-Etsu Chemical), and the like.

  Examples of the fluorine-based wax include shamrock wax SST-1MG, shamrock wax SST-3, shamrock wax fluoroslip 231 [above, manufactured by Shamrock Chemicals Co., Ltd.], POLYFLUO 120, 150, 400 [same]. Micro Powders Co., Ltd.], FC-4430, FC-4432 [manufactured by Sumitomo 3M Limited] and the like.

  Examples of the acrylic wax include BYK-350, BYK-355, BYK-361N, BYK-358N [manufactured by BYKChemie (Bicchemy)] and the like.

  Examples of the polyolefin wax include shamrock wax S-394, shamrock wax S-395 [more than Shamrock Chemicals], Hoechst wax PE-520, Hoechst wax PE-521 [more than Hoechst], Mitsui High wax [Mitsui Chemicals Co., Ltd.] and the like, and animal waxes include, for example, lanolin and beeswax, and plant waxes include, for example, carnauba wax and beeswax. It is done.

  Leveling agents can be used alone or in combination of two or more. The blending amount of the leveling agent is usually 10 parts by weight or less (for example, 0.01 to 10 parts by weight), preferably 0. 10 parts by weight with respect to 100 parts by weight of the curable compound (C) [or (C ′)]. It is 1-5 weight part, More preferably, it is the range of 0.5-3 weight part.

  The sensitizer is blended for the purpose of further improving curability by ultraviolet rays or the like, and examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin. The amount of the sensitizer is usually 10 parts by weight or less, preferably 3 parts by weight or less based on 100 parts by weight of the curable compound (C) [or (C ′)].

  When the modified resin is blended, the modified resin is usually 0.1 to 50 parts by weight, particularly 100 parts by weight of the curable compound (C) [or (C ′)]. It is preferable to use within the range of 5 to 20 parts by weight. Among the modified resins, epoxidized polybutadiene resin is particularly effective for improving the adhesion of the coating film.

  As the organic resin fine particles, organic resin fine particles having a particle diameter in the range of 50 to 500 nm are preferable, and examples thereof include acrylic resin fine particles whose inside is three-dimensionally crosslinked. Organic resin fine particles are obtained by pulverizing an organic polymer into fine particles; polymer fine particles obtained by emulsion polymerization in water in the presence of an emulsifier; dried and pulverized; organic in the presence of a polymer stabilizer. Examples thereof include those obtained by drying and pulverizing polymer fine particles obtained by dispersion polymerization in a solvent. The adhesiveness of the coating film can be improved by blending the organic resin fine particles with the photocurable resin composition of the present invention. When the organic resin fine particles are blended, the amount of the organic resin fine particles is usually 0.1 to 50 parts by weight with respect to 100 parts by weight of the curable compound (C) [or (C ′)], In particular, it is preferably in the range of 1 to 10 parts by weight.

[Production of photocurable resin composition]
The photocurable resin composition of the present invention can be prepared by mixing the components described above and stirring the mixture so as to obtain a uniform coating composition. For example, the components can be mixed, heated as necessary (for example, about 50 ° C.), and stirred for about 10 minutes until uniform with a stirrer such as a dissolver.

  The photocurable resin composition of the present invention has curability to active energy rays such as ultraviolet rays, tin, aluminum, tin-free steel, iron, zinc, copper, galvanized steel sheet, zinc and other Metal plates molded into metal cans such as alloy-plated steel plates with metals (this metal plates may be subjected to chemical conversion treatment such as zinc phosphate treatment or chromate treatment), polyethylene terephthalate, polyethylene naphthalate, etc. Polyester resin, polyolefin resin such as polyethylene and polypropylene, polyamide resin, epoxy resin, polyvinyl chloride, polycarbonate, acrylic resin such as PMMA, ABS resin, AS resin, polystyrene resin, polycycloolefin resin ["ZEONEX" Co., Ltd.), "Arton" (manufactured by JSR Corporation), APEL "painted (Mitsui Chemicals Co., Ltd.)) object to be coated consists of a resin film or the like, such as, can form a cured film by irradiation of ultraviolet rays or the like. Although a coating film thickness can be suitably selected according to a use, it can usually be in the range of about 2-20 micrometers as a dry coating film thickness, Preferably it is in the range of about 2-8 micrometers.

  The photocurable resin composition of the present invention can be applied by a coating method such as roll coating, spray coating, brush coating, bar coating, roller coating, or silk screen printing. When the coating film contains a solvent, after coating, the solvent is removed by heating or the like, and then the coating film is cured by irradiation with ultraviolet rays or the like. The composition can be appropriately changed according to the type and thickness of the composition. The wavelength of the ultraviolet rays to be irradiated is usually within the range of 200 to 600 nm, and an irradiation source having a wavelength with high sensitivity can be appropriately selected and used depending on the type of the photocationic polymerization initiator. it can.

Examples of the ultraviolet irradiation source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. Irradiation condition to the coating film is usually within the range dose is 10~1,000mJ / cm ^2, in particular 50 to 500 mJ / cm ² is suitable. In addition to ultraviolet rays, for example, visible light, infrared rays, X rays, α rays, β rays, γ rays, electron rays, and the like can be used as the active energy rays.

  Moreover, you may heat a coating film after irradiation of active energy rays, such as an ultraviolet-ray, as needed. By heating, unreacted substances in the coating film can be reduced, and the curability of the coating film by irradiation with active energy rays and the distortion of the coating film generated by molding can be reduced. In some cases, the hardness and adhesion of the coating film can be improved by this heating. The said heating can be normally performed on the conditions for 1 to 30 minutes at 150-250 degreeC atmospheric temperature.

  In this way, a painted product such as a painted metal can, a painted metal plate, and a painted resin film can be obtained.

  Since the photocurable resin composition of the present invention contains the alicyclic diepoxy compound (A) [or (A ′)] and the compound (B) as a film-forming resin component, the photocationic polymerization initiator (D) In the presence of, it can be cured by cationic polymerization efficiently even by irradiation with a low irradiation amount of ultraviolet rays or the like without requiring facilities such as nitrogen sealing. Moreover, after hardening, it is excellent in coating-film performance, such as heat resistance, adhesiveness, hardness, and dimensional stability, and can form the coating film which was excellent in especially the coating-film external appearance. Accordingly, the photocurable resin composition of the present invention is particularly suitable as a coating for the outer surface of a metal / resin film, such as an automotive clear coating, a top coat for plastic films, a coating for protecting plastic parts, and a coating for protecting metal materials. Alternatively, it can be used as a coating agent for forming a color filter protective film.

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

[Measurement method and evaluation method for physical properties, etc.]
(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. 5 is a gas chromatogram and an MS spectrum of a peak having a retention time of 17.73 minutes, and FIG. 6 is an enlarged view thereof. FIG. 7 is an MS spectrum of a gas chromatogram and a peak at a retention time of 17.91 minutes, and FIG. 8 is an enlarged view thereof. FIG. 9 is an MS spectrum of a gas chromatogram and a peak at a retention time of 18.13 minutes, and FIG. 10 is an enlarged view thereof. FIG. 11 is an MS spectrum of a gas chromatogram and a peak at a retention time of 18.48 minutes, and FIG. 12 is an enlarged view thereof. FIG. 13 is a gas chromatogram and an MS spectrum of a peak having a retention time of 18.69 minutes, and FIG. 14 is an enlarged view thereof. According to the MS spectrum, any of the above components has a molecular ion peak of m / z = 194.

(4) Curability The curable compositions of Examples 1 to 3 and Comparative Examples 1 to 5 prepared according to Table 1 were coated on an aluminum standard test plate using an applicator so that the dry film thickness was 10 μm, Using a UV irradiation device (trade name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.), the degree of stickiness immediately after the coating film was cured by irradiating with ultraviolet rays (integrated light amount 280 mJ / cm 2) was 3 Judged by stage.
○: No stickiness is observed at all.
Δ: Slight stickiness is observed.
X: Clear stickiness is recognized.

(5) Glass transition temperature (Tg) of UV cured product
The curable compositions of Examples 1 to 3 and Comparative Examples 1 to 5 prepared according to Table 1 were each applied to a thickness of 20 μm on a steel plate using an applicator. Using a UV irradiation device (trade name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 500 mJ / cm ² ) and cured, and then 1 ° C. at 80 ° C. A test piece was prepared by post-curing for hours. Using a rigid pendulum viscoelasticity measuring instrument equipped with a 4mmφ cylindrical edge ("RPT3000" manufactured by A & D Co., Ltd.), measurements were made from 30 ° C to 300 ° C, and multiple logarithmic decay rates were observed. Among these peaks, the peak temperature of the logarithmic decay rate on the lowest temperature side was defined as the glass transition temperature (Tg).

(6) Pencil hardness The curable compositions of Examples 1 to 3 and Comparative Examples 1 to 5 prepared according to Table 1 were coated on an aluminum standard test plate using an applicator so that the dry film thickness was 10 μm. Using a UV irradiation apparatus (trade name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 280 mJ / cm ² ) and cured, and then at 150 ° C. 3 A test piece was prepared by post-curing for a minute. The pencil scratch test prescribed | regulated to JISK5400 8.4.2 (1990) was done to the coating film of the obtained test coating board. Evaluation was carried out by the blurring method.

(7) Adhesiveness The curable compositions of Examples 1 to 3 and Comparative Examples 1 to 5 prepared according to Table 1 were coated on an aluminum standard test plate using an applicator so that the dry film thickness was 10 μm, respectively. Using a UV irradiation apparatus (trade name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 280 mJ / cm ² ) and cured, and then at 150 ° C. 3 A test piece was prepared by post-curing for a minute. In accordance with JIS K5400 8.5.2 (1990) cross-cut tape method, 100 squares of 1.5 mm x 1.5 mm on the painted surface of the test painted plate were created on the coating film of the obtained test painted plate. And the adhesive cellophane tape was stuck on the surface, and the state of the cell after peeling off rapidly was evaluated according to the following criteria.
10 points: Each cut is fine, smooth on both sides, and the intersection of the cuts and the square are not peeled off at a glance.
8 points: There is a slight peeling at the intersection of the cuts, there is no peeling at a glance, and the area of the defect is within 5% of the total square area.
6 points: There is a peeling between both sides of the cut and the intersection, and the area of the defect is 5 to 15% of the total square area.
4 points: The width of the peeling due to the cut is wide, and the area of the defect is 15 to 35% of the total square area.
2 points: The width of the peeling due to the cut is wider than 4 points, and the area of the missing part is 35 to 65% of the total square area.
0 point: The area of peeling is 65% or more of the total square area.

(8) Dimensional stability The curable compositions of Examples 1 to 3 and Comparative Examples 1 to 5 prepared according to Table 1 were coated on a PET film using an applicator so that the dry film thickness was 10 μm, and UV was applied. Using an irradiation device (trade name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 280 mJ / cm ² ) and cured, and then visually cured and contracted. Judged the degree of.
○: The film was not curled at all.
Δ: Slight curling was observed in part.
X: Large curling was observed throughout.

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４参照）。
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 (1) and its isomer was 91: 9 (see FIG. 4).
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%

Synthesis example 2 (isomer ratio 14%)
Into a 3 liter flask equipped with a stirrer, a thermometer, a dehydration tube and a heated distillation pipe, hydrogenated biphenol 840 g (4.24 mol), phosphoric acid 170 g (1.73 mol), undecane 2350 g And the flask was heated. The generation of water was confirmed when the internal temperature exceeded 110 ° C. The temperature was further raised to raise the temperature to the boiling point of undecane (internal temperature 189 to 194 ° C.), and a dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. In addition, p-toluenesulfonic acid was completely dissolved in the reaction solution under the reaction conditions. After about 5 and a half hours, the reaction was terminated because almost the theoretical amount of water (150 g) was distilled. After the reaction was completed, the undecane was distilled off using a 10-stage Oldershaw type distillation column, and then distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 138 to 141 ° C. to obtain 474.2 g of bicyclohexyl. -3,3'-diene was obtained. As a result of GC analysis, the resulting bicyclohexyl-3,3'-diene contained isomers, and the content ratio of bicyclohexyl-3,3'-diene and isomers was 87:13. .
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 261 g of an alicyclic epoxy compound. The yield at this time was 90%. It was 75 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 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 14% ( (See FIG. 2). The isomer ratio was calculated by the following formula.
Isomeric ratio = (2821 + 2108 + 6988) ÷ (2821 + 2108 + 6988 + 20792 + 54602) × 100 = 14%

Comparative Synthesis Example 1
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. 3). The isomer ratio was calculated by the following formula.
Isomeric ratio = (5404 + 3923 + 13067) ÷ (5404 + 3923 + 130 67 + 23563 + 60859) × 100 = 21%

Production Example 1 [Production of Acrylic Copolymer 1]
A flask equipped with a stirrer and a condenser was charged with 1800 parts by weight of “Celoxide 2021P” [manufactured by Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate] and stirred. While warming to 95 ° C. Then, while maintaining the same temperature, 100 parts by weight of glycidyl methacrylate, 150 parts by weight of n-butyl methacrylate, 200 parts by weight of methyl methacrylate, 200 parts by weight of n-butyl acrylate, 2-hydroxyethyl methacrylate 5 A mixture prepared by previously mixing and dissolving 50 parts by weight of 2,2′-azobisisobutyronitrile in toluene over 4 hours was added dropwise over 4 hours, polymerized, and then toluene was removed by vacuum distillation to remove acrylic copolymer. A polymer 1 was obtained. The number average molecular weight of the obtained acrylic copolymer 1 was about 2500.

Production Example 2 [Production of Acrylic Copolymer 2]
A flask equipped with a stirrer and a condenser was charged with 1800 parts by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate [trade name “Celoxide 2021P”, manufactured by Daicel Chemical Industries, Ltd.]. The mixture was heated to 95 ° C. with stirring. Next, while maintaining the same temperature, 150 parts by weight of epoxycyclohexylmethyl methacrylate [trade name “Cyclomer M-100”, manufactured by Daicel Chemical Industries, Ltd.], 200 parts by weight of n-butyl methacrylate, A mixture of 150 parts by weight of methyl methacrylate, 100 parts by weight of n-butyl acrylate and 50 parts by weight of 2,2′-azobisisobutyronitrile previously mixed and dissolved in toluene was added dropwise over 4 hours to carry out polymerization. Thereafter, toluene was removed by distillation under reduced pressure to obtain an acrylic copolymer 2. The number average molecular weight of the obtained acrylic copolymer 2 was about 4500.

Examples 1-8, Comparative Examples 1-5
A photocurable resin composition was prepared at the compounding ratios described in Tables 1 and 2, and the above physical properties were measured. The blending of each component was carried out by mixing with stirring for 20 minutes at room temperature using “Foam Extracting Taro” manufactured by Shinky Corporation. The results are shown in Tables 1 and 2.

The abbreviations in the table are as follows.
Synthetic Example 1: Cycloaliphatic diepoxy compound obtained in Synthetic Example 1 Synthetic Example 2: Cycloaliphatic diepoxy compound obtained in Synthetic Example 2 Comparative Synthetic Example 1: Cycloaliphatic diepoxy compound obtained in Comparative Synthetic Example 1 CEL-2021P: “Celoxide 2021P” (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate) manufactured by Daicel Chemical Industries, Ltd.
CEL-2081: “Celoxide 2081” (epsilon-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate) manufactured by Daicel Chemical Industries, Ltd.
OXE: Ube Industries, Ltd. (3-ethyl-3-hydroxymethyloxetane)
PCL308: “PCL308” (trifunctional polyester polyol) manufactured by Daicel Chemical Industries, Ltd.
VE: manufactured by Nippon Carbide Corporation (cyclohexanedimethanol divinyl ether)
Acrylic copolymer 1: Acrylic copolymer obtained in Production Example 1 (mixture of acrylic copolymer and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate)
Acrylic copolymer 2: Acrylic copolymer obtained in Production Example 2 (mixture of acrylic copolymer and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate)
UVACURE 1590: “UVACURE-1590” manufactured by Daicel Cytec Co., Ltd. (sulfonium salt-based photocationic polymerization initiator)
CHIVACURE 1176: “CHIVACURE 1176” manufactured by Double Bond Chemical Co., Ltd. (sulfonium salt-based photocationic polymerization initiator)
BYK-361N: “BYK-361N” (acrylic leveling agent) manufactured by BYKChemie

  As shown in Tables 1 and 2, the photo-curable resin compositions of the examples show excellent curability when irradiated with ultraviolet rays at a low dose, and are coated with heat resistance, adhesion, hardness, dimensional stability, and the like. A coating film having excellent film performance can be formed.

2 is a GC analysis chart of the alicyclic diepoxy compound obtained in Synthesis Example 1. FIG. 3 is a GC analysis chart of the alicyclic diepoxy compound obtained in Synthesis Example 2. 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 (9)

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 isomers thereof, alicyclic diepoxy compound (A) having a peak area ratio of 18% or less by gas chromatography (including the isomers ) ) Epoxy compound (B1) other than the alicyclic diepoxy compound (A) having 10 to 90% by weight and an alicyclic epoxy group or glycidyl group in the molecule [excluding those contained in the following (B4)] , Oxetane compound (B2), vinyl ether compound (B3), acrylic copolymer (B4) having at least one of an epoxy group and a hydroxyl group, and water in the molecule 2 to 6 functional polyol compound (B5), which is a polymer having 2 to 6 acid groups [ 90 to 10% by weight of at least one compound (B) selected from [excluding those contained in (B4) above] The photocationic polymerization initiator (D) 0.01 to 20 parts by weight was blended with 100 parts by weight of the curable compound (C) consisting of [the total of (A) and (B) is 100% by weight]. Photocurable resin composition.   Furthermore, the photocurable resin composition of Claim 1 which contains a leveling agent 0.01-10 weight part with respect to 100 weight part of sclerosing | hardenable compounds (C). Following formula (2)

(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. )
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 An alicyclic diepoxy compound (A ′) obtained by epoxidizing an alicyclic diene compound having a peak area ratio of 15% or less based on the total sum of the isomers (the isomer is epoxidized) ) and 10 to 90 wt%, including those having an alicyclic epoxy group or a glycidyl group in the molecule, contained in the alicyclic diepoxy compound (a ') other than the epoxy compound (B1) [the following (B4) are excluding, oxetane compound (B2), a vinyl ether compound (B3), 1 or more have at least one of groups of the epoxy group and a hydroxyl group That the acrylic copolymer (B4) and 2-6 functional polyol compound is a polymer having 2 to 6 hydroxyl groups in the molecule (B5) at least selected from the excluding those contained in the (B4)] Photocationic polymerization starts with respect to 100 parts by weight of a curable compound (C ′) consisting of 90 to 10% by weight of one compound (B) [total of (A ′) and (B) is 100% by weight]. A photocurable resin composition containing 0.01 to 20 parts by weight of the agent (D).   Furthermore, the photocurable resin composition of Claim 3 which contains a leveling agent 0.01-10 weight part with respect to 100 weight part of curable compounds (C ').   The light according to any one of claims 1 to 4, which is used as a clear paint for automobiles, a top coat agent for plastic films, a coat agent for protecting plastic parts, a coat agent for protecting metal materials, or a coat agent for forming a color filter protective film. Curable resin composition.   The photocurable resin composition according to any one of claims 1 to 5, wherein the cured product obtained by irradiating active energy rays has a glass transition temperature of 124 ° C or higher.   Hardened | cured material obtained by irradiating an active energy ray to the photocurable resin composition in any one of Claims 1-6.   A coated product obtained by applying the photocurable resin composition according to any one of claims 1 to 6 to the surface of an object to be coated and irradiating with active energy rays.   The coated object according to claim 8, which is a painted metal can, a painted metal plate, or a painted resin film.

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