JP4498769B2 - Tetrahydroxybicyclohexane di (meth) acrylic acid esters, compositions thereof, and cured molded bodies - Google Patents

Description

  The present invention is a novel tetrahydroxybicyclohexanedi (meth) acrylic acid ester having light and / or thermosetting properties, a production method thereof, a curable resin composition containing the same, and a composition obtained by curing the composition. With respect to the molded body, the molded body is excellent in heat resistance and has a high refractive index.

Conventionally, epoxy / acrylate resins obtained by reacting acrylic acid with epoxy resins have been widely used as functional polymer materials. This resin has been used in the fields of photosensitive materials, optical materials, dental materials, various polymer crosslinking agents, and the like. However, in general, acrylic resins have insufficient heat resistance and weather resistance. For example, they are insufficient in a field where a high level of heat resistance is required.
In contrast, various resins have been proposed. For example, JP-A-8-278629 discloses a curable composition containing a reaction product of an epoxy compound having a fluorene skeleton and (meth) acrylic acid (see, for example, Patent Document 1). Although the cured product is relatively excellent in heat resistance and can solve the above-mentioned problems to some extent, it cannot be said that the required performance at the current high level can be sufficiently satisfied.

JP-A-8-278629 (Claim 1, paragraph 0019, Examples 1 to 10)

  An object of the present invention is to obtain a cured product having high hardness and high heat resistance, a curable resin composition used for the cured product, and a novel compound used for the cured product.

  The present inventors have found that a molded product obtained by curing a curable resin composition containing tetrahydroxybicyclohexanedi (meth) acrylic acid esters can solve such problems, and completed the present invention. It came to do.

That is, the first of the present invention provides tetrahydroxybicyclohexane di (meth) acrylic acid esters represented by the following general formula (I).
_{CH 2 = CR-COO-X} -OCO-CR = CH 2 (I)
(In the formula, R represents a hydrogen atom or a methyl group, and two Rs may be the same or different. X represents a divalent bicyclohexylene group represented by the following formula (II).)
(In the formula, R1 to R18 are hydrogen atoms. For R19 to R22, R19 or R20 and R21 or R22 are a bonding group to the (meth) acryloyl group in formula (I), and the remaining R20 or R19 and R22 or R21 is a hydroxyl group.)
A second aspect of the present invention is the tetrahydroxybicyclohexane di (meth) acrylic acid ester according to the first aspect of the present invention in which a diepoxybicyclohexane represented by the following general formula (III) is reacted with (meth) acrylic acid. A manufacturing method is provided.
(In the formula, R1 to R18 are hydrogen atoms .)
A third aspect of the present invention provides a curable resin composition containing the tetrahydroxybicyclohexanedi (meth) acrylic acid ester (referred to as component (A)) according to the first aspect of the present invention.
A fourth aspect of the present invention provides the curable resin composition according to the third aspect of the present invention, which can be cured by light (including radiation) and / or heat.
The fifth of the present invention further contains a curable (meth) acrylate compound (referred to as the component (B)) other than the component (A), the component (A) 30 to 100% by weight and the component (B) 70 to 70%. The curable resin composition according to the third or fourth aspect of the present invention is 0% by weight (the total of the component (A) and the component (B) is 100% by weight).
6th of this invention contains a photoinitiator (P) further, and this photoinitiator (P) is 1 to 1 part with respect to 100 weight part of total amounts of the photocurable component in a composition. The curable resin composition according to any one of Nos. 3 to 5 of the present invention, which is contained in a proportion of 10 parts by weight.
The seventh of the present invention further contains a radical polymerization initiator (T), and the radical polymerization initiator (T) is added in an amount of 0.001 part by weight relative to 100 parts by weight of the total amount of thermosetting components in the composition. The curable resin composition according to any one of Nos. 3 to 5 of the present invention, which is contained at a ratio of 1 to 10 parts by weight.
8th of this invention provides the molded object formed by hardening | curing the curable resin composition in any one of 3rd-7 of this invention.

  According to the present invention, tetrahydroxybicyclohexanedi (meth) acrylic acid esters, which are novel epoxy / acrylate resins having photocurable and / or thermosetting properties, and a method for producing the same are provided. A cured product obtained from a composition containing this resin (for example, a molded article formed on itself or a coating film formed on a substrate) has high hardness, extremely excellent heat resistance, and also has a high refractive index. .

  The tetrahydroxybicyclohexane di (meth) acrylates represented by the general formula (I) of the present invention (hereinafter referred to as the component (A)) are diepoxybicyclohexanes represented by the general formula (III). It is obtained by reacting two (meth) acrylic acids with two epoxy groups, and each one hydroxy group of each cyclo ring of tetrahydroxybicyclohexane and the carboxyl group of (meth) acrylic acid. And have a structure in which an ester is formed.

  The diepoxy bicyclohexanes represented by the general formula (III) include, for example, a double bond of a compound having a bicyclohexyl-3,3′-diene skeleton represented by the general formula (IV), an organic percarboxylic acid or Produced by epoxidation with hydrogen peroxide.

  Specific examples of the compound having a bicyclohexyl-3,3'-diene skeleton represented by the general formula (IV) include bicyclohexyl-3,3'-diene.

  The reaction between the diepoxybicyclohexane (III) and (meth) acrylic acid is usually carried out at 50 to 120 ° C. for 3 to 10 hours. The reaction is performed at 50 to 120 ° C. for 5 to 30 hours using an appropriate solvent as necessary. Examples of the solvent include alkylene monoalkyl ether acetates such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl-1-acetate, and ketones such as methyl ethyl ketone and methyl amyl ketone. Of these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferred.

  The curable resin composition of the present invention contains the component (A) and is light and / or thermosetting, and the component (A) can be used alone or as a mixture of two or more. Can also be used.

Further, the composition may contain a light and / or thermosetting (meth) acrylate compound (component (B)) other than the component (A).
The said (B) component is mix | blended within the predetermined range as a viscosity modifier or a crosslinking agent according to the physical property for which a curable composition is required. Examples of the component (B) include monovalent acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; and ethylene glycol di (meth) ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Squirrel Le Thor tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, of polyhydric alcohols such as glycerol (meth) acrylate (meth) acrylic acid ester.
These compounds can be used alone or in combination of two or more.

The ratio of the component (A) to the component (B) is 30 to 100% by weight of the component (A) and 70 to 0% by weight of the component (B), preferably 30 to 90% by weight of the component (A) and 70% of the component (B). 10% by weight, more preferably 35 to 85% by weight of component (A) and 65 to 15% by weight of component (B) (the total amount of component (A) and component (B) is 100% by weight). .
When the component (B) is more than the above range, the heat resistance is lowered too much, and when it is less than the above range, the toughness is lowered too much.

When the curable resin composition of the present invention is photocurable, a photopolymerization initiator (P) may be added to the curable resin composition, and the curable resin composition is a thermosetting resin composition. A radical polymerization initiator (T) may be added to.
The photopolymerization initiator (P) is 10 parts by weight or less, preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight based on 100 parts by weight of the total amount of the photocurable components in the composition. Added in parts by weight.
The radical polymerization initiator (T) is 10 parts by weight or less, preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight based on 100 parts by weight of the total amount of thermosetting components in the composition. Added in parts by weight.

  The photopolymerization initiator (P) is a compound that functions as a photopolymerization initiator of the component (A) and the photocurable component (B) and / or a compound having a sensitizing effect. Examples of such a photopolymerization initiator (P) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and the like. Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzyldimethyl ketal, Io such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone Compounds; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; and thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Compounds and the like.

  These compounds may be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, a compound that does not act as a photopolymerization initiator per se, but that can increase the ability of the photopolymerization initiator by using it in combination with the above-mentioned compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

  Examples of the radical polymerization initiator (T) that can be contained in the thermosetting resin composition include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, and alkyl peresters. In addition, radical initiators such as percarbonate and azobis are used. In particular, diacyl peroxide type or azobis type radical initiators are suitable, and for example, benzoyl peroxide, α, α'-azobis (isobutyronitrile), etc. are widely used.

As an additive that can be contained in the curable resin composition of the present invention, a thermal polymerization inhibitor, an adhesion assistant, an antifoaming agent, a surfactant, a plasticizer, and the like are used depending on the purpose of use of the composition. .
Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.
The adhesion assistant is added for the purpose of improving the adhesion to the substrate when the resulting composition is applied to the substrate. As the adhesion assistant, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is preferably used. Specific examples of such functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Examples of the antifoaming agent include silicone, fluorine, and acrylic compounds.
The surfactant is added for the purpose of facilitating application of the obtained composition and improving the flatness of the obtained coating film. Examples of the surfactant include silicone-based, fluorine-based, and acrylic compounds. Specifically, for example, BM-1000 [manufactured by BM Hemy Co., Ltd.]; Mega-Fac F142D, F172, F173, and F183 [Dainippon Ink Chemical Co., Ltd.]; Florard FC-135, FC-170C FLORARD FC-430 and FC-431 [manufactured by Sumitomo 3M Co.]; Surflon S-112, S-113, S-131, S-141 and S-145 [Asahi Glass Co., Ltd.] SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 [manufactured by Toray Silicone Co., Ltd.] and the like.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl.

  As light used for photocuring the curable composition of the present invention (meaning active energy rays including radiation), visible light, ultraviolet rays, electron beams, X-rays, γ rays, and the like are used. . Ultraviolet rays are preferable from the viewpoints of economy and efficiency. For ultraviolet irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an arc lamp, a xenon lamp, or the like is used.

  In addition, various solvents may be contained in the curable resin composition of the present invention as necessary. Examples of such solvents include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. Glycol ethers such as ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether; alkylene glycol such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1-acetate Monoalkyl ether acetates; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and 2-hydroxy Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate And esters such as ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in a combination of two or more.

  The curable resin composition of the present invention is a molded product according to the purpose. The molded body may be a product having a desired shape made of a cured product of the composition itself, or a coating film made of a cured product of the composition formed on a substrate.

For example, the component (A) and the component (B) added as necessary, a photopolymerization initiator (P) (in the case of a photocurable resin composition), a radical polymerization initiator (T) (thermosetting resin) In the case of a composition), various additives and the like are mixed, or dispersed or dissolved in an appropriate solvent to obtain a photocurable or thermosetting resin composition.
For example, a cured film can be formed on a substrate by applying and drying a liquid composition containing a solvent on the substrate, and then irradiating with light or heating. Alternatively, the photocurable or thermosetting composition is heated and melted as necessary, poured into a predetermined mold, irradiated with light, or heated to obtain a molded article having a desired shape.
A molded body (including a coating film) formed from the curable resin composition of the present invention has high hardness and is extremely excellent in heat resistance. Various coating agents, particularly high hardness and heat resistance, Used as a coating agent. Furthermore, it is used as a molding material for optical products, a coating agent for optical materials, an adhesive, etc. by utilizing its high refractive index and good adhesion to a substrate.

  Specifically, the curable resin composition of the present invention can be used for resist ink materials for color filters; materials for protective films for electronic components (for example, liquid crystal display elements including color filters, integrated circuit elements, solid-state imaging elements, etc. Material for forming protective film used); Material for forming interlayer insulating and / or planarizing film; Solder resist used for manufacturing printed wiring board; Photosensitive suitable for forming columnar spacer as substitute for bead spacer in liquid crystal display device Composition; materials for various optical components (lenses, LEDs, plastic films, substrates, optical discs, etc.); coating agents for forming protective films on the optical components; adhesives for optical components (adhesives for optical fibers, etc.); polarizing plates It is suitably used as a coating agent for production; a photosensitive resin composition raw material for hologram recording.

(Example)
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following, “part” means “part by weight”.

[Synthesis Example 1]
A reactor is charged with 406 g of bicyclohexyl-3,3′-diene and 1217 g of ethyl acetate as an alicyclic olefin compound represented by the above general formula (IV), and nitrogen is blown into the gas phase portion, and the reaction system While controlling the internal temperature to be 37.5 ° C., 457 g of an ethyl acetate solution containing 30% by weight of peracetic acid was added dropwise over about 3 hours. After completion of the dropwise addition, the mixture was aged at 40 ° C. for 1 hour to complete the reaction. The resulting crude liquid was washed with water at 30 ° C., and low boiling point compounds were removed at 70 ° C./20 mmHg (2660 Pa) to obtain 415 g of 3,4,3 ′, 4′-diepoxy-bicyclohexane, and the yield was 85%. Met.
The obtained compound was identified as 3,4,3 ′, 4′-diepoxy-bicyclohexane from the following analysis results.
Oxirane oxygen concentration: 14.7% by weight (epoxy equivalent 108.8)
¹ HNMR (solvent: CDCl?, Internal standard: TMS): and a peak derived from internal double bond (diene) in the vicinity 4.5~5ppm disappeared, a peak derived from the epoxy group was observed in the vicinity 2.9～3.1Ppm.

[Synthesis Example 2]
Reaction, ripening, washing with water, removal of low-boiling compounds in the same manner as in Synthesis Example 1 except that 243 g of bicyclohexyl-3,3′-diene and 730 g of ethyl acetate were added and 274 g of ethyl acetate solution containing 30% by weight of peracetic acid was added dropwise. And 270 g of 3,4,3 ′, 4′-diepoxy-bicyclohexane was obtained, and the yield was 93%.
As a result of the analysis, the oxirane oxygen concentration was 15.3% by weight (epoxy equivalent 231), and the measurement of ¹ HNMR was the same as in Synthesis Example 1.

[Example 1] Synthesis of tetrahydroxybicyclohexane diacrylic acid ester (A1) In a 1000 ml four-necked flask, 200 g of 3,4,3 ', 4'-diepoxy-bicyclohexane obtained in Synthesis Example 1 Triethylbenzylammonium bromide 450 mg, 2,6-diisobutylphenol 100 mg, acrylic acid 135.0 g, and propylene glycol monomethyl ether acetate (abbreviated as MMPG-AC) 500 g as a solvent were added and stirred. During the reaction, 25 ml of air was added. The mixture was heated to 105 to 115 ° C. while blowing at a rate of 1 minute. The acid value was measured over time, and heating and stirring were continued at the same temperature until the acid value became less than 2.0 mgKOH / g. It took 16 hours for the acid value to reach the target. After completion of the reaction, MMPG-AC was distilled off under reduced pressure, and the mixture was cooled to room temperature to obtain a light yellow transparent bicyclohexyl diacrylate (A1) as the component (A) represented by the formula (I).
The analysis results are shown below.
¹ HNMR (solvent: CDCl3, internal standard: TMS, unit ppm)
Epoxy group-derived peak 3.1-3.3ppm disappeared, acrylic acid ester-derived double bond peaks 5.8ppm (2H), 6.05ppm (2H), 6.4ppm (2H), and acrylic acid and epoxy group reacted A peak of 4.6 to 4.8 ppm (2H) of the produced methine proton was confirmed.
IR (KBr): 1,720 cm ^-1 (ester group: C = O), 1,620 cm ^-1 (vinyl group: C = C), 3,070 cm ^-1 (cycloalkyl: CH), 3500 cm ^-1 (hydroxyl group: OH)
From IR, a hydroxyl group produced by the reaction of an epoxy group and a carboxylic acid and a vinyl group derived from acrylic acid were confirmed.

[Example 2] Synthesis of tetrahydroxybicyclohexanediacrylate (A2) In a 1000 ml four-necked flask, 200 g of 3,4,3 ', 4'-diepoxy-bicyclohexane obtained in Synthesis Example 2; 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol and 141.8 g of acrylic acid, and 500 g of MMPG-AC as a solvent were stirred and heated to 90-100 ° C. while blowing air at 25 ml / min during the reaction. did. Thereafter, heating and stirring were continued at an internal temperature of 120 ° C., and the acid value was measured over time. It took 12 hours until the acid value became less than 2.0 mgKOH / g. After completion of the reaction, MMPG-AC was distilled off under reduced pressure and cooled to room temperature to obtain tetrahydroxybicyclohexane diacrylic acid ester (A2).

[Example 3] Preparation and performance evaluation of photocurable composition 1 part by weight of Irgacure 184 as a photopolymerization initiator was added to 39 parts by weight of tetrahydroxybicyclohexane diacrylate (A1) obtained in Example 1. Then, 60 parts by weight of MMPG-AC was further added and dissolved. The obtained mixture was formed on a glass substrate with a bar coater so that the film thickness after drying was 50 μm, and the physical properties of the paint film were measured.
(1) Photosensitivity: The coating film was cured by irradiating ultraviolet rays with a high-pressure mercury lamp. The amount of irradiation light was 300 mJ / cm ² .
(2) Heat resistance: The weight decrease starting temperature by thermogravimetric analysis (TG) (measured according to JIS 7120) of the cured coating film was 258 ° C.
(3) Optical characteristics: The refractive index of the cured film as measured by an Abbe refractometer was 1.605.
From these results, it can be seen that the epoxy acrylate resin of the present invention has high sensitivity, and the coating film obtained by curing has high heat resistance and refractive index.

[Examples 4 to 7]
As the component (A), the tetrahydroxybicyclohexane diacrylic acid ester (A1) obtained in Example 1 and the component (B) are added as necessary, and a photopolymerization initiator (P) is blended. A curable resin composition having the composition shown in (unit: parts by weight) was obtained.
In addition, abbreviations, such as (B) component in Table 1 and Table 2, are as follows.
Dipentaerythritol hexaacrylate (DPHA)
Pentaerythritol tetraacrylate (PETA)
Neopentyl glycol diacrylate (NPDA)
Bisphenol A / EO adduct diacrylate (BPA / EO / DA)
Ethylene glycol dimethacrylate (EGDMA)
The obtained coating film surface characteristics were measured according to the following test methods, and the results are shown in Table 1.
(1) Abrasion resistance (abrasion resistance): While lightly pressing the cured coating surface on the substrate with # 1000 steel wool, the steel wool was rubbed back and forth 30 times to rub the coating surface. The degree was judged according to the following criteria, and the wear resistance was evaluated. ○: No scratch, Δ: Scratch is maintained but gloss is maintained, ×: Countless scratches and gloss is lost.
(2) Adhesiveness (adhesiveness): evaluated by a cross-cut peel test in accordance with JIS Z1552.
(3) Pencil hardness: Pencil hardness was measured according to JIS K5400.

[Comparative Example 1]
Instead of using (A1) obtained in Example 1, the same as in Example 4 except that diacrylate (Osaka Organic Chemical Co., Ltd., V # 700) of bisphenol A / EO adduct was used. Samples were prepared under conditions and evaluated. The results are shown in Table 1.

[Comparative Example 2]
A sample was prepared and evaluated under the same conditions as in Example 5 except that neopentyl glycol diacrylate (manufactured by Kyoeisha, Light Acrylate NP-A) was used instead of using (A1) obtained in Example 1. Was done. The results are shown in Table 1.

[Examples 8 to 10]
As the component (A), the tetrahydroxybicyclohexanediacrylate (A2) obtained in Example 2 and the component (B) as necessary are added, heated and melted to form a liquid, and this is used as a radical initiator. Benzoyl oxide and manganese naphthenate were added and mixed to obtain a curable resin composition having the composition (unit: parts by weight) shown in Table 2. This was poured into a mold made of Teflon (registered trademark), heated in an oven at 100 ° C. for 30 minutes, and then at 170 ° C. for 1 hour to be thermally cured. Using the obtained molded body, the following items were evaluated. The results are shown in Table 2.
(1) Pencil hardness: measured according to JIS K5400.
(2) Tg (TMA): Measured according to JIS 7196.
(3) Visible light transmittance: Measurement was performed in the range of 800 to 380 nm with a spectrophotometer (U-2000, manufactured by Hitachi, Ltd.).

[Comparative Example 3]
Instead of using (A2) obtained in Example 2, a sample was prepared and evaluated under the same conditions as in Example 8 except that neopentyl glycol diacrylate (manufactured by Kyoeisha, Light Acrylate NP-A) was used. Was done. The results are shown in Table 2.

Claims (8)

Tetrahydroxybicyclohexane di (meth) acrylic acid esters represented by the following general formula (I).
_{CH 2 = CR-COO-X} -OCO-CR = CH 2 (I)
(In the formula, R represents a hydrogen atom or a methyl group, and two Rs may be the same or different. X represents a divalent bicyclohexylene group represented by the following formula (II).)
(In the formula, R1 to R18 are hydrogen atoms. For R19 to R22, R19 or R20 and R21 or R22 are a bonding group to the (meth) acryloyl group in formula (I), and the remaining R20 or R19 and R22 or R21 is a hydroxyl group.) The method for producing tetrahydroxybicyclohexanedi (meth) acrylic acid esters according to claim 1, wherein diepoxybicyclohexanes represented by the following general formula (III) are reacted with (meth) acrylic acid.
(In the formula, R1 to R18 are hydrogen atoms .)   A curable resin composition containing the tetrahydroxybicyclohexane di (meth) acrylic acid ester (referred to as component (A)) according to claim 1.   The curable resin composition according to claim 3, which is curable by light (including radiation) and / or heat.   Further, it contains a curable (meth) acrylate compound other than the component (A) (referred to as the component (B)), the component (A) 30 to 100% by weight, and the component (B) 70 to 0% by weight ((A). The sum of the component and the component (B) is 100% by weight.) The curable resin composition according to claim 3 or 4.   Furthermore, it contains a photopolymerization initiator (P), and the photopolymerization initiator (P) is contained at a ratio of 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the photocurable components in the composition. The curable resin composition according to any one of claims 3 to 5.   Furthermore, it contains a radical polymerization initiator (T), and the radical polymerization initiator (T) is a proportion of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of thermosetting components in the composition. The curable resin composition of any one of Claims 3-5 contained in.   The molded object formed by hardening | curing the curable resin composition of any one of Claims 3-7.