JP2012153794A - Resin composition, resin cured material, and resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve water resistance of a resin cured material obtained by curing a resin composition that contains a thiol compound.SOLUTION: The resin composition comprises: a compound having one of a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group, an allyl ether group, or an epoxy group; and a cyclic compound formed such that a thiol group is bonded thereto directly or through one or more carbon atom.

Description

  The present invention relates to a resin composition, a cured resin obtained by curing the resin composition, and a resin molded body using the cured resin, and more specifically, a resin composition containing a thiol compound having a thiol group (-SH). Further, the present invention relates to a cured resin product obtained by curing the resin, and a resin molded body using the cured resin product.

  In recent years, a cured resin containing a thiol compound has been used in a wide range of fields such as a coating material, a sealing material, an adhesive, and a resist agent (see, for example, Patent Document 1).

JP 2009-126974 A

  However, since most of the conventional thiol compounds are ester-based or ether-based compounds, a cured resin obtained by curing a resin composition containing such a thiol compound has an ester group or an ether group of the thiol compound. Therefore, it is difficult to use in applications where water resistance is required, for example, coating materials used outdoors.

  This invention is made | formed in view of the above-mentioned point, Comprising: It aims at improving the water resistance of the resin cured material which hardened | cured the resin composition containing a thiol compound.

  In order to achieve the above object, the present invention is configured as follows.

  That is, the resin composition of the present invention comprises a compound having any of a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group, an allyl ether group, or an epoxy group, and a thiol group directly or one or more carbon atoms. And a cyclic compound bonded thereto.

  This cyclic compound is a thiol compound in which a thiol group is bonded directly or via one or more carbon atoms to atoms contained in the ring structure, and among them, a thiol compound represented by the following formula (1) is preferable. .

[Wherein, A is a ring structure and may have a substituent other than the group in [], R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n R ₁ and R ₂ may be the same or different. n represents an integer of 0 to 4, m represents an integer of 2 to 6, and the groups in [] may be the same or different.
The ring structure of A in the above formula (1) is not particularly limited, but any one of a benzene ring, a cyclohexane ring, a dicyclopentadiene ring, and an isocyanurate ring is preferable.

  The thiol compound represented by the formula (1) is at least one compound selected from the group consisting of the following formulas (2), (3), (4), (5) and (6). preferable.

  The cured resin of the present invention is obtained by irradiating and / or heating an active energy ray to the resin composition of the present invention.

  Examples of active energy rays include ultraviolet rays, electron beams, and X-rays.

  The resin molded product of the present invention is coated with the cured resin product of the present invention.

  The cyclic compound having a thiol group contained in the resin composition of the present invention does not have an ester group or an ether group, and has a rigid and hydrophobic ring structure. The cured resin cured product eliminates the possibility of hydrolysis by an ester group or an ether group and makes it difficult for water to enter a molecular network having high density and hydrophobicity, thereby further improving water resistance.

  Hereinafter, the resin composition, the cured resin, and the resin molded body of the present invention will be described in detail.

  The resin composition of the present invention comprises a compound having any one of a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group, an allyl ether group, or an epoxy group (hereinafter also referred to as “compound having a vinyl group”), thiol And cyclic compounds in which the groups are bonded directly or via one or more carbon atoms.

  This cyclic compound is a thiol compound in which a thiol group is bonded to an atom contained in the ring structure directly or via one or more carbon atoms. As this thiol compound, a thiol compound represented by the following formula (1) is particularly effective because it is effective in improving water resistance.

[Wherein, A is a ring structure and may have a substituent other than the group in [], R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n R ₁ and R ₂ may be the same or different. n represents an integer of 0 to 4, m represents an integer of 2 to 6, and the groups in [] may be the same or different.
Although there is no restriction | limiting in particular about the ring structure of A in the said Formula (1), It consists of a saturated carbon-carbon bond, such as cyclopentane, cyclobutane, cyclopropane, cyclopentane, a cyclohexane, as a commercially available industrial material. Ring structure and a ring structure in combination thereof, a ring composed of carbon-carbon bonds containing unsaturation such as cyclopropene, cyclobutene, cyclopentene, cycloheptene, cyclohexene, cyclohexadiene, cyclopentadiene, dicyclopentadiene, benzene, naphthalene, anthracene Structures or ring structures in which benzene rings such as diphenyl and terphenyl are linked, piperidine, piperazine, morpholine, pyrrolidine, melamine, isocyanurate, and so-called heterocyclic structures in which atoms other than carbon are bonded, indene, benzo Orchids, etc. ring structure a benzene ring and a heterocyclic ring is bonded such as indole and the like.

  Of these, a ring structure of any one of a benzene ring, a cyclohexane ring, a dicyclopentadiene ring, and an isocyanurate ring is preferable because of its high effect of improving water resistance.

  In the thiol compound represented by the above formula (1), the group in the above [] including the thiol group is bonded to any carbon or nitrogen constituting the ring A.

  In the thiol compound, ring A may have other substituents other than the thiol group, for example, an alkyl group, an alkenyl group, a carbonyl group, a carboxyalkyl group, a nitrile group, an acrylic group, or a phosphoryl group. Good.

  As an example of a suitable thing of the said thiol compound contained in the resin composition of this invention, the ring structure of said A is a dicyclopentadiene ring, n is 0, m is 2, Two thiols in the dicyclopentadiene ring An octahydro-4,7-methano-1H-indene-1,5 dithiol (commonly referred to as dicyclopentadiene dithiol, hereinafter also referred to as “DPT”) of the following formula (2) in which a group is directly bonded.

Another example of a suitable thiol compound is an isocyanurate ring in which the ring structure of A is an isocyanurate ring, R ₁ and R ₂ are hydrogen atoms, n is 3 and m is 3. 2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3-mercaptopropyl) of the following formula (3) in which a thiol group is bonded to each nitrogen through a carbon atom -1,3,5-triazine (commonly called trithiol isocyanurate, hereinafter also referred to as “TTIC”).

As still another example of a suitable thiol compound, a cyclohexane ring in which the ring structure of A is a cyclohexane ring, R ₁ and R ₂ are hydrogen atoms, n is 2 and m is 3 Examples include 1,2,4-cyclohexanetriethanethiol of the following formula (4) in which three thiol groups are bonded via carbon atoms (commonly referred to as “TTCH” hereinafter).

As another example of a suitable thiol compound, the ring structure of A is a cyclohexane ring, R ₁ and R ₂ are hydrogen atoms, n is 1 and m is 2, 1,4-cyclohexanedimethanethiol (commonly referred to as bismercaptomethylcyclohexane, hereinafter also referred to as “DMCH”) represented by the following formula (5) in which two thiol groups are bonded via a carbon atom.

As still another example of a suitable thiol compound, a ring structure of A is a benzene ring, R ₁ and R ₂ are hydrogen atoms, n is 1 and m is 2, Examples include 1,3-benzenedimethanethiol (commonly referred to as m-xylenyldithiol (hereinafter also referred to as “MXDT”) of the following formula (6) in which two thiol groups are bonded via a carbon atom.

  The thiol compound can be produced by a general alicyclic thiol synthesis method.

  For example, J. et al. Org. Chem. 1969, 34, 3112, etc., addition reaction with hydrogen sulfide to olefin compounds such as cyclohexene, or J. Org. Amer. Chem. Soc. 1946, 68, 2103, etc., reaction via an isothioronium salt, or dicyclopentadiene described in US Pat. No. 3,632,654 or JP-A-2005-35968 was reacted with thioacetic acid Bis (thioacetoxy) tricyclo [5.2.1.02,6] decane can be used as an intermediate, and can be produced by a method of alkali hydrolysis.

  In addition to the cyclohexene and dicyclopentadiene used in the above production, the raw materials used include cyclopropene, methylcyclopropene, cyclopropene carboxylic acid, cyclobutene, methylcyclobutene, methylmethylenecyclobutene, cyclopentene, methyl, including isomers. Cyclopentene, cycloheptene, methylcycloheptene, ethylcyclohexene, vinylcyclohexene, methylcyclohexene, cyclohexadiene, methylcyclopentadiene, n-butylcyclopentadiene, n-propylcyclopentadiene, butylmethylcyclopentadiene, divinylcyclohexane, trivinylcyclohexane, etc. Is mentioned.

  In the case of an aromatic thiol compound, divinylbenzene, trivinylbenzene, divinylethylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, diallylbenzene, triallylbenzene and the like containing isomers can be mentioned.

  The isocyanuric acid allyl ester used for the production of the thiol compound includes isocyanuric acid (N-propyl) diallyl ester, isocyanuric acid (N-ethyl) diallyl ester, isocyanuric acid (N-ethyl) allyl vinyl ester, Isocyanuric acid (tri) homoallyl ester, isocyanuric acid triacryloyl ester, isocyanuric acid monovinyl ester, isocyanuric acid divinyl ester, isocyanuric acid monomethyl monovinyl ester, isocyanuric acid dimethyl monovinyl ester, isocyanuric acid monoallyl ester, isocyanuric acid diallyl ester, isocyanuric acid And monomethyl monoallyl ester.

  Examples of the thiolic acid include thiol formic acid, thiol acetic acid, thiol propionic acid, and thiol butyric acid.

  As a suitable example of the thiol compound contained in the resin composition of the present invention, any structure of the benzene ring, cyclohexane ring, dicyclopentadiene ring and isocyanurate ring in the molecule and the thiol group are directly bonded, or Those bonded via one or more carbon atoms are preferred.

  The thiol compound contained in the resin composition of this invention may be used individually by 1 type, and may use 2 or more types together. Further, these thiol compounds and other compounds such as acid anhydrides can be used in combination.

  As the compound having any of a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group, an allyl ether group, or an epoxy group contained in the resin composition of the present invention, a known compound can be used without particular limitation.

  Examples of the compound having a vinyl group contained in the resin composition of the present invention include vinyl silane, ethylene, propylene and the like.

  Examples of the compound having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, Examples thereof include tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, and pentaerythritol type tetravinyl ether.

  Examples of the compound having an acrylate group include lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate, phenoxyethyl. Acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, nonylphenoxyethyl acrylate, nonylphenoxytetraethylene glycol acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, butoxyethyl acrylate, butoxytriethylene glycol Acrylate, 2-ethylhexyl polyethylene glycol acrylate, nonylphenyl polypropylene glycol acrylate, methoxydipropylene glycol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, etc. .

  Examples of the compound having a methacrylate group include lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl. Methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, nonylphenoxyethyl methacrylate, nonylphenoxytetraethylene glycol methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, butoxyethyl methacrylate , Butoxytriethylene glycol methacrylate, 2-ethylhexyl polyethylene glycol methacrylate, nonylphenyl polypropylene glycol methacrylate, methoxydipropylene glycol methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycerol methacrylate, polyethylene glycol methacrylate, Examples thereof include polypropylene glycol methacrylate.

  Examples of the compound having an allyl ether group include trimethylolpropane diallyl ether and pentaerythritol triallyl ether.

  Compounds having an epoxy group are obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols and polyhydric alcohols, for example, bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type. Glycidyl ether type epoxy resins such as bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolak type, phenol novolak type, orthocresol novolak type, tris (hydroxyphenyl) methane type, tetraphenylolethane type And so on.

  The above-mentioned compounds having any of vinyl groups, vinyl ether groups, acrylate groups, methacrylate groups, allyl ether groups, or epoxy groups (compounds having vinyl groups, etc.) are used alone or in admixture of two or more. You can also.

  The compounding ratio of the thiol compound and the compound having a vinyl group is, for example, when the compound having a vinyl group or the like is a compound having an epoxy group, the number of functional groups of the compound having an epoxy group and the thiol compound. Are blended so as to have the same level. The SH group is preferably 70 to 120 with respect to the epoxy group 100, and more preferably the SH group is 80 to 110 with respect to the epoxy group 100. When a curing agent such as an acid anhydride is used in combination, the epoxy group consumed by the curing agent is subtracted, and the remaining epoxy group 100 is preferably an SH group of 70 to 120, more preferably an SH group of 80 to 110. It is.

  Further, when the compound having a vinyl group or the like is, for example, a compound having a vinyl group, the compound having the vinyl group and the thiol compound are blended so that the number of functional groups is approximately the same. The SH group is preferably 70 to 120 with respect to the vinyl group 100, and more preferably the SH group is 80 to 110 with respect to the vinyl group 100.

  In the resin composition of the present invention, other additives such as a curing accelerator, a coupling agent, a colorant, a release agent, a flame retardant and the like can be blended as necessary.

  Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited to these examples.

(Examples 1 to 9, Comparative Examples 1 and 2)
The components shown in Table 1 below were weighed and blended in the proportions (parts by mass) shown in the same table, and dispersed for 5 minutes with an ultrasonic cleaning device to obtain a resin composition.

  As an epoxy compound shown in Table 1, “Celoxide 2021P (product name)”, which is 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexenecarboxylate manufactured by Daicel Chemical Industries, Ltd. (epoxy equivalent 130 ( g / eq)), and “Ricacid MH-700 (product name)”, which is methylhexahydrophthalic anhydride (MeHHPA) manufactured by Shin Nippon Rika Co., Ltd., was used as the acid anhydride. Moreover, the product name PEMP (SH value 25.4%) which is pentaerythritol-tetrakis-3-mercaptopropionate manufactured by SC Organic Chemical Co., Ltd. was used as the thiol compound of the conventional example.

Moreover, each polythiol compound (DPT, TTIC, TTCH, DMCH, MXDT) shown in Table 1 was synthesized as follows. Each compound synthesized was identified by comparing the existence of the SH group stretching absorption wavelength (2550-2600 cm ^-1 ) with an infrared spectrophotometer (Shimadzu FT-4200) and the sulfur concentration calculated from the SH value with the theoretical value. It was done by doing.

[Synthesis of DPT]
For example, DPT was synthesized as follows.

  Specifically, 13.2 g (0.1 mol) of dicyclopentadiene (Wako Pure Chemical Reagent) and 0.23 g (1.0 mmol) of benzoyl peroxide (Wako Pure Chemical Reagent) were charged into a 100 ml reactor under a nitrogen atmosphere. The internal temperature was adjusted to 16 ° C. with stirring. Thereto, 18.3 g (0.24 mol) of thioacetic acid (Wako Pure Chemical Reagent) was dropped over 1 hour while keeping the internal temperature at 30 ° C. or lower, and stirring was continued at around 40 ° C. for 1 hour. After completion of the reaction, excess thioacetic acid was removed by distillation, and 16.8 g (0.4 mol) of sodium hydroxide (Wako Pure Chemical Reagent), 16.8 g of water and ethylene glycol (Wako Pure Chemical Industries, Ltd.) were obtained. 16.9 g of a chemical reagent) was added and stirring was continued at 80 ° C. for 12 hours. After completion of the reaction, toluene (Wako Pure Chemical Reagent) was added, and hydrochloric acid water was added until the reaction solution reached pH 1, followed by liquid separation extraction and water washing to obtain a pale yellow solution.

  Subsequently, after concentrating the reaction treatment liquid, distillation under reduced pressure (column top temperature 87-92 ° C./vacuum degree 0.1 kPa) was performed to obtain 15.0 g of a pale yellow transparent liquid. The SH value of DPT calculated as described later was 34.5%.

[Synthesis of TTIC]
TTIC was synthesized, for example, as follows.

  That is, 24.9 g (0.1 mol) of triallyl isocyanurate (Nippon Kasei Tyco) and 0.23 g (1.0 mmol) of benzoyl peroxide (Wako Pure Chemical Reagent) were placed in a 100 ml reactor under a nitrogen atmosphere. The internal temperature was adjusted to 16 ° C. while charging and stirring. Thereto, 27.4 g (0.36 mol) of thioacetic acid (Wako Pure Chemical Reagent) was added dropwise over 1 hour while maintaining the internal temperature at 30 ° C. or lower, and stirring was continued at around 40 ° C. for 1 hour. After completion of the reaction, excess thioacetic acid was distilled off, and 25.2 g (0.6 mol) of sodium hydroxide (Wako Pure Chemical Reagent), 25.2 g of water and ethylene glycol (Wako Pure Chemical Industries, Ltd.) were added to the resulting concentrate. 25.2 g of a chemical reagent) was added, and stirring was continued with heating at 80 ° C. for 12 hours. After completion of the reaction, toluene (Wako Pure Chemical Reagent) was added, and hydrochloric acid water was added until the reaction solution reached pH 1, followed by liquid separation extraction and water washing to obtain a pale yellow solution.

  Next, the reaction treatment liquid was concentrated to obtain 31.6 g of a pale yellow transparent liquid. The SH value of TTIC was 27.5%.

[Synthesis of TTCH]
TTCH was synthesized, for example, as follows.

  That is, under a nitrogen atmosphere, a 100 ml reactor was charged with 16.2 g (0.1 mol) of trivinylcyclohexane (Tokyo Kasei Reagent) and 0.23 g (1.0 mmol) of benzoyl peroxide (Wako Pure Chemical Reagent) and stirred. The internal temperature was set to 16 ° C. Thereto, 27.4 g (0.36 mol) of thioacetic acid (Wako Pure Chemical Reagent) was added dropwise over 1 hour while maintaining the internal temperature at 30 ° C. or lower, and stirring was continued at around 40 ° C. for 1 hour. After completion of the reaction, excess thioacetic acid was distilled off, and 25.2 g (0.6 mol) of sodium hydroxide (Wako Pure Chemical Reagent), 25.2 g of water and ethylene glycol (Wako Pure Chemical Industries, Ltd.) were added to the resulting concentrate. 25.2 g of a chemical reagent) was added, and stirring was continued with heating at 80 ° C. for 12 hours. After completion of the reaction, toluene (Wako Pure Chemical Reagent) was added, and hydrochloric acid water was added until the reaction solution reached pH 1, followed by liquid separation extraction and water washing to obtain a pale yellow solution.

  Next, the reaction treatment liquid was concentrated to obtain 23.8 g of a pale yellow transparent liquid. The SH value of TTCH was 35.8%.

[Synthesis of DMCH]
DMCH, J. Chem. Soc. It was synthesized by the following method described in 1951,123.

  Specifically, 13.6 g (0.1 mol) of cyclohexanedivinyl (Wako Pure Chemical Reagent) and 0.23 g (1.0 mmol) of benzoyl peroxide (Wako Pure Chemical Reagent) were charged into a 100 ml reactor under a nitrogen atmosphere and stirred. The internal temperature was set to 16 ° C. Thereto, 18.3 g (0.24 mol) of thioacetic acid (Wako Pure Chemical Reagent) was dropped over 1 hour while keeping the internal temperature at 30 ° C. or lower, and stirring was continued at around 40 ° C. for 1 hour. After completion of the reaction, excess thioacetic acid was removed by distillation, and 16.8 g (0.4 mol) of sodium hydroxide (Wako Pure Chemical Reagent), 16.8 g of water and ethylene glycol (Wako Pure Chemical Industries, Ltd.) were obtained. 16.9 g of a chemical reagent) was added and stirring was continued at 80 ° C. for 12 hours. After completion of the reaction, toluene (Wako Pure Chemical Reagent) was added, and hydrochloric acid water was added until the reaction solution reached pH 1, followed by liquid separation extraction and water washing to obtain a pale yellow solution.

  Next, the reaction treatment liquid was concentrated to obtain 15.1 g of a pale yellow transparent liquid. The SH value of DMCH was 36.0%.

[Synthesis of MXDT]
MXDT was manufactured as follows, for example.

  Specifically, 13.0 g (0.1 mol) of divinylbenzene (Wako Pure Chemical Reagent) and 0.23 g (1.0 mmol) of benzoyl peroxide (Wako Pure Chemical Reagent) were charged into a 100 ml reactor in a nitrogen atmosphere and stirred. The internal temperature was set to 16 ° C. Thereto, 18.3 g (0.24 mol) of thioacetic acid (Wako Pure Chemical Reagent) was dropped over 1 hour while keeping the internal temperature at 30 ° C. or lower, and stirring was continued at around 40 ° C. for 1 hour. After completion of the reaction, excess thioacetic acid was removed by distillation, and 16.8 g (0.4 mol) of sodium hydroxide (Wako Pure Chemical Reagent), 16.8 g of water and ethylene glycol (Wako Pure Chemical Industries, Ltd.) were obtained. 16.9 g of a chemical reagent) was added and stirring was continued at 80 ° C. for 12 hours. After completion of the reaction, recrystallization was performed with ethanol to obtain 13.0 g of a white solid. The SH value of MXDT was 38.8%.

  The physical property values of the five types of polythiol compounds (DPT, TTIC, TTCH, DMCH, MXDT) are shown in Table 2 below. Table 2 also shows the sulfur concentration calculated from the SH value and its theoretical value.

  All of the above five types of polythiol compounds are colorless and transparent liquids except for MXDT. The sulfur concentration in Table 2 is the sulfur atomic weight concentration (%) with respect to the molecular weight.

  In addition, in the said Table 1 in which the mixture ratio of each component is shown, the ratio (epoxy group / SH group) of the epoxy group and SH group which were calculated | required as follows is shown collectively.

  The epoxy group was calculated from the epoxy equivalent, and the SH group was calculated from the SH value.

  The epoxy equivalent (sample mass containing 1 mol of epoxy group) is 1 mol / L perchloric acid / acetic acid solution (N / 10) after dissolving the sample in methyl ethyl ketone and adding glacial acetic acid and cetyltrimethylammonium bromide according to JISK-7236. ). In Examples 6 to 9 and Comparative Example 2 in which an acid anhydride is used in combination, the remaining amount excluding the amount consumed by the acid anhydride is used.

  The SH value (weight concentration of SH group) was calculated in terms of SH mass% by iodine oxidation titration. Iodine titration was conducted using Hiranuma Sangyo Co., Ltd. automatic titrator COM-2500, indicator electrode PT-301, and reference electrode RE-201, and the reaction product was dissolved in a methanol / chloroform (1: 1) solution to give 0.05 mol. The SH mass% was determined by potentiometric titration with the / L iodine solution as the titrant and the inflection point as the end point.

  Each component shown in Table 1 was blended, and the resin composition dispersed for 5 minutes with an ultrasonic cleaning device was poured into a mold of φ19 mm × 1 mm, and baked under the conditions of 130 ° C. × 2 hr and further 170 ° C. × 2 hr. Thus, a molded product of a cured resin was obtained.

  The water resistance of the obtained cured resin was evaluated as follows.

  That is, 4 pieces of the above-mentioned molded bodies were put into a flask, sufficiently immersed water was added, and subjected to a water resistance test at 24 at reflux under 1 atm. The mixture was allowed to cool to room temperature as appropriate, taken out, wiped with moisture on the surface, weighed, and the water absorption was calculated.

  As for the water resistance, there is no change in the appearance (◎), there is a change in the surface (○), partly dissolved (△), and it is dissolved so as not to retain the original shape (×). Evaluation was performed in four stages.

  Furthermore, in order to evaluate the refractive index, the resin composition was applied to lead glass so that the final thickness was 1 mm. The coated material was heated under the conditions of 130 ° C. × 2 hr and further 170 ° C. × 2 hr to obtain a sample for refractive index measurement. The refractive index was measured at 25 ° C. using an Abbe refractometer (1T manufactured by Atago Co., Ltd.).

  The evaluation results of water resistance (appearance and water absorption) and refractive index are shown in Table 1 above.

  As shown in Table 1, in Comparative Example 1 in which PMP, which is a conventional thiol compound, was blended without blending an acid anhydride, the appearance was dissolved so as not to remain the prototype (x), and the water absorption was measured. Was impossible. On the other hand, in Examples 1 to 5 in which DPT, TTIC, TTCH, DMCH, and MXDT were blended without blending acid anhydrides, there was no change in appearance (◎), or that surface was seen ( (Circle)) and a water absorption rate are 5.9%-13%, and it turns out that water resistance is improving significantly.

  Further, in Comparative Example 2 in which acid anhydride and PEMP which is a conventional thiol compound were blended, the appearance was partially dissolved (Δ), whereas acid anhydride and DPT, TTIC, TTCH, In Examples 6 to 9 in which DMCH and MXDT were respectively blended, there was no change in appearance (）) or the appearance of that on the surface (○). Regarding the water absorption rate, Comparative Example 2 is 16%, while Examples 6 to 9 are 3.7% to 5.6%, which shows that the water resistance is greatly improved. .

  In addition, it can be seen that most of the examples are improved as compared to the comparative example.

(Example 10, Comparative Examples 3 and 4)
Next, the following coverings were prepared as resin moldings, and water resistance and pencil hardness were evaluated.

  That is, each component shown in Table 3 below was weighed and blended in the proportions (parts by mass) shown in the same table, and dispersed for 5 minutes with an ultrasonic cleaning device to obtain a resin composition.

  As TMVS in Table 3, trimethoxyvinylsilane manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  The product name EGMP-4 (SH value 17.0%) which is tetraethylene glycol bis (3-mercaptopropionate) manufactured by SC Organic Chemical Industry Co., Ltd. was used as the thiol compound of the conventional example.

  As the methyl silicate, “MS-51” which is a tetramethyl silicate condensate manufactured by Fuso Chemical Industry Co., Ltd. was used.

  As a photoacid generator, “IRGACURE 184 (product name)”, which is 1-hydroxy-cyclohexyl-phenyl ketone manufactured by BASF, was used.

  MXDT, which is a thiol compound in Table 3, was produced by the synthesis method described above.

The coated body as a resin molded body is placed on “A-4100” manufactured by Toyobo Co., Ltd., which is a PET film having a thickness of 125 μm, and the resin composition shown in Table 3 is placed in a bar so that the final thickness is 4 to 5 μm. The coating was applied by a coater, further dried at 30 ° C. for 5 minutes, UV-irradiated under the condition of 2000 mJ / cm ² , and then heat-treated at 120 ° C. for 20 minutes.

  The pencil hardness of the coated body was measured according to JIS-K-5600-5-4.

  Further, the prepared covering was held in a constant temperature and high humidity chamber at 80 ° C. × 90% for 500 hours, and then judged by the rate of change in glossiness of the surface before and after holding. Glossiness measured 20 degree specular luminous intensity (JISK5600-4-7) with a haze meter (model GM-3D) made by Nippon Denshoku Industries Co., Ltd.

  The measurement results of water resistance and pencil hardness are shown in Table 3 above.

  As shown in Table 3, in Comparative Examples 3 and 4 in which PEMP and EGMP-4, which are conventional thiol compounds, were blended, respectively, the water resistance (gloss retention) was 90% and 70%. In Example 10 where MXDT was blended, it was 95%, indicating that the water resistance was improved. It can also be seen that the pencil hardness is equal to or higher than that of the conventional example.

  As described above, the thiol compound contained in the resin composition of each example does not have an ester group or an ether group, and has a rigid and hydrophobic ring structure unlike the thiol compound of the conventional example. Therefore, the cured resin obtained by curing this resin composition has no possibility of hydrolysis due to ester groups or ether groups, and water does not easily enter a molecular network having high density and hydrophobicity. As a result, the water resistance is further improved. Accordingly, it can be widely used for applications requiring water resistance.

  In the above-described embodiments, the resin composition of the present invention has been described as being applied to a covering as a resin molded body. However, the resin composition of the present invention is not limited to a covering, that is, a coating material, but a sealing material, an adhesive, an electrical insulating material, It can be applied to other uses such as a protective film and a resist agent.

Claims (6)

  A resin comprising a compound having any of a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group, an allyl ether group, or an epoxy group, and a cyclic compound in which a thiol group is bonded directly or via one or more carbon atoms. Composition. The resin composition according to claim 1, wherein the cyclic compound is a thiol compound represented by the following formula (1).

[Wherein, A is a ring structure and may have a substituent other than the group in [], R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n R ₁ and R ₂ may be the same or different. n represents an integer of 0 to 4, m represents an integer of 2 to 6, and the groups in [] may be the same or different.   The resin composition according to claim 2, wherein A is a ring structure of any one of a benzene ring, a cyclohexane ring, a dicyclopentadiene ring, and an isocyanurate ring. The resin composition according to claim 3, wherein the thiol compound is at least one compound selected from the group consisting of the following formulas (2), (3), (4), (5) and (6). .

  A cured resin obtained by irradiating and / or heating an active energy ray to the resin composition according to any one of claims 1 to 4.   A resin molded body coated with the cured resin according to claim 5.