TWI608029B - Resin hardener and one-component epoxy resin composition - Google Patents

Description

Resin hardener and one-component epoxy resin composition

The present invention relates to a resin curing agent which is excellent in low-temperature rapid hardening property, and a liquid epoxy resin composition which is excellent in low-temperature rapid hardenability and excellent in storage safety (storage stability).

A composition containing a thiol group (alias: sulfonyl group or fluorenyl group, -SH) as a curing agent for an epoxy resin is excellent in low-temperature hardenability, and various studies have been conducted. For example, Patent Document 1 discloses a resin composition comprising a thiol group-containing polyether polymer having a polyether moiety in the main chain and three or more terminals at the terminal. The hydroxyl group of the hydroxyl group is obtained by reacting a halogen-terminated polyether polymer obtained by addition of an epihalohydrin with a hydrogen sulfide base and/or a polysulfide base in a decylamine.

Patent Document 1 discloses that an epoxy resin composition containing a thiol group-containing polyether polymer having a structural unit represented by -CH ₂ CH(OH)CH ₂ -SH at the end exhibits good curability. However, if the thiol group-containing polyether polymer is used as a curing agent for an epoxy resin, the pot life is shortened, and when the epoxy resin and the thiol group-containing polyether polymer are mixed, the curing starts, so that it is used. Conditions are limited. Further, Patent Document 1 does not describe the storage stability of the epoxy resin composition. Therefore, when the epoxy resin composition containing the thiol group-containing polyether polymer is stored for a long period of time, it starts during curing. Hardening. Thus, although a liquid epoxy resin composition using a thiol compound as a curing agent is known, the storage stability of the composition is not sufficient, and the advantage of using a thiol compound as a curing agent is sufficiently utilized. A low-temperature, fast-curing one-component epoxy resin composition was not found.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-269203

An object of the present invention is to provide a resin hardener having excellent low-temperature rapid hardenability, and a one-pack epoxy resin composition containing the hardener which has both low-temperature rapid hardenability and storage stability.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be attained by using a specific compound as a resin curing agent. That is, the present invention is as follows.

[1] A resin curing agent which is composed of a compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000.

[2] A resin curing agent which is a compound having a molecular weight of 100 to 2,000 having one or more hydroxyl groups and two or more thiol groups in the molecule (wherein -CH ₂ CH(OH)CH is present at the terminal ₂ , except for the compound of the structural unit represented by SH.

[3] The resin curing agent according to [1] or [2] above, which is a curing agent for a one-component epoxy resin composition.

[4] The resin curing agent according to any one of the above [1], wherein a compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is used. Further, one or more partial esters of two or more thiol-based aliphatic monocarboxylic acids having 2 to 8 carbon atoms are bonded to trimethylolpropane, neopentyl alcohol or dipentaerythritol.

[5] The resin curing agent according to any one of the above [1], which has one or more hydroxyl groups and two or more thiol groups in the molecule, and has a molecular weight of from 100 to 2,000. a compound selected from the group consisting of trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane double (4-mercaptobutyrate), pentaerythritol bis(mercaptoacetate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol bis(3-mercaptobutyrate), new Pentaerythritol bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyric acid) Ester), neopentyl alcohol tris(4-mercaptobutyrate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(3-mercaptopropionate), dipentaerythritol Bis(3-mercaptobutyrate), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol tris(mercaptoacetate), dipentaerythritol tris(3-mercaptopropionic acid) Ester), dipentaerythritol tris(3-mercaptobutyrate), dipentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(thioglycolic acid) ), Two new pentaerythritol tetrakis (3-mercaptopropionic acid Ester), dipentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol penta(mercaptoacetate), dipentaerythritol At least one of alcohol penta(3-mercaptopropionate), dipentaerythritol penta(3-mercaptobutyrate), and dipentaerythritol penta(4-mercaptobutyrate).

[6] The resin curing agent according to any one of the above [1], which has one or more hydroxyl groups and two or more thiol groups in the molecule, and has a molecular weight of from 100 to 2,000. a compound selected from the group consisting of trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), and trimethylolpropane double At least one of (4-mercaptobutyrate).

[7] The resin curing agent according to any one of the above [1], which has one or more hydroxyl groups and two or more thiol groups in the molecule, and has a molecular weight of from 100 to 2,000. The compound is 2-ethyl-2-(hydroxymethyl)propane-1,3-dioleyl bis(3-mercaptopropionate).

[8] A one-component epoxy resin composition comprising: a component (1) having a hydroxyl group having two or more hydroxyl groups and two or more thiol groups in the molecule, and a compound having a molecular weight of from 100 to 2,000. (2) An epoxy resin having an average of two or more epoxy groups per molecule and a latent curing accelerator of the component (3).

[9] The liquid epoxy resin composition according to the above [8], wherein the content of the component (3) is 0.1 to 100 parts by weight based on 100 parts by weight of the component (2).

[10] A liquid epoxy resin composition as described in [8] or [9] above The component (1) is a partial ester of a mercapto aliphatic monocarboxylic acid having 2 or more carbon atoms of 2 to 8 bonded to trimethylolpropane, neopentyl alcohol or dipentaerythritol. More than one species.

[11] The liquid epoxy resin composition according to the above [8] or [9] wherein the component (1) is selected from the group consisting of trimethylolpropane bis(mercaptoacetate) and trimethylolpropane. Bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol bis(mercaptoacetate), Pentaerythritol bis(3-mercaptopropionate), pentaerythritol bis(3-mercaptobutyrate), pentaerythritol bis(4-mercaptobutyrate), pentaerythritol III (mercapto B) Acid ester), neopentyl alcohol tris(3-mercaptopropionate), neopentyl alcohol tris(3-mercaptobutyrate), pentaerythritol tris(4-mercaptobutyrate), dipentaerythritol Alcohol bis(mercaptoacetate), dipentaerythritol bis(3-mercaptopropionate), dipentaerythritol bis(3-mercaptobutyrate), dipentaerythritol bis(4-mercaptobutyrate) Acid ester), dipentaerythritol tris(mercaptoacetate), dipentaerythritol tris(3-mercaptopropionate), dipentaerythritol tris(3-mercaptobutyrate), dioxane Tetrahydrin tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercapto) Butyrate Dipentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol penta(mercaptoacetate), dipentaerythritol penta(3-mercaptopropionate), dipentaerythritol five ( At least one of 3-mercaptobutyrate) and dipentaerythritol penta(4-mercaptobutyrate).

[12] The liquid epoxy resin composition according to the above [8] or [9] wherein the component (1) is selected from the group consisting of trimethylolpropane bis(mercaptoacetate) and trimethylolpropane. Bis(3-mercaptopropionate), trimethylolpropane double (3- At least one of decylbutyrate), trimethylolpropane bis(4-mercaptobutyrate).

[13] A liquid epoxy resin composition according to the above [8] or [9] wherein the component (1) is 2-ethyl-2-(hydroxymethyl)propane-1,3- Dioleyl bis(3-mercaptopropionate).

[14] The liquid epoxy resin composition according to any one of the above [8] to [13] further comprising the component (4) selected from the group consisting of a borate compound, a titanate compound, and an aluminate. One or more of an ester compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto organic acid.

[15] The liquid epoxy resin composition according to the above [14], wherein the content of the component (4) is 0.001 to 50 parts by weight based on 100 parts by weight of the component (2).

[16] The liquid epoxy resin composition according to any one of [8] to [15] further comprising the component (5) having two or more thiol groups in the molecule, and having no a compound of a hydroxyl group.

[17] The liquid epoxy resin composition according to the above [16], wherein the component (5) is ethylene glycol, trimethylolpropane, neopentyl alcohol or dipentaerythritol and carbon number One or more of the complete esters of the fluorenyl aliphatic monocarboxylic acid of 2 to 8.

[18] The liquid epoxy resin composition according to the above [16], wherein the component (5) is selected from the group consisting of ethylene glycol bis(mercaptoacetate) and ethylene glycol bis(3-mercaptopropyl acrylate). Acid ester), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3- Mercaptopropionate, trimethylolpropane tris(3-mercaptobutyric acid Ester), trimethylolpropane tris(4-mercaptobutyrate), neopentyltetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), neopentyltetraol (3) -mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(3-mercaptopropionate), two At least one of neopentyl alcohol hexa(3-mercaptobutyrate) and dipentaerythritol hexa(4-mercaptobutyrate).

[19] The liquid epoxy resin composition according to the above [16], wherein the component (5) is selected from the group consisting of trimethylolpropane tris(mercaptoacetate) and trimethylolpropane tris(3-) At least one of mercaptopropionate, trimethylolpropane tris(3-mercaptobutyrate), and trimethylolpropane tris(4-mercaptobutyrate).

[20] The liquid epoxy resin composition according to the above [16], wherein the component (5) is trimethylolpropane tris(3-mercaptopropionate).

[21] The liquid epoxy resin composition according to any one of the above [16] to [20], wherein the component (1) is based on the total weight of the component (1) and the component (5). The weight ratio (weight of the component (1) / total weight of the component (1) and the component (5) is 0.001 to 0.8.

[22] The liquid epoxy resin composition according to any one of the above [16] to [20], wherein the component (1) is based on the total weight of the component (1) and the component (5). The weight ratio (weight of the component (1) / total weight of the component (1) and the component (5) is 0.03 to 0.2.

[23] The liquid epoxy resin composition according to any one of the above [16] to [20], wherein the component (1) is based on the total weight of the component (1) and the component (5). The weight ratio (weight of the component (1) / total weight of the component (1) and the component (5) is 0.1 to 0.2.

[24] A liquid epoxy resin composition according to any one of the above [8], wherein the component (1) is equivalent to the equivalent of the epoxy group contained in the component (2). The equivalent ratio of the thiol group to be contained (the equivalent of the thiol group contained in the component (1) / the equivalent of the epoxy group contained in the component (2)) is 0.2 to 2.0.

[25] The liquid epoxy resin composition according to any one of [16] to [23] wherein the component (1) and the equivalent of the epoxy group contained in the component (2) are The total equivalent ratio of the thiol groups contained in the component (5) (the equivalent of the thiol group contained in the component (1) and the component (5) / the equivalent of the epoxy group contained in the component (2)) is 0.2~ 2.0.

[26] An epoxy resin cured product obtained by heating one of the liquid epoxy resin compositions described in any one of the above [8] to [25].

[27] A functional product comprising the cured epoxy resin according to [26] above.

[28] A compound having one or more hydroxyl groups and two or more thiol groups in a molecule and having a molecular weight of from 100 to 2,000 (wherein -CH ₂ CH(OH)CH ₂ - at the terminal) The use of a resin hardener other than the compound of the structural unit represented by SH).

[29] The resin hardener used in the above [28], which is a hardener for a one-component epoxy resin composition.

[30] The use according to the above [28] or [29], wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is a trihydroxy group. Methylpropane, pentaerythritol or dipentaerythritol is bonded to one or more kinds of partial esters of two or more thiol-group aliphatic monocarboxylic acids having 2 to 8 carbon atoms.

[31] The use according to the above [28] or [29], wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is selected from the group consisting of three Hydroxymethylpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyric acid) Ester), neopentyl alcohol bis(mercaptoacetate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol bis(3-mercaptobutyrate), pentaerythritol double (4) - mercaptobutyrate), neopentyl alcohol tris(mercaptoacetate), neopentyl alcohol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), neopentyl Alcohol tris(4-mercaptobutyrate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(3-mercaptopropionate), dipentaerythritol bis(3-mercaptobutylate) Acid ester), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol tris(mercaptoacetate), dipentaerythritol tris(3-mercaptopropionate), dioxane Tetrahydrin tris(3-mercaptobutyrate), dipentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dicotyl Alcohol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol five (mercapto B) Acidate), dipentaerythritol penta(3-mercaptopropionate), dipentaerythritol penta(3-mercaptobutyrate) and dinepentaerythritol penta(4-mercaptobutyrate) At least one.

[32] The use according to the above [28] or [29], wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is selected from the group consisting of three Hydroxymethylpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate) and trimethylolpropane bis(4-mercaptobutyric acid) At least one of esters By.

[33] The use according to the above [28] or [29], wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is 2-B. Base-2-(hydroxymethyl)propane-1,3-dioleyl bis(3-mercaptopropionate).

[34] A method of using a compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 in order to cure the cured resin (wherein at the end - Except for the structural unit of the compound represented by CH ₂ CH(OH)CH ₂ -SH)

[35] The method according to [34] above, wherein the resin composition is a one-component epoxy resin composition.

[36] The method according to the above [34] or [35], wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is a trihydroxy group. Methylpropane, pentaerythritol or dipentaerythritol is bonded to one or more kinds of partial esters of two or more thiol-group aliphatic monocarboxylic acids having 2 to 8 carbon atoms.

[37] The method according to the above [34] or [35] wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is selected from the group consisting of three Hydroxymethylpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyric acid) Ester), neopentyl alcohol bis(mercaptoacetate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol bis(3-mercaptobutyrate), pentaerythritol double (4) -mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), neopentyl Tetrahydrin tris(3-mercaptobutyrate), pentaerythritol tris(4-mercaptobutyrate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(3-mercaptopropane) Acid ester), dipentaerythritol bis(3-mercaptobutyrate), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol tris(mercaptoacetate), dioxane Tetrahydrin tris(3-mercaptopropionate), dipentaerythritol tris(3-mercaptobutyrate), dipentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(fluorenyl) Acetate), dipentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol tetrakis(4-mercaptobutyrate), Dipentaerythritol penta (mercaptoacetate), dipentaerythritol penta(3-mercaptopropionate), dipentaerythritol penta(3-mercaptobutyrate) and dinepentaerythritol five ( At least one of 4-mercaptobutyrate.

[38] The method according to the above [34] or [35] wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is selected from the group consisting of three Hydroxymethylpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate) and trimethylolpropane bis(4-mercaptobutyric acid) At least one of the esters.

[39] The method according to the above [34] or [35] wherein the compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 is 2-B. Base-2-(hydroxymethyl)propane-1,3-dioleyl bis(3-mercaptopropionate).

The resin hardener of the present invention can make a resin composition even at a low temperature It is sufficiently hardened and is excellent in rapid hardenability. Further, by combining the resin curing agent (component (1)) of the present invention with the component (2) and the component (3), and optionally the component (4), the component (5), and other components, it is possible to exhibit A liquid epoxy resin composition which is excellent in low temperature rapid hardenability and storage stability.

Further, the rapid hardenability in the present invention means that the time for curing after the start of heating is short, and more specifically, the time from the start of heating to the start of hardening is short.

Fig. 1 is a graph showing the results of the hardenability of the resin compositions of Example 1 and Comparative Examples 1 to 4 (heat generation curves of differential scanning calorimetry (DSC)).

In the present invention, the resin curing agent is a compound having one or more hydroxyl groups and two or more thiol groups in the molecule and having a molecular weight of from 100 to 2,000 (hereinafter, simply referred to as "component (1)").

[Resin hardener (ingredient (1))]

The resin curing agent of the present invention is composed of a compound having one or more hydroxyl groups and two or more thiol groups in the molecule. These compounds may be used alone or in combination of two or more. It is presumed that one or more hydroxyl groups of the compound contribute to rapid hardenability, and two or more thiol groups contribute to low-temperature curability. The molecular weight of the compound is considered from the viewpoint of the curing speed. It must be 100~2000, preferably 150~1000. Here, when the molecular weight of the compound is 1000 or more, the molecular weight thereof can be measured by a gel permeation chromatography (GPC). When the molecular weight is less than 1,000, the molecular weight thereof can be measured by a mass spectrometer (for example, ESI-MS).

The component (1) can be produced, for example, in the following manner.

(a) The component (1) can be obtained by subjecting a hydroxyl group which is a part of a molecule to an acetal or a thiol group, and the like, to esterification reaction with a mercapto organic acid, and deprotecting the obtained protective ester. Here, the sulfhydryl organic acid refers to an organic compound having a thiol group and a carboxyl group.

(b) esterifying the polyalcohol with a mercapto organic acid in an amount such that the carboxyl group of the mercapto organic acid is less than the hydroxyl group of the polyalcohol, and the resulting reaction mixture is subjected to a known method (for example, cerium oxide gel chromatography) The component (1) can be obtained by purifying.

The polyhydric alcohol may, for example, be trimethylolpropane, neopentylol or dipentaerythritol.

The mercapto organic acid may, for example, be a mercapto aliphatic monocarboxylic acid such as mercaptoacetic acid, mercaptopropionic acid (for example, 3-mercaptopropionic acid) or mercaptobutyric acid (for example, 3-mercaptobutyric acid or 4-mercaptobutyric acid). An acid; an ester containing a thiol group and a carboxyl group obtained by esterification of a hydroxy acid with a mercapto organic acid; a mercapto aliphatic dicarboxylic acid such as mercapto succinic acid or dimercaptosuccinic acid (for example, 2,3-dimercaptosuccinic acid) An acid; a mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid (for example, 4-mercaptobenzoic acid). The carbon number of the above mercapto aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, more preferably 2 to 4, and particularly preferably 3. Among the above sulfhydryl organic acids, a mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms is preferred, and more preferably ruthenium. Further, acetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferably 3-mercaptopropionic acid.

The component (1) is preferably a partial ester of a thiol-based aliphatic monocarboxylic acid having 2 or more carbon atoms of 2 to 8 bonded to trimethylolpropane, pentaerythritol or dipentaerythritol. More than one type. The partial ester herein refers to an ester of a polyalcohol and a carboxylic acid, and a hydroxyl group of a polyalcohol remains.

Component (1), preferably selected from the group consisting of trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate) , trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol bis(mercaptoacetate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol bis(3-mercapto) Butyrate), neopentyl alcohol bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), neopentyl alcohol (3-mercaptobutyrate), neopentyl alcohol tris(4-mercaptobutyrate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(3-mercaptopropionate) , dipentaerythritol bis(3-mercaptobutyrate), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol tris(mercaptoacetate), dipentaerythritol (3-mercaptopropionate), dipentaerythritol tris(3-mercaptobutyrate), dipentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate) ), dipentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol tetrakis(4-mercaptobutyrate), dioxane Tetrahydrin five (巯Acetate), dipentaerythritol penta(3-mercaptopropionate), dipentaerythritol penta(3-mercaptobutyrate) and dineopentaerythritol penta(4-mercaptobutyrate) At least one of them; More preferably, it is selected from the group consisting of trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), and trimethylolpropane At least one of bis(4-mercaptobutyrate); particularly preferably, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(3-mercaptopropionate) (alias : Trimethylolpropane bis(3-mercaptopropionate)).

Further, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(3-mercaptopropionate) is a compound of the following structure.

Since the component (1) can cure the epoxy resin, it can be used as a resin curing agent. Here, the term "resin hardener" means the agent used for hardening a resin. The resin hardener of the present invention is preferably a hardener for an epoxy resin, more preferably a hardener for a one-pack epoxy resin composition. When the resin hardener (component (1)) of the present invention is used in the one-component epoxy resin composition, the epoxy resin (component (2)) having two or more epoxy groups per molecule per molecule is used. The equivalent ratio of the epoxy group to be contained, the equivalent ratio of the thiol group contained in the component (1) (the equivalent of the thiol group contained in the component (1) / the equivalent of the epoxy group contained in the component (2), That is, the number of the thiol groups contained in the component (1) / the number of the epoxy groups contained in the component (2) is preferably adjusted to 0.2 to 2.0, more preferably 0.6. ~1.2.

[One-component epoxy resin composition]

The present invention provides a compound (component (1)) having one or more hydroxyl groups and two or more thiol groups in a molecule and having a molecular weight of from 100 to 2,000, and having an average of two or more rings per molecule. A one-component epoxy resin composition of an epoxy resin (component (2)) and a latent curing accelerator (component (3)). The liquid epoxy resin composition of the present invention has both low-temperature rapid hardenability and storage stability. The liquid epoxy resin composition of the present invention may further comprise any one selected from the group consisting of a boric acid ester compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto organic compound. One or more of the acids (ingredient (4)) and/or a compound having two or more thiol groups in the molecule and having no hydroxyl group (ingredient (5)). In the liquid epoxy resin composition of the present invention, the components (1) to (5) and other components described later may be used alone or in combination of two or more. The description of the component (1) in the one-liquid epoxy resin composition is the same as described above. Hereinafter, it will be described in order from the component (2).

[ingredient (2)]

The epoxy resin of the component (2) used in the present invention may be any one having two or more epoxy groups per molecule. For example, polyphenols obtained by reacting polyhydric phenol such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcin or polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin Ether; reaction of hydroxy acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid with epichlorohydrin a polyglycidyl ether obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; and an epoxidized novolac resin, an epoxidized cresol varnish resin, and a ring Oxidized polyolefin, cyclic aliphatic epoxy resin, other polyurethane modified epoxy resin, etc., but are not limited thereto.

The component (2) is preferably a bisphenol A, a bisphenol F type epoxy resin, a novolak type epoxy resin, or a biphenyl aralkyl type epoxy resin, from the viewpoint of maintaining high heat resistance and low moisture permeability. , phenol aralkyl type epoxy resin, aromatic epoxy propylamine type epoxy resin, epoxy resin having a structure of dicyclopentadiene, more preferably, bisphenol A type epoxy resin and bisphenol F type epoxy resin More preferably, it is a bisphenol A type epoxy resin.

The epoxy resin of the component (2) may be in the form of a liquid or a solid. Further, as the component (2), a mixture of a liquid epoxy resin and a solid epoxy resin may be used. Here, "liquid" and "solid shape" mean the state of the epoxy resin at normal temperature (25 ° C). From the viewpoints of coatability, workability, and adhesion, it is preferred that at least 10% by weight or more of the entire epoxy resin to be used is a liquid epoxy resin. Specific examples of the liquid epoxy resin include liquid bisphenol A epoxy resin ("jER epoxy resin 828EL" manufactured by Mitsubishi Chemical Corporation, "jER epoxy resin 827"), and liquid bisphenol F epoxy resin. Resin ("JER Epoxy Resin 807" manufactured by Mitsubishi Chemical Corporation), naphthalene type bifunctional epoxy resin ("HP4032" and "HP4032D" manufactured by DIC Corporation), and liquid bisphenol AF epoxy resin (manufactured by Tohto Kasei Co., Ltd.) "ZX1 O59"), epoxy resin of the structure of hydrogenation ("jER epoxy resin YX8000" manufactured by Mitsubishi Chemical Corporation). Among them, "JER Epoxy" manufactured by Mitsubishi Chemical Co., Ltd. with high heat resistance and low viscosity Resin 828EL", "jER epoxy resin 827", and "jER epoxy resin 807" are preferred, and jER epoxy resin 828EL" is more preferable. Further, specific examples of the solid-state epoxy resin include a naphthalene type tetrafunctional epoxy resin ("HP4700" manufactured by DIC Corporation) and a dicyclopentadiene type polyfunctional epoxy resin (HP7200 manufactured by DIC Corporation). "), a naphthol type epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), an epoxy resin having a butadiene structure ("PB-3600" manufactured by Daisuke Chemical Industry Co., Ltd.), and a biphenyl structure. Epoxy resin ("NC3000H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd., "YX4000" manufactured by Mitsubishi Chemical Corporation).

The content of the component (2) in the liquid epoxy resin composition of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, more preferably 20% by weight or more, still more preferably 30% by weight or more. Preferably, 40% by weight or more is more preferably 50% by weight or more. Further, the content is preferably 95% by weight or less, more preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, still more preferably 75% by weight or less, still more preferably 70% by weight or less. Very good.

[ingredient (3)]

The latent hardening accelerator of the component (3) used in the present invention refers to a solid compound which is insoluble in the epoxy resin of the component (2) at room temperature, but which can be hardened by heating and hardened by epoxy resin. The meaning of the compound that promotes the function of the agent. For example, an imidazole compound which is solid at normal temperature and an amine-additive latent curing accelerator are mentioned, but it is not limited to these. Among these, an amine addition-based latent curing accelerator is preferred. Amine adducts are potentially hard Examples of the chemical accelerator include a reaction product of an amine compound and an epoxy compound (an amine-epoxy adduct-based latent curing accelerator), and a reaction product of an amine compound and an isocyanate compound (amine-isocyanate system). Potential hardening accelerator) and the like.

The above imidazole compound which is solid at normal temperature, and examples thereof include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, and 2-phenyl-4-methyl. 5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-B Base-S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Cyanuric acid adduct, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole - trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitic acid ester, N-(2-methylimidazolyl-1-ethyl)-urea, etc., but not limited thereto Wait.

The epoxy compound used as one of the raw materials for producing the amine-epoxy adduct-based latent curing accelerator may, for example, be a multivalent such as bisphenol A, bisphenol F, catechol or resorcin. Polyepoxypropyl ether obtained by reacting a polyol such as phenol or glycerin or polyethylene glycol with epichlorohydrin; polyepoxy resin obtained by reacting a hydroxy acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid with epichlorohydrin a polyglycidyl ether obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin; 4,4'-diaminodiphenylmethane or m-aminophenol; a glycidylamine compound obtained by the reaction of chlorohydrin; and an epoxidized novolac resin, an epoxidized cresol varnish resin, a polyfunctional epoxy compound of an epoxidized polyolefin, a butyl epoxidized propyl ether, a phenyl epoxidized ether, A monofunctional epoxy compound such as glycidyl methacrylate is not limited thereto.

The amine compound used as a raw material for producing the amine-based additive-based latent curing accelerator has one or more active hydrogens capable of undergoing an addition reaction with an epoxy group or an isocyanate group (island name: isocyanate group) in the molecule. And it is sufficient if it has one or more amine groups (at least one of a primary amine group, a secondary amine group, and a tertiary amine group) in the molecule. Examples of such an amine compound include diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane, and the like. An aliphatic amine compound; an aromatic amine compound such as 4,4'-diaminodiphenylmethane or 2-methylaniline; 2-ethyl-4-methylimidazole, 2-ethyl-4-methyl Imidazoline, 2,4-dimethylimidazoline, piperidine, piperidine A heterocyclic compound or the like containing a nitrogen atom. However, the invention is not limited to these.

Further, when the compound having a tertiary amino group in the molecule is used in particular among the above raw materials, a latent curing accelerator having excellent curing ability can be produced. A compound having a tertiary amino group in the molecule, and examples thereof include dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminoethylamine. , diethylaminoethylamine, N-methylper An amine having a 3-stage amine group in the molecule, such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole; 2-dimethylamino group Ethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl- 2-Dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl 4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl 4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methyl Imidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorphine, 2-dimethyl Aminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, 2-picolinic acid, N,N-dimethylglycolate, N,N-dimethyl propionate, Base acid acyl hydrazide, isonicotinic acid hydrazide, etc. acyl group having the three alcohols, phenols, thiols, carboxylic acids, acyl hydrazines and the like in the molecule.

When the above-mentioned epoxy compound and the amine compound are subjected to an addition reaction to produce an amine adduct-based latent curing agent, an active hydrogen compound having two or more active hydrogens in the molecule may be further added. Examples of such an active hydrogen compound include polyvalent phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcin, gallic phenol, and novolac resin, and trimethylolpropane. Polyvalent carboxylic acids such as polyhydric alcohols, adipic acid, and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethane, 1-mercapto-3-phenoxy-2-propanol, Mercaptoacetic acid, o-amine benzoic acid, lactic acid, etc., but are not limited thereto.

The isocyanate compound used as a raw material for the production of the amine-based latent curing agent may, for example, be a monofunctional isocyanate compound such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate or benzyl isocyanate; Diisocyanate, methylphenyl diisocyanate (for example: 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4 , 4'-diisocyanate, a polyfunctional isocyanate compound such as isophorone diisocyanate, decyl diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptene triisocyanate, or the like; A terminal isocyanate group-containing compound obtained by reacting a polyfunctional isocyanate compound with an active hydrogen compound. Examples of the compound containing a terminal isocyanate group include, for example, an addition compound having a terminal isocyanate group, a methylphenylene diisocyanate, and a novel tetraol obtained by reacting methylphenyl diisocyanate with trimethylolpropane. The addition compound having a terminal isocyanate group obtained by the reaction is not limited to these.

The latent curing accelerator of the component (3), for example, may be appropriately mixed with the above-mentioned raw materials, reacted at room temperature to 200 ° C, and then solidified and then pulverized, or methyl ethyl ketone or dioxane. The above-mentioned raw materials are reacted in a solvent such as tetrahydrofuran, and after the solvent is removed, the solid component is pulverized, whereby the raw material can be easily obtained.

A commercially available product can also be used as the latent hardening accelerator of the component (3). The amine-epoxy adduct is a latent hardening accelerator, and for example, "Ajicure PN-23" (trade name of Ajinomoto Precision Technology Co., Ltd.) and "Ajicure PN-H" (trade name of Ajinomoto Precision Technology Co., Ltd.) ), "Hardener-X-3661S" (trade name of ACR company), "Hardener-X-3670S" (trade name of ACR company), "NOVACURE HX-3742" (trade name of Asahi Kasei Corporation), "NOVACURE HX- In addition, the amine-isocyanate-based latent curing accelerator, for example, "FUJICUREFXE-1000" (trade name of Fuji Chemical Co., Ltd.) and "FUJICUREFXE-1030" (Fuji Chemical Co., Ltd.) Product name) and so on. However, the invention is not limited to these.

The content of the component (3) in the one-component epoxy resin composition is preferably 0.1 to 100 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of the component (2), and more preferably 5 to 30 parts by weight. Better yet.

[ingredient (4)]

In order to achieve excellent storage stability, the liquid epoxy resin composition of the present invention preferably contains the component (4) selected from the group consisting of a borate compound, a titanate compound, an aluminate compound, and a zirconate. One or more of a compound, an isocyanate compound, a carboxylic acid, an acid anhydride, and a mercapto organic acid.

Examples of the boric acid ester compound include trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, triamyl borate, triallyl borate, and tribasic boric acid. Ester, tricyclohexyl borate, trioctyl borate, tridecyl borate, tridecyl borate, tri-dodecyl borate, tri-hexadecyl borate, tri-octadecyl borate, tris(2-ethyl Cyclohexyloxy)borane, bis(1,4,7,10-tetraoxadecyl)(1,4,7,10,13-pentaoxatetradecyl) (1,4,7- Trioxadecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-cresyl borate, triethanolamine borate, and the like.

Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

The zirconate compound may, for example, be tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate or tetrabutyl zirconate.

Examples of the isocyanate compound include butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, and 2-ethylbenzene. Isocyanate, 2,6-dimethylphenylisocyanate, methylphenylene diisocyanate (for example: 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate), 1,5- Naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, decyl diisocyanate, p-phenylene diisocyanate, bicycloheptene triisocyanate, and the like.

Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, valeric acid, caproic acid, and citric acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid, and monochloroacetic acid. Fatty acid such as halogenated fatty acid such as dichloroacetic acid, glycolic acid, lactic acid or gluconic acid, aliphatic aldehyde acid such as glyoxylic acid, and fat of keto acid, oxalic acid, malonic acid, succinic acid, maleic acid, etc. An aromatic polybasic acid such as a polybasic acid, a benzoic acid, a halogenated benzoic acid, a toluic acid, a phenylacetic acid, a cinnamic acid or a mandelic acid, an aromatic polybasic acid such as a phthalic acid or a benzenetricarboxylic acid.

Examples of the acid anhydride include succinic anhydride, dodecynyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic acid. A fatty acid polybasic acid anhydride such as an acid anhydride; an aromatic polybasic acid anhydride such as phthalic anhydride, trimellitic anhydride or pyroic acid anhydride.

The above-mentioned mercapto organic acid may, for example, be mercaptoacetic acid, mercaptopropionic acid (for example, 3-mercaptopropionic acid) or mercaptobutyric acid (for example, 3-mercaptobutyric acid, 4-mercaptobutyric acid) a mercapto fatty acid monocarboxylic acid; an ester containing a thiol group and a carboxyl group obtained by esterification of a hydroxyl group with a mercapto organic acid; mercapto succinic acid, dimercaptosuccinic acid (eg, 2,3-dimercaptosuccinic acid), etc. A mercapto aromatic dicarboxylic acid such as a mercapto fatty acid dicarboxylic acid; mercaptobenzoic acid (for example, 4-mercaptobenzoic acid).

The component (4) is preferably a boric acid ester compound from the viewpoints of high versatility, high safety, and improved storage stability, and more preferably, triethyl borate, tripropyl borate, triisopropyl borate, boric acid Butyl ester is more preferably triethyl borate.

The content of the component (4) in the one-liquid epoxy resin composition is not particularly limited as long as the storage stability of the composition can be improved, and is 0.001 to 50 parts by weight based on 100 parts by weight of the component (2). Preferably, it is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight.

The component (4) and the components (1) to (3) and optionally the component (5) and other components may be simultaneously mixed to produce a liquid epoxy resin composition of the present invention, or the component may be previously prepared. (3) and (4) mixing, preparing the mixture, mixing the mixture with the components other than the above, to produce a liquid epoxy resin composition of the present invention. The mixing of the component (3) and the component (4) can be carried out in a solvent such as methyl ethyl ketone or toluene, or can be carried out without a solvent. Further, when a liquid epoxy resin is used as the component (2), the components (3) and (4) may be mixed in a liquid epoxy resin, and the mixture may be prepared, and the mixture may be mixed with the components other than the components. To produce a liquid epoxy resin composition of the present invention.

[ingredient (5)]

The liquid epoxy resin composition containing one of the components (1) to (3) or the liquid epoxy resin composition containing one of the components (1) to (4) is preferably a low-temperature curing property. A compound (5) having two or more thiol groups in the molecule and having no hydroxyl group is blended.

The component (5) may, for example, be a complete ester of a polyhydric alcohol and a mercapto organic acid. Here, the complete ester refers to an ester of a polyhydric alcohol and a carboxylic acid, and the hydroxyl group of the polyhydric alcohol forms an ester bond. Examples of the polyhydric alcohol include ethylene glycol, trimethylolpropane, neopentyl alcohol, and dipentaerythritol. The mercapto organic acid may, for example, be a mercapto aliphatic monocarboxylic acid such as mercaptoacetic acid, mercaptopropionic acid (for example, 3-mercaptopropionic acid) or mercaptobutyric acid (for example, 3-mercaptobutyric acid or 4-mercaptobutyric acid). An acid; an ester containing a thiol group and a carboxyl group obtained by esterification of a hydroxy acid with a mercapto organic acid; a mercapto aliphatic dicarboxylic acid such as mercapto succinic acid or dimercaptosuccinic acid (for example, 2,3-dimercaptosuccinic acid) An acid; a mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid (for example, 4-mercaptobenzoic acid). The carbon number of the above mercapto aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, more preferably 2 to 4, and particularly preferably 3. Among the above sulfhydryl organic acids, a mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms is preferred, and more preferably thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid or 4-mercaptobutyric acid, and more Jia is 3-mercaptopropionic acid.

Specific examples of complete esters of a polyhydric alcohol and a mercapto organic acid, ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), Ethylene glycol bis(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyric acid) Ester), trimethylolpropane tris(4-mercaptobutyrate), neopentyl alcohol tetrakis(mercaptoacetate), neopentyl alcohol tetrakis(3-mercaptopropane) Acid ester), neopentyl alcohol tetrakis(3-mercaptobutyrate), neopentyl alcohol tetrakis(4-mercaptobutyrate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol Hexa(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptobutyrate), and dipentaerythritol hexa(4-mercaptobutyrate) and the like. Further, from the viewpoint of preservation stability, the above-mentioned complete ester is preferably one having a minimum amount of basic impurities, and more preferably a substance which does not require the use of an alkaline substance in production.

Further, as the component (5), an alkyl polythiol compound such as 1,4-butanedithiol, 1,6-hexanedithiol or 1,10-decanedithiol; or a terminal mercaptan may be used; a polyether; a polythiol containing a terminal thiol group; a polythiol compound obtained by reacting an epoxy compound with hydrogen sulfide; a polythiol having a terminal thiol group obtained by reacting a polythiol compound with an epoxy compound A polythiol compound produced by using an alkaline substance as a reaction catalyst for an alcohol compound or the like at the production step thereof. The polythiol compound produced using a basic substance is preferably subjected to a dealkalation treatment to have an alkali metal ion concentration of 50 ppm by weight or less.

The de-alkali treatment of the polythiol compound produced by using a basic substance may be, for example, a method in which a polythiol compound is dissolved in an organic solvent such as acetone or methanol, and an acid such as alkene hydrochloride or an enesulfuric acid is added to neutralize the acid. A method of desalting by extraction, washing, etc.; a method of performing adsorption using an ion exchange resin; a method of purifying by distillation, etc., but is not limited thereto.

Further, as the component (5), tris[(3-mercaptopropenyloxy)-ethyl]-trimeric isocyanate, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3 can be used. , 5-triazine-2,4,6-(1H,3H,5H)-trione and the like.

Ingredient (5), Preferably, one or more of ethylene glycol, trimethylolpropane, neopentyl alcohol or dipentaerythritol and a complete ester of a fluorenyl aliphatic monocarboxylic acid having 2 to 8 carbon atoms; more preferably, selected from the group consisting of Ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), Trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyl) Acid ester), neopentyl alcohol tetrakis(mercaptoacetate), neopentyl alcohol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), neopentyltetraol 4-mercaptobutyrate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptobutyrate) And at least one of dipentaerythritol hexa(4-mercaptobutyrate); more preferably, selected from the group consisting of trimethylolpropane tris(mercaptoacetate) and trimethylolpropane tris(3-mercaptopropane) At least one of an acid ester), trimethylolpropane tris(3-mercaptobutyrate), and trimethylolpropane tris(4-mercaptobutyrate); , trimethylolpropane tris(3-mercaptopropionate).

When the component (5) is used in the one-component epoxy resin composition, the weight ratio of the component (1) to the total weight of the component (1) and the component (5) (weight/component of the component (1) ( 1) and the total weight of the component (5), preferably 0.001 to 0.8. The lower limit of the ratio is preferably 0.01, more preferably 0.03, and most preferably 0.1. The upper limit of the ratio is not particularly limited, but is preferably 0.6, more preferably 0.4, and 0.2 is particularly preferable.

The component (1) and the component with respect to the equivalent of the epoxy group contained in the component (2) (5) The total equivalent ratio of the thiol groups contained (the total equivalent of the thiol groups contained in the component (1) and the component (5) / the equivalent of the epoxy group contained in the component (2), that is, the component (1) The total number of thiol groups contained in the component (5) and the number of epoxy groups contained in the component (2) are preferably 0.2 to 2.0 and more preferably 0.6 to 1.2.

[Other ingredients]

In the liquid epoxy resin composition of the present invention, a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a chelating agent, an antioxidant, a thixotropic agent, and a dispersing agent which are commonly used in the field may be added as needed. And other additives. Among these, a thixotropic agent is preferably used.

The thixotropic agent can be, for example, precipitated cerium oxide, fired cerium oxide, smoky cerium oxide (smoked cerium oxide), or the like, and among them, hazy cerium oxide (smoked cerium oxide) is preferred. The specific surface area (hereinafter referred to as BET specific surface area) obtained by the BET method of the solubility improving agent is preferably 50 m ² /g or more, more preferably 50 to 600 m ² /g, still more preferably 100 to 400 m ² /g. . When the thixotropic agent is used, the content in the one-liquid epoxy resin composition is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, per 100 parts by weight.

[Manufacture of a liquid epoxy resin composition]

It is not particularly difficult to produce a liquid epoxy resin composition of the present invention. The composition can be mixed by a known method by using the component (1), the component (2), the component (3), the optional component (4), the component (5), and other components, for example, a Henschel mixer. The mixers are mixed to make. One of the liquidity The temperature of the epoxy resin composition is usually 10 to 50 ° C, preferably 20 to 40 ° C, and the mixing time is usually 1 second to 5 minutes, preferably 5 seconds to 3 minutes.

[Epoxy resin hardened]

It is also not particularly difficult to harden a liquid epoxy resin composition of the present invention. The hardening can be carried out according to a conventional method, for example, by hardening a liquid epoxy resin composition of the present invention. The liquid epoxy resin composition of the present invention has a low temperature rapid hardening property, so the heating temperature for hardening it is usually 50 to 30 ° C, preferably 60 to 100 ° C, and the heating time is 1 second. 90 minutes, preferably 1 minute to 60 minutes.

The present invention also includes an epoxy resin cured product obtained by heating one of the above liquid epoxy resin compositions, and also includes a functional product of the cured epoxy resin. The functional product may, for example, be an adhesive, a casting agent, a sealant, a sealant, a fiber-reinforced resin, a coating agent, a paint, or the like.

[Coating agent]

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. In addition, the "parts" in the following description means "parts by weight".

<Synthesis Example 1 (Synthesis of Component (1))>

Into the reaction vessel, packed with 4L of toluene, 1,1,1-tris(hydroxymethyl)propane 280 g (2.08 mol) and 443 g (4.17 mol) of 3-mercaptopropionic acid were stirred and heated at 50 ° C to dissolve the reactants (1,1,1-tris(hydroxymethyl)propane and 3-mercaptopropionic acid) in toluene. . After heating and stirring, 2.8 g (14.7 mol) of p-toluenesulfonic acid monohydrate was added to the reaction solution at 30 ° C, and a Dean-Stark water separator was installed in the reaction vessel to prepare a reaction solution. Warm up. The reflux was started at a reaction temperature of 110 ° C, and water began to flow out. After heating and stirring for 12 hours, the outflow of water was stopped, and the reaction was detected by thin layer chromatography (TLC). Since 3-mercaptopropionic acid disappeared, post-treatment was carried out. The reaction solution was left to cool, and water was added for liquid separation, and 5.0% by weight of sodium hydrogencarbonate water and brine were sequentially used, and the organic layer was washed. The organic layer was separated, and sodium sulfate was added to dehydrate, and then the toluene was distilled off under reduced pressure to give 620 g of crude product. Next, the crude product was purified by cerium oxide gel chromatography to obtain 230 g of 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(3-mercaptopropionate).

The materials other than the component (1) used in the examples and the comparative examples are as follows.

<Component (2)>

"jER Epoxy Resin 828EL" (trade name of Mitsubishi Chemical Corporation, the following is described as "jER-828"): bisphenol A type epoxy resin (epoxy equivalent: 184~194 (average 189), per molecule Epoxy group: 2.0 (average))

<ingredient (3)>

"Ajicure PN-23" (trade name of Ajinomoto Precision Technology Co., Ltd., also described below as "PN-23"): Amine-epoxy adduct is a latent hardening accelerator

<ingredient (4)>

Triethyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<ingredient (5)>

"DPMP" (trade name of SC Organic Chemical Co., Ltd.): dipentaerythritol Hexa(3-mercaptopropionate) (hydroxyl group in the molecule: 0, thiol group in the molecule: 6)

"TEMPIC" (trade name of SC Organic Chemical Co., Ltd.): tris[(3-mercaptopropoxy)-ethyl]-trimeric isocyanate (hydroxyl group in the molecule: 0, thiol group in the molecule: 3 )

"PE-1" (trade name of Showa Denko Co., Ltd.): Pentaerythritol Tetrakis(3-mercaptobutyrate) (hydroxyl group in the molecule: 0, thiol group in the molecule: 4)

"NR1" (trade name of Showa Denko Co., Ltd.): 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione (hydroxyl group in the molecule: 0, thiol group in the molecule: 3)

"TMTP" (trade name of Sigma-Aldrich Co., Ltd.): Trimethylolpropane tris(3-mercaptopropionate) (hydroxyl group in the molecule: 0, thiol group in the molecule: 3)

<Other components (shake-soluble agent)>

"AEROSIL 200" (trade name of Japan Aerosil Co., Ltd.): untreated fumed cerium oxide (BET specific surface area: 200 m ² /g)

(evaluation method) [Measurement of gelation time]

The epoxy resin composition was heated to 80 ° C in accordance with JIS C 6521 by a hot plate gelation tester (GT-D: manufactured by Nisshin Scientific Co., Ltd.), and the gelation time of the epoxy resin composition was measured. Specifically, after applying about 0.5 g of the epoxy resin composition to a hot plate type gelation test machine, the code table is activated at a time point of about 80 ° C, and is applied to a hot plate type gelation test. The epoxy resin composition on the machine was rotated in a manner of being limited to a diameter of 25 mm, and a blade having a front end width of 5 mm was used to repeat the rotation operation of the epoxy resin composition in a circular shape. When the viscosity of the epoxy resin composition is low, the above-described rotation operation is repeated at a speed of one second without rotating the blade. After the viscosity of the epoxy resin composition began to rise, the blade was repeatedly lifted up and down by a hot plate type gelation test machine from time to time by about 30 mm. At the beginning of the vertical operation, a linear epoxy resin composition adheres to the blade. When the blade is vertically lifted by the heating plate by about 30 mm, the linear epoxy resin composition is cut, and the state in which the composition does not adhere to the blade is regarded as gelation. The time from the time of 80 ° C to the time of gelation was taken as the gelation time.

[Evaluation of preservation stability]

The initial viscosity of the epoxy resin composition (i.e., the viscosity before storage after preparation) was measured using an E-type viscometer at 25 ° C and 20 rpm. Next, the epoxy resin composition was stored in a constant temperature room at 25 ° C for 3 days and 1 week, and an E-type viscometer was used at 25 ° C and 20 rpm to measure the epoxy resin composition. The viscosity after 3 days of storage and the viscosity after 1 week of storage. Calculate the viscosity ratio after 3 days of storage relative to the initial viscosity (viscosity/initial viscosity after 3 days of storage), and the viscosity ratio after 1 week of storage of the initial viscosity (preservation of viscosity/initial viscosity after 1 week), The storage stability of the epoxy resin composition was evaluated in terms of the ratio.

[Measurement of hardenability]

The heat generation curve of the epoxy resin composition was measured by differential scanning calorimetry (DSC). Specifically, a differential scanning calorimeter manufactured by Mettler-Toledo Co., Ltd. was used to carry out differential scanning by using a sample of about 5 mg (epoxy resin composition) from 25 ° C at a heating rate of 5 ° C / min to 250 ° C. Calorimetry.

Example 1 and Comparative Examples 1 to 4

To the bisphenol A type epoxy resin jER-828, triethyl borate was mixed, and the compound of Synthesis Example 1, DPMP, TEMPIC, PE-1, NR1 as a hardener was added in an amount shown in Table 1, and mixed at 25 ° C. Evenly. Finally, fine powder cerium oxide AEROSIL 200 of PN-23 and a thixotropy-imparting agent was added in an amount shown in Table 1, and the mixture was well stirred at 25 ° C to prepare a uniform epoxy resin composition. The hardenability of the obtained epoxy resin composition was measured in the above manner. The results are shown in Fig. 1.

As shown in Fig. 1, the heat generation curve of the DSC of Example 1 was faster than that of Comparative Examples 1 to 4, and it was found that the epoxy resin composition obtained in Example 1 was rapidly hardenable. In this way, when a compound having one or more hydroxyl groups and two or more thiol groups in the molecule and a molecular weight of 100 to 2,000 is used as a resin curing agent, a one-liquid type having sufficient rapid hardening property can be obtained. Epoxy resin composition.

Example 2~18

To the bisphenol A type epoxy resin jER-828, triethyl borate was mixed, and the compound of Synthesis Example 1 and TMTP were added in an amount shown in Tables 2 to 4, and the mixture was uniformly mixed at 25 °C. Finally, the fine powder cerium oxide AEROSIL 200 of PN-23 and a thixotropy-imparting agent was added in an amount shown in Tables 2 to 4, and the mixture was well stirred at 25 ° C to prepare a uniform epoxy resin composition. The hardenability of the obtained epoxy resin composition was measured in the above manner. The results are shown in Tables 2 to 4. Further, "'" in the gelation time described in Tables 2 to 4 indicates "minute" and "" indicates "second".

The epoxy resin composition of Examples 2 to 7 shown in Table 2, based on the equivalent of the epoxy group contained in the component (2), the total equivalent of the thiol group contained in the component (1) and the component (5) The epoxy resin of the examples 8 to 12 shown in Table 3 is 1.0 (the total equivalent of the thiol group contained in the component (1) and the component (5) / the equivalent of the epoxy group contained in the component (2)). The resin composition, the above ratio was 0.8, and the epoxy resin compositions of Examples 13 to 18 shown in Table 4, the ratio was 0.6. Further, in Tables 2 to 4, the weight ratio of the component (1) to the total weight of the component (1) and the component (5) (weight of the component (1) / component (1) and component (5) Total weight) (also referred to as "component (1) / (component (1) + component (5))") in Tables 2 to 4).

As shown in Tables 2 to 4, the total weight of the component (1)/component (1) and the component (5) is a liquid epoxy resin composition of 0.03 to 0.2, and the viscosity/initial viscosity after 1 week of storage is stored. Is less than 1.1, and gelation at 80 ° C The time is less than 12 minutes, and it is known that both good storage stability and rapid hardenability are obtained. Further, it is known that the weight ratio of the liquid epoxy resin composition is from 0.1 to 2.0, and the initial viscosity is low and the operation is easy.

The liquid epoxy resin composition containing one of the resin hardeners of the present invention has a small increase in viscosity at 25 ° C for one week, and is excellent in storage stability. Moreover, this one-component epoxy resin composition exhibits low-temperature rapid hardenability (rapid hardening property at 80 ° C) which is not obtained by one of the conventional liquid epoxy resin compositions.

[Industrial availability]

According to the present invention, it is possible to provide a resin hardener which can sufficiently harden an epoxy resin composition at a low temperature. The resin hardener (component (1)) of the present invention can provide a low temperature fast by combining with the component (2) and the component (3), and any of the components (4), (5) and other components. A liquid epoxy resin composition which is excellent in hardenability and storage stability. The liquid epoxy resin composition of the present invention is suitable for an adhesive, a casting agent, a sealant, a sealant, a fiber-reinforced resin, a coating agent or a coating in all fields requiring an electronic relationship of low-temperature rapid hardenability. The purpose of the use.

The present invention is based on Japanese Patent Application No. 2012-259336, the entire disclosure of which is incorporated herein.

Claims (23)

A resin hardener selected from the group consisting of trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(4-mercaptobutyrate), Pentaerythritol bis(mercaptoacetate), pentaerythritol bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(4-mercaptobutyrate) ), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol tris(mercaptoacetate), dipentaerythritol III ( 4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol penta(mercaptoacetate), and At least one of dipentaerythritol penta(4-mercaptobutyrate) is formed. The resin hardener according to item 1 of the patent application, which is a hardener for a one-component epoxy resin composition. A resin hardener according to claim 1 or 2, which is selected from the group consisting of trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(mercaptoacetate), and pentaerythritol. (mercaptoacetate), neopentyl alcohol tris(mercaptoacetate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(4-mercaptobutyrate), dioxane Tetrahydrin tris(mercaptoacetate), dipentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(4-mercaptobutyric acid) At least one of ester) and dipentaerythritol penta (mercaptoacetate). A resin hardener according to claim 1 or 2, which is at least one selected from the group consisting of trimethylolpropane bis(3-mercaptopropionate) and trimethylolpropane bis(mercaptoacetate) Composition. A resin hardener according to claim 1 or 2, which is composed of trimethylolpropane bis(3-mercaptopropionate). A one-liquid epoxy resin composition comprising: component (1) selected from the group consisting of trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(mercaptoacetate), and trishydroxyl Propane bis(4-mercaptobutyrate), pentaerythritol bis(mercaptoacetate), pentaerythritol bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), new Pentaerythritol tris(4-mercaptobutyrate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol bis(4-mercaptobutyrate), dipentaerythritol tris(decyl) Acid ester), dipentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(4-mercaptobutyrate), dioxane a ring having at least one of tetraol penta (mercaptoacetate) and dipentaerythritol penta (4-mercaptobutyrate), and an average of component (2) having 2 or more epoxy groups per molecule An oxygen hardener and a latent hardening accelerator for the component (3). The liquid epoxy resin composition according to any one of the sixth aspect of the invention, wherein the content of the component (3) is 0.1 to 100 parts by weight based on 100 parts by weight of the component (2). The liquid epoxy resin composition according to claim 6 or 7, wherein the component (1) is selected from the group consisting of trimethylolpropane bis(3-mercaptopropionate) and trimethylolpropane bis (indenyl) Acetate), neopentyl alcohol bis(mercaptoacetate), neopentyl alcohol tris(mercaptoacetate), dipentaerythritol bis(mercaptoacetate), dipentaerythritol double (4) - mercaptobutyrate), dipentaerythritol tris(mercaptoacetate), dipentaerythritol tris(4-mercaptobutyrate), dioxane At least one of tetraol tetra(mercaptoacetate), dipentaerythritol tetrakis(4-mercaptobutyrate), and dipentaerythritol penta(mercaptoacetate). A liquid epoxy resin composition according to any one of claims 6 or 7, wherein the component (1) is selected from the group consisting of trimethylolpropane bis(3-mercaptopropionate) and trimethylolpropane bis ( At least one of thioglycolate). A liquid epoxy resin composition according to any one of claims 6 or 7, wherein the component (1) is trimethylolpropane bis(3-mercaptopropionate). The liquid epoxy resin composition according to any one of claims 6 or 7, which further comprises the component (4) selected from the group consisting of a borate compound, a titanate compound, an aluminate compound, a zirconate compound, and an isocyanate. One or more of a compound, a carboxylic acid, an acid anhydride, and a mercapto organic acid. The liquid epoxy resin composition according to claim 11, wherein the content of the component (4) is 0.001 to 50 parts by weight based on 100 parts by weight of the component (2). A liquid epoxy resin composition according to any one of claims 6 or 7, which further comprises a component (5) having a compound having two or more thiol groups in the molecule and having no hydroxyl group. A liquid epoxy resin composition according to claim 13 wherein the component (5) is ethylene glycol, trimethylolpropane, neopentyl alcohol or dipentaerythritol and carbon number 2-8 One or more of the complete esters of the mercapto aliphatic monocarboxylic acid. A liquid epoxy resin composition according to claim 13 wherein component (5) is selected from the group consisting of ethylene glycol bis(mercaptoacetate) and Diol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), Trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), neopentyltetraol (mercapto B) Acid ester), neopentyl alcohol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol Alcohol hexa(mercaptoacetate), dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptobutyrate), and dipentaerythritol hexa(4-mercapto) At least one of butyrate). A liquid epoxy resin composition according to claim 13, wherein the component (5) is selected from the group consisting of trimethylolpropane tris(mercaptoacetate) and trimethylolpropane tris(3-mercaptopropionic acid). At least one of ester), trimethylolpropane tris(3-mercaptobutyrate), and trimethylolpropane tris(4-mercaptobutyrate). A liquid epoxy resin composition according to claim 13, wherein the component (5) is trimethylolpropane tris(3-mercaptopropionate). The liquid epoxy resin composition according to claim 13, wherein the weight ratio of the component (1) to the total weight of the component (1) and the component (5) (weight/component of the component (1) (1) and the total weight of the component (5) are 0.001 to 0.8. The liquid epoxy resin composition according to claim 13, wherein the weight ratio of the component (1) to the total weight of the component (1) and the component (5) (weight/component of the component (1) (1) and the total weight of the component (5) are 0.1 to 0.2. The liquid epoxy resin composition according to claim 6 or 7, wherein the equivalent ratio of the thiol group contained in the component (1) is equivalent to the equivalent of the epoxy group contained in the component (2) ( The equivalent of the thiol group contained in the component (1) / the equivalent of the epoxy group contained in the component (2) is 0.2 to 2.0. The liquid epoxy resin composition according to any one of claim 13 wherein the thiol group contained in the component (1) and the component (5) is equivalent to the equivalent of the epoxy group contained in the component (2). The total equivalent ratio (the equivalent of the thiol group contained in the component (1) and the component (5) / the equivalent of the epoxy group contained in the component (2)) is 0.2 to 2.0. An epoxy resin cured product obtained by heating a liquid epoxy resin composition according to any one of claims 6 to 21. A functional product comprising an epoxy resin cured material as in claim 22 of the patent application.