WO2016171150A1

WO2016171150A1 - Radical-polymerizable, water-containing resin composition, curing method thereof, and method for producing radical-polymerizable, water-containing resin composition

Info

Publication number: WO2016171150A1
Application number: PCT/JP2016/062447
Authority: WO
Inventors: 一博黒木; 三浦　賢治; 陽一郎坂口
Original assignee: 昭和電工株式会社
Priority date: 2015-04-21
Filing date: 2016-04-19
Publication date: 2016-10-27
Also published as: CN107531813A; JPWO2016171150A1; PH12017501926A1; PH12017501926B1; CN107531813B; JP6690638B2; TWI593729B; MY182723A; TW201704308A

Abstract

This radical-polymerizable, water-containing resin composition contains a metal-containing compound (A), a thiol compound (B), a radical-polymerizable compound (C), a surfactant (D), water (E), and a radical polymerization initiator (F), wherein there are 0.05-10 parts by mass of the surfactant (D) per total 100 parts by mass of the metal component of the metal-containing compound (A), the thiol compound (B), the radical-polymerizable compound (C), the water (E) and the radical polymerization initiator (F), and there are 0.3-10 parts by mass of the radical polymerization initiator (F) per 100 parts by mass of the radical-polymerizable compound (C), and this radical-polymerizable, water-containing resin compound can be stably cured even in a state containing water.

Description

Radical polymerizable water-containing resin composition, curing method thereof, and method for producing radical polymerizable water-containing resin composition

The present invention relates to a radical polymerizable water-containing resin composition capable of performing radical curing even when water is present inside the composition, a curing method thereof, and a method for producing a radical polymerizable water-containing resin composition.

Metal soap has good solubility in resins and solvents, and has various functions. Curing accelerators such as unsaturated polyester resins, dryers for paints and printing inks, adhesives for rubber and tires It is used in a wide range of applications such as extreme oil pressure lubricants, auxiliary combustion agents, and polymerization catalysts.
However, when metal soap is used as a curing accelerator under conditions where water is present, there is a problem that the function is not sufficiently developed (Non-Patent Document 1).
As a method for solving this problem, a method of using a promoter aid can be mentioned. Examples of the promoter aid include β-diketones, aromatic tertiary amines, mercaptans (thiol compounds), phosphorus compounds and the like. As a technique using such a promoter, for example, in Patent Document 1, in a cement admixture containing a copolymer as an essential component, a hydrocarbon group having 3 or more carbon atoms is used for the production of the copolymer. It describes that a chain transfer agent such as a thiol compound is used as a promoter.
Patent Document 2 describes the use of accelerating aids such as aniline derivatives, toluidine derivatives, metal soaps, and thiourea derivatives in aqueous resin compositions used for automobile interior materials and the like.
Furthermore, Non-Patent Document 2 describes that a complex formed of an aromatic tertiary amine and a cobalt salt is used as a promoter.

Japanese Patent No. 4518773 Japanese Patent No. 4469484

It has been difficult for the curing accelerator described in Patent Document 1 that has been conventionally used to be sufficiently cured in the presence of water. In addition, the metal (cobalt) salts or metal complexes described in Patent Document 2 and Non-Patent Document 2 easily form a complex with water and inhibit the cobalt redox reaction. It was difficult to perform sufficient curing.
Note that Patent Document 2 discloses the use of Rongalite or a thiourea derivative, but the use of a secondary thiol compound has not been studied.
The present invention has been made in view of the above-described conventional circumstances, and includes a radically polymerizable water-containing resin composition that can be stably cured even in a state containing water, a curing method thereof, and radically polymerizable properties. A method for producing a water-containing resin composition is provided.

As a result of intensive studies to solve the above-described conventional problems, the present inventors have found that in the presence of water, the metal in the metal-containing compound is deactivated by water and cannot be cured. Then, after repeated studies on methods for preventing metal deactivation, when a metal-containing compound and a secondary or tertiary thiol compound are used in combination, a secondary or tertiary thiol compound is coordinated in the vicinity of the metal of the metal-containing compound. As a result, it becomes difficult for water to approach the metal, and the deactivation of the metal can be prevented, and as a result, the composition is stably cured even under conditions where water is present inside the composition. As a result, the present invention has been completed.

The gist of the present invention is the following [1] to [23].
[1] From one or more metal-containing compounds (A), secondary thiol compounds (B1) and tertiary thiol compounds (B2) selected from metal soaps (A1) and metal complexes (A2) having a β-diketone skeleton Containing one or more selected thiol compounds (B), radical polymerizable compounds (C), surfactants (D), water (E), and radical polymerization initiators (F), the metal-containing compound (A ) Of the surfactant (D) with respect to a total of 100 parts by mass of the metal component of), the thiol compound (B), the radical polymerizable compound (C), the water (E) and the radical polymerization initiator (F). Is a radical polymerizable water-containing resin composition in which the amount of the radical polymerization initiator (F) is 0.3 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). object.
[2] The thiol compound (B) has at least one structure represented by the following formula (Q), and includes 2 mercapto groups in the structure represented by the following formula (Q). The radically polymerizable water-containing resin composition according to the above [1], which is a compound having two or more mercapto groups bonded to a secondary or tertiary carbon atom.

(In the formula (Q), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and R ² is an alkyl group or carbon having 1 to 10 carbon atoms. An aromatic group of formula 6 to 18, wherein * is linked to an arbitrary organic group, a is an integer of 0 to 2.) [3] R ¹ in the formula (Q) is The radically polymerizable water-containing resin composition according to the above [2], which is a hydrogen atom and the thiol compound (B) has two or more mercapto groups bonded to a secondary carbon atom in the molecule.

[4] The radically polymerizable water-containing resin composition according to [2] or [3], wherein the thiol compound (B) has at least one ester structure represented by the following formula (Q-1).

(In the formula ^{(Q-1), R 1} , R 2, * and a ^{are, ^R} 1, ^R 2 in the formula (Q), the same meanings as * and a.)

[5] The radically polymerizable water-containing resin composition according to the above [4], wherein a in the formula (Q-1) is 1.
[6] The thiol compound (B) having an ester structure represented by the formula (Q-1) is derived from a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol. The radically polymerizable water-containing resin composition according to [4] or [5].

(In the formula ^(S), R 1, ^{R 2} and a have the same meanings as ^R 1, ^{R 2} and a in the formula (Q).)
[7] The secondary thiol compound (B1) contains 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris [2- ( 3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate) and trimethylolpropane tris ( The radically polymerizable water-containing resin composition according to any one of [1] to [6], which is at least one selected from 3-mercaptobutyrate).

[8] The radical polymerization according to any one of [1] to [7], wherein the thiol compound (B) is a compound having two mercapto groups bonded to a secondary or tertiary carbon atom in the molecule. Water-containing resin composition.
[9] The radically polymerizable water-containing resin composition according to any one of [1] to [8], wherein the thiol compound (B) has a molecular weight of 5,000 or less.
[10] In any one of [1] to [9], the total amount of the thiol compound (B) is 0.01 to 15 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). The radically polymerizable water-containing resin composition described.
[11] The molar ratio [(B) / (A)] of the thiol compound (B) to the metal component of the metal-containing compound (A) is 0.1 to 15, The radically polymerizable water-containing resin composition according to any one of the above.

[12] The radically polymerizable water-containing solution according to any one of [1] to [11], wherein the content of the radically polymerizable compound (C) in the radically polymerizable water-containing resin composition is 20 to 95% by mass. Resin composition.
[13] The metal element constituting the metal-containing compound (A) is lithium, magnesium, calcium, barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold The radically polymerizable water-containing resin composition according to any one of the above [1] to [12], which is at least one selected from zinc, aluminum, indium, tin, lead, neodymium, and cerium.
[14] The long chain fatty acid constituting the metal soap (A1) is a linear or cyclic saturated fatty acid having 7 to 15 carbon atoms or an unsaturated fatty acid having 7 to 15 carbon atoms. 13] The radically polymerizable water-containing resin composition according to any one of [13].
[15] The radically polymerizable water-containing resin composition according to any one of [1] to [14], wherein the metal soap (A1) is manganese octylate, cobalt octylate or cobalt naphthenate.

[16] The radical according to any one of [1] to [15], wherein the surfactant (D) contains one or more selected from an anionic surfactant and a nonionic surfactant. Polymerizable water-containing resin composition.
[17] The above [1] to [1], wherein the radical polymerizable compound (C) is one selected from a vinyl ester resin, an unsaturated polyester resin, or a mixture of these and a radical polymerizable unsaturated monomer. [16] The radically polymerizable water-containing resin composition according to any one of [16].
[18] The radically polymerizable water-containing solution according to [17], wherein the radically polymerizable unsaturated monomer is styrene, and the content of styrene in the radically polymerizable compound (C) is 20% by mass or less. Resin composition.
[19] The radically polymerizable water-containing resin composition according to any one of [1] to [18], further containing a filler (H).

[20] The radically polymerizable water-containing resin composition according to [19], wherein the filler (H) is cement and aggregate.
[21] The [1], wherein the water (E) is at least one selected from ion-exchanged water, tap water, seawater, river water, well water, factory water, distilled water, and water containing a radioactive substance. The radically polymerizable water-containing resin composition according to any one of to [20].
[22] A state in which the water (E) is contained in the radical polymerizable water-containing resin composition, a state in which the radical polymerizable water-containing resin composition is in contact with water, or the radical polymerizable water-containing resin composition The method for curing a radically polymerizable water-containing resin composition according to any one of the above [1] to [21], wherein the resin is cured in any state immersed in water.
[23] Step 1 of obtaining a mixed liquid (i) by mixing the metal-containing compound (A) and the radical polymerizable compound (C), the mixed liquid (i) and the thiol compound (B). Step 2 for obtaining a liquid mixture (ii) by mixing, Step 3 for obtaining a liquid mixture (iii) by mixing the liquid mixture (ii), the surfactant (D) and the water (E), And the method for producing a radically polymerizable water-containing resin composition according to any one of the above [1] to [21], which comprises the step 4 of mixing the mixed solution (iii) and the radical polymerization initiator (F).

According to the present invention, a radically polymerizable hydrated resin composition that can be stably cured despite the presence of water in the composition, a method for curing the same, and a method for producing a radically polymerizable hydrated resin composition Can be provided.

[Radically polymerizable resin composition]
The radically polymerizable water-containing resin composition of the present invention comprises at least one metal-containing compound (A) selected from a metal soap (A1) and a metal complex (A2) having a β-diketone skeleton, and a secondary thiol compound (B1). And at least one thiol compound (B) selected from the tertiary thiol compound (B2), radical polymerizable compound (C), surfactant (D), water (E), and radical polymerization initiator (F). And 100 parts by mass in total of the metal component of the metal-containing compound (A), the thiol compound (B), the radical polymerizable compound (C), the water (E) and the radical polymerization initiator (F). The amount of the surfactant (D) is 0.05 to 10 parts by mass, and the amount of the radical polymerization initiator (F) is 0.3 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). Too A and, it is also possible to stably cure regardless containing water at.

<Metal-containing compound (A)>
The radically polymerizable water-containing resin composition of the present invention contains at least one metal-containing compound (A) selected from a metal soap (A1) and a metal complex (A2) having a β-diketone skeleton as a curing accelerator. In addition, the metal soap (A1) in the present invention refers to a salt of a long chain fatty acid or an organic acid other than the long chain fatty acid and a metal element other than potassium and sodium. The metal complex (A2) having a β-diketone skeleton in the present invention refers to a complex in which a compound having a structure having one carbon atom between two carbonyl groups is coordinated to a metal element.

[Metal soap (A1)]
The long-chain fatty acid in the metal soap (A1) is not particularly limited, but for example, a fatty acid having 7 to 30 carbon atoms is preferable. Specifically, octanoic acid such as heptanoic acid and 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid Preferred are chain or cyclic saturated fatty acids such as hexacosanoic acid, octacosanoic acid, triacontanoic acid and naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid.
Also included are rosin acid, linseed oil fatty acid, soybean oil fatty acid, tall oil acid and the like.

The organic acid other than the long chain fatty acid in the metal soap (A1) is not particularly limited, but is preferably a weak acid compound having a carboxy group, a hydroxy group, and an enol group and soluble in an organic solvent.
Examples of the compound having a carboxy group include formic acid; acetic acid; carboxylic acid such as oxalic acid; hydroxy acid such as citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, folic acid; alanine, arginine Amino acids such as benzoic acid, phthalic acid and the like.
Examples of the compound having a hydroxy group and an enol group include ascorbic acid, α acid, imide acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, tycoic acid, dehydroacetic acid, delta acid, uric acid, Examples include hydroxamic acid, humic acid, fulvic acid, phosphonic acid, acetylacetone and the like.
Among these, long-chain fatty acids are preferable, linear or cyclic saturated fatty acids having 7 to 15 carbon atoms, or unsaturated fatty acids having 7 to 15 carbon atoms are more preferable, octanoic acid and naphthenic acid are further preferable, and 2- More preferred are ethylhexanoic acid and naphthenic acid.

The metal elements constituting the metal soap (A1) include group 1 and 2 metal elements such as lithium, magnesium, calcium and barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, Group 3-12 metal elements such as platinum, copper, silver, gold and zinc, Group 13-14 metal elements such as aluminum, indium, tin and lead, and rare earth metal elements such as neodymium and cerium Is mentioned.
Among these, Group 2 metal elements and Group 3-12 metal elements are preferable, barium, vanadium, manganese, iron, cobalt, copper, titanium, and zinc are more preferable, and manganese, iron, cobalt, Copper, titanium, and zinc are more preferable, and manganese, cobalt, and titanium are still more preferable.

Specific metal soaps (A1) include manganese octylate, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, vanadium acetoacetate, cobalt acetoacetate, and iron acetoacetate. Acetate and the like are preferable, and manganese octylate, cobalt octylate, cobalt naphthenate, and the like are more preferable.

The content of the metal soap (A1) in the radical polymerizable water-containing resin composition of the present invention in terms of metal component is preferably 0.001 to 5 mass with respect to 100 mass parts of the radical polymerizable compound (C) described later. Part, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.7 part by weight, and still more preferably 0.02 to 0.5 part by weight. If the content of the metal soap (A1) in terms of metal component is within the above range, curing proceeds rapidly even in a state containing water.

[Metal complex having β-diketone skeleton (A2)]
Examples of the metal complex (A2) having a β-diketone skeleton (hereinafter also referred to as “metal complex (A2)”) include those obtained by complexing metal with acetylacetone, ethyl acetoacetate, benzoylacetone, and the like. These metal complexes (A2) also exhibit functions similar to those of the metal soap (A1).
As a metal element which comprises a metal complex (A2), the metal element similar to the said metal soap (A1) is mentioned.

Specific metal complexes (A2) include vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis (acetylacetonate), iron acetylacetonate, and acetoacetic acid ethyl ester cobalt. Of these, titanium acetylacetonate and titanium dibutoxybis (acetylacetonate) are more preferable.

The preferred range of the content of the metal complex (A2) in terms of metal component is the same as the preferred range of the content of the metal soap (A1) in terms of metal component. In addition, when the metal soap (A1) and the metal complex (A2) are used in combination, the preferred range of the content in terms of the total metal component is the same as the preferred range of the content in terms of the metal component of the metal soap (A1). is there.

<Thiol compound (B)>
The radically polymerizable resin composition of the present invention contains one or more thiol compounds (B) selected from the secondary thiol compound (B1) and the tertiary thiol compound (B2). In the present invention, the thiol compound (B) has a function as a curing accelerator, coordinates in the vicinity of the metal of the metal-containing compound (A), and also has a function of preventing metal deactivation by water. Guessed.
The thiol compound (B) used in the present invention may be referred to as a mercapto group bonded to a secondary or tertiary carbon atom in the molecule (hereinafter referred to as “secondary mercapto group” or “tertiary mercapto group”, respectively). ) Is not particularly limited as long as it is a compound having one or more), but from the viewpoint of quickly curing even in a state containing water, and from the viewpoint of preventing the metal of the metal-containing compound from being deactivated by water, A polyfunctional thiol which is a compound having two or more secondary or tertiary mercapto groups is preferable, and among them, a bifunctional thiol which is a compound having two secondary or tertiary mercapto groups in the molecule is preferable. The secondary thiol compound (B1) is more preferable than the tertiary thiol compound (B2).
As used herein, “polyfunctional thiol” means a thiol compound having two or more mercapto groups as functional groups, and “bifunctional thiol” means two mercapto groups as functional groups. Means a thiol compound.

The compound having two or more secondary or tertiary mercapto groups in the molecule is not particularly limited. For example, the compound has at least one structure represented by the following formula (Q) and is represented by the following formula (Q). A compound having two or more secondary or tertiary mercapto groups in the molecule including the mercapto group in the structure is preferred.

(In the formula (Q), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and R ² is an alkyl group having 1 to 10 carbon atoms, or An aromatic group having 6 to 18 carbon atoms, * is linked to an arbitrary organic group, and a is an integer of 0 to 2.)

R ¹ in formula (Q) is more preferably a compound having a hydrogen atom and having two or more secondary mercapto groups in the molecule. That is, the thiol compound (B) is preferably a secondary thiol compound (B1) in which the carbon atom to which the mercapto group in the formula (Q) is bonded is a secondary carbon atom.

In addition, the alkyl group having 1 to 10 carbon atoms in R ¹ and R ² in the formula (Q) may be linear or branched. Specific examples include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. The “various” means various isomers including n-, sec-, tert-, and iso-.
Among these alkyl groups, a methyl group and an ethyl group are preferable.
In addition, examples of the aromatic group having 6 to 18 carbon atoms in R ¹ and R ² in the formula (Q) include a phenyl group, a benzyl group, a naphthyl group, an anthryl group, and a phenanthryl group. In addition, these aromatic groups may be substituted with a halogen atom, an amino group, a nitro group, a cyano group, or the like.
A in the formula (Q) is an integer of 0 to 2, preferably 1.

Furthermore, the thiol compound (B) preferably has at least one ester structure represented by the following formula (Q-1).

A in formula (Q-1) is preferably 1. When a is 1 and R ¹ is a hydrogen atom, that is, when the compound having an ester structure represented by (Q-1) is a secondary thiol compound (B1), the following formula ( As represented by T), the carbonyl oxygen and the mercapto group are easily coordinated to the metal element of the metal-containing compound (A), and the metal element of the metal-containing compound (A) is surrounded by the thiol compound. As a result, it is considered that the contact between the metal element and water can be suppressed. In the case of the tertiary thiol compound (B2), R ¹ and R ² are both bulkier substituents than hydrogen, and from the viewpoint of steric hindrance in the coordination of the mercapto group to the metal element, the secondary thiol compound (B1) It is considered that can better exhibit curing acceleration performance. However, even in the tertiary thiol compound (B2), when the carbonyl oxygen and the mercapto group are stably coordinated to the metal element, the contact between the metal element and water is further suppressed than in the secondary thiol compound (B1). It is thought to get.

(Formula (T), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (Q-1), M represents a metal element derived from the metal-containing compound (A).)

The thiol compound (B) having an ester structure represented by the formula (Q-1) is a compound derived from a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol. preferable.

(In the formula ^(S), R 1, ^{R 2} and a have the same meanings as ^R 1, ^{R 2} and a in the formula (Q).)

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propanediol, 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecane dimethanol, 2,2-bis (2-hydroxyethoxyphenyl) propane, bisphenol A alkyleneoxy Adduct, bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-hexanediol, 2,3- Hexanediol, 1,4-hexanediol, 2,4-hexanediol, 3,4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 9,9-bis Divalent alcohols such as [4- (2-hydroxyethyl) phenyl] fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, sorbitol , Penta Risuritoru, dipentaerythritol, sucrose, 2,2-bis (2,3-dihydroxy propyloxy phenyl) trivalent or more alcohols such as propane and the like; polycarbonate diol, and dimer acid polyester polyol and the like.

Among these, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, etc. from the viewpoint of availability and the improvement of curability in a state containing water Dihydric alcohols such as: glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane, etc. A trivalent or higher alcohol; polycarbonate diol and dimer acid polyester polyol are preferable. From the viewpoint of the number of functional groups and vapor pressure, 1,4-butanediol, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate , Bae Data erythritol, polycarbonate diols, dimer acid polyester polyol is more preferred.

[Secondary thiol compound (B1)]
When the thiol compound (B) having the structure represented by the formula (Q) is a secondary thiol compound (B1), specific examples thereof include 3-mercaptobutyric acid, 3-mercaptophthalic acid di (1- Mercaptoethyl), di (2-mercaptopropyl) phthalate, di (3-mercaptobutyl) phthalate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3 -Mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) ), Pentaerythritol tetrakis (3 Mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate) ), Butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate) ), Dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), diethylene glycol bis (4-mercaptovalerate), Diol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4 -Mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octane Diol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol Tall hexakis (3-mercaptovalerate), hydrogenated bisphenol A bis (3-mercaptobutyrate), bisphenol A dihydroxyethyl ether-3-mercaptobutyrate, 4,4 ′-(9-fluorenylidene) bis (2- Phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate), diethylene glycol bis (3-mercapto-3- Phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto-3-phenylpropionate), trimethylolpropane tris (3-mercapto-3-pheny) Lupropionate), tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate), dipentaerythritol hexakis (3-mercapto-3-phenylpropionate) Honate).

When the secondary thiol compound (B1) is a compound having an ester structure represented by the formula (Q-1), the compound is represented by the polyhydric alcohol and the formula (S). It is preferably derived from a carboxylic acid containing a secondary mercapto group. Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto-3-phenylpropionic acid, and the like.

Among the secondary thiol compounds (B1), as a commercial product of a compound having two or more secondary mercapto groups in the molecule, 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK) Karenz MT (registered trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (produced by Showa Denko KK, Karenz MT (registered trademark) PE1), 1,3,5-tris [2- (3-mercaptobuty Ryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko KK, Karenz MT (registered trademark) NR1), trimethylolethane tris (3 -Mercaptobutyrate (manufactured by Showa Denko KK, TEMB), trimethylolpropane tris (3-mercaptobutyrate) (Showa Denko Co., Ltd.) Ltd., TPMB) and the like, it is preferable to use one or more of these.

[Tertiary thiol compound (B2)]
When the thiol compound (B) having the structure represented by the formula (Q) is a tertiary thiol compound (B2), specific examples thereof include di (2-mercaptoisobutyl) phthalate, ethylene glycol bis ( 2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercapto) Isobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2 -Mercap Isobutyrate), di (3-mercapto-3-methylbutyl) phthalate, ethylene glycol bis (3-mercapto-3-methylbutyrate), propylene glycol bis (3-mercapto-3-methylbutyrate), diethylene glycol bis (3 -Mercapto-3-methylbutyrate), butanediol bis (3-mercapto-3-methylbutyrate), octanediol bis (3-mercapto-3-methylbutyrate), trimethylolethane tris (3-mercapto-3) -Methylbutyrate), trimethylolpropane tris (3-mercapto-3-methylbutyrate), pentaerythritol tetrakis (3-mercapto-3-methylbutyrate), dipentaerythritol hexakis (3-mercapto-3-methyl) Butyrate Etc. The.

When the tertiary thiol compound (B2) is a compound having an ester structure represented by the formula (Q-1), the compound is represented by the polyhydric alcohol and the formula (S). It is preferably derived from a carboxylic acid containing a tertiary mercapto group. Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptoisobutyric acid and 3-mercapto-3-methylbutyric acid.

[Esterification reaction of mercapto group-containing carboxylic acid represented by formula (S) and polyhydric alcohol]
There is no restriction | limiting in particular in the esterification reaction of the mercapto group containing carboxylic acid represented by the said Formula (S), and a polyhydric alcohol, It can manufacture by a general esterification reaction.
The reaction temperature of the esterification reaction is preferably 60 to 160 ° C., more preferably 60 to 135 ° C. from the viewpoint of promptly proceeding the reaction and suppressing the formation of by-products. In addition, it is preferable to react, removing the water produced | generated by esterification reaction from a viewpoint of suppressing the production | generation of a by-product.

In the esterification reaction, a solvent may or may not be used, but from the viewpoint of improving the reaction rate, it is preferable to use a solvent azeotropic with water. Examples of the solvent azeotropic with water include toluene, xylene, cyclohexane, and ethylbenzene. Toluene is preferable from the viewpoint of the balance between the manufacturing cost and the obtained effect. The amount of the solvent azeotroped with water is preferably 10 to 90% by mass in the reaction system.
The mercapto group-containing carboxylic acid represented by the formula (S) and the polyhydric alcohol are those in which the carboxy group of the mercapto group-containing carboxylic acid represented by the formula (S) is 1. It is preferably used so as to be 0 to 4.0 equivalent. When the carboxy group equivalent of the mercapto group-containing carboxylic acid represented by the formula (S) is 1.0 equivalent or more, the amount of unreacted hydroxyl groups can be suppressed, and the number of mercapto groups in one molecule is 2 or more. Therefore, curability is improved, and when the carboxy group is 4.0 equivalents or less, the production cost can be suppressed.

As the catalyst used in the esterification reaction, a non-volatile acid catalyst is preferable. Specifically, inorganic acids such as sulfuric acid, perchloric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, levulinic acid and the like are used. Organic acids are mentioned. Among these, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like are preferable from the viewpoint of reaction rate.
In addition, a non-volatile acid catalyst means the acid catalyst whose vapor pressure in 25 degreeC is 1 kPa or less.
The amount of the catalyst used is preferably 0.01 to 1.0 mole per mole of hydroxyl group of the polyhydric alcohol. When the amount of the catalyst used is 0.01 mol or more, the reaction rate is sufficiently high, and when it is 1.0 mol or less, the amount of the basic substance used for neutralization after the completion of the reaction is reduced. Can do.

The reaction pressure of the esterification reaction is not particularly limited, but is preferably 100 to 760 mmHg from the viewpoint of improving the reaction rate, and more preferably 300 to 550 mmHg from the viewpoint of dehydration efficiency. When the reaction pressure is within the above range, the temperature in the reaction system becomes high, so that the reaction easily proceeds.

The completion of the reaction can be judged by the amount of water extracted from the reaction system, and it is preferable to carry out the reaction until the amount of water reaches the theoretical dehydration amount by the esterification reaction, but when the reaction takes a long time The reaction can be completed when 80% by mass or more of the theoretical value of water has been extracted. If the water content is 80% by mass or more of the theoretical value of the dehydration amount by the esterification reaction, the amount of unreacted polyhydric alcohol is small, so that the curability of the radical polymerizable water-containing resin composition of the present invention is improved.

After completion of the reaction, it is preferable to neutralize the acid catalyst. The basic substance for neutralization is not particularly limited, but sodium bicarbonate and caustic soda are preferable from the viewpoint of cost reduction, and sodium bicarbonate is more preferable from the viewpoint of ease of pH adjustment.
Further, after the reaction is completed, extraction may be performed from the viewpoint of purifying the target product. As the extraction solvent for extraction, toluene, ethyl acetate, isopropyl acetate, and butyl acetate are preferable from the viewpoint of easiness of volatilization, and toluene and ethyl acetate are more preferable from the viewpoint of the cost of the extraction solvent. For the purpose of improving the separation speed during extraction, a hydrophobic solvent may be added to the extraction solvent. From the viewpoint of the separation speed and the cost of the hydrophobic solvent, hexane and heptane are more preferred. preferable.

In the solvent distillation step, the solvent is distilled off under heating and reduced pressure conditions, and the distillation temperature is preferably 80 to 150 ° C. regardless of the degree of vacuum. When the temperature is within the above range, the solvent can be completely distilled off and polymerization of the synthesized thiol compounds can be prevented.

Although there is no restriction | limiting in particular in the molecular weight of the thiol compound (B) in this invention, It is preferable that it is a low molecular weight, Specifically, 5,000 or less are preferable, 2,500 or less are more preferable, 1,500 or less are further Preferably, 750 or less is still more preferable. Moreover, 100 or more are preferable, 150 or more are more preferable, and 200 or more are still more preferable. In addition, in this invention, molecular weight points out the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC method).

The total amount of the thiol compound (B) in the radically polymerizable water-containing resin composition of the present invention is preferably 0.01 to 15 parts by weight, more preferably 100 parts by weight of the radically polymerizable compound (C) described later. Is 0.1 to 12 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 10 parts by mass. If the amount of the thiol compound (B) is 0.01 parts by mass or more, a sufficient curing function can be obtained, and if it is 15 parts by mass or less, curing proceeds rapidly.

The total molar ratio [(B) / (A)] of the thiol compound (B) to the metal component of the metal-containing compound (A) is preferably from 0.1 to 15, more preferably from 0.3 to 10, 6 to 8 is more preferable, and 0.8 to 5 is still more preferable. When the molar ratio [(B) / (A)] is 0.1 or more, the thiol compound (B) can be sufficiently coordinated in the vicinity of the metal of the metal-containing compound (A), and the molar ratio When the value is 15 or less, the balance between the manufacturing cost and the effect is improved.

A thiol compound (B) may be used individually by 1 type, and may use 2 or more types together. When the secondary thiol compound (B1) and the tertiary thiol compound (B2) are used in combination, the molar ratio [(B1) / (B2)] of both is preferably 0.001 to 1000, more preferably 1 to 10 preferable. When the molar ratio [(B1) / (B2)] is within the above range, the metal-containing compound (A) and the thiol compound (B) in the radical polymerizable water-containing resin composition are as shown in the above formula (T). It is stable in a state, and a disulfide compound is not generated as a by-product due to a bond between thiol compounds (B). From the viewpoint of keeping the metal-containing compound (A) and the thiol compound (B) in a stable state as in the formula (T), the secondary thiol compound (B1) or the tertiary thiol compound (B2) is used alone. It is preferable.

<Radically polymerizable compound (C)>
The radically polymerizable water-containing resin composition of the present invention uses a radically polymerizable compound (C) (hereinafter also referred to as “component (C)”) as a base material. In the present invention, the radical polymerizable compound refers to a compound having an ethylenically unsaturated group in the molecule and capable of proceeding a polymerization reaction by a radical.
Examples of radical polymerizable compounds include vinyl ester resins (epoxy (meth) acrylate resins), unsaturated polyester resins, polyester (meth) acrylate resins, urethane (meth) acrylate resins, (meth) acrylate resins, radical polymerizable unsaturated monomers. And a mixture of the above resin and a radically polymerizable unsaturated monomer, among others, a vinyl ester resin, an unsaturated polyester resin, or a mixture of these and a radically polymerizable unsaturated monomer. More than species are preferred. In the present specification, “(meth) acrylate” means “one or both of acrylate and methacrylate”.

[Vinyl ester resin]
As the vinyl ester resin, one obtained by reacting an unsaturated monobasic acid with an epoxy resin can be used.

Examples of the epoxy resin include bisphenol A diglycidyl ether and high molecular weight homologues thereof, novolak glycidyl ethers, and the like.
Specifically, bisphenol-type epoxy resins (for example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, or glycidyl of bisphenol A, And the like obtained by reacting a condensate of ether and the above bisphenol with epichlorohydrin and / or methyl epichlorohydrin), biphenyl type epoxy resin (for example, obtained by reacting biphenol with epichlorohydrin and / or methyl epichlorohydrin) , Naphthalene type epoxy resins (for example, those obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methyl epichlorohydrin), Aralkyl diphenol type epoxy resin (for example, obtained by reacting aralkyl phenol with epichlorohydrin and / or methyl epichlorohydrin), diglycidyl type epoxy resin (for example, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester) Alicyclic epoxy resins (for example, alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxycarboxylates, etc.), having an oxazolidone ring obtained by reacting the epoxy resin with diisocyanate Epoxy resins (as specific examples, Araldite AER4152 made by Asahi Kasei Epoxy), novolak type epoxy resins (for example, phenol novolak or cresol novolak and epichlorohydrin) And / or methyl epichlorohydrin), trisphenolmethane type epoxy resins (for example, those obtained by reacting trisphenolmethane, triscresol methane with epichlorohydrin and / or methyl epichlorohydrin). Can be mentioned.

Known unsaturated monobasic acids can be used, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid and the like. In addition, a reaction product of a compound having one hydroxy group and one or more (meth) acryloyl groups and a polybasic acid anhydride may be used. In the present specification, “(meth) acrylic acid” means “one or both of acrylic acid and methacrylic acid”, and “(meth) acryloyl group” means “acryloyl group and methacryloyl group”. Means one or both.
The said polybasic acid is used in order to increase the molecular weight of the said epoxy resin, and can use a well-known thing. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol 2 mol maleic anhydride adduct, polyethylene Glycol 2 mol maleic anhydride adduct, propylene glycol 2 mol maleic anhydride adduct, polypropylene glycol 2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16- (6 -Ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, carboxyl group-terminated butadiene / acrylonitrile copolymer (trade name Hycar CTBN), and the like.

[Unsaturated polyester resin]
As unsaturated polyester resin, what was obtained by esterifying the unsaturated dibasic acid and the dibasic acid component containing a saturated dibasic acid as needed, and a polyhydric alcohol component can be used. .
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like, and these may be used alone or in combination of two or more.
Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and isosebacic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, and terephthalic acid. , Tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4 , 4′-biphenyldicarboxylic acid, aromatic dibasic acids such as dialkyl esters, halogenated saturated dibasic acids, and the like. These may be used alone or in combination of two or more.

The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, and 1,3-butanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butane Diol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl 1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2- Chlohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexane dimethanol, para-xylene glycol, bicyclohexyl-4,4'-diol Dihydric alcohols such as 2, 6-decalin glycol and 2,7-decalin glycol;
Adducts of hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and the like with an alkylene oxide typified by propylene oxide or ethylene oxide, etc. Of dihydric alcohols;
Examples thereof include trivalent or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

The unsaturated polyester may be modified with a dicyclopentadiene compound within a range not impairing the effects of the present invention. Regarding the modification method using dicyclopentadiene compounds, for example, after obtaining dicyclopentadiene and a maleic acid addition product (sidecanol monomaleate), the dicyclopentadiene skeleton is introduced using this as a monobasic acid. The publicly known methods such as the method to do.
An oxidative polymerization group can be introduced into the vinyl ester resin or unsaturated polyester resin used in the present invention. The introduction method is not particularly limited. For example, addition of an oxidatively polymerizable group-containing polymer, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether with a hydroxyl group and allyl ether And a method of adding a reaction product of a compound having a group and an acid anhydride.

[Polyester (meth) acrylate resin, urethane (meth) acrylate resin, and (meth) acrylate resin]
As the polyester (meth) acrylate resin in the present invention, for example, a polyester obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, specifically, with respect to hydroxyl groups at both ends such as polyethylene terephthalate, ) A resin obtained by reacting acrylic acid can be used.
Moreover, as urethane (meth) acrylate resin, for example, it was obtained by making (meth) acrylic acid react with the hydroxyl group or isocyanato group of the both ends of the polyurethane obtained by making isocyanate and a polyhydric alcohol react. Resin can be used.
Examples of the (meth) acrylate resin include a poly (meth) acrylic resin having one or more substituents selected from a hydroxyl group, an isocyanato group, a carboxy group, and an epoxy group, ) A resin obtained by reacting a (meth) acrylic acid ester having a hydroxyl group with a substituent of a polymer with acrylate can be used.

[Radically polymerizable unsaturated monomer]
In the present invention, a radical polymerizable unsaturated monomer can be used as the radical polymerizable compound (C).
Although the radical polymerizable unsaturated monomer may be used alone, it is used as a mixture of the radical polymerizable unsaturated monomer and at least one of the vinyl ester resin and the unsaturated polyester resin. It is preferable.
Although there is no restriction | limiting in particular in the said radically polymerizable unsaturated monomer, What has a vinyl group or a (meth) acryloyl group is preferable.
Specific examples of the monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl isocyanurate. Etc.

Specific examples of the monomer having a (meth) acryloyl group include acrylic acid esters and methacrylic acid esters. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl Ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate , Neopentyl glycol di (meth) acrylate, PTMG dimethacrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 2-hydroxy 1,3 dimethacryloxypropane, 2,2-bis [4- (methacryloylethoxy) phenyl Propane, 2,2-bis [4- (methacryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane, tetraethylene glycol diacrylate, bisphenol AEO modified (n = 2) Diacrylate, isocyanuric acid EO-modified (n = 3) diacrylate, pentaerythritol di (meth) acrylate monostearate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meta ) Acrylate, tricyclodecanyl methacrylate or tris (2-hydroxyethyl) isocyanurate.

Furthermore, as the polyfunctional (meth) acrylic acid ester, for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1, Alkanediol di- (meth) acrylates such as 4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate;
Polyoxyalkylene-glycol di (meth) such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate and polyethylene glycol (meth) acrylate Acrylate;
Trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Examples include tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
Furthermore, the following compounds can also be used as the radical polymerizable unsaturated monomer. Specifically, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate, allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl Ether, vinylbenzyl- (2-ethylhexyl) ether, vinylbenzyl (β-methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzylcyclohexyl ether, vinylbenzyl- (β-phenoxyethyl) ether, vinylbenzyl Dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxyethyl ether, vinyl benzyl dicyclopentenyl methyl ether, divinyl Mention may be made of rubenzyl ether.
These may be used alone or in combination of two or more.

The radically polymerizable unsaturated monomer can be used to lower the viscosity of the radically polymerizable water-containing resin composition of the present invention and improve hardness, strength, chemical resistance, water resistance, etc. If the amount is too large, it may lead to deterioration of the cured product or environmental pollution. Therefore, the content of the radical polymerizable unsaturated monomer is preferably 90% by mass or less in the radical polymerizable compound (C).
Further, when the radically polymerizable compound (C) particularly contains styrene as the radically polymerizable unsaturated monomer, the content thereof is preferably 60% by mass or less, more preferably 50% by mass or less, and 20% by mass or less. Is more preferable, and 5 mass% or less is still more preferable. When the content of styrene in the radical polymerizable compound (C) exceeds 60% by mass, styrene is eluted in water and the cured product may become brittle.

The radical polymerizable compound (C) is a catalyst or polymerization inhibitor used when synthesizing vinyl ester resin, unsaturated polyester resin, polyester (meth) acrylate resin, urethane (meth) acrylate resin, and (meth) acrylate resin. May remain.
Examples of the catalyst include compounds containing tertiary nitrogen such as triethylamine, pyridine derivatives, imidazole derivatives and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; and phosphorus compounds such as trimethylphosphine and triphenylphosphine. Can be mentioned.
Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, phenothiazine and the like.
When the catalyst or polymerization inhibitor remains in the radically polymerizable compound (C), the amount thereof is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass in total of the vinyl ester resin and the unsaturated polyester resin, respectively. It is.

The content of the radically polymerizable compound (C) in the radically polymerizable water-containing resin composition of the present invention is preferably 20 to 95% by mass, more preferably 25 to 90% by mass. When the content of the radical polymerizable compound (C) in the radical polymerizable water-containing resin composition is within the above range, the hardness of the cured product is further improved.

<Surfactant (D)>
The radical polymerizable water-containing resin composition of the present invention comprises a surfactant (D) (hereinafter also referred to as “component (D)”) for the purpose of improving the familiarity between the radical polymerizable compound (C) and water. Use. When a resin composition not containing a surfactant is cured in a water-containing state, water in the resin composition is ejected out of the cured product, and only the resin tends to be cured. The radically polymerizable water-containing resin composition of the present invention is particularly suitable for use in the application of curing while embracing water in the resin composition, so that the compatibility between the resin and water is improved. It is necessary to use a surfactant to help cure the resin while it is entrapped in the resin.
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. These surfactants may be used alone or in combination of two or more.
Among these surfactants, one or more selected from anionic surfactants and nonionic surfactants are preferable.
Examples of the anionic surfactant include alkyl sulfate esters such as sodium lauryl sulfate and triethanolamine lauryl sulfate, polyoxyethylene alkyl such as polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene alkyl ether sulfate triethanolamine. Fatty acid salts such as ether sulfate ester salt, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalene sulfonate, sodium dialkylsulfosuccinate, sodium stearate soap, oleic acid potassium soap, castor oil potassium soap , Naphthalene sulfonic acid formalin condensate, special polymer system and the like.
Among these, sulfonates are preferable, sodium dialkylsulfosuccinate is more preferable, and sodium dioctylsulfosuccinate is still more preferable.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, Polyoxyethylene derivatives such as polyoxyethylene tribenzylphenyl ether and polyoxyethylene polyoxypropylene glycol; polyoxyalkylene alkyl ethers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate; polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Polyoxyethylene sorbitan fatty acid esters such as Tate: polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbit tetraoleate; glycerol monostearate, glycerine fatty acid esters such as glycerol monooleate.
In these, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, are preferable. Further, the nonionic surfactant HLB (Hydrophile-Lipophil Balance) is preferably 5-15, more preferably 6-12.

The amount of the surfactant (D) in the radically polymerizable water-containing resin composition of the present invention is the metal component of the component (A), the component (B), the component (C), water (E) described later and 0.05 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0 to 100 parts by mass of the radical polymerization initiator (F). 0.06 to 1 part by mass, still more preferably 0.07 to 0.5 part by mass. Since the fall of the water absorption of the filler mixed in resin can be prevented as the quantity of surfactant is 0.05 mass part or more, the effect of a filler can be exhibited. Moreover, while being 10 mass parts or less, while being able to suppress the fall of a resin physical property, the balance of the performance obtained and cost improves.

<Water (E)>
The radically polymerizable water-containing resin composition of the present invention contains water (E) (hereinafter also referred to as “component (E)”).
Specific examples of water include water containing at least one selected from ion-exchanged water, tap water, seawater, river water, well water, factory water, distilled water, and radioactive substances. Since the radically polymerizable water-containing resin composition of the present invention can be cured in a state of containing water as described above and can further retain water in the cured product, it is contaminated with the factory water and radioactive substances. By using fresh water, it becomes easy to store contaminated water.
The amount of water (E) in the radical polymerizable water-containing resin composition of the present invention is preferably 5 to 50 parts by mass, more preferably 7 to 40 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). More preferably, it is 10 to 30 parts by mass.

<Radical polymerization initiator (F)>
The radically polymerizable water-containing resin composition of the present invention contains a radical polymerization initiator (F) (hereinafter also referred to as “component (F)”) as a curing agent. Examples of the radical polymerization initiator (F) include at least one initiator selected from a thermal radical polymerization initiator and a photo radical polymerization initiator.
Examples of the thermal radical polymerization initiator include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, and dialkyls such as dicumyl peroxide. Organic peroxides such as peroxides, ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, peroxyketals, alkyl peresters, and carbonates may be mentioned.
Examples of photo radical polymerization initiators include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone and 2-hydroxy-2-methylpro Examples include acetophenones such as piophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone, and thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone. It is done.

The amount of the radical polymerization initiator (F) in the radical polymerizable water-containing resin composition of the present invention is 0.3 to 10 parts by mass, preferably 0, relative to 100 parts by mass of the radical polymerizable compound (C). 3 to 7 parts by mass, more preferably 0.4 to 6 parts by mass, still more preferably 0.5 to 5 parts by mass.
When the amount of the radical polymerization initiator (F) is 0.3 parts by mass or more, the radically polymerizable water-containing resin composition of the present invention can be sufficiently cured, and when it is 10 parts by mass or less, the obtained effect And the balance of manufacturing costs.

<Curing accelerator (G)>
The radically polymerizable water-containing resin composition of the present invention is a curing accelerator (G) other than the metal-containing compound (A) and the thiol compound (B) (hereinafter “(G) component”) for the purpose of improving curability. May also be included).
Examples of the curing accelerator (G) include amines such as aniline, N, N-substituted aniline, N, N-substituted-p-toluidine, and 4- (N, N-substituted amino) benzaldehyde. Are aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2 -Hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, Enirimoruhorin, piperidine, N, N-bis (hydroxyethyl) aniline, the diethanol aniline can be used.
However, if a curing accelerator (G) is added, some or all of it may dissolve or dissolve in water or may form a complex with water, so there is a possibility of dissolution in water. It is preferable not to use the agent (G).

<Filler (H)>
The radically polymerizable water-containing resin composition of the present invention may contain a filler (H) (hereinafter also referred to as “component (H)”) for the purpose of improving workability and adjusting physical properties. And inorganic fillers and organic fillers.
Examples of inorganic fillers include cement, quicklime, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, silica sand and other artificial aggregates such as ceramic and glass waste, talc. However, from the viewpoint of heat generation and shrinkage due to the hydration reaction of cement, a combination of cement having hydration reactivity and dry aggregate such as river gravel is preferable.
As cement, normal Portland cement, early-strong Portland cement, ultra-early strong Portland cement, moderately hot Portland cement, portland cement such as sulfate-resistant Portland cement, mixed cements such as blast furnace cement, silica cement, fly ash cement, Special cements such as ultrafast cement, alumina cement, oil well cement, geothermal cement, color cement, fine powder cement, and various gypsums can be used.
In addition, aluminum hydroxide can be used from the viewpoint of imparting flame retardancy, and fumed silica, talc, and the like can also be used from the viewpoint of adjusting fluidity. Further, from the viewpoint of coloring, a colorant such as titanium oxide or an inorganic pigment can be used, and a molecular sieve can also be used.
Furthermore, from the viewpoint of removing contaminants and radioactive substances contained in water, zeolite, activated carbon, and the like can be used.
As the organic filler, organic fillers such as amide wax and water-absorbing polymer can also be used.
When the radically polymerizable water-containing resin composition of the present invention contains the filler (H), the amount thereof is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C). If the amount of the inorganic filler is within the above range, sufficient strength can be expressed when the radical polymerizable water-containing resin composition is cured, and if it exceeds the above range, troubles such as injection work occur. There is a case.

<Other ingredients>
(Polymerization inhibitor)
The radically polymerizable water-containing resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization and controlling the reaction rate.
Examples of the polymerization inhibitor include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, 4-tert-butylcatechol.
When the radically polymerizable water-containing resin composition contains a polymerization inhibitor, the amount thereof is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C).

[Curing retarder]
The radically polymerizable water-containing resin composition of the present invention may contain a curing retarder for the purpose of delaying the curing of the radically polymerizable compound (C). Examples of the curing retarder include free radical curing retarders such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6- TEMPO such as tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4-Oxo-TEMPO) and derivatives thereof . Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO) is preferable from the viewpoint of cost and ease of handling.
Moreover, when the radically polymerizable water-containing resin composition of the present invention contains an inorganic filler such as cement, a setting retarder selected from oxycarboxylic acid, phosphonic acid and derivatives thereof can also be used. Specifically, examples of the oxycarboxylic acid and derivatives thereof include gluconic acid, glucoheptonic acid, arabonic acid, malic acid, tartaric acid, citric acid, and alkali metal salts and alkaline earth metal salts thereof. Examples of phosphonic acid and its derivatives include aluminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta ( Methylenephosphonic acid), their alkali metal salts and alkaline earth metal salts.
When the radically polymerizable water-containing resin composition contains a curing retardant, the amount thereof is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C).
[Coupling agent]
In the radically polymerizable water-containing resin composition of the present invention, a coupling agent may be used for the purpose of improving processability and for improving the adhesion to a substrate. Examples of coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like.
An example of such a coupling agent is a silane coupling agent represented by R ³ —Si (OR ⁴ ) ₃ . Examples of R ³ include an aminopropyl group, a glycidyloxy group, a methacryloxy group, an N-phenylaminopropyl group, a mercapto group, and a vinyl group. Examples of R ⁴ include a methyl group and an ethyl group. Etc.
When the radical polymerizable water-containing resin composition contains a coupling agent, the amount thereof is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C).

[Polyisocyanate compound]
The radically polymerizable water-containing resin composition of the present invention may contain a polyisocyanate compound. The polyisocyanate compound reacts with the hydroxyl group of the radical polymerizable compound (C) to form a cured coating film.
The polyisocyanate compound contains two or more isocyanate groups in the molecule, and the isocyanate groups may be blocked with a blocking agent or the like.
Examples of polyisocyanate compounds not blocked with a blocking agent include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or Cycloaliphatic diisocyanates such as 2,6) -diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; aromatics such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate Diisocyanates; polyisocyanates such as polyisocyanates having a valence of 3 or more such as lysine triisocyanate; Examples include adducts of reisocyanates and polyhydric alcohols, low molecular weight polyester resins or water, cyclized polymers of the above-described diisocyanates (for example, isocyanurates), biuret type adducts, and the like. Of these, isocyanurate of hexamethylene diisocyanate is preferable.
These polyisocyanate compounds may be used alone or in combination of two or more.

When the radically polymerizable water-containing resin composition contains a polyisocyanate compound, the amount thereof is preferably 0.1 parts by mass to 50 parts by mass, more preferably 1 part per 100 parts by mass of the radically polymerizable compound (C). -30 parts by mass, more preferably 2-20 parts by mass.

The blocked polyisocyanate compound is obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent.
Examples of the blocking agent include phenols such as phenol, cresol, xylenol; ε-caprolactam; δ-valerolactam, γ-butyrolactam, β-propiolactam and other lactams; methanol, ethanol, n- or iso-propyl alcohol N-, iso- or tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, or the like; formamide Xime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone Oxime, cyclohexane oxime oxime; dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, blocking agent active methylene such as acetylacetone and the like. By mixing the polyisocyanate and the blocking agent, the isocyanate group of the polyisocyanate can be easily blocked.

When the polyisocyanate compound is a non-blocked polyisocyanate compound, since the reaction of both occurs when the radical polymerizable compound (C) and the polyisocyanate compound in the radical polymerizable water-containing resin composition of the present invention are mixed, It is preferable to separate the radically polymerizable compound (C) and the polyisocyanate compound and mix them at the time of use.
In addition, since a radically polymerizable compound (C) and a polyisocyanate compound are made to react, a curing catalyst can be used. Suitable curing catalysts include, for example, tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyl And organometallic catalysts such as tin oxide and lead 2-ethylhexanoate.
When the radical polymerizable water-containing resin composition contains the curing catalyst amount, the amount is preferably 0.01 parts by mass to 5 parts by mass, more preferably 100 parts by mass with respect to the radical polymerizable compound (C). 0.05 to 4 parts by mass.
(Wet dispersant)
The radically polymerizable water-containing resin composition of the present invention may contain a wetting and dispersing agent.
Examples of the wetting and dispersing agent include a fluorine-based wetting and dispersing agent and a silicon-based wetting and dispersing agent, and these may be used alone or in combination of two or more.
Commercially available fluorine-based wetting and dispersing agents include Megafac (registered trademark) F176, Megafac (registered trademark) R08 (manufactured by Dainippon Ink and Chemicals), PF656, PF6320 (manufactured by OMNOVA), Troisol S- 366 (manufactured by Troy Chemical Co., Ltd.), Florard FC430 (manufactured by 3M Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Commercially available silicone-based wetting and dispersing agents include BYK (registered trademark) -322, BYK (registered trademark) -377, BYK (registered trademark) -UV3570, BYK (registered trademark) -330, BYK (registered trademark) -302. BYK (registered trademark) -UV3500, BYK-306 (manufactured by BYK Japan), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Moreover, it is preferable that a silicone type wet dispersing agent is a silicone type wet dispersing agent containing the compound represented by a following formula (U).

(Wherein R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 200 carbon atoms which may contain an aromatic ring, or — (CH ₂ ) ₃ O (C ₂ H ₄ O) _p ( CH ₂ CH (CH ₃ ) O) _q R ′, n is an integer of 1 to 200, R ′ is an alkyl group having 1 to 12 carbon atoms, p and q are each an integer, and q / p = 0 to 10 is satisfied.)
In addition, examples of commercially available silicone-based wetting and dispersing agents containing the compound represented by the formula (U) include BYK (registered trademark) -302 and BYK (registered trademark) -322 (manufactured by Big Chemie Japan Co., Ltd.). It is done.
When the radically polymerizable water-containing resin composition of the present invention contains a wetting and dispersing agent, the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0 with respect to 100 parts by mass of the radically polymerizable compound (C). .01 to 2 parts by mass.

〔wax〕
The radically polymerizable water-containing resin composition of the present invention may contain a wax.
Examples of the wax include paraffin waxes and polar waxes, and these may be used alone or in combination of two or more.
Known paraffin waxes having various melting points can be used as the paraffin waxes. Moreover, as polar waxes, those having both a polar group and a nonpolar group in the structure can be used. Specifically, NPS (registered trademark) -8070, 9125 (manufactured by Nippon Seiwa Co., Ltd.), Emanon (registered trademark) 3199, 3299 (manufactured by Kao Corporation) and the like.
When the radically polymerizable water-containing resin composition of the present invention contains a wax, the amount thereof is preferably 0.05 to 4 parts by mass, more preferably 0.004 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C). 1 to 2.0 parts by mass.

[Thixotropic agent]
The radical polymerizable water-containing resin composition of the present invention may use a thixotropic agent for the purpose of adjusting the viscosity for ensuring workability on a vertical surface or a ceiling surface.
Examples of the thixotropic agent include an inorganic thixotropic agent and an organic thixotropic agent. Examples of the organic thixotropic agent include hydrogenated castor oil type, amide type, polyethylene oxide type, vegetable oil polymerized oil type, interface. An activator system and a composite system using these in combination are exemplified. Specifically, DISPARLON (registered trademark) 6900-20X (Enomoto Kasei Co., Ltd.) and the like can be mentioned.
In addition, examples of inorganic thixotropic agents include silica and bentonite, and hydrophobic ones include Leolosil (registered trademark) PM-20L (gas phase method silica manufactured by Tokuyama Corporation) and Aerosil (registered trademark) AEROSIL. R-106 (Nippon Aerosil Co., Ltd.) and the like, and examples of hydrophilic ones include Aerosil (registered trademark) AEROSIL-200 (Nippon Aerosil Co., Ltd.). From the viewpoint of further improving thixotropic properties, those obtained by adding BYK (registered trademark) -R605 or BYK (registered trademark) -R606 (manufactured by BYK Japan) to hydrophilic calcined silica. Can also be suitably used.
When the radical polymerizable water-containing resin composition of the present invention contains a thixotropic agent, the amount thereof is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). The amount is preferably 0.1 to 5 parts by mass.

[Method for producing radically polymerizable water-containing resin composition]
The method for producing a radically polymerizable water-containing resin composition of the present invention comprises the step 1 of obtaining the mixed liquid (i) by mixing the metal-containing compound (A) and the radically polymerizable compound (C), the mixed liquid Step 2 of obtaining a mixed liquid (ii) by mixing (i) and the thiol compound (B), mixing the mixed liquid (ii), the surfactant (D) and the water (E). This is a method comprising the step 3 of obtaining the liquid mixture (iii) and the step 4 of mixing the liquid mixture (iii) and the radical polymerization initiator (F).
When the radically polymerizable water-containing resin composition of the present invention is produced by the above method, the thiol compound (B) can be efficiently coordinated in the vicinity of the metal of the metal-containing compound (A).
There is no restriction | limiting in particular in the mixing method in each said process, It can carry out by a well-known method. In addition, the temperature at the time of each mixing is preferably 20 to 40 ° C. from the viewpoint of uniformly mixing and suppressing the deterioration of each component.
In Step 3, it is preferable to mix the surfactant (D) and water (E) in advance from the viewpoint of uniform mixing.
The order of mixing optional components other than components (A) to (F) is not particularly limited and can be mixed in any step, but from the viewpoint of uniform mixing before radical polymerization is started, It is preferable to mix in any one of 1 to 3, and it is more preferable to mix in step 3.

In addition to the above-described production method of the present invention, the radical polymerizable water-containing resin composition of the present invention can be produced, but a uniform composition may not be obtained. It is preferable to manufacture by.

[Method of curing radically polymerizable water-containing resin composition]
The method for curing the radically polymerizable water-containing resin composition of the present invention comprises a state where the water (E) is contained in the radically polymerizable water-containing resin composition of the present invention, the radically polymerizable water-containing resin composition and water. It is a curing method for curing in either a contacted state or a state in which the radical polymerizable water-containing resin composition is immersed in water.
By using said radical polymerization initiator (F), the radically polymerizable water-containing resin composition of the present invention can be cured preferably at a temperature of 5 ° C. or higher.
The “state in which water (E) is contained in the radical polymerizable water-containing resin composition” in the curing method of the present invention means that water (E) is removed from the radical polymerizable water-containing resin composition of the present invention by drying or the like. It means no state. In addition, the “state in which the radical polymerizable water-containing resin composition and water are brought into contact with each other” means that all or part of the radical polymerizable water-containing resin composition of the present invention and water other than the water (E), A state in which water present in the environment around the radical polymerizable water-containing resin composition is in contact. Furthermore, the “state in which the radical polymerizable water-containing resin composition is immersed in water” refers to a state in which all or part of the radical polymerizable water-containing resin composition of the present invention is immersed in water.
Since the radically polymerizable water-containing resin composition of the present invention can be cured even in a water-containing state as described above, it can be cured even in a state where it is in contact with water and further immersed. Is possible.
By the above curing method, all or a part of the water (E) in the radical polymerizable water-containing resin composition is taken into the cured resin component without solid-liquid separation.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by an Example.
The raw materials used in Examples and Comparative Examples are as follows.
<Metal soap (A)>
・ Metal soap (A-1)
Cobalt octylate (manufactured by Toei Chemical Co., Ltd., hexoate cobalt, content of cobalt in the total amount of product 8% by mass, molecular weight 345.34)
・ Metal soap (A-2)
Cobalt naphthenate (Nippon Kagaku Sangyo Co., Ltd., Naphtex Cobalt, Cobalt content 6% by mass, molecular weight 401.28)

<Secondary or tertiary thiol compound (B)>
・ Secondary thiol compound (B-1)
Bifunctional secondary thiol, manufactured by Showa Denko KK, Karenz MT (registered trademark) BD1 (1,4-bis (3-mercaptobutyryloxy) butane, molecular weight 299.43)
・ Secondary thiol compound (B-2)
Tetrafunctional secondary thiol, manufactured by Showa Denko KK, Karenz MT (registered trademark) PE1 (pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight 544.76)

・ Secondary thiol compound (B-3)
Cyanuric acid skeleton trifunctional secondary thiol, manufactured by Showa Denko KK, Karenz MT (registered trademark) NR1 (1,3,5-tris [2- (3-mercaptobutyryloxy) ethyl] -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione, molecular weight 567.67)
・ Secondary thiol compound (B-4)
Trifunctional secondary thiol, manufactured by Showa Denko KK, TPMB (trimethylolpropane tris (3-mercaptobutyrate), molecular weight 440.64)
・ Tertiary thiol compound (B-5)
Trifunctional tertiary thiol: trimethylolpropane tris (2-mercaptoisobutyrate) synthesized in the following synthesis example, molecular weight 440.64

<Primary thiol compound (B ')>
・ Primary thiol compound (B'-1)
Trifunctional primary thiol, manufactured by Sakai Chemical Co., Ltd., TMTP (trimethylolpropane tris (3-mercaptopropionate))
・ Primary thiol compound (B'-2)
Tetrafunctional primary thiol, manufactured by SC Organic Chemical Co., Ltd., PEMP (pentaerythritol tetrakis (3-mercaptopropionate))

<Radically polymerizable compound (C)>
.Radically polymerizable compound (C-1)
Vinyl ester resin Lipoxy (registered trademark), manufactured by Showa Denko KK, NSR-112 (without styrene)
.Radically polymerizable compounds (C-2)
Unsaturated polyester resin Rigolac (registered trademark), Showa Denko KK, SR-110N (styrene content 40% by mass)
.Radically polymerizable compounds (C-3)
Vinyl ester resin Lipoxy (registered trademark), manufactured by Showa Denko KK, NSR-1000W-1 (without styrene)

<Surfactant (D)>
・ Surfactant (D-1)
Sodium dialkylsulfosuccinate (manufactured by Kao Corporation, Perex OT-P, sodium dialkylsulfosuccinate 70% by mass)
<Water (E)>
・ Water (E-1)
Ion exchange water

<Radical polymerization initiator (F)>
・ Radical polymerization initiator (F-1)
Methyl ethyl ketone peroxide, NOF Corporation, Permec N
・ Radical polymerization initiator (F-2)
Hardener for vinyl ester resin, 328E manufactured by Kayaku Akzo Corporation
.Radical polymerization initiator (F-3)
Cumene hydroperoxide, NOF Corporation, Park Mill H-80

<Curing accelerator (G)>
Dimethylaniline, manufactured by Tokyo Chemical Industry Co., Ltd., DMA

<Filler (H)>
・ Filler (H-1)
Portland cement JIS standard product, manufactured by HOKUSEI Cement, ordinary cement and filler (H-2)
Aggregate, manufactured by Mishu Kosan Co., Ltd.

<Synthesis Example> Synthesis of trimethylolpropane tris (2-mercaptoisobutyrate) (B-5) 2.68 g (20 mmol) of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-mercaptoisobutanoic acid (Showa Denko KK) 7.57 g (63 mmol), p-toluenesulfonic acid monohydrate 0.23 g (1.2 mmol), and toluene (manufactured by Junsei Chemical Co., Ltd.) 20 g were charged into a 100 mL eggplant flask, and Dean-Stark apparatus and cooling tube Attached.
The contents were heated using a 145 ° C. oil bath while stirring. After stirring for 3 hours, the mixture was allowed to cool to room temperature and neutralized with 50 ml of a 5 mass% aqueous sodium hydrogen carbonate solution. Further, the organic layer was washed twice with ion-exchanged water, dehydrated and dried over anhydrous magnesium sulfate, toluene was distilled off, and the residue was subjected to column chromatography using silica gel (silica gel: Wakogel C-200, developing solvent). : N-hexane / ethyl acetate = 5/1 (volume ratio)) to give white crystalline trimethylolpropane tris (2-mercaptoisobutyrate) (B2-1).

<Examples 1 to 13 and Comparative Examples 1 to 4>
Example 1
[Step 1 and Step 2]
0.2 parts by weight of metal soap (A-1) is added to 80 parts by weight of the radical polymerizable compound (C-1), and the mixture is thoroughly stirred at room temperature (25 ° C.) to obtain a mixed liquid (i). The mixture (ii) was obtained by thoroughly stirring the mixture (i) and 2.5 parts by mass of the secondary thiol compound (B-1).

[Step 3 and Step 4]
A surfactant (D-1) 0.28 part by mass was added to 19.6 parts by mass of water (E-1) to prepare a 1.4% by mass aqueous surfactant solution. Then, the mixed solution (ii) and the total amount of the surfactant aqueous solution are thoroughly stirred to obtain a mixed solution (iii), and the mixed solution (iii) and the radical polymerization initiator (F-1) 2. A radical polymerizable water-containing resin composition was obtained by stirring 5 parts by mass. The obtained radical polymerizable water-containing resin composition was evaluated according to the following method. The results are shown in Table 1.
The blending amount of the metal soap shown in Examples 1 to 13 and Comparative Examples 1 to 4 is not a solid blending amount but a blending amount converted to the amount of the metal component in the metal soap, and the surfactant. The blending amount is a blending amount converted to the active ingredient amount of the surfactant.

Examples 2 to 13 and Comparative Examples 1 to 4
A radical polymerizable water-containing resin composition was obtained in the same manner as in Example 1 except that the respective components were blended according to the descriptions in Tables 1 to 3. The obtained radical polymerizable water-containing resin composition was evaluated according to the following method. The results are shown in Tables 1 to 3.

<Measurement of gelation time, curing time, and curing temperature>
The radically polymerizable water-containing resin compositions obtained in Examples and Comparative Examples were put into a test tube (outer diameter: 18 mm, length: 165 mm) from the bottom to 100 mm under conditions of 25 ° C., and radically polymerizable water-containing water was used using a thermocouple. The temperature of the resin composition was measured.
The time taken for the temperature of the radical polymerizable water-containing resin composition to reach 25 ° C. to 30 ° C. was defined as the gel time. Further, the time until the temperature of the radical polymerizable water-containing resin composition reached the maximum exothermic temperature from 25 ° C. was defined as the curing time, and the maximum exothermic temperature was defined as the curing temperature, and measured according to JIS K-6901.

<Separation of water and resin>
The radically polymerizable water-containing resin compositions obtained in the examples and comparative examples were visually observed to evaluate whether water and the radically polymerizable compound (C) were separated.

As is clear from the results of Examples and Comparative Examples, the radical polymerizable water-containing resin composition of the present invention containing a specific amount of each component has good results such as gelation time, curing temperature, etc. No separation from water was observed.

<Examples 14 to 22, Comparative Examples 5 to 10, and Reference Examples 1 to 3>
Example 14
[Step 1 and Step 2]
0.16 parts by mass of metal soap (A-1) is added to 80 parts by mass of the radical polymerizable compound (C-1), and the mixture is thoroughly stirred at room temperature (25 ° C.) to obtain a mixed liquid (i). A mixed liquid (ii) was obtained by adding the mixed liquid (i) and 2 parts by mass of the secondary thiol compound (B-1) and stirring well.

[Step 3 and Step 4]
A surfactant (D-1) 0.28 part by mass was added to 19.6 parts by mass of water (E-1) to prepare a 1.4% by mass aqueous surfactant solution. Then, the mixture (ii) and the total amount of the surfactant aqueous solution are thoroughly stirred to obtain a mixture (iii), and the mixture (iii) and the radical polymerization initiator (F-3) 2 mass The radical polymerizable water-containing resin composition was obtained by stirring the part. About the obtained radically polymerizable water-containing resin composition, the gelation time, the curing time, and the curing temperature were measured in the same manner as described above. Moreover, the weight change of hardened | cured material was evaluated according to the following method. The results are shown in Table 4.
In addition, the compounding amount of the metal soap shown in Examples 14 to 22, Comparative Examples 5 to 10, and Reference Examples 1 to 3 is not a solid compounding amount but a compounding amount converted to the amount of the metal component in the metal soap. The amount of the surfactant is the amount converted to the amount of the active ingredient of the surfactant.

Examples 15 to 22, Comparative Examples 5 to 10, and Reference Examples 1 to 3
A radically polymerizable water-containing resin composition was obtained in the same manner as in Example 14 except that the respective components were blended according to the descriptions in Tables 5 to 7. About the obtained radically polymerizable water-containing resin composition, the gelation time, the curing time, and the curing temperature were measured in the same manner as described above. Moreover, the weight change of hardened | cured material was evaluated according to the following method. The results are shown in Tables 5-7.

<Measurement method of weight change>
The radical polymerizable water-containing resin compositions obtained in Examples and Comparative Examples were poured into a mold having a square of 4 cm on a side and a thickness of 3 mm. The first weight measurement was performed when poured into the mold.
Next, the radically polymerizable water-containing resin composition poured into the mold was dried at 25 ° C. for 2 hours, and then the second weight measurement was performed to calculate the difference from the first weight measurement (in the table) , Indicated as “weight change after drying at 25 ° C.”)
After the second weight measurement, drying was performed in an oven at 80 ° C. for 6 hours, and then the third weight measurement was performed to calculate the difference from the second weight measurement (in the table, “after 80 ° C. drying” Change in weight ").
Finally, the cured product of the radically polymerizable water-containing resin composition is removed from the mold, and the cured product is split so that it becomes 6 pieces. It was. The weight of the debris of the cured product taken out from the oven was measured, and the weight change before and after drying at 100 ° C. was measured (shown as “weight change after drying at 100 ° C.” in the table).
A value obtained by dividing the total of each weight change by the weight before drying was calculated as a weight reduction rate.

Examples 14 to 22 have good results such as gelation time and curing temperature.
In the examples, the amount of water that can be retained by using a dryer at 80 ° C. to 100 ° C. is evaluated. Cement or the like can be selected as appropriate.
On the other hand, in Comparative Examples 5, 9 and 10, the weight reduction rate is larger than the value of the example, so that it can be seen that almost all the water was removed from the cured product by the drying treatment. That is, it can be said that moisture is not held in the cured product.
Reference Examples 1 to 3 are test examples for control, which were tested without using any of water and each component. From the results of these reference examples, it can be seen that the factor that decreases the weight of the cured products of the examples and comparative examples is water.

<Examples 23 to 28 and Reference Examples 4 to 5>
Example 24 (Example 23 will be described later)
[Step 1 and Step 2]
A mixed liquid (i) is obtained by adding 0.04 part by weight of metal soap (A-1) to 100 parts by weight of the radical polymerizable compound (C-1) and stirring well, and the mixed liquid (i) The mixture (ii) was obtained by thoroughly stirring 0.5 parts by mass of the secondary thiol compound (B-1).

[Step 3 and Step 4]
0.175 parts by mass of surfactant (D-1) was added to 24.75 parts by mass of water (E-1) to prepare a 0.7% by mass aqueous surfactant solution. And after fully stirring the said liquid mixture (ii) and the whole quantity of the said surfactant aqueous solution, 0.01 part of polymerization inhibitors were added and stirred well. Thereafter, 240 parts by mass of Portland cement (H-1) as a filler was added and stirred to obtain a mixed liquid (iii). The mixed liquid (iii) and 0.5 parts by mass of the radical polymerization initiator (F-3) And a radical polymerizable water-containing resin composition was obtained.
About the obtained radical polymerizable water-containing resin composition, a PET film is pasted on a glass plate having a side of 30 cm as a base, and a mold is formed in four sides with a rubber having a thickness of 4 mm, and the radical polymerizable water-containing resin is formed there. The composition was poured into a mold, covered with a 30 cm side glass plate prepared separately and covered with a PET film, covered with a weight of about 5 kg and allowed to stand for 24 hours to cure. .
The cured product of the obtained resin composition was cut into a size described later, and various tests were evaluated. The results are shown in Table 8.
The blending amount of the metal soap shown in Examples 23 to 28 and Reference Examples 4 to 5 is not a solid blending amount but a blending amount converted to the amount of the metal component in the metal soap, and has a surface activity. The blending amount of the agent is a blending amount converted to the amount of the active ingredient of the surfactant.

Examples 23, 25 to 28 and Reference Examples 4 to 5
A radical polymerizable water-containing resin composition was obtained in the same manner as in Example 24 except that each component was blended according to the descriptions in Tables 8 and 9. About the obtained radical polymerizable water-containing resin composition, the hardened | cured material was obtained by the method similar to the above-mentioned method, and various tests were evaluated. The results are shown in Tables 8 and 9.

<Method for measuring compressive stress>
A compressive stress measurement test was performed according to JIS K7181 (2011).
The test specimen was prepared in accordance with the section 6.1.2 of JIS K7181 (2011). The dimensions of the test piece were 10 mm long, 10 mm wide, and 4 mm thick.

<Compressive modulus>
In accordance with JIS K7181 (2011), a measurement test of the compressive elastic modulus was performed.
The procedure for preparing the test specimen was in accordance with JIS K7181 (2011), section 6.1.2. The dimensions of the test specimen were 50 mm long, 10 mm wide, and 4 mm thick.

[Apparatus used for bending strength test]
UCT-1T (1t Tensilon (registered trademark)) manufactured by ORIENTEC was used.
The test speed in the bending test was 2.0 mm / min.

<Bending strength, flexural modulus>
According to JISK7171 (2008), a measurement test of bending strength and bending elastic modulus was performed.
The procedure for preparing the test specimen was in accordance with JIS K7171 (2008), section 6.1.2. The dimensions of the test specimen were 80 mm long, 10 mm wide, and 4 mm thick.

[Apparatus used for compressive strength test and compressive modulus test]
This was performed using 5900R manufactured by INSTRON.
The compression speed in the compression test was 1 mm / min.

As is clear from the above results, Examples 23 to 28 are excellent in bending strength, bending elastic modulus, compressive stress, and compressive elastic modulus.
The radically polymerizable water-containing resin composition of the present invention can be cured despite containing water, and the cured product is superior to the cured product of the resin composition not containing water. It can be seen that it exhibits properties.

The radically polymerizable water-containing resin composition of the present invention can be cured despite containing water. In addition, since it can be cured on a surface where a large amount of water exists or on a surface wet with water, for example, a surface wet with water such as polymer cement mortar or cement concrete, further brackish water, sea water, It is also useful as a coating agent, repair agent, or paint for concrete surfaces immersed in water such as river areas. Further, since the curing speed can be controlled, it can be used as a repair material for water leakage such as tunnels and dams. Furthermore, it is also possible to replace concrete floor boards for expressways and concrete flooring for factories, warehouses, parking lots, etc. with a water-containing resin composition. In that case, based on Japanese Patent Application Nos. 2015-087055, 2015-227706, 2016-000614, 2015-203990, 2015-240437, 2016-033646, and 2016-040829 The radical resin composition described in the specification of the later application can be used in various applications, particularly in combination with a primer for flooring or a surface finishing agent for flooring to form a multilayer structure.
In addition, since the water contained in the radically polymerizable water-containing resin composition of the present invention is retained in the cured product without being subjected to solid-liquid separation, for example, the radioactive material generated in large quantities due to an accident at a nuclear power plant, etc. By containing a substance that adsorbs radioactive substances in the radically polymerizable water-containing resin composition containing contaminated water and curing it, the contaminated water is stored in a solid state until the radioactive substance is safe for the human body. be able to. Similarly, factory effluent can be stored in a solid state.

Claims

1 selected from one or more metal-containing compounds (A) selected from metal soaps (A1) and metal complexes (A2) having a β-diketone skeleton, secondary thiol compounds (B1) and tertiary thiol compounds (B2) A metal of the metal-containing compound (A) containing at least one kind of thiol compound (B), radical polymerizable compound (C), surfactant (D), water (E), and radical polymerization initiator (F) The amount of the surfactant (D) relative to a total of 100 parts by mass of the component, the thiol compound (B), the radical polymerizable compound (C), the water (E), and the radical polymerization initiator (F) is 0.00. A radically polymerizable water-containing resin composition, which is 05 to 10 parts by mass, and the amount of the radical polymerization initiator (F) is 0.3 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C).
The thiol compound (B) has at least one structure represented by the following formula (Q), and includes a mercapto group in the structure represented by the following formula (Q). The radically polymerizable water-containing resin composition according to claim 1, which is a compound having two or more mercapto groups bonded to a secondary carbon atom.

(In the formula (Q), R 1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and R 2 is an alkyl group or carbon having 1 to 10 carbon atoms. (It is an aromatic group of formulas 6 to 18, and * indicates that it is linked to an arbitrary organic group. A is an integer of 0 to 2.)
The radically polymerizable water-containing water according to claim 2, wherein R 1 in the formula (Q) is a hydrogen atom, and the thiol compound (B) has two or more mercapto groups bonded to secondary carbon atoms in the molecule. Resin composition.
The radically polymerizable water-containing resin composition according to claim 2 or 3, wherein the thiol compound (B) has at least one ester structure represented by the following formula (Q-1).

(In the formula (Q-1), R 1 , R 2, * and a are, R 1, R 2 in the formula (Q), the same meanings as * and a.)
The radical polymerizable water-containing resin composition according to claim 4, wherein a in the formula (Q-1) is 1.
5. The thiol compound (B) having an ester structure represented by the formula (Q-1) is derived from a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol. Or the radically polymerizable water-containing resin composition of 5.

(In the formula (S), R 1, R 2 and a have the same meanings as R 1, R 2 and a in the formula (Q).)
The secondary thiol compound (B1) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris [2- (3-mercapto Butyryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate) and trimethylolpropane tris (3-mercapto The radically polymerizable water-containing resin composition according to any one of claims 1 to 6, which is one or more selected from butyrate).
The radically polymerizable water-containing resin composition according to any one of claims 1 to 7, wherein the thiol compound (B) is a compound having two mercapto groups bonded to a secondary or tertiary carbon atom in the molecule.
The radical polymerizable water-containing resin composition according to any one of claims 1 to 8, wherein the thiol compound (B) has a molecular weight of 5,000 or less.
The radically polymerizable water-containing solution according to any one of claims 1 to 9, wherein the total amount of the thiol compound (B) is 0.01 to 15 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C). Resin composition.
The radical according to any one of claims 1 to 10, wherein the molar ratio [(B) / (A)] of the thiol compound (B) to the metal component of the metal-containing compound (A) is 0.1 to 15. Polymerizable water-containing resin composition.
12. The radical polymerizable water-containing resin composition according to claim 1, wherein the content of the radical polymerizable compound (C) in the radical polymerizable water-containing resin composition is 20 to 95% by mass.
The metal element constituting the metal-containing compound (A) is lithium, magnesium, calcium, barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, The radically polymerizable water-containing resin composition according to any one of claims 1 to 12, which is at least one selected from aluminum, indium, tin, lead, neodymium, and cerium.
The long-chain fatty acid constituting the metal soap (A1) is a linear or cyclic saturated fatty acid having 7 to 15 carbon atoms or an unsaturated fatty acid having 7 to 15 carbon atoms. The radically polymerizable water-containing resin composition described.
The radical polymerizable water-containing resin composition according to any one of claims 1 to 14, wherein the metal soap (A1) is at least one selected from manganese octylate, cobalt octylate and cobalt naphthenate.
The radically polymerizable water-containing resin composition according to any one of claims 1 to 15, wherein the surfactant (D) contains one or more selected from an anionic surfactant and a nonionic surfactant. .
The radically polymerizable compound (C) is one selected from vinyl ester resins, unsaturated polyester resins, or a mixture of these and a radically polymerizable unsaturated monomer. The radically polymerizable water-containing resin composition described.
The radical polymerizable water-containing resin composition according to claim 17, wherein the radical polymerizable unsaturated monomer is styrene, and the content of styrene in the radical polymerizable compound (C) is 20% by mass or less.
The radically polymerizable water-containing resin composition according to any one of claims 1 to 18, further comprising a filler (H).
The radical-polymerizable hydrous resin composition according to claim 19, wherein the filler (H) is cement and aggregate.
The water (E) is at least one selected from ion-exchanged water, tap water, seawater, river water, well water, factory water, distilled water, and water containing a radioactive substance. The radically polymerizable water-containing resin composition according to claim 1.
A state in which the water (E) is contained in the radical polymerizable water-containing resin composition, a state in which the radical polymerizable water-containing resin composition is in contact with water, or the radical polymerizable water-containing resin composition in water The method for curing a radically polymerizable hydrous resin composition according to any one of claims 1 to 21, wherein the curing is performed in any of the immersed states.
Step 1 of obtaining a mixed solution (i) by mixing the metal-containing compound (A) and the radical polymerizable compound (C), mixing the mixed solution (i) and the thiol compound (B). Step 2 to obtain a mixed solution (ii) by the step 2, Step 3 to obtain a mixed solution (iii) by mixing the mixture (ii), the surfactant (D) and the water (E), and the mixing The method for producing a radically polymerizable water-containing resin composition according to any one of claims 1 to 21, further comprising a step 4 of mixing the liquid (iii) and the radical polymerization initiator (F).