JP6690638B2 - Radical-polymerizable water-containing resin composition, method for curing the same, and method for producing radical-polymerizable water-containing resin composition - Google Patents

Description

  TECHNICAL FIELD 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 method for curing the same, and a method for producing a radical-polymerizable water-containing resin composition.

Metal soaps have good solubility in resins and solvents, and also have various functions, such as curing accelerators for unsaturated polyester resins, dryers for paints and printing inks, and adhesives for rubber and tires. It is used in a wide range of applications such as, lubricant extreme pressure agents, combustion improvers, and polymerization catalysts.
However, when a metal soap is used as a curing accelerator under the condition that water is present, there is a problem that its function is not sufficiently expressed (Non-Patent Document 1).
As a method for solving this problem, there is a method of using an accelerating aid. Examples of the accelerating aid include β-diketones, aromatic tertiary amines, mercaptans (thiol compounds), phosphorus compounds and the like. As a technique using such an accelerating aid, 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 is described to use a chain transfer agent such as a thiol compound which it has as an accelerating aid.
Further, 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.

Patent No. 4518773 Patent No. 4469484

Eiichiro Takiyama, "Polyester Resin Handbook", First Edition, Japan, Nikkan Kogyo Shimbun, June 30, 1988, p. 119 Shigeki Matsunaga, "Electronic State and Curing Performance of Cobalt-Amine Composite Dryer", DIC Technical Review, Japan, 1999, No. 5, pages 51-56

It has been difficult to sufficiently cure the curing accelerator described in Patent Document 1 which has been generally used in the past 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 redox reaction of cobalt, and therefore, in the presence of water. It was difficult to perform sufficient curing.
Patent Document 2 discloses the use of Rongalit or a thiourea derivative, but the use of a secondary thiol compound has not been examined.
The present invention has been made in view of the above-mentioned conventional circumstances, and a radically polymerizable water-containing resin composition capable of being stably cured even in a state containing water, a curing method thereof, and a radically polymerizable resin composition. A method for producing a water-containing resin composition is provided.

  As a result of earnest studies to solve the above-mentioned conventional problems, the present inventors have found that in the presence of water, the metal in the metal-containing compound is deactivated by water, so that curing cannot be performed. Then, after repeatedly studying a method for preventing deactivation of a metal, when a metal-containing compound and a secondary or tertiary thiol compound are used together, a secondary or tertiary thiol compound is coordinated in the vicinity of the metal of the metal-containing compound. As it exists, it becomes difficult for water to approach the metal, and deactivation of the metal can be prevented. As a result, the composition cures stably even under the condition that water is present inside the composition. It was found that 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 compound (B1) and tertiary thiol compound (B2) selected from metal soap (A1) and metal complex (A2) having a β-diketone skeleton The metal-containing compound (A) containing at least one selected thiol compound (B), radically polymerizable compound (C), surfactant (D), water (E), and radical polymerization initiator (F). ), The thiol compound (B), the radically polymerizable compound (C), the water (E), and the radical polymerization initiator (F) in an amount of 100 parts by mass 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). object.
[2] The thiol compound (B) has at least one structure represented by the following formula (Q), and 2 in the molecule including the mercapto group 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 primary or tertiary carbon atom.

(In 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 a carbon atom. It is an aromatic group of the formulas 6 to 18, and * indicates that it 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 [2], which is a hydrogen atom and has two or more mercapto groups bonded to a secondary carbon atom in the molecule of the thiol compound (B).

[4] The radical-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 radical-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 the above [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) is 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, trimethylolethane tris (3-mercaptobutyrate) and trimethylolpropane tris ( Radical-polymerizable water-containing resin composition according to any one of [1] to [6] above, which is one or more 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 radical-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 the above [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). The radically polymerizable water-containing resin composition described.
[11] In the above [1] to [10], 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 as described in any one of the above.

[12] The radical-polymerizable water-containing resin according to any one of [1] to [11], wherein the content of the radical-polymerizable compound (C) in the radical-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 [1] to [12] above, which is one or more selected from zinc, aluminum, indium, tin, lead, neodymium, and cerium.
[14] The long-chain fatty acid constituting the metal soap (A1) is a chain or cyclic saturated fatty acid having 7 to 15 carbon atoms or an unsaturated fatty acid having 7 to 15 carbon atoms, [1] to [[1]. [13] The radically polymerizable water-containing resin composition as described in any one of [13].
[15] The radical-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 at least one selected from anionic surfactants and nonionic surfactants. Polymerizable water-containing resin composition.
[17] The above-mentioned [1]-[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 as described in any one of [16].
[18] The radical-polymerizable hydrous water according to [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. Resin composition.
[19] The radical-polymerizable water-containing resin composition according to any one of [1] to [18], further containing a filler (H).

[20] The radical-polymerizable water-containing resin composition according to the above [19], wherein the filler (H) is a cement and an aggregate.
[21] The water (E) is one or more selected from ion-exchanged water, tap water, seawater, river water, well water, factory water, distilled water, and water containing radioactive substances, [1] ~ The radically polymerizable water-containing resin composition as described in any one of [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 the radical-polymerizable water-containing resin composition according to any one of [1] to [21] above, wherein the method is cured in any state of being immersed in water.
[23] Step 1 of obtaining a mixed solution (i) by mixing the metal-containing compound (A) and the radically polymerizable compound (C), the mixed solution (i) and the thiol compound (B) Step 2 of obtaining a mixed solution (ii) by mixing, Step 3 of obtaining the mixed solution (iii) by mixing the mixed solution (ii), the surfactant (D) and the water (E), And the manufacturing method of the radical-polymerizable water-containing resin composition in any one of said [1]-[21] which has the process 4 which mixes the said mixed liquid (iii) and the said radical polymerization initiator (F).

  According to the present invention, a radically polymerizable water-containing resin composition capable of being stably cured despite the presence of water inside the composition, a method for curing the same, and a method for producing a radically polymerizable water-containing resin composition Can be provided.

[Radical polymerizable resin composition]
The radically polymerizable water-containing resin composition of the present invention comprises one or more metal-containing compounds (A) and secondary thiol compounds (B1) selected from metal soaps (A1) and metal complexes (A2) having a β-diketone skeleton. And at least one thiol compound (B) selected from a tertiary thiol compound (B2), a radical polymerizable compound (C), a surfactant (D), water (E), and a radical polymerization initiator (F). Containing 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). 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). Is also A and, it is also possible to stably cure regardless containing water at.

<Metal-containing compound (A)>
The radical-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. The metal soap (A1) in the present invention refers to a salt of a long-chain fatty acid or an organic acid other than a long-chain fatty acid and a metal element other than potassium and sodium. Further, 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 with a metal element.

[Metallic 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, heptanoic acid, octanoic acid such as 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.
Further, rosin acid, linseed oil fatty acid, soybean oil and fat acid, tall oil acid and the like can also be mentioned.

The organic acid other than the long chain fatty acid in the metal soap (A1) is not particularly limited, but a weak acid compound having a carboxy group, a hydroxy group and an enol group, which is soluble in an organic solvent, is preferable.
Examples of the compound having a carboxy group include formic acid; acetic acid; carboxylic acids such as oxalic acid; citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, folic acid and other hydroxy acids; alanine, arginine. And the like; aromatic carboxylic acids such as benzoic acid and phthalic acid, and the like.
Further, as the compound having a hydroxy group and an enol group, for example, ascorbic acid, α acid, imidic acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, Examples thereof include hydroxamic acid, humic acid, fulvic acid, phosphonic acid, acetylacetone and the like.
Among these, long chain fatty acids are preferable, chain 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- Even more preferred are ethylhexanoic acid and naphthenic acid.

Examples of the metal element constituting the metal soap (A1) include metal elements of Group 1 to 2 such as lithium, magnesium, calcium, and barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, Platinum, copper, silver, gold, zinc, and other group 3-12 metal elements, aluminum, indium, tin, lead, and other group 13-14 metal elements, neodymium, cerium, and other rare earth metal elements, etc. 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 preferred, and manganese, cobalt and titanium are even more preferred.

  Specific examples of the metal soap (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 parts by mass with respect to 100 parts by mass of the radical-polymerizable compound (C) described below. Parts, more preferably 0.01 to 1 parts by mass, further preferably 0.02 to 0.7 parts by mass, still more preferably 0.02 to 0.5 parts by mass. If the content of the metal soap (A1) in terms of metal component is within the above range, curing will proceed rapidly even in the state of 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 in which a metal is complexed with acetylacetone, ethyl acetoacetate, benzoylacetone and the like. The metal complex (A2) also exhibits the same function as the metal soap (A1).
Examples of the metal element forming the metal complex (A2) include the same metal elements as those of the metal soap (A1).

  Specific examples of the metal complex (A2) include vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis (acetylacetonate), iron acetylacetonate, and acetoacetic acid ethyl ester cobalt. Among them, titanium acetylacetonate and titanium dibutoxybis (acetylacetonate) are more preferable.

  The preferable range of the content of the metal complex (A2) calculated as the metal component is the same as the preferable range of the content of the metal soap (A1) calculated as the metal component. Further, when the metal soap (A1) and the metal complex (A2) are used in combination, the preferable range of the total metal component conversion content is the same as the preferable range of the metal soap conversion content (A1) content. is there.

<Thiol compound (B)>
The radically polymerizable resin composition of the present invention contains at least one thiol compound (B) selected from a secondary thiol compound (B1) and a tertiary thiol compound (B2). In the present invention, the thiol compound (B) has a function as a curing accelerator and also has a function of coordinating in the vicinity of the metal of the metal-containing compound (A) and preventing the metal from being deactivated by water. Guessed.
The thiol compound (B) used in the present invention may have 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 1 or more of), but from the viewpoint of rapidly curing even in a water-containing state and from the viewpoint of preventing the metal of the metal-containing compound from deactivating with water, A polyfunctional thiol which is a compound having two or more secondary or tertiary mercapto groups is preferable, and a bifunctional thiol which is a compound having two secondary or tertiary mercapto groups in the molecule is preferable. Further, the secondary thiol compound (B1) is more preferable than the tertiary thiol compound (B2).
The term "polyfunctional thiol" as used herein means a thiol compound having two or more functional mercapto groups, and the term "bifunctional thiol" has two functional mercapto groups. Is a thiol compound.

  There is no particular limitation on the compound having two or more secondary or tertiary mercapto groups in the molecule, but for example, it 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 is preferable, including the mercapto group in the structure.

(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 (It is an aromatic group having 6 to 18 carbon atoms, and * is linked to any organic group. A is an integer of 0 to 2.)

It is more preferable that R ¹ in the formula (Q) is a hydrogen atom and the compound has 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) binds is a secondary carbon atom.

Further, 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, various octyl groups, and the like. In addition, "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, and preferably 1.

  Furthermore, the thiol compound (B) preferably 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.)

It is preferable that a in the formula (Q-1) is 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 with 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. It is thought that the contact between the metal element and water can be suppressed as a result. In the case of the tertiary thiol compound (B2), both R ¹ and R ² are substituents which are bulkier than hydrogen, and from the viewpoint of steric hindrance in coordination of the mercapto group with the metal element, the secondary thiol compound (B1) It is considered that the above can exert the curing acceleration performance more. However, even in the case of the tertiary thiol compound (B2), when the carbonyl oxygen and the mercapto group are stably coordinated with the metal element, the contact between the metal element and water is more suppressed than that of 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) may be 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, tricyclodecanedimethanol, 2,2-bis (2-hydroxyethoxyphenyl) propane, bisphenol A alkylene oxide Additive, 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 Dihydric alcohols such as [4- (2-hydroxyethyl) phenyl] fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, sorbitol. , Pentae Suritoru, 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 and the like from the viewpoint of easy availability and improving the curability in a state containing water. Dihydric alcohols; glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane, etc. Polycarbonate diol and dimer acid polyester polyol are preferable, and 1,4-butanediol, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate are preferred from the viewpoint of the number of functional groups and vapor pressure. ,pen 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 the secondary thiol compound (B1), specific examples thereof include 3-mercaptobutyric acid and 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-mercapto valerate), diethylene glycol bis (4-mercapto valerate), Bis (4-mercapto valerate), octane diol bis (4-mercapto valerate), trimethylolpropane tris (4-mercapto valerate), pentaerythritol tetrakis (4-mercapto valerate), dipentaerythritol hexakis (4) -Mercapto valerate), ethylene glycol bis (3-mercapto valerate), propylene glycol bis (3-mercapto valerate), diethylene glycol bis (3-mercapto valerate), butanediol bis (3-mercapto valerate), octane Diolbis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythri 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-phenyl) Lepropionate), tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate), dipentaerythritol hexakis (3-mercapto-3-phenylpropionate) Onate) and the like.

  When the secondary thiol compound (B1) is a compound having an ester structure represented by the formula (Q-1), this 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, and 3-mercapto-3-phenylpropionic acid.

  Among the secondary thiol compounds (B1), commercially available compounds having two or more secondary mercapto groups in the molecule include 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK, Karenz MT (registered trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT (registered trademark) PE1 manufactured by Showa Denko KK), 1,3,5-tris [2- (3-mercaptobutyrate). Ryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenzu MT (registered trademark) NR1 manufactured by Showa Denko KK), trimethylolethane tris (3 -Mercaptobutyrate) (TEMB manufactured by Showa Denko KK), trimethylolpropane tris (3-mercaptobutyrate) (Showa Denko KK) , 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 the tertiary thiol compound (B2), specific examples thereof include di (2-mercaptoisobutyl) phthalate and 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-methylbutylate) 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.

  Moreover, 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]
The esterification reaction of the mercapto group-containing carboxylic acid represented by the formula (S) and the polyhydric alcohol is not particularly limited, and it can be produced 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. From the viewpoint of suppressing the production of by-products, it is preferable to carry out the reaction while removing the water produced by the esterification reaction.

In the esterification reaction, a solvent may or may not be used, but it is preferable to use a solvent that is azeotropic with water from the viewpoint of improving the reaction rate. Examples of the solvent azeotropic with water include toluene, xylene, cyclohexane, and ethylbenzene, and toluene is preferable from the viewpoint of the balance between the production cost and the effect obtained. The amount of the solvent azeotropic 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 such that the carboxy group of the mercapto group-containing carboxylic acid represented by the formula (S) is 1. It is preferable to use it in an amount of 0 to 4.0 equivalents. 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, the curability is improved, and when the carboxy group is 4.0 equivalents or less, the production cost can be suppressed.

The catalyst used in the esterification reaction is preferably a non-volatile acid catalyst, and specifically, inorganic acids such as sulfuric acid, perchloric acid and phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, levulinic acid and the like. Organic acids are mentioned. Among these, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like are preferable from the viewpoint of reaction rate.
The non-volatile acid catalyst means an acid catalyst having a vapor pressure of 1 kPa or less at 25 ° C.
The amount of the catalyst used is preferably 0.01 to 1.0 mol with respect to 1 mol of the hydroxyl group of the polyhydric alcohol. When the amount of the catalyst used is 0.01 mol or more, the reaction rate becomes sufficiently high, and when it is 1.0 mol or less, the amount of the basic substance used in the neutralization performed after the reaction is reduced. You can

  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 and 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 value of the dehydration amount by the esterification reaction, but when the reaction requires a long time, Can complete the reaction at the stage when 80% by mass or more of the theoretical value of water is extracted. When the water content is 80% by mass or more of the theoretical value of the dehydration amount due to the esterification reaction, the 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 easy pH adjustment.
Further, after the completion of the reaction, 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 preferred from the viewpoint of volatility, and toluene and ethyl acetate are more preferred from the viewpoint of the cost of the extraction solvent. For the purpose of improving the liquid separation speed during extraction, a hydrophobic solvent may be added to the extraction solvent. From the viewpoint of the liquid separation speed and the cost of the hydrophobic solvent, hexane and heptane are more preferable. preferable.

  In the solvent distillation step, the solvent is distilled off under heating and reduced pressure conditions, but the distillation temperature is preferably 80 to 150 ° C regardless of the degree of reduced pressure. 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.

  The molecular weight of the thiol compound (B) in the present invention is not particularly limited, but it is preferably a low molecular weight, specifically 5,000 or less, preferably 2,500 or less, more preferably 1,500 or less. It is preferably 750 or less, and even more preferably 750 or less. Moreover, 100 or more is preferable, 150 or more is more preferable, and 200 or more is still more preferable. In the present invention, the molecular weight refers to the polystyrene equivalent number average molecular weight 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 mass, more preferably 100 parts by mass of the radically polymerizable compound (C) described below. Is 0.1 to 12 parts by mass, more preferably 0.3 to 10 parts by mass, still more preferably 0.5 to 10 parts by mass. When the amount of the thiol compound (B) is 0.01 part by mass or more, the curing function can be sufficiently obtained, and when it is 15 parts by mass or less, the 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 0.1 to 15, more preferably 0.3 to 10, and 0. 0.6-8 is more preferable, and 0.8-5 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 is By setting 15 to 15 or less, the balance between the manufacturing cost and the effect is improved.

  The thiol compound (B) may be used alone or in combination of two or more. 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 the same as those in the formula (T). It is stable in the state, and a disulfide compound due to the bond between the thiol compounds (B) is not generated as a by-product. From the viewpoint of keeping the metal-containing compound (A) and the thiol compound (B) in a stable state as in the above formula (T), the secondary thiol compound (B1) or the tertiary thiol compound (B2) is used alone. It is preferable.

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

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

Examples of the epoxy resin include bisphenol A diglycidyl ether, high molecular weight homologues thereof, and novolak type glycidyl ethers.
Specifically, bisphenol type epoxy resin (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 Those obtained by reacting a condensate of ether with the above bisphenol with epichlorohydrin and / or methylepichlorohydrin), biphenyl type epoxy resin (for example, those obtained by reacting biphenol with epichlorohydrin and / or methylepichlorohydrin) A naphthalene-type epoxy resin (for example, one obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methylepichlorohydrin), Ralkyl diphenol type epoxy resin (for example, one obtained by reacting aralkyl phenol with epichlorohydrin and / or methylepichlorohydrin), diglycidyl type epoxy resin (for example, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester) , An alicyclic epoxy resin (for example, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, etc.), and an oxazolidone ring obtained by reacting the epoxy resin with a diisocyanate Epoxy resin (as a specific example, Asahi Kasei Epoxy Araldite AER4152 etc.), novolac type epoxy resin (for example, phenol novolac or cresol novolac and epichlorohydrin) And / or those obtained by reacting methyl epichlorohydrin), and trisphenolmethane type epoxy resins (for example, those obtained by reacting trisphenolmethane, triscresolmethane with epichlorohydrin and / or methylepichlorohydrin). Can be mentioned.

Known unsaturated monobasic acids can be used, and examples thereof include (meth) acrylic acid, crotonic acid, and cinnamic acid. Further, 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 addition, in this specification, "(meth) acrylic acid" means "one or both of acrylic acid and methacrylic acid", and "(meth) acryloyl group" means "acryloyl group and methacryloyl group". "One or both".
The polybasic acid is used to increase the molecular weight of the epoxy resin, and known ones can be used. 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, a carboxyl group-terminated butadiene / acrylonitrile copolymer (trade name Hycar CTBN) and the like can be mentioned.

[Unsaturated polyester resin]
As the unsaturated polyester resin, an unsaturated dibasic acid and, if necessary, a dibasic acid component containing a saturated dibasic acid and a polyhydric alcohol component obtained by esterification reaction can be used. .
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride, 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 anhydride, 4 , 4'-biphenyldicarboxylic acid, aromatic dibasic acids such as dialkyl esters thereof, halogenated saturated dibasic acids, and the like, and these may be used alone or in combination of two or more kinds.

The polyhydric alcohol is not particularly limited, but 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- Chlorohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-dio- Dihydric alcohols such as alcohol, 2,6-decalin glycol and 2,7-decalin glycol;
Hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, an adduct of a divalent phenol typified by tetrabromobisphenol A with an alkylene oxide typified by propylene oxide or ethylene oxide, and the like. Dihydric alcohol;
Examples include trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

The unsaturated polyester may be modified with a dicyclopentadiene compound so long as the effects of the present invention are not impaired. Regarding the modification method using a dicyclopentadiene compound, for example, after obtaining a dicyclopentadiene and a maleic acid addition product (sidedecanol monomale), this is used as a monobasic acid to introduce a dicyclopentadiene skeleton. A known method such as a method of
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, but for example, addition of a polymer containing an oxidative polymerization group, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether to a hydroxyl group and an allyl ether. Examples thereof include 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]
The polyester (meth) acrylate resin in the present invention is, for example, a polyester obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, specifically, for a hydroxyl group at both terminals such as polyethylene terephthalate (meth). ) A resin obtained by reacting acrylic acid can be used.
Further, the urethane (meth) acrylate resin is obtained, for example, by reacting (meth) acrylic acid with hydroxyl groups or isocyanato groups at both ends of polyurethane obtained by reacting isocyanate with a polyhydric alcohol. A resin can be used.
Examples of the (meth) acrylate resin include a poly (meth) acrylic resin having one or more kinds of substituents selected from a hydroxyl group, an isocyanato group, a carboxy group and an epoxy group, and a monomer having the above-mentioned substituents (meth ) 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.

[Radical polymerizable unsaturated monomer]
In the present invention, a radically polymerizable unsaturated monomer can be used as the radically polymerizable compound (C).
The radically polymerizable unsaturated monomer may be used alone, but it is used as a mixture of the radically polymerizable unsaturated monomer and at least one of the vinyl ester resin and the unsaturated polyester resin. It is preferable.
The radical polymerizable unsaturated monomer is not particularly limited, but those having a vinyl group or a (meth) acryloyl group are 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 and triallyl isocyanurate. Etc.

  Specific examples of the monomer having a (meth) acryloyl group include acrylic acid ester and methacrylic acid ester. 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- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) 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 (meth) ) Acrylate, tricyclodecanyl methacrylate, tris (2-hydroxyethyl) isocyanuric acrylate, and the like.

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, 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 thereof include tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
Further, the following compounds can be used as the radically polymerizable unsaturated monomer. Specifically, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate, allyl methacrylate, vinylbenzyl butyl ether, vinylbenzyl hexyl ether, vinylbenzyl octyl. Ether, vinylbenzyl- (2-ethylhexyl) ether, vinylbenzyl (β-methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzylcyclohexyl ether, vinylbenzyl- (β-phenoxyethyl) ether, vinylbenzyl Dicyclopentenyl ether, vinylbenzyldicyclopentenyloxyethyl ether, vinylbenzyldicyclopentenyl methyl ether, divinyl Mention may be made of rubenzyl ether.
These may be used alone or in combination of two or more.

The radical-polymerizable unsaturated monomer can be used to reduce the viscosity of the radical-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 radically polymerizable unsaturated monomer is preferably 90% by mass or less in the radically polymerizable compound (C).
Furthermore, when the radically polymerizable compound (C) particularly contains styrene as a 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 radically polymerizable compound (C) exceeds 60% by mass, styrene may be eluted in water and the cured product may become brittle, which is not preferable.

The radically polymerizable compound (C) is a catalyst or a polymerization inhibitor used when synthesizing a vinyl ester resin, an unsaturated polyester resin, a polyester (meth) acrylate resin, a urethane (meth) acrylate resin, and a (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, methylhydroquinone, phenothiazine and the like.
When the catalyst or the polymerization inhibitor remains in the radically polymerizable compound (C), the amount thereof is preferably 0.001 to 2 parts by mass based on 100 parts by mass of the vinyl ester resin and the unsaturated polyester resin. 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 radically polymerizable compound (C) in the radically 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 contains a surfactant (D) (hereinafter also referred to as “(D) component”) for the purpose of improving the compatibility between the radical-polymerizable compound (C) and water. To use. When a resin composition containing no surfactant is cured in a water-containing state, water in the resin composition tends to be ejected out of the cured product, and only the resin tends to cure. The radical-polymerizable water-containing resin composition of the present invention is particularly preferably used in an application of curing while hugging water in the resin composition, so that the resin is well compatible with water and water. It is necessary to use a surfactant to help cure the resin while it is entrapped in the resin.
Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.
Among these surfactants, at least one selected from anionic surfactants and nonionic surfactants is preferable.
Examples of the anionic surfactant include alkyl sulfate ester salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl salts such as polyoxyethylene alkyl ether sulfate triethanolamine. Sulfonates such as ether sulfate ester salt, dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium dialkylsulfosuccinate, fatty acid salts such as sodium stearate soap, potassium oleate soap, castor oil potassium soap, etc. , Naphthalene sulfonic acid formalin condensate, special polymer type and the like.
Among these, sulfonates are preferable, sodium dialkylsulfosuccinate is more preferable, and sodium dioctylsulfosuccinate is further preferable.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene distyrenated phenyl ether, Polyoxyethylene derivatives such as polyoxyethylene tribenzyl phenyl ether and polyoxyethylene polyoxypropylene glycol; polyoxyalkylene alkyl ethers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate and other sorbitan fatty acid esters; 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.
Among these, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether are preferable. The nonionic surfactant HLB (Hydrophile-Lipophil Balance) is preferably from 5 to 15, more preferably from 6 to 12.

  The amount of the surfactant (D) in the radical-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 below, and It is 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 further preferably 0 to 100 parts by mass of the total amount of the radical polymerization initiator (F). 0.06 to 1 part by mass, more preferably 0.07 to 0.5 part by mass. When the amount of the surfactant is 0.05 parts by mass or more, it is possible to prevent a decrease in water absorption of the filler mixed in the resin, and thus the effect of the filler can be exhibited. Further, when the amount is 10 parts by mass or less, deterioration of the physical properties of the resin can be suppressed and the balance between the obtained performance and the cost is improved.

<Water (E)>
The radical-polymerizable water-containing resin composition of the present invention contains water (E) (hereinafter, also referred to as “(E) component”).
Specific examples of water include ion-exchanged water, tap water, sea water, river water, well water, factory water, distilled water, and water containing at least one selected from radioactive substances and the like. The radical-polymerizable water-containing resin composition of the present invention can be cured in a state of containing water as described above, and since the cured product can retain water, it is contaminated with the factory water or radioactive substances. The use of clean water facilitates storage of contaminated water.
The amount of water (E) in the radically 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 radically polymerizable compound (C). And more preferably 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 “(F) component”) 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 dialkyl such as dicumyl peroxide. Examples thereof include organic peroxides such as peroxides, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters and percarbonates.
Examples of the photo-radical polymerization initiator include benzoin ether-based compounds such as benzoin alkyl ether, benzophenone-based compounds such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone and 2-hydroxy-2-methylproton. Acetophenone-based compounds such as piophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone, and thioxanthone-based compounds such as 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone. To be

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, based on 100 parts by mass of the radical-polymerizable compound (C). 0.3 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 radical-polymerizable water-containing resin composition of the present invention can be sufficiently cured, and when the amount is 10 parts by mass or less, the effect obtained. And the balance of manufacturing cost is improved.

<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 referred to as “(G) component”) for the purpose of improving curability. (Also referred to as)) may 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. Is 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, when a curing accelerator (G) is added, part or all of it may dissolve and elute in water, or form a complex with water, so there is a possibility that elution may occur in water. It is preferable not to use the agent (G).

<Filler (H)>
The radical-polymerizable water-containing resin composition of the present invention may contain a filler (H) (hereinafter also referred to as “(H) component”) for the purpose of improving workability and adjusting physical properties, for example, Inorganic fillers and organic fillers can be mentioned.
Examples of the inorganic filler include cement, quick lime, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, sand mainly containing silica such as silica sand, artificial aggregate such as ceramic and glass scrap, talc. Although known materials such as the above can be used, the combination of the cement having the hydration reactivity and the dry aggregate such as river gravel is preferable from the viewpoint of heat generation and shrinkage due to the hydration reaction of the cement.
As the cement, ordinary Portland cement, early strength Portland cement, ultra early strength Portland cement, moderate heat Portland cement, Portland cements such as sulfate resistant Portland cement, blast furnace cement, silica cement, mixed cements such as fly ash cement, Special cements such as ultra-rapid cement, alumina cement, oil well cement, geothermal cement, color cement, fine powder cement and various plasters can be used.
Further, from the viewpoint of imparting flame retardancy, aluminum hydroxide can be used, and from the viewpoint of adjusting fluidity, fumed silica, talc and the like can also be used. From the viewpoint of coloring, a coloring agent such as titanium oxide or an inorganic pigment may be used, and further a molecular sieve may be used.
Further, 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 radical-polymerizable water-containing resin composition of the present invention contains the filler (H), its amount is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the radical-polymerizable compound (C). When the amount of the inorganic filler is within the above range, sufficient strength can be exhibited when the radical-polymerizable water-containing resin composition is cured, and when it exceeds the above range, work such as injection may be hindered. There are cases.

<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 and 4-tert-butylcatechol.
When the radical-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 radical-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) and 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 can be mentioned. . Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO) is preferable from the viewpoint of cost and handleability.
When the radical-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 its derivatives can be used. Specific examples of the oxycarboxylic acid and its derivative include gluconic acid, glucoheptonic acid, arabonic acid, malic acid, tartaric acid, citric acid, and their alkali metal salts and alkaline earth metal salts. Examples of the phosphonic acid and its derivative include aluminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta ( Methylenephosphonic acid), these alkali metal salts and alkaline earth metal salts are exemplified.
When the radical-polymerizable water-containing resin composition contains a curing retarder, 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).
[Coupling agent]
The radical-polymerizable water-containing resin composition of the present invention may contain a coupling agent for the purpose of improving processability, improving the adhesion to a substrate, and the like. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.
Examples of such a coupling agent include a silane coupling agent represented by R ³ —Si (OR ⁴ ) ₃ . In addition, examples of R ³ include aminopropyl group, glycidyloxy group, methacryloxy group, N-phenylaminopropyl group, mercapto group, vinyl group, and the like, and examples of R ⁴ include methyl group, 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 radically 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 the polyisocyanate compound 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 Cyclic aliphatic diisocyanates such as 2,6) -diisocyanate, 4,4′-methylenebis (cyclohexylisocyanate) and 1,3- (isocyanatomethyl) cyclohexane; aromatics such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate Diisocyanates; polyisocyanates such as polyisocyanates having a valence of 3 or more such as lysine triisocyanate, and their respective Examples thereof include an adduct of a reisocyanate and a polyhydric alcohol, a low molecular weight polyester resin or water, a cyclized polymer of the above diisocyanates (for example, isocyanurate), a biuret type adduct, and the like. Among these, isocyanurate of hexamethylene diisocyanate is preferable.
These polyisocyanate compounds may be used alone or in combination of two or more kinds.

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

The blocked polyisocyanate compound is obtained by blocking the isocyanato group of the above 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 and the like; formamide Oxime, acetoaldoxime, acetoxime, methylethylketoxime, diacetylmonoxime, 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 isocyanato group of the polyisocyanate can be easily blocked.

When the polyisocyanate compound is a non-blocked polyisocyanate compound, when the radical polymerizable compound (C) and the polyisocyanate compound in the radical polymerizable water-containing resin composition of the present invention are mixed, a reaction between the two occurs, It is preferable to separate the radically polymerizable compound (C) and the polyisocyanate compound and mix them at the time of use.
A curing catalyst can be used to react the radically polymerizable compound (C) with the polyisocyanate compound. Suitable curing catalysts include, for example, tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyl. Examples thereof include organic metal catalysts such as tin oxide and lead 2-ethylhexanoate.
When the radically polymerizable water-containing resin composition contains the curing catalyst amount, the amount thereof is preferably 0.01 parts by mass to 5 parts by mass, more preferably 100 parts by mass of the radically polymerizable compound (C). It is 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 dispersant include a fluorine-based wetting dispersant and a silicon-based wetting dispersant, and these may be used alone or in combination of two or more kinds.
Commercially available fluorine-based wetting and dispersing agents include Megafac (registered trademark) F176, Megafac (registered trademark) R08 (manufactured by Dainippon Ink and Chemicals, Inc.), 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, and BYK (registered trademark) -302. , BYK (registered trademark) -UV3500, BYK-306 (manufactured by BYK Japan KK), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
Further, the silicone-based wetting and dispersing agent is preferably a silicone-based wetting and dispersing agent containing a compound represented by the following formula (U).

(In the formula, R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 200 carbon atoms which may include an aromatic ring, or — (CH ₂ ) ₃ O (C ₂ H ₄ O) _p ( _{CH 2 CH (CH 3) O} ) ' indicates, n represents an integer of 1 to 200, R' _q R is an alkyl group having 1 to 12 carbon atoms, p and q are each integers, and, q / p = 0 to 10 is satisfied.)
Commercially available products of the silicone-based wetting and dispersing agent containing the compound represented by the formula (U) include BYK (registered trademark) -302 and BYK (registered trademark) -322 (manufactured by BYK Japan KK). To be
When the radical-polymerizable water-containing resin composition of the present invention contains a wetting dispersant, the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0 to 100 parts by mass of the radical-polymerizable compound (C). 0.01 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, which may be used alone or in combination of two or more kinds.
Known paraffin waxes having various melting points can be used. As the polar wax, those having both a polar group and a non-polar group in the structure can be used, and specifically, NPS (registered trademark) -8070, 9125 (manufactured by Nippon Seiro Co., Ltd.), Emanone (registered trademark) 3199, 3299 (manufactured by Kao Corporation) and the like can be mentioned.
When the radical-polymerizable water-containing resin composition of the present invention contains a wax, its amount is preferably 0.05 to 4 parts by mass, more preferably 0. 4 parts by mass with respect to 100 parts by mass of the radical-polymerizable compound (C). 1 to 2.0 parts by mass.

[Thixotropic agent]
The radically polymerizable water-containing resin composition of the present invention may use a thixotropic agent for the purpose of adjusting viscosity for ensuring workability on a vertical surface or a ceiling surface.
Examples of the thixotropic agent include inorganic thixotropic agents, and organic thixotropic agents, and as the organic thixotropic agents, hydrogenated castor oil type, amide type, polyethylene oxide type, vegetable oil polymerized oil type, interface Examples thereof include an activator system and a composite system using these in combination, and specifically, DISPARLON (registered trademark) 6900-20X (Kusumoto Kasei Co., Ltd.) and the like.
Examples of the inorganic thixotropic agent include silica and bentonite, and hydrophobic ones include Leoroseal (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 are mentioned, and hydrophilic ones include Aerosil (registered trademark) AEROSIL-200 (Nippon Aerosil Co., Ltd.) and the like. From the viewpoint of further improving thixotropy, one obtained by adding a thixotropic modifier BYK (registered trademark) -R605 or BYK (registered trademark) -R606 (manufactured by BYK Japan KK) to hydrophilic pyrogenic silica. Can also be preferably used.
When the radically 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, more preferably 100 parts by mass of the radically polymerizable compound (C). It 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 a step 1 of obtaining a mixed solution (i) by mixing the metal-containing compound (A) and the radically polymerizable compound (C), the mixed solution. Step 2 of obtaining a mixed solution (ii) by mixing (i) and the thiol compound (B), mixing the mixed solution (ii), the surfactant (D), and the water (E). This is a method having a step 3 of obtaining a mixed solution (iii) and a step 4 of mixing the mixed solution (iii) with the radical polymerization initiator (F).
When the radical-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).
The mixing method in each of the above steps is not particularly limited, and a known method can be used. Moreover, the temperature at the time of each mixing is preferably 20 to 40 ° C. from the viewpoint of uniform mixing and the viewpoint of suppressing alteration of each component.
Further, in the step 3, from the viewpoint of uniform mixing, it is preferable to previously mix the surfactant (D) and water (E).
The mixing order of the optional components other than the components (A) to (F) is not particularly limited, and they can be mixed in any process, but from the viewpoint of uniform mixing before the radical polymerization is started, Mixing in any one of 1 to 3 is preferable, and mixing in step 3 is more preferable.

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

[Curing Method of Radical Polymerizable Hydrous Resin Composition]
The method for curing the radical-polymerizable water-containing resin composition of the present invention includes a method in which the radical-polymerizable water-containing resin composition of the present invention contains the water (E), the radical-polymerizable water-containing resin composition and water. It is a curing method in which the radical-polymerizable water-containing resin composition is cured either in contact with it or in a state of being immersed in water.
By using the above 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 that there is no such thing. Further, "a state in which the radical-polymerizable water-containing resin composition and water are brought into contact with each other" means the whole or a part of the radical-polymerizable water-containing resin composition of the present invention, and water other than the water (E), that is, The state in which the radically polymerizable water-containing resin composition is in contact with water existing in the surrounding environment. Furthermore, the "state in which the radical-polymerizable water-containing resin composition is immersed in water" refers to the state in which the radical-polymerizable water-containing resin composition of the present invention is wholly or partially immersed in water.
Since the radical-polymerizable water-containing resin composition of the present invention can be cured even in the water-containing state as described above, it can be cured even in the state of being in contact with water, and further in the state of being dipped. It is possible.
By the above curing method, all or part of water (E) in the radically polymerizable water-containing resin composition is incorporated into the cured resin component without solid-liquid separation.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples.
The raw materials used in the examples and comparative examples are as follows.
<Metal soap (A)>
・ Metallic soap (A-1)
Cobalt octylate (manufactured by Toei Kako Co., Ltd., hexoate cobalt, content of cobalt in the total amount of the product is 8% by mass, molecular weight is 345.34)
・ Metal soap (A-2)
Cobalt naphthenate (manufactured by Nippon Kagaku Sangyo Co., Ltd., Naphtex Cobalt, 6% by mass of cobalt in the total amount of the product, molecular weight 401.28)

<Secondary or tertiary thiol compound (B)>
-Secondary thiol compound (B-1)
Bifunctional secondary thiol, 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, 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, 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, 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 Yodo Chemical Co., Ltd., TMTP (trimethylolpropane tris (3-mercaptopropionate))
・ Primary thiol compound (B'-2)
Tetrafunctional primary thiol, SC Organic Chemical Co., PEMP (pentaerythritol tetrakis (3-mercaptopropionate))

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

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

<Radical polymerization initiator (F)>
・ Radical polymerization initiator (F-1)
Methyl ethyl ketone peroxide, NOF CORPORATION Permek N
・ Radical polymerization initiator (F-2)
Hardener for vinyl ester resin, 328E manufactured by Kayaku Akzo Co., Ltd.
・ 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, HOKUSEI Cement Co., ordinary cement / filler (H-2)
Aggregate, manufactured by Bishu Kosan Co., Ltd., Aggregate for intermediate coating

<Synthesis example> Synthesis of trimethylolpropane tris (2-mercaptoisobutyrate) (B-5) 2.68 g (20 mmol) of trimethylolpropane (manufactured by Tokyo Kasei 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 in a 100 mL eggplant flask, and a Dean-Stark apparatus and a cooling tube I put on.
The contents were heated using an oil bath at 145 ° C. 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% sodium hydrogen carbonate aqueous solution. Further, the organic layer is washed twice with ion-exchanged water, dehydrated and dried over anhydrous magnesium sulfate, toluene is distilled off, and the residue is subjected to column chromatography on silica gel (silica gel: Wakogel C-200, developing solvent). : N-hexane / ethyl acetate = 5/1 (volume ratio)) to obtain white crystals of trimethylolpropane tris (2-mercaptoisobutyrate) (B2-1).

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

[Step 3 and Step 4]
0.28 parts by mass of the surfactant (D-1) 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 aqueous surfactant solution are thoroughly stirred to obtain a mixed solution (iii), and the mixed solution (iii) and the radical polymerization initiator (F-1) 2. A radically polymerizable water-containing resin composition was obtained by stirring with 5 parts by mass. The obtained radically polymerizable water-containing resin composition was evaluated according to the following methods. The results are shown in Table 1.
In addition, the compounding amount of the metal soap shown in Examples 1 to 13 and Comparative Examples 1 to 4 is not the compounding amount in a physical form but the compounding amount converted into the amount of the metal component in the metal soap. The compounding amount of is a compounding amount converted into the amount of the active ingredient of the surfactant.

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

<Measurement of gelation time, curing time, and curing temperature>
The radical-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 up to 100 mm under the condition of 25 ° C., and the radical-polymerizable water-containing water was added using a thermocouple. The temperature of the resin composition was measured.
The time required for the temperature of the radically polymerizable water-containing resin composition to change from 25 ° C to 30 ° C was defined as the gelation time. Further, the time required for the temperature of the radical-polymerizable water-containing resin composition to reach the maximum exothermic temperature from 25 ° C. was defined as the curing time, and the maximum exothermic temperature was defined as the curing temperature, which was measured according to JIS K-6901.

<Separation of water and resin>
The radically polymerizable water-containing resin compositions obtained in Examples and Comparative Examples were visually observed to evaluate whether or not 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 each component in a specific amount has good results such as gelation time and curing temperature, and also with a resin. 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]
The mixed solution (i) was obtained by adding 0.16 parts by mass of the metal soap (A-1) to 80 parts by mass of the radically polymerizable compound (C-1) and stirring well at room temperature (25 ° C.). A mixed solution (ii) and 2 parts by mass of the secondary thiol compound (B-1) were added and well stirred to obtain a mixed solution (ii).

[Step 3 and Step 4]
0.28 parts by mass of the surfactant (D-1) 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 liquid (ii) and the total amount of the aqueous surfactant solution are well stirred to obtain a mixed liquid (iii), and the mixed liquid (iii) and the radical polymerization initiator (F-3) 2 mass A radical-polymerizable water-containing resin composition was obtained by stirring with a part. The gelation time, the curing time, and the curing temperature of the obtained radically polymerizable water-containing resin composition were measured by the same method as described above. The weight change of the cured product was evaluated according to the following method. The results are shown in Table 4.
In addition, the compounding quantity of the metal soap shown in Examples 14-22, the comparative examples 5-10, and the reference examples 1-3 is not the compounding quantity in the appearance, but the compounding quantity converted into the amount of the metal component in the metal soap. The amount of the surfactant is the amount converted into the amount of the active ingredient of the surfactant.

-Examples 15-22, comparative examples 5-10, and reference examples 1-3.
A radically polymerizable water-containing resin composition was obtained in the same manner as in Example 14, except that the components were blended as described in Tables 5 to 7. The gelation time, the curing time, and the curing temperature of the obtained radically polymerizable water-containing resin composition were measured by the same method as described above. The weight change of the cured product 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 side of 4 cm and a thickness of 3 mm. The first weight measurement was performed when it was 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). , “Change in weight 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 drying at 80 ° C. Change in weight ”).
Finally, the cured product of the radical-polymerizable water-containing resin composition was removed from the mold, the cured product was divided into 6 pieces, the weight was measured, and then the pieces were dried in an oven at 100 ° C. for 2 hours. It was The weight of the fragment of the cured product taken out from the oven was measured, and the weight change before and after drying at 100 ° C was measured (indicated as "weight change after drying at 100 ° C" in the table).
The total weight change was divided by the weight before drying to calculate the 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 is evaluated by using a drier at 80 ° C to 100 ° C. Cement or the like can be appropriately selected.
On the other hand, in Comparative Examples 5, 9 and 10, the weight reduction rate was larger than the value in the Example, so 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 water is not retained in the cured product.
In addition, Reference Examples 1 to 3 are test examples for comparison, which were tested without using water or any of the components. From the results of these reference examples, it can be seen that water is a factor that reduces the weight of the cured products of the examples and comparative examples.

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

[Step 3 and Step 4]
0.175 parts by mass of the surfactant (D-1) was added to 24.75 parts by mass of water (E-1) to prepare a 0.7% by mass aqueous solution of the surfactant. Then, after thoroughly stirring the mixed solution (ii) and the total amount of the aqueous surfactant solution, 0.01 part of a polymerization inhibitor was added and well stirred. Then, 240 parts by mass of Portland cement (H-1) as a filler is added and stirred to obtain a mixed solution (iii), and the mixed solution (iii) and a radical polymerization initiator (F-3) 0.5 part by mass. A radically polymerizable water-containing resin composition was obtained by stirring and.
About the obtained radical-polymerizable water-containing resin composition, a PET film was attached to a glass plate having a side of 30 cm as a base, and a mold having a thickness of 4 mm was used to form a mold in four directions, and the radical-polymerizable water-containing resin was added thereto. The composition was poured into a mold, and a glass plate with a side of 30 cm prepared separately was pasted with a PET film, covered with a lid, and placed with a weight of about 5 kg, and allowed to stand for 24 hours for curing. ..
A cured product of the obtained resin composition was cut into a size described below, and various tests were evaluated. The results are shown in Table 8.
In addition, the compounding amount of the metal soap shown in Examples 23 to 28 and Reference Examples 4 to 5 is not the compounding amount in a physical form, but is the compounding amount converted into the amount of the metal component in the metal soap, and the surface activity. The compounding amount of the agent is the compounding amount converted into the amount of the active ingredient of the surfactant.

-Examples 23, 25-28, and Reference Examples 4-5
A radically polymerizable water-containing resin composition was obtained in the same manner as in Example 24 except that the components were blended as described in Tables 8 and 9. With respect to the obtained radically polymerizable water-containing resin composition, a cured product was obtained by the same method as described above, and various tests were evaluated. The results are shown in Tables 8 and 9.

<Method of measuring compressive stress>
A measurement test of compressive stress was performed according to JIS K7181 (2011).
The procedure for producing the test body was in accordance with the section 6.1.2 of JIS K7181 (2011), and the dimensions of the test piece were 10 mm in length, 10 mm in width, and 4 mm in thickness.

<Compression modulus>
According to JIS K7181 (2011), the measurement test of the compression elastic modulus was performed.
The procedure for producing the test body was in accordance with the section 6.1.2 of JIS K7181 (2011), and the dimensions of the test body were 50 mm in length, 10 mm in width, and 4 mm in thickness.

[Device used for bending strength test]
The measurement was performed using UCT-1T (1t Tensilon (registered trademark)) manufactured by ORIENTEC.
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 body was in accordance with the section 6.1.2 of JIS K7171 (2008), and the dimensions of the test body were 80 mm in length, 10 mm in width and 4 mm in thickness.

[Device used for compressive strength test and compressive elastic modulus test]
It 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, it is understood that Examples 23 to 28 are excellent in bending strength, bending elastic modulus, compressive stress, and compressive elastic modulus.
The radical-polymerizable water-containing resin composition of the present invention can be cured even if it contains water, and the cured product is as excellent as the cured product of the resin composition containing no water. It turns out that it shows the property.

The radical-polymerizable water-containing resin composition of the present invention can be cured despite containing water. Further, in the presence of a large amount of water in the surroundings, or because it can be cured on a surface wet with water, for example, a surface wet with water such as polymer cement mortar or cement concrete, brackish water area, seawater area, It is also useful as a coating agent, repair agent, or paint for concrete surfaces that are 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 in tunnels, dams, etc. Furthermore, it is possible to substitute concrete floorboards for expressways and concrete flooring materials for factories, warehouses, parking lots, etc. with a water-containing resin composition. In that case, based on Japanese patent application No. 2015-087055, No. 2015-227706, No. 2016-000614, No. 2015-203990, No. 2015-240437, No. 2016-033646, and No. 2016-040829. The radical resin composition described in the specification of the following application may be used in various applications, particularly in combination with a primer for a flooring material, a surface finishing agent for a flooring material or the like to form a multilayer structure.
Further, since the water contained in the radically polymerizable water-containing resin composition of the present invention is retained in the cured product without solid-liquid separation, for example, in a radioactive material generated in a large amount due to an accident at a nuclear power plant, etc. A radically polymerizable water-containing resin composition containing contaminated water is further stored with a substance that adsorbs a radioactive substance, and cured to store the contaminated water in a solid state until the radioactive substance is in a safe state for the human body. be able to. Similarly, factory wastewater can be stored in a solid state.

Claims (21)

1 selected from a metal-containing compound (A) selected from a metal soap (A1) and a metal complex (A2) having a β-diketone skeleton, a secondary thiol compound (B1) and a tertiary thiol compound (B2) A metal of the metal-containing compound (A) containing at least one thiol compound (B), a radically polymerizable compound (C), a surfactant (D), water (E), and a radical polymerization initiator (F). Component, the thiol compound (B), the radical polymerizable compound (C), the water (E), and the radical polymerization initiator (F) in an amount of 0. a 05 to 10 parts by weight, the amount of the radical polymerizable compound (C) the radical polymerization initiator to 100 parts by mass (F) is 0.3 to 10 parts by weight, met radical polymerizable water-containing resin composition hand,
In the molecule, the thiol compound (B) has at least one ester structure represented by the following formula (Q-1) and includes a mercapto group in the structure represented by the following formula (Q-1). A radically polymerizable water-containing resin composition, which is a compound having two or more mercapto groups bonded to secondary or tertiary carbon atoms.

(In the formula (Q-1), 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. Alternatively, it is an aromatic group having 6 to 18 carbon atoms, and * indicates that it is linked to an arbitrary organic group. A is an integer of 0 to 2.) R ¹ is hydrogen atom in the formula (Q-1), with the thiol compound (B) is two or more mercapto groups attached to secondary carbon atoms in the molecule, a radical polymerization according to claim 1 Water-containing resin composition. The radically polymerizable water-containing resin composition according to claim 1 or 2 , wherein a in the formula (Q-1) is 1. The thiol compound having an ester structure represented by the formula (Q-1) (B) is a derived from a mercapto group-containing carboxylic acid and a polyhydric alcohol represented by the following formula (S), according to claim 1 The radically polymerizable water-containing resin composition as described in any one of 1 to 3 .

(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-1).) 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) it is at least one selected from the butyrate), a radical polymerizable water-containing resin composition according to any one of claims 1-4. The thiol compound (B) is a compound having two mercapto groups attached to secondary or tertiary carbon atom in the molecule, radical-polymerizable water-containing resin composition according to any one of claims 1-5. Molecular weight of 5,000 or less of the thiol compound (B), the radical polymerizable water-containing resin composition according to any one of claims 1-6. The total amount of the thiol compound (B) is the a radical polymerizable compound (C) 0.01 to 15 parts by weight per 100 parts by weight, the radical polymerizable water according to any one of claims 1-7 Resin composition. Radical according to any one of claims 1 to 9 , 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. The radical polymerizable radically polymerizable compound of the water-containing resin composition (C) content is 20 to 95 wt%, the radical polymerizable water-containing resin composition according to any one of claims 1-9. 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, aluminum, indium, tin, lead, neodymium, and it is at least one selected from cerium, radically polymerizable water-containing resin composition according to any one of claims 1-10. Long chain fatty acid constituting the metal soap (A1) is a linear or cyclic, saturated fatty acids having 7 to 15 carbon atoms, or an unsaturated fatty acid having 7 to 15 carbon atoms, in any one of claims 1 to 11 The radically polymerizable water-containing resin composition described. The metal soap (A1) is, manganese octylate, is at least one selected from cobalt octoate and cobalt naphthenate, a radical polymerizable water-containing resin composition according to any one of claims 1 to 12. Wherein the surfactant (D) is, it contains one or more selected from anionic surfactants and non-ionic surfactants, radical polymerizable water-containing resin composition according to any one of claims 1 to 13 . The radical polymerizable compound (C), vinyl ester resin, is one selected from a mixture of unsaturated polyester resin, or these with radically polymerizable unsaturated monomer, in any one of claims 1-14 The radically polymerizable water-containing resin composition described. The radically polymerizable water-containing resin composition according to claim 15 , 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. Further, a filler (H), a radical polymerizable water-containing resin composition according to any one of claims 1-16. The radically polymerizable water-containing resin composition according to claim 17 , wherein the filler (H) is cement and aggregate. The water (E) is ion-exchanged water, tap water, sea water, river water, well water, factory water is distilled water, and one or more selected from water containing radioactive substances, any claim 1 to 18 The radically polymerizable water-containing resin composition as described in 1. The state of containing the water (E) in the radical-polymerizable water-containing resin composition, the state of contacting the radical-polymerizable water-containing resin composition with water, or the radical-polymerizable water-containing resin composition in water. cured at any of the conditions was immersed, method for curing the radical polymerizable water-containing resin composition according to any one of claims 1 to 19. Step 1 of obtaining a mixed solution (i) by mixing the metal-containing compound (A) and the radically polymerizable compound (C); mixing the mixed solution (i) and the thiol compound (B) Step 2 for obtaining a mixed solution (ii) by the above, Step 3 for obtaining the mixed solution (iii) by mixing the mixed solution (ii) with the surfactant (D) and the water (E), and the mixing a step 4 of mixing the liquid (iii) and the radical polymerization initiator (F), the manufacturing method of the radical polymerizable water-containing resin composition according to any one of claims 1 to 19.