WO2016171150A1 - Composition de résine contenant de l'eau, polymérisable par voie radicalaire, son procédé de durcissement, et procédé de production d'une composition de résine contenant de l'eau, polymérisable par voie radicalaire - Google Patents

Composition de résine contenant de l'eau, polymérisable par voie radicalaire, son procédé de durcissement, et procédé de production d'une composition de résine contenant de l'eau, polymérisable par voie radicalaire Download PDF

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Publication number
WO2016171150A1
WO2016171150A1 PCT/JP2016/062447 JP2016062447W WO2016171150A1 WO 2016171150 A1 WO2016171150 A1 WO 2016171150A1 JP 2016062447 W JP2016062447 W JP 2016062447W WO 2016171150 A1 WO2016171150 A1 WO 2016171150A1
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Prior art keywords
water
resin composition
compound
containing resin
radically polymerizable
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PCT/JP2016/062447
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English (en)
Japanese (ja)
Inventor
一博 黒木
三浦　賢治
陽一郎 坂口
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昭和電工株式会社
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Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to JP2017514144A priority Critical patent/JP6690638B2/ja
Priority to CN201680022529.0A priority patent/CN107531813B/zh
Priority to MYPI2017703938A priority patent/MY182723A/en
Publication of WO2016171150A1 publication Critical patent/WO2016171150A1/fr
Priority to PH12017501926A priority patent/PH12017501926B1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase

Definitions

  • the present invention relates to a radical polymerizable water-containing resin composition capable of performing radical curing even when water is present inside the composition, a curing method thereof, and a method for producing a radical polymerizable water-containing resin composition.
  • Metal soap has good solubility in resins and solvents, and has various functions. Curing accelerators such as unsaturated polyester resins, dryers for paints and printing inks, adhesives for rubber and tires It is used in a wide range of applications such as extreme oil pressure lubricants, auxiliary combustion agents, and polymerization catalysts. However, when metal soap is used as a curing accelerator under conditions where water is present, there is a problem that the function is not sufficiently developed (Non-Patent Document 1). As a method for solving this problem, a method of using a promoter aid can be mentioned. Examples of the promoter aid include ⁇ -diketones, aromatic tertiary amines, mercaptans (thiol compounds), phosphorus compounds and the like.
  • Patent Document 1 in a cement admixture containing a copolymer as an essential component, a hydrocarbon group having 3 or more carbon atoms is used for the production of the copolymer. It describes that a chain transfer agent such as a thiol compound is used as a promoter. Patent Document 2 describes the use of accelerating aids such as aniline derivatives, toluidine derivatives, metal soaps, and thiourea derivatives in aqueous resin compositions used for automobile interior materials and the like. Furthermore, Non-Patent Document 2 describes that a complex formed of an aromatic tertiary amine and a cobalt salt is used as a promoter.
  • Patent Document 2 discloses the use of Rongalite or a thiourea derivative, but the use of a secondary thiol compound has not been studied.
  • the present invention has been made in view of the above-described conventional circumstances, and includes a radically polymerizable water-containing resin composition that can be stably cured even in a state containing water, a curing method thereof, and radically polymerizable properties.
  • a method for producing a water-containing resin composition is provided.
  • the present inventors have found that in the presence of water, the metal in the metal-containing compound is deactivated by water and cannot be cured. Then, after repeated studies on methods for preventing metal deactivation, when a metal-containing compound and a secondary or tertiary thiol compound are used in combination, a secondary or tertiary thiol compound is coordinated in the vicinity of the metal of the metal-containing compound. As a result, it becomes difficult for water to approach the metal, and the deactivation of the metal can be prevented, and as a result, the composition is stably cured even under conditions where water is present inside the composition. As a result, the present invention has been completed.
  • the gist of the present invention is the following [1] to [23]. [1] From one or more metal-containing compounds (A), secondary thiol compounds (B1) and tertiary thiol compounds (B2) selected from metal soaps (A1) and metal complexes (A2) having a ⁇ -diketone skeleton Containing one or more selected thiol compounds (B), radical polymerizable compounds (C), surfactants (D), water (E), and radical polymerization initiators (F), the metal-containing compound (A ) Of the surfactant (D) with respect to a total of 100 parts by mass of the metal component of), the thiol compound (B), the radical polymerizable compound (C), the water (E) and the radical polymerization initiator (F).
  • the thiol compound (B) has at least one structure represented by the following formula (Q), and includes 2 mercapto groups in the structure represented by the following formula (Q).
  • 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
  • R 2 is an alkyl group or carbon having 1 to 10 carbon atoms.
  • R 1 in the formula (Q) is The radically polymerizable water-containing resin composition according to the above [2], which is a hydrogen atom and the thiol compound (B) has two or more mercapto groups bonded to a secondary carbon atom in the molecule.
  • 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 secondary thiol compound (B1) contains 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris [2- ( 3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate) and trimethylolpropane tris ( The radically polymerizable water-containing resin composition according to any one of [1] to [6], which is at least one selected from 3-mercaptobutyrate).
  • the molar ratio [(B) / (A)] of the thiol compound (B) to the metal component of the metal-containing compound (A) is 0.1 to 15, The radically polymerizable water-containing resin composition according to any one of the above.
  • the metal element constituting the metal-containing compound (A) is lithium, magnesium, calcium, barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold
  • the radically polymerizable water-containing resin composition according to any one of the above [1] to [12], which is at least one selected from zinc, aluminum, indium, tin, lead, neodymium, and cerium.
  • the long chain fatty acid constituting the metal soap (A1) is a linear or cyclic saturated fatty acid having 7 to 15 carbon atoms or an unsaturated fatty acid having 7 to 15 carbon atoms.
  • Step 1 of obtaining a mixed liquid (i) by mixing the metal-containing compound (A) and the radical polymerizable compound (C), the mixed liquid (i) and the thiol compound (B).
  • Step 2 for obtaining a liquid mixture (ii) by mixing Step 3 for obtaining a liquid mixture (iii) by mixing the liquid mixture (ii), the surfactant (D) and the water (E), And the method for producing a radically polymerizable water-containing resin composition according to any one of the above [1] to [21], which comprises the step 4 of mixing the mixed solution (iii) and the radical polymerization initiator (F).
  • a radically polymerizable hydrated resin composition that can be stably cured despite the presence of water in the composition, a method for curing the same, and a method for producing a radically polymerizable hydrated resin composition Can be provided.
  • the radically polymerizable water-containing resin composition of the present invention comprises at least one metal-containing compound (A) selected from a metal soap (A1) and a metal complex (A2) having a ⁇ -diketone skeleton, and a secondary thiol compound (B1). And at least one thiol compound (B) selected from the tertiary thiol compound (B2), radical polymerizable compound (C), surfactant (D), water (E), and radical polymerization initiator (F).
  • the amount of the surfactant (D) is 0.05 to 10 parts by mass, and the amount of the radical polymerization initiator (F) is 0.3 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). Too A and, it is also possible to stably cure regardless containing water at.
  • the radically polymerizable water-containing resin composition of the present invention contains at least one metal-containing compound (A) selected from a metal soap (A1) and a metal complex (A2) having a ⁇ -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 the long chain fatty acid and a metal element other than potassium and sodium.
  • the metal complex (A2) having a ⁇ -diketone skeleton in the present invention refers to a complex in which a compound having a structure having one carbon atom between two carbonyl groups is coordinated to a metal element.
  • 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.
  • octanoic acid such as heptanoic acid and 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid
  • 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
  • the organic acid other than the long chain fatty acid in the metal soap (A1) is not particularly limited, but is preferably a weak acid compound having a carboxy group, a hydroxy group, and an enol group and soluble in an organic solvent.
  • the compound having a carboxy group include formic acid; acetic acid; carboxylic acid such as oxalic acid; hydroxy acid such as citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, folic acid; alanine, arginine Amino acids such as benzoic acid, phthalic acid and the like.
  • Examples of the compound having a hydroxy group and an enol group include ascorbic acid, ⁇ acid, imide acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, tycoic acid, dehydroacetic acid, delta acid, uric acid, Examples include hydroxamic acid, humic acid, fulvic acid, phosphonic acid, acetylacetone and the like.
  • long-chain fatty acids are preferable, linear or cyclic saturated fatty acids having 7 to 15 carbon atoms, or unsaturated fatty acids having 7 to 15 carbon atoms are more preferable, octanoic acid and naphthenic acid are further preferable, and 2- More preferred are ethylhexanoic acid and naphthenic acid.
  • the metal elements constituting the metal soap (A1) include group 1 and 2 metal elements such as lithium, magnesium, calcium and barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, Group 3-12 metal elements such as platinum, copper, silver, gold and zinc, Group 13-14 metal elements such as aluminum, indium, tin and lead, and rare earth metal elements such as neodymium and cerium Is mentioned.
  • group 1 and 2 metal elements such as lithium, magnesium, calcium and barium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium
  • Group 3-12 metal elements such as platinum, copper, silver, gold and zinc
  • Group 13-14 metal elements such as aluminum, indium, tin and lead
  • rare earth metal elements such as neodymium and cerium Is mentioned.
  • Group 2 metal elements and Group 3-12 metal elements are preferable, barium, vanadium, manganese, iron, cobalt, copper, titanium, and zinc are more preferable, and manganese, iron, cobalt, Copper, titanium, and zinc are more preferable, and manganese, cobalt, and titanium are still more preferable.
  • Specific metal soaps (A1) include manganese octylate, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, vanadium acetoacetate, cobalt acetoacetate, and iron acetoacetate. Acetate and the like are preferable, and manganese octylate, cobalt octylate, cobalt naphthenate, and the like are more preferable.
  • the content of the metal soap (A1) in the radical polymerizable water-containing resin composition of the present invention in terms of metal component is preferably 0.001 to 5 mass with respect to 100 mass parts of the radical polymerizable compound (C) described later. Part, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.7 part by weight, and still more preferably 0.02 to 0.5 part by weight. If the content of the metal soap (A1) in terms of metal component is within the above range, curing proceeds rapidly even in a state containing water.
  • Metal complex having ⁇ -diketone skeleton (A2) examples include those obtained by complexing metal with acetylacetone, ethyl acetoacetate, benzoylacetone, and the like. These metal complexes (A2) also exhibit functions similar to those of the metal soap (A1). As a metal element which comprises a metal complex (A2), the metal element similar to the said metal soap (A1) is mentioned.
  • Specific metal complexes (A2) include vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis (acetylacetonate), iron acetylacetonate, and acetoacetic acid ethyl ester cobalt. Of these, titanium acetylacetonate and titanium dibutoxybis (acetylacetonate) are more preferable.
  • the preferred range of the content of the metal complex (A2) in terms of metal component is the same as the preferred range of the content of the metal soap (A1) in terms of metal component.
  • the preferred range of the content in terms of the total metal component is the same as the preferred range of the content in terms of the metal component of the metal soap (A1). is there.
  • the radically polymerizable resin composition of the present invention contains one or more thiol compounds (B) selected from the secondary thiol compound (B1) and the tertiary thiol compound (B2).
  • the thiol compound (B) has a function as a curing accelerator, coordinates in the vicinity of the metal of the metal-containing compound (A), and also has a function of preventing metal deactivation by water. Guessed.
  • the thiol compound (B) used in the present invention may be referred to as a mercapto group bonded to a secondary or tertiary carbon atom in the molecule (hereinafter referred to as “secondary mercapto group” or “tertiary mercapto group”, respectively).
  • a polyfunctional thiol which is a compound having two or more secondary or tertiary mercapto groups is preferable, and among them, a bifunctional thiol which is a compound having two secondary or tertiary mercapto groups in the molecule is preferable.
  • the secondary thiol compound (B1) is more preferable than the tertiary thiol compound (B2).
  • polyfunctional thiol means a thiol compound having two or more mercapto groups as functional groups
  • bifunctional thiol means two mercapto groups as functional groups. Means a thiol compound.
  • the compound having two or more secondary or tertiary mercapto groups in the molecule is not particularly limited.
  • the compound has at least one structure represented by the following formula (Q) and is represented by the following formula (Q).
  • a compound having two or more secondary or tertiary mercapto groups in the molecule including the mercapto group in the structure is preferred.
  • 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
  • R 2 is an alkyl group having 1 to 10 carbon atoms, or An aromatic group having 6 to 18 carbon atoms, * is linked to an arbitrary organic group, and a is an integer of 0 to 2.
  • R 1 in formula (Q) is more preferably a compound having a hydrogen atom and having two or more secondary mercapto groups in the molecule. That is, the thiol compound (B) is preferably a secondary thiol compound (B1) in which the carbon atom to which the mercapto group in the formula (Q) is bonded is a secondary carbon atom.
  • the alkyl group having 1 to 10 carbon atoms in R 1 and R 2 in the formula (Q) may be linear or branched. Specific examples include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups.
  • the “various” means various isomers including n-, sec-, tert-, and iso-. Among these alkyl groups, a methyl group and an ethyl group are preferable.
  • 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.
  • these aromatic groups may be substituted with a halogen atom, an amino group, a nitro group, a cyano group, or the like.
  • a in the formula (Q) is an integer of 0 to 2, preferably 1.
  • the thiol compound (B) preferably has at least one ester structure represented by the following formula (Q-1).
  • R 1 , R 2, * and a are, R 1, R 2 in the formula (Q), the same meanings as * and a.
  • a in formula (Q-1) is preferably 1.
  • R 1 is a hydrogen atom
  • R 1 is a hydrogen atom
  • the carbonyl oxygen and the mercapto group are easily coordinated to the metal element of the metal-containing compound (A), and the metal element of the metal-containing compound (A) is surrounded by the thiol compound.
  • T the contact between the metal element and water can be suppressed.
  • the secondary thiol compound (B1) It is considered that can better exhibit curing acceleration performance.
  • the tertiary thiol compound (B2) when the carbonyl oxygen and the mercapto group are stably coordinated to the metal element, the contact between the metal element and water is further suppressed than in the secondary thiol compound (B1). It is thought to get.
  • the thiol compound (B) having an ester structure represented by the formula (Q-1) is a compound derived from a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol. preferable.
  • R 1, R 2 and a have the same meanings as R 1, R 2 and a in the formula (Q).
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propanediol, 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecane dimethanol, 2,2-bis (2-hydroxyethoxyphenyl) propane, bisphenol A alkyleneoxy Adduct, bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct
  • ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, etc. from the viewpoint of availability and the improvement of curability in a state containing water
  • Dihydric alcohols such as: glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane, etc.
  • a trivalent or higher alcohol; polycarbonate diol and dimer acid polyester polyol are preferable.
  • thiol compound (B1) When the thiol compound (B) having the structure represented by the formula (Q) is a secondary thiol compound (B1), specific examples thereof include 3-mercaptobutyric acid, 3-mercaptophthalic acid di (1- Mercaptoethyl), di (2-mercaptopropyl) phthalate, di (3-mercaptobutyl) phthalate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3 -Mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) ), Pentaerythritol tetrakis (3 Mercaptobutyrate), dipentaerythri
  • the secondary thiol compound (B1) is a compound having an ester structure represented by the formula (Q-1)
  • the compound is represented by the polyhydric alcohol and the formula (S). It is preferably derived from a carboxylic acid containing a secondary mercapto group.
  • Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto-3-phenylpropionic acid, and the like.
  • secondary thiol compounds (B1) as a commercial product of a compound having two or more secondary mercapto groups in the molecule, 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK) Karenz MT (registered trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (produced by Showa Denko KK, Karenz MT (registered trademark) PE1), 1,3,5-tris [2- (3-mercaptobuty Ryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko KK, Karenz MT (registered trademark) NR1), trimethylolethane tris (3 -Mercaptobutyrate (manufactured by Showa Denko KK, TEMB), trimethylolpropane tris (3-mercap
  • thiol compound (B2) When the thiol compound (B) having the structure represented by the formula (Q) is a tertiary thiol compound (B2), specific examples thereof include di (2-mercaptoisobutyl) phthalate, ethylene glycol bis ( 2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercapto) Isobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2 -Mercap Isobutyrate
  • the compound (B2) is a compound having an ester structure represented by the formula (Q-1)
  • the compound is represented by the polyhydric alcohol and the formula (S). It is preferably derived from a carboxylic acid containing a tertiary mercapto group.
  • Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptoisobutyric acid and 3-mercapto-3-methylbutyric acid.
  • esterification reaction of mercapto group-containing carboxylic acid represented by formula (S) and polyhydric alcohol There is no restriction
  • 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.
  • a solvent may or may not be used, but from the viewpoint of improving the reaction rate, it is preferable to use a solvent azeotropic with water.
  • the solvent azeotropic with water include toluene, xylene, cyclohexane, and ethylbenzene. Toluene is preferable from the viewpoint of the balance between the manufacturing cost and the obtained effect.
  • the amount of the solvent azeotroped with water is preferably 10 to 90% by mass in the reaction system.
  • the mercapto group-containing carboxylic acid represented by the formula (S) and the polyhydric alcohol are those in which the carboxy group of the mercapto group-containing carboxylic acid represented by the formula (S) is 1.
  • the carboxy group equivalent of the mercapto group-containing carboxylic acid represented by the formula (S) is 1.0 equivalent or more, the amount of unreacted hydroxyl groups can be suppressed, and the number of mercapto groups in one molecule is 2 or more. Therefore, curability is improved, and when the carboxy group is 4.0 equivalents or less, the production cost can be suppressed.
  • a non-volatile acid catalyst is preferable.
  • inorganic acids such as sulfuric acid, perchloric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, levulinic acid and the like are used.
  • Organic acids are mentioned.
  • sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like are preferable from the viewpoint of reaction rate.
  • a non-volatile acid catalyst means the acid catalyst whose vapor pressure in 25 degreeC is 1 kPa or less.
  • the amount of the catalyst used is preferably 0.01 to 1.0 mole per mole of hydroxyl group of the polyhydric alcohol.
  • the amount of the catalyst used is 0.01 mol or more, the reaction rate is sufficiently high, and when it is 1.0 mol or less, the amount of the basic substance used for neutralization after the completion of the reaction is reduced. Can do.
  • the reaction pressure of the esterification reaction is not particularly limited, but is preferably 100 to 760 mmHg from the viewpoint of improving the reaction rate, and more preferably 300 to 550 mmHg from the viewpoint of dehydration efficiency.
  • the reaction pressure is within the above range, the temperature in the reaction system becomes high, so that the reaction easily proceeds.
  • the completion of the reaction can be judged by the amount of water extracted from the reaction system, and it is preferable to carry out the reaction until the amount of water reaches the theoretical dehydration amount by the esterification reaction, but when the reaction takes a long time
  • the reaction can be completed when 80% by mass or more of the theoretical value of water has been extracted. If the water content is 80% by mass or more of the theoretical value of the dehydration amount by the esterification reaction, the amount of unreacted polyhydric alcohol is small, so that the curability of the radical polymerizable water-containing resin composition of the present invention is improved.
  • the basic substance for neutralization is not particularly limited, but sodium bicarbonate and caustic soda are preferable from the viewpoint of cost reduction, and sodium bicarbonate is more preferable from the viewpoint of ease of pH adjustment.
  • extraction may be performed from the viewpoint of purifying the target product.
  • the extraction solvent for extraction toluene, ethyl acetate, isopropyl acetate, and butyl acetate are preferable from the viewpoint of easiness of volatilization, and toluene and ethyl acetate are more preferable from the viewpoint of the cost of the extraction solvent.
  • a hydrophobic solvent may be added to the extraction solvent. From the viewpoint of the separation speed and the cost of the hydrophobic solvent, hexane and heptane are more preferred. preferable.
  • the solvent is distilled off under heating and reduced pressure conditions, and the distillation temperature is preferably 80 to 150 ° C. regardless of the degree of vacuum.
  • the temperature is within the above range, the solvent can be completely distilled off and polymerization of the synthesized thiol compounds can be prevented.
  • molecular weight of the thiol compound (B) in this invention it is preferable that it is a low molecular weight, Specifically, 5,000 or less are preferable, 2,500 or less are more preferable, 1,500 or less are further Preferably, 750 or less is still more preferable. Moreover, 100 or more are preferable, 150 or more are more preferable, and 200 or more are still more preferable.
  • molecular weight points out the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC method).
  • the total amount of the thiol compound (B) in the radically polymerizable water-containing resin composition of the present invention is preferably 0.01 to 15 parts by weight, more preferably 100 parts by weight of the radically polymerizable compound (C) described later. Is 0.1 to 12 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 10 parts by mass. If the amount of the thiol compound (B) is 0.01 parts by mass or more, a sufficient curing function can be obtained, and if it is 15 parts by mass or less, curing proceeds rapidly.
  • the total molar ratio [(B) / (A)] of the thiol compound (B) to the metal component of the metal-containing compound (A) is preferably from 0.1 to 15, more preferably from 0.3 to 10, 6 to 8 is more preferable, and 0.8 to 5 is still more preferable.
  • the thiol compound (B) can be sufficiently coordinated in the vicinity of the metal of the metal-containing compound (A), and the molar ratio When the value is 15 or less, the balance between the manufacturing cost and the effect is improved.
  • a thiol compound (B) may be used individually by 1 type, and may use 2 or more types together.
  • the molar ratio [(B1) / (B2)] of both is preferably 0.001 to 1000, more preferably 1 to 10 preferable.
  • the metal-containing compound (A) and the thiol compound (B) in the radical polymerizable water-containing resin composition are as shown in the above formula (T).
  • the secondary thiol compound (B1) or the tertiary thiol compound (B2) is used alone. It is preferable.
  • the radically polymerizable water-containing resin composition of the present invention uses a radically polymerizable compound (C) (hereinafter also referred to as “component (C)”) as a base material.
  • the radical polymerizable compound refers to a compound having an ethylenically unsaturated group in the molecule and capable of proceeding a polymerization reaction by a radical.
  • radical polymerizable compounds examples include vinyl ester resins (epoxy (meth) acrylate resins), unsaturated polyester resins, polyester (meth) acrylate resins, urethane (meth) acrylate resins, (meth) acrylate resins, radical polymerizable unsaturated monomers. And a mixture of the above resin and a radically polymerizable unsaturated monomer, among others, a vinyl ester resin, an unsaturated polyester resin, or a mixture of these and a radically polymerizable unsaturated monomer. More than species are preferred.
  • “(meth) acrylate” means “one or both of acrylate and methacrylate”.
  • Vinyl ester resin As the vinyl ester resin, one obtained by reacting an unsaturated monobasic acid with an epoxy resin can be used.
  • the epoxy resin examples include bisphenol A diglycidyl ether and high molecular weight homologues thereof, novolak glycidyl ethers, and the like.
  • bisphenol-type epoxy resins for example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, or glycidyl of bisphenol A, And the like obtained by reacting a condensate of ether and the above bisphenol with epichlorohydrin and / or methyl epichlorohydrin
  • biphenyl type epoxy resin for example, obtained by reacting biphenol with epichlorohydrin and / or methyl epichlorohydrin
  • Naphthalene type epoxy resins for example, those obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methyl epichlorohydrin
  • Known unsaturated monobasic acids can be used, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid and the like.
  • 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.
  • (meth) acrylic acid means “one or both of acrylic acid and methacrylic acid”
  • (meth) acryloyl group” means “acryloyl group and methacryloyl group”. Means one or both.
  • the said polybasic acid is used in order to increase the molecular weight of the said epoxy resin, and can use a well-known thing.
  • succinic acid glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol 2 mol maleic anhydride adduct, polyethylene Glycol 2 mol maleic anhydride adduct, propylene glycol 2 mol maleic anhydride adduct, polypropylene glycol 2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16- (6 -Ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, carboxyl group-terminated butadiene / acrylonitrile copolymer (trade name Hycar CTBN), and the like.
  • unsaturated polyester resin As unsaturated polyester resin, what was obtained by esterifying the unsaturated dibasic acid and the dibasic acid component containing a saturated dibasic acid as needed, and a polyhydric alcohol component can be used.
  • unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like, and these may be used alone or in combination of two or more.
  • saturated dibasic acid examples 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.
  • 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.
  • the polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, and 1,3-butanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butane Diol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl 1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2- Chlohexane glycol, 1,3-cyclohexane glycol,
  • the unsaturated polyester may be modified with a dicyclopentadiene compound within a range not impairing the effects of the present invention.
  • a dicyclopentadiene compound for example, after obtaining dicyclopentadiene and a maleic acid addition product (sidecanol monomaleate), the dicyclopentadiene skeleton is introduced using this as a monobasic acid.
  • the publicly known methods such as the method to do.
  • An oxidative polymerization group can be introduced into the vinyl ester resin or unsaturated polyester resin used in the present invention. The introduction method is not particularly limited.
  • polyester (meth) acrylate resin for example, a polyester obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, specifically, with respect to hydroxyl groups at both ends such as polyethylene terephthalate, ) A resin obtained by reacting acrylic acid can be used.
  • urethane (meth) acrylate resin for example, it was obtained by making (meth) acrylic acid react with the hydroxyl group or isocyanato group of the both ends of the polyurethane obtained by making isocyanate and a polyhydric alcohol react. Resin can be used.
  • Examples of the (meth) acrylate resin include a poly (meth) acrylic resin having one or more substituents selected from a hydroxyl group, an isocyanato group, a carboxy group, and an epoxy group, ) A resin obtained by reacting a (meth) acrylic acid ester having a hydroxyl group with a substituent of a polymer with acrylate can be used.
  • a radical polymerizable unsaturated monomer can be used as the radical polymerizable compound (C).
  • the radical polymerizable unsaturated monomer may be used alone, it is used as a mixture of the radical polymerizable unsaturated monomer and at least one of the vinyl ester resin and the unsaturated polyester resin. It is preferable.
  • limiting in particular in the said radically polymerizable unsaturated monomer What has a vinyl group or a (meth) acryloyl group is preferable.
  • the monomer having a vinyl group examples include styrene, p-chlorostyrene, vinyltoluene, ⁇ -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl isocyanurate. Etc.
  • the monomer having a (meth) acryloyl group include acrylic acid esters and methacrylic acid esters. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate,
  • polyfunctional (meth) acrylic acid ester for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1, Alkanediol di- (meth) acrylates such as 4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Polyoxyalkylene-glycol di (meth) such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate and polyethylene glycol (meth) acrylate Acrylate; Trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pent
  • the following compounds can also be used as the radical polymerizable unsaturated monomer. Specifically, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate, allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl Ether, vinylbenzyl- (2-ethylhexyl) ether, vinylbenzyl ( ⁇ -methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzylcyclohexyl ether, vinylbenzyl- ( ⁇ -phenoxyethyl) ether, vinylbenzyl Dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxyethyl ether, vinyl benzyl dicyclopentenyl methyl methyl
  • the radically polymerizable unsaturated monomer can be used to lower the viscosity of the radically polymerizable water-containing resin composition of the present invention and improve hardness, strength, chemical resistance, water resistance, etc. If the amount is too large, it may lead to deterioration of the cured product or environmental pollution. Therefore, the content of the radical polymerizable unsaturated monomer is preferably 90% by mass or less in the radical polymerizable compound (C). Further, when the radically polymerizable compound (C) particularly contains styrene as the radically polymerizable unsaturated monomer, the content thereof is preferably 60% by mass or less, more preferably 50% by mass or less, and 20% by mass or less.
  • the radical polymerizable compound (C) is a catalyst or polymerization inhibitor used when synthesizing vinyl ester resin, unsaturated polyester resin, polyester (meth) acrylate resin, urethane (meth) acrylate resin, and (meth) acrylate resin. May remain.
  • 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.
  • the polymerization inhibitor examples include hydroquinone, methyl hydroquinone, phenothiazine and the like.
  • the amount thereof is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass in total of the vinyl ester resin and the unsaturated polyester resin, respectively. It is.
  • the content of the radically polymerizable compound (C) in the radically polymerizable water-containing resin composition of the present invention is preferably 20 to 95% by mass, more preferably 25 to 90% by mass.
  • the content of the radical polymerizable compound (C) in the radical polymerizable water-containing resin composition is within the above range, the hardness of the cured product is further improved.
  • the radical polymerizable water-containing resin composition of the present invention comprises a surfactant (D) (hereinafter also referred to as “component (D)”) for the purpose of improving the familiarity between the radical polymerizable compound (C) and water.
  • component (D) a surfactant for the purpose of improving the familiarity between the radical polymerizable compound (C) and water.
  • surfactant it is necessary to use a surfactant to help cure the resin while it is entrapped in the resin.
  • the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. These surfactants may be used alone or in combination of two or more. Among these surfactants, one or more selected from anionic surfactants and nonionic surfactants are preferable.
  • anionic surfactant examples include alkyl sulfate esters such as sodium lauryl sulfate and triethanolamine lauryl sulfate, polyoxyethylene alkyl such as polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene alkyl ether sulfate triethanolamine.
  • Fatty acid salts such as ether sulfate ester salt, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalene sulfonate, sodium dialkylsulfosuccinate, sodium stearate soap, oleic acid potassium soap, castor oil potassium soap , Naphthalene sulfonic acid formalin condensate, special polymer system and the like.
  • sulfonates are preferable, sodium dialkylsulfosuccinate is more preferable, and sodium dioctylsulfosuccinate is still more preferable.
  • nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, Polyoxyethylene derivatives such as polyoxyethylene tribenzylphenyl ether and polyoxyethylene polyoxypropylene glycol; polyoxyalkylene alkyl ethers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate; polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Polyoxyethylene sorbitan fatty acid esters such as Tate: polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbit tetraoleate; glycerol monostearate, glycerine fatty acid esters
  • polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, are preferable.
  • the nonionic surfactant HLB Hydrophil Balance
  • HLB Hydrophil Balance
  • the amount of the surfactant (D) in the radically polymerizable water-containing resin composition of the present invention is the metal component of the component (A), the component (B), the component (C), water (E) described later and 0.05 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0 to 100 parts by mass of the radical polymerization initiator (F). 0.06 to 1 part by mass, still more preferably 0.07 to 0.5 part by mass. Since the fall of the water absorption of the filler mixed in resin can be prevented as the quantity of surfactant is 0.05 mass part or more, the effect of a filler can be exhibited. Moreover, while being 10 mass parts or less, while being able to suppress the fall of a resin physical property, the balance of the performance obtained and cost improves.
  • the radically polymerizable water-containing resin composition of the present invention contains water (E) (hereinafter also referred to as “component (E)”).
  • water include water containing at least one selected from ion-exchanged water, tap water, seawater, river water, well water, factory water, distilled water, and radioactive substances. Since the radically polymerizable water-containing resin composition of the present invention can be cured in a state of containing water as described above and can further retain water in the cured product, it is contaminated with the factory water and radioactive substances. By using fresh water, it becomes easy to store contaminated water.
  • the amount of water (E) in the radical polymerizable water-containing resin composition of the present invention is preferably 5 to 50 parts by mass, more preferably 7 to 40 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C). More preferably, it is 10 to 30 parts by mass.
  • the radically polymerizable water-containing resin composition of the present invention contains a radical polymerization initiator (F) (hereinafter also referred to as “component (F)”) as a curing agent.
  • a radical polymerization initiator (F) include at least one initiator selected from a thermal radical polymerization initiator and a photo radical polymerization initiator.
  • the thermal radical polymerization initiator include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, and dialkyls such as dicumyl peroxide.
  • Organic peroxides such as peroxides, ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, peroxyketals, alkyl peresters, and carbonates may be mentioned.
  • photo radical polymerization initiators include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone and 2-hydroxy-2-methylpro
  • benzoin ethers such as benzoin alkyl ether
  • benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate
  • benzyl dimethyl ketal 2,2-diethoxyacetophenone and 2-hydroxy-2-methylpro
  • acetophenones such as piophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone
  • thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone. It is done.
  • the amount of the radical polymerization initiator (F) in the radical polymerizable water-containing resin composition of the present invention is 0.3 to 10 parts by mass, preferably 0, relative to 100 parts by mass of the radical polymerizable compound (C). 3 to 7 parts by mass, more preferably 0.4 to 6 parts by mass, still more preferably 0.5 to 5 parts by mass.
  • the amount of the radical polymerization initiator (F) is 0.3 parts by mass or more, the radically polymerizable water-containing resin composition of the present invention can be sufficiently cured, and when it is 10 parts by mass or less, the obtained effect And the balance of manufacturing costs.
  • the radically polymerizable water-containing resin composition of the present invention is a curing accelerator (G) other than the metal-containing compound (A) and the thiol compound (B) (hereinafter “(G) component”) for the purpose of improving curability. May also be included).
  • 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.
  • the radically polymerizable water-containing resin composition of the present invention may contain a filler (H) (hereinafter also referred to as “component (H)”) for the purpose of improving workability and adjusting physical properties.
  • a filler (H) hereinafter also referred to as “component (H)”
  • inorganic fillers and organic fillers examples include cement, quicklime, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, silica sand and other artificial aggregates such as ceramic and glass waste, talc.
  • a combination of cement having hydration reactivity and dry aggregate such as river gravel is preferable.
  • cement normal Portland cement, early-strong Portland cement, ultra-early strong Portland cement, moderately hot Portland cement, portland cement such as sulfate-resistant Portland cement, mixed cements such as blast furnace cement, silica cement, fly ash cement, Special cements such as ultrafast cement, alumina cement, oil well cement, geothermal cement, color cement, fine powder cement, and various gypsums can be used.
  • aluminum hydroxide can be used from the viewpoint of imparting flame retardancy, and fumed silica, talc, and the like can also be used from the viewpoint of adjusting fluidity.
  • a colorant such as titanium oxide or an inorganic pigment can be used, and a molecular sieve can also be used.
  • the organic filler organic fillers such as amide wax and water-absorbing polymer can also be used.
  • the amount of the inorganic filler is within the above range, sufficient strength can be expressed when the radical polymerizable water-containing resin composition is cured, and if it exceeds the above range, troubles such as injection work occur. There is a case.
  • 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.
  • the polymerization inhibitor include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, 4-tert-butylcatechol.
  • the amount thereof is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C).
  • 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).
  • a curing retarder for the purpose of delaying the curing of the radically polymerizable compound (C).
  • the curing retarder include free radical curing retarders such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6- TEMPO such as tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4-Oxo-TEMPO) and derivatives thereof .
  • 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO) is preferable from the viewpoint of cost and ease of handling.
  • a setting retarder selected from oxycarboxylic acid, phosphonic acid and derivatives thereof can also be used.
  • the oxycarboxylic acid and derivatives thereof include gluconic acid, glucoheptonic acid, arabonic acid, malic acid, tartaric acid, citric acid, and alkali metal salts and alkaline earth metal salts thereof.
  • Examples of phosphonic acid and its derivatives include aluminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta ( Methylenephosphonic acid), their alkali metal salts and alkaline earth metal salts.
  • the amount thereof is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C).
  • a coupling agent may be used for the purpose of improving processability and for improving the adhesion to a substrate.
  • Examples of coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like.
  • An example of such a coupling agent is a silane coupling agent represented by R 3 —Si (OR 4 ) 3 .
  • R 3 include an aminopropyl group, a glycidyloxy group, a methacryloxy group, an N-phenylaminopropyl group, a mercapto group, and a vinyl group.
  • Examples of R 4 include a methyl group and an ethyl group. Etc.
  • 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).
  • the radically polymerizable water-containing resin composition of the present invention may contain a polyisocyanate compound.
  • the polyisocyanate compound reacts with the hydroxyl group of the radical polymerizable compound (C) to form a cured coating film.
  • the polyisocyanate compound contains two or more isocyanate groups in the molecule, and the isocyanate groups may be blocked with a blocking agent or the like.
  • polyisocyanate compounds not blocked with a blocking agent examples include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or Cycloaliphatic diisocyanates such as 2,6) -diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; aromatics such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate Diisocyanates; polyisocyanates such as polyisocyanates having a valence of 3 or more such as lysine triisocyanate; Examples include adducts of reisocyanates and polyhydric alcohols,
  • the amount thereof is preferably 0.1 parts by mass to 50 parts by mass, more preferably 1 part per 100 parts by mass of the radically polymerizable compound (C). -30 parts by mass, more preferably 2-20 parts by mass.
  • the blocked polyisocyanate compound is obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent.
  • the blocking agent include phenols such as phenol, cresol, xylenol; ⁇ -caprolactam; ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam and other lactams; methanol, ethanol, n- or iso-propyl alcohol N-, iso- or tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, or the like; formamide Xime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone Oxime, cyclohe
  • the polyisocyanate compound is a non-blocked polyisocyanate compound
  • the reaction of both occurs when the radical polymerizable compound (C) and the polyisocyanate compound in the radical polymerizable water-containing resin composition of the present invention are mixed It is preferable to separate the radically polymerizable compound (C) and the polyisocyanate compound and mix them at the time of use.
  • a radically polymerizable compound (C) and a polyisocyanate compound are made to react, a curing catalyst can be used.
  • Suitable curing catalysts include, for example, tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyl And organometallic catalysts such as tin oxide and lead 2-ethylhexanoate.
  • the amount is preferably 0.01 parts by mass to 5 parts by mass, more preferably 100 parts by mass with respect to the radical polymerizable compound (C). 0.05 to 4 parts by mass.
  • the radically polymerizable water-containing resin composition of the present invention may contain a wetting and dispersing agent.
  • the wetting and dispersing agent include a fluorine-based wetting and dispersing agent and a silicon-based wetting and dispersing agent, and these may be used alone or in combination of two or more.
  • fluorine-based wetting and dispersing agents include Megafac (registered trademark) F176, Megafac (registered trademark) R08 (manufactured by Dainippon Ink and Chemicals), PF656, PF6320 (manufactured by OMNOVA), Troisol S- 366 (manufactured by Troy Chemical Co., Ltd.), Florard FC430 (manufactured by 3M Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • silicone-based wetting and dispersing agents include BYK (registered trademark) -322, BYK (registered trademark) -377, BYK (registered trademark) -UV3570, BYK (registered trademark) -330, BYK (registered trademark) -302. BYK (registered trademark) -UV3500, BYK-306 (manufactured by BYK Japan), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • a silicone type wet dispersing agent is a silicone type wet dispersing agent containing the compound represented by a following formula (U).
  • examples of commercially available silicone-based wetting and dispersing agents containing the compound represented by the formula (U) include BYK (registered trademark) -302 and BYK (registered trademark) -322 (manufactured by Big Chemie Japan Co., Ltd.).
  • the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0 with respect to 100 parts by mass of the radically polymerizable compound (C). .01 to 2 parts by mass.
  • the radically polymerizable water-containing resin composition of the present invention may contain a wax.
  • the wax include paraffin waxes and polar waxes, and these may be used alone or in combination of two or more.
  • Known paraffin waxes having various melting points can be used as the paraffin waxes.
  • polar waxes those having both a polar group and a nonpolar group in the structure can be used.
  • NPS registered trademark
  • 9125 manufactured by Nippon Seiwa Co., Ltd.
  • Emanon registered trademark
  • 3199, 3299 manufactured by Kao Corporation
  • the amount thereof is preferably 0.05 to 4 parts by mass, more preferably 0.004 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (C). 1 to 2.0 parts by mass.
  • the radical polymerizable water-containing resin composition of the present invention may use a thixotropic agent for the purpose of adjusting the viscosity for ensuring workability on a vertical surface or a ceiling surface.
  • a thixotropic agent examples include an inorganic thixotropic agent and an organic thixotropic agent.
  • examples of the organic thixotropic agent include hydrogenated castor oil type, amide type, polyethylene oxide type, vegetable oil polymerized oil type, interface.
  • An activator system and a composite system using these in combination are exemplified. Specifically, DISPARLON (registered trademark) 6900-20X (Enomoto Kasei Co., Ltd.) and the like can be mentioned.
  • examples of inorganic thixotropic agents include silica and bentonite
  • hydrophobic ones include Leolosil (registered trademark) PM-20L (gas phase method silica manufactured by Tokuyama Corporation) and Aerosil (registered trademark) AEROSIL. R-106 (Nippon Aerosil Co., Ltd.) and the like
  • examples of hydrophilic ones include Aerosil (registered trademark) AEROSIL-200 (Nippon Aerosil Co., Ltd.).
  • radical polymerizable water-containing resin composition of the present invention contains a thixotropic agent
  • the amount thereof is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (C).
  • the amount is preferably 0.1 to 5 parts by mass.
  • the method for producing a radically polymerizable water-containing resin composition of the present invention comprises the step 1 of obtaining the mixed liquid (i) by mixing the metal-containing compound (A) and the radically polymerizable compound (C), the mixed liquid Step 2 of obtaining a mixed liquid (ii) by mixing (i) and the thiol compound (B), mixing the mixed liquid (ii), the surfactant (D) and the water (E).
  • This is a method comprising the step 3 of obtaining the liquid mixture (iii) and the step 4 of mixing the liquid mixture (iii) and the radical polymerization initiator (F).
  • the thiol compound (B) can be efficiently coordinated in the vicinity of the metal of the metal-containing compound (A).
  • the temperature at the time of each mixing is preferably 20 to 40 ° C. from the viewpoint of uniformly mixing and suppressing the deterioration of each component.
  • the order of mixing optional components other than components (A) to (F) is not particularly limited and can be mixed in any step, but from the viewpoint of uniform mixing before radical polymerization is started, It is preferable to mix in any one of 1 to 3, and it is more preferable to mix in step 3.
  • the radical polymerizable water-containing resin composition of the present invention can be produced, but a uniform composition may not be obtained. It is preferable to manufacture by.
  • the method for curing the radically polymerizable water-containing resin composition of the present invention comprises a state where the water (E) is contained in the radically polymerizable water-containing resin composition of the present invention, the radically polymerizable water-containing resin composition and water. It is a curing method for curing in either a contacted state or a state in which the radical polymerizable water-containing resin composition is immersed in water.
  • said radical polymerization initiator (F) the radically polymerizable water-containing resin composition of the present invention can be cured preferably at a temperature of 5 ° C. or higher.
  • the “state in which water (E) is contained in the radical polymerizable water-containing resin composition” in the curing method of the present invention means that water (E) is removed from the radical polymerizable water-containing resin composition of the present invention by drying or the like. It means no state.
  • the “state in which the radical polymerizable water-containing resin composition and water are brought into contact with each other” means that all or part of the radical polymerizable water-containing resin composition of the present invention and water other than the water (E), A state in which water present in the environment around the radical polymerizable water-containing resin composition is in contact.
  • the “state in which the radical polymerizable water-containing resin composition is immersed in water” refers to a state in which all or part of the radical polymerizable water-containing resin composition of the present invention is immersed in water. Since the radically polymerizable water-containing resin composition of the present invention can be cured even in a water-containing state as described above, it can be cured even in a state where it is in contact with water and further immersed. Is possible. By the above curing method, all or a part of the water (E) in the radical polymerizable water-containing resin composition is taken into the cured resin component without solid-liquid separation.
  • Secondary thiol compound (B-3) Cyanuric acid skeleton trifunctional secondary thiol, manufactured by Showa Denko KK, Karenz MT (registered trademark) NR1 (1,3,5-tris [2- (3-mercaptobutyryloxy) ethyl] -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione, molecular weight 567.67) ⁇ Secondary thiol compound (B-4) Trifunctional secondary thiol, manufactured by Showa Denko KK, TPMB (trimethylolpropane tris (3-mercaptobutyrate), molecular weight 440.64) ⁇ Tertiary thiol compound (B-5) Trifunctional tertiary thiol: trimethylolpropane tris (2-mercaptoisobutyrate) synthesized in the following synthesis example, molecular weight 440.64
  • Radically polymerizable compound (C-1) Vinyl ester resin Lipoxy (registered trademark), manufactured by Showa Denko KK, NSR-112 (without styrene) .
  • Radically polymerizable compounds (C-2) Unsaturated polyester resin Rigolac (registered trademark), Showa Denko KK, SR-110N (styrene content 40% by mass) .Radically polymerizable compounds (C-3) Vinyl ester resin Lipoxy (registered trademark), manufactured by Showa Denko KK, NSR-1000W-1 (without styrene)
  • Example 1 [Step 1 and Step 2] 0.2 parts by weight of metal soap (A-1) is added to 80 parts by weight of the radical polymerizable compound (C-1), and the mixture is thoroughly stirred at room temperature (25 ° C.) to obtain a mixed liquid (i). The mixture (ii) was obtained by thoroughly stirring the mixture (i) and 2.5 parts by mass of the secondary thiol compound (B-1).
  • Step 3 and Step 4 A surfactant (D-1) 0.28 part by mass was added to 19.6 parts by mass of water (E-1) to prepare a 1.4% by mass aqueous surfactant solution. Then, the mixed solution (ii) and the total amount of the surfactant aqueous solution are thoroughly stirred to obtain a mixed solution (iii), and the mixed solution (iii) and the radical polymerization initiator (F-1) 2.
  • a radical polymerizable water-containing resin composition was obtained by stirring 5 parts by mass. The obtained radical polymerizable water-containing resin composition was evaluated according to the following method. The results are shown in Table 1.
  • the blending amount of the metal soap shown in Examples 1 to 13 and Comparative Examples 1 to 4 is not a solid blending amount but a blending amount converted to the amount of the metal component in the metal soap, and the surfactant.
  • the blending amount is a blending amount converted to the active ingredient amount of the surfactant.
  • Examples 2 to 13 and Comparative Examples 1 to 4 A radical polymerizable water-containing resin composition was obtained in the same manner as in Example 1 except that the respective components were blended according to the descriptions in Tables 1 to 3. The obtained radical polymerizable water-containing resin composition was evaluated according to the following method. The results are shown in Tables 1 to 3.
  • the radical polymerizable water-containing resin composition of the present invention containing a specific amount of each component has good results such as gelation time, curing temperature, etc. No separation from water was observed.
  • Example 14 [Step 1 and Step 2] 0.16 parts by mass of metal soap (A-1) is added to 80 parts by mass of the radical polymerizable compound (C-1), and the mixture is thoroughly stirred at room temperature (25 ° C.) to obtain a mixed liquid (i). A mixed liquid (ii) was obtained by adding the mixed liquid (i) and 2 parts by mass of the secondary thiol compound (B-1) and stirring well.
  • Step 3 and Step 4 A surfactant (D-1) 0.28 part by mass was added to 19.6 parts by mass of water (E-1) to prepare a 1.4% by mass aqueous surfactant solution. Then, the mixture (ii) and the total amount of the surfactant aqueous solution are thoroughly stirred to obtain a mixture (iii), and the mixture (iii) and the radical polymerization initiator (F-3) 2 mass
  • the radical polymerizable water-containing resin composition was obtained by stirring the part. About the obtained radically polymerizable water-containing resin composition, the gelation time, the curing time, and the curing temperature were measured in the same manner as described above. Moreover, the weight change of hardened
  • the compounding amount of the metal soap shown in Examples 14 to 22, Comparative Examples 5 to 10, and Reference Examples 1 to 3 is not a solid compounding amount but a compounding amount converted to the amount of the metal component in the metal soap.
  • the amount of the surfactant is the amount converted to the amount of the active ingredient of the surfactant.
  • Example 15 to 22 Comparative Examples 5 to 10, and Reference Examples 1 to 3
  • a radically polymerizable water-containing resin composition was obtained in the same manner as in Example 14 except that the respective components were blended according to the descriptions in Tables 5 to 7.
  • About the obtained radically polymerizable water-containing resin composition, the gelation time, the curing time, and the curing temperature were measured in the same manner as described above.
  • cured material was evaluated according to the following method. The results are shown in Tables 5-7.
  • Examples 14 to 22 have good results such as gelation time and curing temperature.
  • the amount of water that can be retained by using a dryer at 80 ° C. to 100 ° C. is evaluated. Cement or the like can be selected as appropriate.
  • the weight reduction rate is larger than the value of the example, so that it can be seen that almost all the water was removed from the cured product by the drying treatment. That is, it can be said that moisture is not held in the cured product.
  • Reference Examples 1 to 3 are test examples for control, which were tested without using any of water and each component. From the results of these reference examples, it can be seen that the factor that decreases the weight of the cured products of the examples and comparative examples is water.
  • Example 24 (Example 23 will be described later) [Step 1 and Step 2] A mixed liquid (i) is obtained by adding 0.04 part by weight of metal soap (A-1) to 100 parts by weight of the radical polymerizable compound (C-1) and stirring well, and the mixed liquid (i) The mixture (ii) was obtained by thoroughly stirring 0.5 parts by mass of the secondary thiol compound (B-1).
  • Step 3 and Step 4 0.175 parts by mass of surfactant (D-1) was added to 24.75 parts by mass of water (E-1) to prepare a 0.7% by mass aqueous surfactant solution. And after fully stirring the said liquid mixture (ii) and the whole quantity of the said surfactant aqueous solution, 0.01 part of polymerization inhibitors were added and stirred well. Thereafter, 240 parts by mass of Portland cement (H-1) as a filler was added and stirred to obtain a mixed liquid (iii). The mixed liquid (iii) and 0.5 parts by mass of the radical polymerization initiator (F-3) And a radical polymerizable water-containing resin composition was obtained.
  • a PET film is pasted on a glass plate having a side of 30 cm as a base, and a mold is formed in four sides with a rubber having a thickness of 4 mm, and the radical polymerizable water-containing resin is formed there.
  • the composition was poured into a mold, covered with a 30 cm side glass plate prepared separately and covered with a PET film, covered with a weight of about 5 kg and allowed to stand for 24 hours to cure. .
  • the cured product of the obtained resin composition was cut into a size described later, and various tests were evaluated. The results are shown in Table 8.
  • the blending amount of the metal soap shown in Examples 23 to 28 and Reference Examples 4 to 5 is not a solid blending amount but a blending amount converted to the amount of the metal component in the metal soap, and has a surface activity.
  • the blending amount of the agent is a blending amount converted to the amount of the active ingredient of the surfactant.
  • Examples 23, 25 to 28 and Reference Examples 4 to 5 A radical polymerizable water-containing resin composition was obtained in the same manner as in Example 24 except that each component was blended according to the descriptions in Tables 8 and 9. About the obtained radical polymerizable water-containing resin composition, the hardened
  • a compressive stress measurement test was performed according to JIS K7181 (2011).
  • the test specimen was prepared in accordance with the section 6.1.2 of JIS K7181 (2011).
  • the dimensions of the test piece were 10 mm long, 10 mm wide, and 4 mm thick.
  • Examples 23 to 28 are excellent in bending strength, bending elastic modulus, compressive stress, and compressive elastic modulus.
  • the radically polymerizable water-containing resin composition of the present invention can be cured despite containing water, and the cured product is superior to the cured product of the resin composition not containing water. It can be seen that it exhibits properties.
  • the radically polymerizable water-containing resin composition of the present invention can be cured despite containing water.
  • a surface wet with water such as polymer cement mortar or cement concrete, further brackish water, sea water
  • the curing speed can be controlled, it can be used as a repair material for water leakage such as tunnels and dams.
  • radical resin composition described in the specification of the later application can be used in various applications, particularly in combination with a primer for flooring or a surface finishing agent for flooring to form a multilayer structure.
  • water contained in the radically polymerizable water-containing resin composition of the present invention is retained in the cured product without being subjected to solid-liquid separation, for example, the radioactive material generated in large quantities due to an accident at a nuclear power plant, etc.
  • the contaminated water is stored in a solid state until the radioactive substance is safe for the human body. be able to.
  • factory effluent can be stored in a solid state.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne une composition de résine contenant de l'eau, polymérisable par voie radicalaire qui renferme un composé contenant un métal (A), un composé thiol (B), un composé polymérisable par voie radicalaire (C), un tensioactif (D), de l'eau (E), et un initiateur de polymérisation par voie radicalaire (F), où sont présentes de 0,05 à 10 parties en masse du tensioactif (D) pour 100 parties en masse totales du constituant de métal du composé contenant du métal (A), du composé thiol (B), du composé polymérisable par voie radicalaire (C), de l'eau (E) et de l'initiateur de polymérisation par voie radicalaire (F), et sont présentes de 0,3 à 10 parties en masse de l'initiateur de polymérisation par voie radicalaire (F) pour 100 parties en masse du composé polymérisable par voie radicalaire (C), et ce composé de résine contenant de l'eau, polymérisable par voie radicalaire peut être durci de manière stable même sous un état renfermant de l'eau.
PCT/JP2016/062447 2015-04-21 2016-04-19 Composition de résine contenant de l'eau, polymérisable par voie radicalaire, son procédé de durcissement, et procédé de production d'une composition de résine contenant de l'eau, polymérisable par voie radicalaire WO2016171150A1 (fr)

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JP2017514144A JP6690638B2 (ja) 2015-04-21 2016-04-19 ラジカル重合性含水樹脂組成物、その硬化方法、及びラジカル重合性含水樹脂組成物の製造方法
CN201680022529.0A CN107531813B (zh) 2015-04-21 2016-04-19 自由基聚合性含水树脂组合物、其固化方法及自由基聚合性含水树脂组合物的制造方法
MYPI2017703938A MY182723A (en) 2015-04-21 2016-04-19 Radical-polymerizable, water-containing resin composition, curing method thereof, and method for producing radical-polymerizable, water-containing resin composition
PH12017501926A PH12017501926B1 (en) 2015-04-21 2017-10-20 Radical-polymerizable, water-containing resin composition, curing method thereof, and method for producing radical-polymerizable, water-containing resin composition

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JP2018172495A (ja) * 2017-03-31 2018-11-08 株式会社Adeka 硬化性組成物、硬化物の製造方法、その硬化物、それを用いた積層フィルムおよび接着剤
JP2018203876A (ja) * 2017-06-05 2018-12-27 昭和電工株式会社 ラジカル重合性樹脂組成物
WO2019004125A1 (fr) * 2017-06-26 2019-01-03 昭和電工株式会社 Composition de résine polymérisable par voie radicalaire, et matériau de réparation de construction
CN112851874A (zh) * 2019-11-26 2021-05-28 昭和电工株式会社 热固性树脂组合物

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JPWO2021132139A1 (fr) * 2019-12-26 2021-07-01
WO2022224988A1 (fr) * 2021-04-23 2022-10-27 昭和電工株式会社 Kit de matériau de remplissage d'évidement, produit durci de celui-ci et procédé de remplissage d'évidement

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JP2004149755A (ja) * 2002-02-28 2004-05-27 Showa Denko Kk チオール化合物、光重合開始剤組成物および感光性組成物
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WO2018078997A1 (fr) * 2016-10-26 2018-05-03 昭和電工株式会社 Composition de résine polymérisable par voie radicalaire
JP2018172495A (ja) * 2017-03-31 2018-11-08 株式会社Adeka 硬化性組成物、硬化物の製造方法、その硬化物、それを用いた積層フィルムおよび接着剤
JP2018203876A (ja) * 2017-06-05 2018-12-27 昭和電工株式会社 ラジカル重合性樹脂組成物
WO2019004125A1 (fr) * 2017-06-26 2019-01-03 昭和電工株式会社 Composition de résine polymérisable par voie radicalaire, et matériau de réparation de construction
CN110799558A (zh) * 2017-06-26 2020-02-14 昭和电工株式会社 自由基聚合性树脂组合物及结构物修复材料
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CN112851874A (zh) * 2019-11-26 2021-05-28 昭和电工株式会社 热固性树脂组合物
JP2021084940A (ja) * 2019-11-26 2021-06-03 昭和電工株式会社 熱硬化性樹脂組成物
CN112851874B (zh) * 2019-11-26 2023-09-26 株式会社力森诺科 热固性树脂组合物
JP7358940B2 (ja) 2019-11-26 2023-10-12 株式会社レゾナック 熱硬化性樹脂組成物

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JP6690638B2 (ja) 2020-04-28
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