CN112851874A - Thermosetting resin composition - Google Patents
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- CN112851874A CN112851874A CN202011193979.0A CN202011193979A CN112851874A CN 112851874 A CN112851874 A CN 112851874A CN 202011193979 A CN202011193979 A CN 202011193979A CN 112851874 A CN112851874 A CN 112851874A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
A thermosetting resin composition comprising: the thermosetting resin composition comprises a thermosetting resin (A) having a plurality of ethylenically unsaturated bonds, an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex compound (D), an inorganic aggregate (E), and water (F), wherein the content of a surfactant is 0 part by mass or more and less than 0.05 part by mass relative to 100 parts by mass of the total content of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F), and the content of the water (F) is 0.5 part by mass or more and less than 5 parts by mass relative to 100 parts by mass of the total content of the thermosetting resin (A) and the ethylenically unsaturated compound (B).
Description
Technical Field
The present invention relates to a thermosetting resin composition.
Background
Thermosetting resins are used in a wide range of applications such as molding materials, adhesives, primers, paints, inorganic structural repair materials for repairing concrete fracture surfaces, injecting cracks, stopping water, fillers, gap-filling materials, and fiber-reinforced composite materials.
Among thermosetting resins, radical polymerizable thermosetting resins such as unsaturated polyester resins, vinyl ester resins, and urethane acrylate resins have advantages such as moldability, curability, and adhesion to substrates, and are widely used in the above fields.
In order to improve the mechanical strength of a cured product of a thermosetting resin, the thermosetting resin composition may be used by mixing with an inorganic aggregate. Such thermosetting resin compositions are called resin concrete and resin mortar, and have the advantage of being superior in specific strength and chemical resistance to cement mortar.
Here, the crack injection agent and the mortar coating agent are required to be in close contact with an inorganic structural base material such as concrete even in a wet state. However, there is a problem that the thermosetting resin and the inorganic aggregate are gradually peeled off in water or other chemical solutions to deteriorate the mechanical strength.
Therefore, conventionally, a method of increasing the double bond effect of a thermosetting resin (non-patent document 1), a method of forming a structure having hydrophobicity (non-patent document 1), and a method of adding a surface modifier called a coupling agent which reacts or interacts with a thermosetting resin to an inorganic aggregate (non-patent document 2) have been employed. Among them, the coupling agent treatment of the inorganic aggregate is a means which is often used because it can improve the adhesion between the resin and the inorganic aggregate without changing the mechanical strength inherent in the thermosetting resin.
Further, there are disclosed techniques for stably curing a radically polymerizable thermosetting resin composition by suppressing a decrease in the function of a metal soap used as a curing accelerator even in the presence of water in the thermosetting resin composition or in the use environment of the thermosetting resin composition (patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2016/171150
Patent document 2: international publication No. 2016/171151
Non-patent document
Non-patent document 1: Koichi Ochi, "フェノール硬化エポキシ樹脂の吸水性に及ぼす自由体積と極性基濃度の影響(Effects of Free Volume and Polar Group Concentration on Water Absorption of Phenolic Cured Epoxy Resin)", 熱硬化性樹脂 (Thermosetting Epoxy Resin) ), Vol.15 No.1 (1994)
Non-patent document 2: Yoshinobu Nakamura, "シランカップリング剤処理における加水分解および縮合反応のコントロール(Control of Hydrolysis and Condensation Reactions in Silane Coupling Agent Treatment)" , 日本接着学会誌(Journal of Japan Adhesive Society), Vol.52 No.1 (2016)
Disclosure of Invention
Problems to be solved by the invention
However, the methods of non-patent documents 1 and 2 have problems that initial physical properties of the thermosetting resin are changed, compatibility with various additives is deteriorated, the operation is complicated because a surface treatment step using a coupling agent is increased, and methanol is generated as a by-product in the coupling treatment.
In addition, in recent years, there has been an increasing demand for a caulking material that exhibits high strength in a short time by filling in a wet space, can further hold it for a long time, and can stop water. In addition, in the case where the caulking material is used for pipe renovation and tunnel construction, it is required to be quickly filled between the base material and the base material. Further, unlike crack injection agents and mortar coating agents, which are temporary repair means, it is required to maintain strength for a long period of time even if the crack injection agent or the mortar coating agent has an influence of water leakage or the like. In the above patent documents 1 and 2, although the thermosetting resin composition can be stably cured even in the presence of water, there is no mention of maintaining the long-term mechanical strength of the cured product.
Accordingly, an object of the present invention is to provide a thermosetting resin composition which can be cured in a wet space, has a cured product with good mechanical strength, and can suppress a decrease in mechanical strength even when it is in contact with water for a long period of time.
Means for solving the problems
The present invention is based on the following findings: by adding an inorganic aggregate and water to a thermosetting resin composition containing a metal complex compound as a curing accelerator and a thiol compound as a curing accelerator, it is possible to suppress a decrease in mechanical strength even when a cured product of the thermosetting resin composition is exposed to water for a long period of time.
Namely, the present invention provides the following [1] to [10 ].
[1] A thermosetting resin composition comprising: a thermosetting resin (A) having a plurality of ethylenically unsaturated bonds, an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex compound (D), an inorganic aggregate (E), and water (F),
the content of the surfactant is 0 part by mass or more and less than 0.05 part by mass relative to 100 parts by mass of the total content of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F),
the content of the water (F) is 0.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (a) and the ethylenically unsaturated compound (B).
[2] The thermosetting resin composition according to the above [1], which has a viscosity of 2.5 pas or less at 25 ℃.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the thermosetting resin (A) contains 1 or more of an unsaturated polyester resin and a vinyl ester resin.
[4] The thermosetting resin composition according to any one of the above [1] to [3], wherein the metal complex compound (D) is a metal soap.
[5] The thermosetting resin composition according to any one of the above [1] to [4], wherein the inorganic aggregate (E) contains at least 1 kind of any one of alumina, aluminum hydroxide, silica sand, glass powder, talc and fused silica.
[6] The thermosetting resin composition according to any one of the above [1] to [5], wherein the inorganic aggregate (E) has a center particle diameter of 1 to 300 μm.
[7] The thermosetting resin composition according to any one of the above [1] to [6], further comprising a radical polymerization initiator (G).
[8] A space-filling material comprising the thermosetting resin composition according to any one of the above [1] to [7 ].
[9] A cured product of the thermosetting resin composition according to any one of the above [1] to [7 ].
[10] A canal or tunnel using the cured product according to [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a thermosetting resin composition which can be cured in a wet space, has a cured product with good mechanical strength, and can suppress a decrease in mechanical strength even when it is in contact with water for a long period of time can be provided.
Detailed Description
The present invention will be described in further detail below.
In the present specification, "to" means not less than the preceding value in the description of "to" and not more than the following value in the description of "to".
Further, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth) acrylate" is a general term for acrylate and methacrylate.
The term "ethylenically unsaturated bond" refers to a double bond formed between carbon atoms other than those forming an aromatic ring, and the term "ethylenically unsaturated monomer" refers to a monomer having an ethylenically unsaturated bond.
[ thermosetting resin composition ]
The thermosetting resin composition comprises: a thermosetting resin (A) having a plurality of ethylenically unsaturated bonds, an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex compound (D), an inorganic aggregate (E), and water (F).
The thermosetting resin composition can be cured in a wet space, and the cured product has good mechanical strength, and can be inhibited from lowering in mechanical strength even when it is in contact with water for a long period of time, and therefore the cured product thereof has excellent water resistance.
(thermosetting resin (A) having a plurality of ethylenically unsaturated bonds)
The thermosetting resin (a) having a plurality of ethylenically unsaturated bonds is not particularly limited as long as it is a compound having a plurality of ethylenically unsaturated bonds and being polymerized by a radical polymerization initiator.
Examples of the thermosetting resin (a) include unsaturated polyester resins, vinyl ester resins, and urethane (meth) acrylate resins. Among them, the thermosetting resin (a) preferably contains 1 or more of an unsaturated polyester resin and a vinyl ester resin from the viewpoint of the mechanical strength of the cured product. The thermosetting resin (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
(unsaturated polyester resin (A1))
The unsaturated polyester resin (a1) is not particularly limited as long as it is obtained by polycondensation of a polyhydric alcohol with an unsaturated polybasic acid and, if necessary, at least one selected from the group consisting of a saturated polybasic acid and a monobasic acid. The unsaturated polybasic acid is a polybasic acid having an ethylenically unsaturated bond. The saturated polybasic acid is a polybasic acid having no ethylenically unsaturated bond. The unsaturated polyester resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
< polyol >
The polyol is not particularly limited as long as it is a compound having 2 or more hydroxyl groups. Among them, preferred are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentyl glycol, tetraethylene glycol, polyethylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, cyclohexane-1, 4-dimethanol, hydrogenated bisphenol a, glycerin, an ethylene oxide adduct of bisphenol a, and a propylene oxide adduct of bisphenol a, and more preferred are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol a, an ethylene oxide adduct of bisphenol a, and a propylene oxide adduct of bisphenol a. The polyhydric alcohols may be used alone or in combination of 2 or more.
< unsaturated polybasic acid >
The unsaturated polybasic acid is not particularly limited as long as it is a compound having an ethylenically unsaturated bond and having 2 or more carboxyl groups or an acid anhydride thereof. Examples thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, and chloromaleic acid. Among them, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, and chloromaleic acid are preferable, and maleic anhydride and fumaric acid are more preferable, from the viewpoint of heat resistance and mechanical strength of the cured product. The unsaturated polybasic acids may be used alone or in combination of 2 or more.
< saturated polybasic acid >
The saturated polybasic acid is not particularly limited as long as it is a compound having 2 or more carboxyl groups and no ethylenic unsaturated bond, or an acid anhydride thereof. Examples thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endomethylenetetrahydrophthalic anhydride, nitrophthalic acid, tetrahydrophthalic anhydride, halophthalic anhydride, oxalic acid, malonic acid, azelaic acid, glutaric acid, and hexahydrophthalic anhydride. Among them, from the viewpoint of heat resistance and mechanical strength of the cured product, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, endomethylenetetrahydrophthalic anhydride, and tetrahydrophthalic anhydride are preferable, and phthalic anhydride, isophthalic acid, and terephthalic acid are more preferable. The saturated polybasic acids may be used alone or in combination of 2 or more.
< monoacid >)
Examples of the monobasic acid include dicyclopentadiene maleate, benzoic acid and a derivative thereof, cinnamic acid and a derivative thereof, and dicyclopentadiene maleate is preferable. The dicyclopentadiene maleate can be synthesized from maleic anhydride and dicyclopentadiene by a known method. By using a monobasic acid, the viscosity of the unsaturated polyester resin can be reduced, and the amount of styrene used can be reduced. The monoacid may be used alone, or 2 or more types may be used in combination.
The weight average molecular weight (Mw) of the unsaturated polyester resin (a1) is not particularly limited. The unsaturated polyester resin (A1) preferably has a weight average molecular weight of 2,000 to 25,000, more preferably 3,000 to 20,000, and still more preferably 3,500 to 10,000. When the weight average molecular weight is 2,000 to 25,000, the moldability of the unsaturated polyester resin composition becomes further excellent. In the present specification, "weight average molecular weight" is a value converted to standard polystyrene measured by Gel Permeation Chromatography (GPC).
The unsaturated polyester resin (a1) preferably has an unsaturation degree of 50 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 70 to 100 mol%. If the degree of unsaturation is in the above range, the moldability of the thermosetting resin composition containing the unsaturated polyester resin (A1) becomes further favorable. The unsaturation degree of the unsaturated polyester resin (a1) can be calculated by the following formula using the molar numbers of the unsaturated polybasic acid and the saturated polybasic acid used as raw materials. The number of unsaturated groups in the unsaturated polybasic acid is 1.
Unsaturation degree (% by mole) { (the number of moles of unsaturated polybasic acid)/(the number of moles of unsaturated polybasic acid + the number of moles of saturated polybasic acid) } × 100
The unsaturated polyester resin (a1) can be synthesized by a known method using the above-mentioned raw materials. Various conditions in the synthesis of the unsaturated polyester resin (a1) can be appropriately set depending on the raw materials used and the amounts thereof. Generally, an esterification reaction is carried out in a stream of an inert gas such as nitrogen under increased or reduced pressure at a temperature of 140 to 230 ℃. For the esterification reaction, an esterification catalyst may be used as needed. Examples of the esterification catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate. The esterification catalyst may be used alone, or 2 or more kinds may be used in combination.
Examples of commercially available products of the unsaturated polyester resin (a1) include "リゴラック (registered trademark)" manufactured by showa electric corporation.
(vinyl ester resin (A2))
The vinyl ester resin (a2) is generally a compound having an ethylenically unsaturated bond obtained by a ring-opening reaction of an epoxy group in an epoxy compound (a) having 2 or more epoxy groups and a carboxyl group in an unsaturated monobasic acid (b) having an ethylenically unsaturated bond and a carboxyl group. The unsaturated monoacid is a monoacid having an ethylenically unsaturated bond. Such a vinyl ester resin (a2) is described in, for example, ポリエステル, colophony ハンドブック (handbook of polyester resins) (japanese patent No. , new , published in 1988), and the like. The vinyl ester resin may be used alone, or 2 or more kinds may be used in combination.
< epoxy Compound (a) >
The epoxy compound (a) is not particularly limited as long as it is a compound having 2 or more epoxy groups. For example, at least 1 selected from the group consisting of a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, and a novolak phenol type epoxy resin can be used. Such an epoxy resin can further improve the mechanical strength and corrosion resistance of a cured product.
Examples of the bisphenol epoxy resin include those obtained by reacting a bisphenol such as bisphenol a, bisphenol F, bisphenol S, or tetrabromobisphenol a with epichlorohydrin or methyl epichlorohydrin, and those obtained by reacting a glycidyl ether of bisphenol a, a condensate of the above bisphenol compound, and epichlorohydrin or methyl epichlorohydrin.
Examples of the hydrogenated bisphenol epoxy resin include those obtained by reacting a glycidyl ether of hydrogenated bisphenol a with a bisphenol compound such as bisphenol a, bisphenol F, bisphenol S, and tetrabromobisphenol a.
Examples of the novolak phenol type epoxy resin include those obtained by reacting a phenol novolak or a cresol novolak with epichlorohydrin or methyl epichlorohydrin.
Among the epoxy resins, bisphenol a epoxy resins are preferred from the viewpoint of chemical resistance.
< unsaturated monobasic acid (b) >)
The unsaturated monocarboxylic acid (b) is not particularly limited as long as it is a monocarboxylic acid having an ethylenically unsaturated bond. For example, at least one selected from acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid is preferable, acrylic acid or methacrylic acid is more preferable, and methacrylic acid is particularly preferable. Since the vinyl ester resin (a2) obtained by the reaction of methacrylic acid with an epoxy resin has high hydrolysis resistance to acids and bases, the corrosion resistance of the cured product can be further improved.
The amount of the unsaturated monobasic acid (b) used in the ring-opening reaction of the epoxy compound (a) and the unsaturated monobasic acid (b) is preferably 0.3 to 1.5 equivalents, more preferably 0.4 to 1.2 equivalents, and particularly preferably 0.5 to 1.0 equivalent, based on 1 equivalent of the epoxy group of the epoxy compound (a). When the amount of the unsaturated monobasic acid (b) used is in the range of 0.3 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy compound (a), a cured product having sufficient hardness can be obtained by radical polymerization of the thermosetting resin composition containing the vinyl ester resin (a 2).
The vinyl ester resin (a2) can be synthesized by a known synthesis method. For example, a method of reacting an epoxy compound and an unsaturated monobasic acid group, optionally dissolved in a solvent, at 70 to 150 ℃, preferably 80 to 140 ℃, and more preferably 90 to 130 ℃ in the presence of an esterification catalyst.
The commercially available product of the vinyl ester resin (a2) is not particularly limited, and examples thereof include "リポキシ (registered trademark)" manufactured by showa electric corporation.
The unreacted unsaturated monobasic acid (B) after the synthesis of the vinyl ester resin (a2) is regarded as the ethylenically unsaturated monomer (B) described later.
(urethane (meth) acrylate resin (A3))
As the urethane (meth) acrylate resin, for example, a resin obtained by reacting (meth) acrylic acid with hydroxyl groups or isocyanate groups at both ends of polyurethane obtained by reacting a polyol with a polyisocyanate can be used.
The urethane (meth) acrylate resin may be used alone, or 2 or more kinds may be used in combination.
(ethylenically unsaturated Compound (B))
The ethylenically unsaturated compound (B) is not particularly limited as long as it is a monomer compound having an ethylenically unsaturated group. The number of the ethylenically unsaturated groups may be 1 or more.
Examples of the ethylenically unsaturated compound (B) include styrene, vinyltoluene, t-butylstyrene, a-alkyl group, o-alkyl group, m-alkyl group, p-alkyl group, nitro group, cyano group, amide, chlorine, dichloro or ester derivative of styrene, vinyl compounds such as vinyl acetate, methoxystyrene, divinylbenzene, vinylnaphthalene and acenaphthene; diene compounds such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, allyl (meth) acrylate, isobornyl (meth) acrylate, di (meth) allyl phthalate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, and mixtures thereof, 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, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethacrylate of PTMG, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, PTMG, and the like, Neopentyl glycol di (meth) acrylate, 2-hydroxy 1, 3-dimethacryloxypropane, 2-bis [4- (methacryloyloxyethoxy) phenyl ] propane, 2-bis [4- (methacryloyloxy-diethoxy) phenyl ] propane, 2-bis [4- (methacryloyloxy-polyethoxy) phenyl ] propane, tetraethylene glycol diacrylate, bisphenol AEO-modified (n ═ 2) diacrylate, (meth) acrylates such as isocyanuric acid EO-modified (n ═ 3) diacrylate, pentaerythritol di (meth) acrylate monostearate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tris (meth) allylisocyanurate; (meth) acrylamides such as (meth) acrylamide, N '-dimethyl (meth) acrylamide, and N, N' -diisopropyl (meth) acrylamide; unsaturated dicarboxylic acid diesters such as diethyl citraconate; mono-maleimide compounds such as N-phenylmaleimide; n- (meth) acryloylphthalimide, and the like. Among them, styrene, vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene, vinyl toluene, and methyl (meth) acrylate are preferable from the viewpoint of physical properties and surface drying properties of the cured product. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the ethylenically unsaturated compound (B) is preferably 10 to 95% by mass, more preferably 30 to 75% by mass, and still more preferably 40 to 60% by mass, based on the total amount of the thermosetting resin (a) and the ethylenically unsaturated compound (B). The content of the ethylenically unsaturated compound (B) is 10 to 95% by mass relative to the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B), and the mechanical strength of the cured product can be further improved.
(thiol Compound (C))
The thiol compound (C) is a compound having a mercapto group.
The thiol compound (C) functions as a curing accelerator by being used in combination with the metal complex compound (D) functioning as a curing accelerator in the thermosetting resin composition. As described later, the thiol compound (C) is believed to exert a curing acceleration ability by changing the electronic state of the metal complex through coordination to the metal atom of the metal complex (D).
The thiol compound (C) preferably has an ester structure represented by the following formula (Q-1).
In the formula (Q-1), R1And R2Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. But is not R1And R2Both are hydrogen atoms. Denotes a linkage to any organic group. a is an integer of 0 to 3.
It is considered that when a is 1, the thiol compound (C) has the above structure, particularly as shown in the following formula (T), an oxygen atom in a carbonyl group and a sulfur atom in a mercapto group are easily coordinated to a metal atom of the metal complex (D), and the metal atom of the metal complex (D) is surrounded by the thiol compound (C).
In the following formula (T), R is1And R2And R in the above formula (Q-1)1And R2The same meaning, M represents a metal element derived from the metal complex (D).
When the thermosetting resin composition is used under wet conditions, the thiol compound (C) coordinates as in the above formula (T), whereby the coordination of water to the metal atom can be suppressed and the curing acceleration ability can be stably exhibited.
Therefore, in particular, when the thermosetting resin composition is used under wet conditions, the thiol compound (C) is preferably a secondary thiol compound, and more preferably a polyfunctional thiol, from the viewpoint of the length of time available for curing.
Among them, ester compounds of a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol are more preferable. Such a compound is obtained by esterification of a mercapto group-containing carboxylic acid with a polyhydric alcohol by a known method.
In the following formula (S), R is1、R2And a and R in the above formula (Q-1)1、R2And a have the same meanings.
When the mercapto group-containing carboxylic acid represented by the above formula (S) is a compound derived from a secondary thiol compound, specific examples thereof include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto-3-phenylpropionic acid and the like.
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-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-bis (2-hydroxyethoxyphenyl) propane, bisphenol A adduct, bisphenol F oxyalkylene compound, bisphenol S oxyalkylene compound, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 2-hexanediol, 2-membered alcohols such as 1, 3-cyclohexanediol, 2, 3-hexanediol, 1, 4-hexanediol, 2, 4-hexanediol, 3, 4-hexanediol, 1, 5-hexanediol, 2, 5-hexanediol, 1, 6-hexanediol, and 9, 9-bis [4- (2-hydroxyethyl) phenyl ] fluorene; 3-or more-membered alcohols such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, sucrose, and 2, 2-bis (2, 3-dihydroxypropyloxyphenyl) propane; and polycarbonate diols, dimer acid polyester polyols, and the like.
Among them, from the viewpoint of easy availability and exhibiting curing acceleration ability even under wet conditions, 2-membered alcohols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, and 1, 4-butanediol are preferable; 3-or more-membered alcohols such as glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, and 2, 2-bis (2, 3-dihydroxypropyloxyphenyl) propane; polycarbonate diol and dimer acid polyester polyol are more preferably 1, 4-butanediol, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, polycarbonate diol and dimer acid polyester polyol from the viewpoint of the number of functional groups and vapor pressure.
Specific examples of the thiol compound (C) include 1, 4-bis (3-mercaptobutanoyloxy) butane (manufactured by Showa Denko K.K. "カレンズ MT (registered trademark) BD 1"), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K. "カレンズ MT (registered trademark) PE 1"), 1,3, 5-tris [2- (3-mercaptobutanoyloxyethyl) ] -1,3, 5-triazine-2, 4,6(1,3,5) -trione (manufactured by Showa Denko K.K. "カレンズ MT (registered trademark) NR 1"), trimethylolethane tris (3-mercaptobutyrate) (manufactured by Showa Denko K.K. "カレンズ MT (registered trademark)" TEMB), trimethylolpropane tris (3-mercaptobutyrate) (manufactured by Showa Denko K.K. "カレンズ MT (registered trademark) TPMB"), and the like .
The thiol compound (C) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
In view of the balance between the ability of the thiol compound (C) to coordinate the metal atom of the metal complex (D) and the cost and the curing acceleration ability, the content of the thiol compound (C) in the thermosetting resin composition is preferably 0.1 to 15 moles, more preferably 1 to 12 moles, and still more preferably 5 to 10 moles, based on the total mole of the metal complex (D) (i.e., the molar ratio [ (C)/(D) ].
The total amount of the thiol compound (C) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on the total 100 parts by mass of the thermosetting resin (a) and the ethylenically unsaturated compound (B), from the viewpoint of preferably an amount that does not affect the resin properties in a cured product of the thermosetting resin composition.
(Metal Complex Compound (D))
The metal complex (D) is not particularly limited as long as it is a compound in which an organic compound is coordinated to a metal atom via a coordination bond.
Examples of the metal element of the metal complex (D) include zirconium, cobalt, manganese, iron, copper, titanium, lead, tin, barium, bismuth, yttrium, vanadium, and calcium. Among them, from the viewpoint of the curing acceleration performance, zirconium, cobalt, manganese, iron, copper, and vanadium are preferable, cobalt, manganese, iron, and vanadium are more preferable, and cobalt, manganese, and iron are even more preferable.
Examples of the organic compound include a long-chain fatty acid and an organic acid other than a long-chain fatty acid, and a long-chain fatty acid is preferable.
As an example of the long-chain fatty acid, for example, a fatty acid having 7 to 30 carbon atoms is preferable. Specifically, preferable examples thereof include octanoic acids 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, hexacosanoic acid, octacosanoic acid, triacontanoic acid, and naphthenic acids, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid.
The organic acid other than the long-chain fatty acid is not particularly limited, and is preferably a compound having a weak acid such as a carboxyl group, a hydroxyl group, or an enol group and dissolved in an organic solvent.
The metal complex compound (D) is preferably a metal soap.
Specific examples of the metal soap (D) include manganese octylate, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, vanadium acetoacetate, cobalt acetoacetate, and iron acetoacetate, and more preferably include manganese octylate, cobalt octylate, and cobalt naphthenate.
The metal complex (D) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the metal complex (D) is preferably 0.05 to 5.00 parts by mass, more preferably 0.20 to 3.00 parts by mass, and still more preferably 0.50 to 1.50 parts by mass, based on 100 parts by mass of the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B).
The content of the metal complex (D) is 0.05 to 5.00 parts by mass relative to 100 parts by mass of the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B), and the resin composition can be cured more easily even under humid conditions and in water.
(inorganic aggregate (E))
The inorganic aggregate (E) is not particularly limited as long as it is not dissolved by the components in the thermosetting resin composition. The inorganic aggregate (E) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The inorganic aggregate (E) preferably contains any 1 or more of alumina, aluminum hydroxide, silica sand, glass powder, talc, and fused silica.
Furthermore, the inorganic aggregate (E) preferably has a center particle diameter of 1 to 300. mu.m, more preferably 3 to 200. mu.m, and further preferably 5 to 150. mu.m. If the center particle diameter of the inorganic aggregate (E) is 1 to 200 μm, the increase in viscosity of the thermosetting resin composition due to the addition of the inorganic aggregate can be suppressed. The above-mentioned central particle size is a median particle size in which the cumulative frequency of volumes from the small diameter side reaches 50% in a volume-based particle size distribution obtained by a laser diffraction scattering particle size distribution measurement method.
The content of the inorganic aggregate (E) is preferably 10 to 500 parts by mass, more preferably 25 to 300 parts by mass, and still more preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B).
The content of the inorganic aggregate (E) is 10 to 500 parts by mass relative to 100 parts by mass of the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B), and the mechanical strength of the cured product can be further improved.
(Water (F))
Specific examples of the water (F) include ion-exchanged water, tap water, sea water, river water, well water, industrial water, distilled water, and water containing 1 or more kinds selected from radioactive substances and the like.
The thermosetting resin composition can be cured in a state containing water as described above.
The content of the water (F) in the thermosetting resin composition is 0.5 parts by mass or more and less than 5 parts by mass, preferably 0.5 to 4 parts by mass, and more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total content of the thermosetting resin (a) and the ethylenically unsaturated compound (B).
If the content of the water (F) is less than 0.5 parts by mass relative to 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B), the water resistance of the cured product cannot be expected. On the other hand, if the amount is 5 parts by mass or more, the mechanical strength of the cured product tends to be impaired when the cured product is in contact with water for a long period of time, and it is difficult to improve the water resistance. When the content of water (F) is within the above range and the content of a surfactant described later is small or no surfactant is contained, the mechanical strength such as the elastic modulus and the elastic retention rate of the cured product becomes good, and the decrease in the mechanical strength can be suppressed even when the cured product is in contact with water for a long period of time, and the water resistance of the cured product is improved. The reason for this is not clear, but it is presumed that when the thermosetting resin composition contains water (F) in the above-mentioned content, an appropriate peeling state is formed at the interface between the resin and other components in the cured product, and even when the cured product is in contact with water, the interface hardly changes, and the elastic modulus is maintained.
(surfactant)
In the thermosetting resin composition, a surfactant is an ingredient that may be optionally contained.
Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
Examples of the anionic surfactant include alkyl sulfate salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate salts such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, sulfonate salts such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate and sodium dialkylsulfosuccinate, fatty acid salts such as sodium stearate soap, potassium oleate soap and potassium castor oil soap, and naphthalene sulfonic acid-formaldehyde condensate.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene derivatives such as polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, and polyoxyethylene polyoxypropylene glycol; polyoxyalkylene alkyl ethers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate; glycerin fatty acid esters such as glycerin monostearate and glycerin monooleate.
Examples of the cationic surfactant include fatty acid amides and salts thereof, alkyl ether amines and salts or quaternary salts thereof, fatty acid amide type quaternary ammonium salts, and cationic surfactants containing a silicone skeleton.
Examples of the amphoteric surfactant include carboxybetaine-type compounds, aminocarboxylates, and imidazolines
Betaine, and the like.
The content of the surfactant in the thermosetting resin composition is 0 part by mass or more and less than 0.05 part by mass with respect to 100 parts by mass of the total content of the thermosetting resin (a), the ethylenically unsaturated compound (B), and the water (F). The content of the surfactant is preferably 0.03 parts by mass or less, more preferably 0.01 parts by mass or less, and still more preferably 0 parts by mass.
If the content of the surfactant is 0.05 parts by mass or more per 100 parts by mass of the total of the thermosetting resin (a), the ethylenically unsaturated compound (B), and the water (F), it becomes difficult to suppress a decrease in mechanical strength when the cured product is in contact with water for a long period of time. When the content of the surfactant is less than 0.05 part by mass, and it is more preferable that the surfactant is not contained, it is expected that the water resistance, chemical resistance and mechanical properties can be improved.
(radical polymerization initiator (G))
The thermosetting resin composition preferably contains a radical polymerization initiator (G) because it cures by a radical polymerization reaction.
When the radical polymerization initiator (G) is stored under conditions such that the radical polymerization reaction of the thermosetting resin (a) is not started, it may be contained in the thermosetting resin composition in advance from the viewpoint of work efficiency and the like. In addition, the radical polymerization initiator (G) may be added to and mixed with the resin composition in which the thermosetting resin (a), the ethylenically unsaturated compound (B), the thiol compound (C), the metal complex compound (D), the inorganic aggregate (E), the water (F), and other components are mixed immediately before curing.
The kind of the radical polymerization initiator (G) is appropriately selected depending on the kind of the thermosetting resin (a), the use condition of the resin composition, the reaction condition, and the like, and a known thermal radical polymerization initiator, photo radical polymerization initiator, and the like can be used. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Specific examples of the thermal radical polymerization initiator include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butyl peroxybenzoate, peroxyesters such as cumene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals such as cyclohexane peroxide, alkyl peresters such as decane peroxide, and percarbonate organic peroxides such as peroxydicarbonate.
Specific examples of the photo radical polymerization initiator include benzoin ether systems such as benzoin alkyl ether, benzophenone systems such as benzophenone and methyl benzoylbenzoate, acetophenone systems such as benzildimethyl ketal, 2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and acetophenone systems such as 1, 1-dichloroacetophenone, and thioxanthone systems such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.
The content of the radical polymerization initiator (G) in the thermosetting resin composition is appropriately set depending on the kind of the thermosetting resin (a), the use condition of the resin composition, the reaction condition, and the like. The content of the radical polymerization initiator (G) is usually preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B). If the content of the radical polymerization initiator (G) is 0.1 parts by mass or more, the radical polymerization reaction can be favorably carried out, and if it is 10 parts by mass or less, the balance between the obtained effect and the production cost is favorable.
(other Components)
The thermosetting resin composition may contain various additives such as a curing accelerator, a solvent, a colorant, a fiber, a coupling agent, a wax, and a thixotropic agent, as required, depending on the purpose of use, the application, and the like.
The curing accelerator may be used to improve the curability of the thermosetting resin composition.
Specific examples of the curing accelerator include amines such as aniline, N-substituted p-toluidine, and 4- (N, N-substituted amino) benzaldehyde. More specifically, there may be mentioned aniline, N-dimethylaniline, N-diethylaniline, p-toluidine, N-dimethyl-p-toluidine, 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-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N-bis (hydroxyethyl) aniline, diethanol aniline, and the like. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
From the viewpoint of uniformly mixing the respective components contained in the thermosetting resin composition, a solvent may be used as necessary. The content is not particularly limited, and may be appropriately adjusted depending on the handling property and the like at the time of use. The kind of the solvent is appropriately selected depending on the kind of the resin, the use application, and the like, within a range not affecting the curing performance and the storage stability of the thermosetting resin composition. Examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, and chain carbonates. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Specific examples of the aliphatic hydrocarbon include mineral spirits such as cyclohexane, n-hexane, petroleum solvent, and odorless mineral spirits. Examples of the aromatic hydrocarbon include cycloalkane, a mixture of cycloalkane and paraffin, benzene, toluene, and quinoline. Examples of the ether include diethyl ether and diisopropyl ether. Examples of the ketone include acetone, methyl ethyl ketone, and cyclohexanone. Examples of the ester include ethyl acetate, butyl acetate, diethyl malonate, diethyl succinate, dibutyl maleate, 2, 4-trimethylpentanediol diisobutyrate, monoesters and diesters of ketoglutaric acid, pyruvic acid esters such as ethyl pyruvate, monoesters and diesters of ascorbic acid such as palmitic acid ester, and the like. Examples of the chain carbonate include dimethyl carbonate and diethyl carbonate. Further, 1, 2-dioximes such as 1, 2-cyclohexanedione dioxime, methyl pyrrolidone, ethyl pyrrolidone, dimethylformamide and the like can be used.
These solvents may be contained in a commercially available product of the thermosetting resin (a), the ethylenically unsaturated compound (B), the thiol compound (C), the metal complex compound (D), the inorganic aggregate (E), and water (F).
Examples of the colorant include known pigments such as coloring pigments, extender pigments and rust preventive pigments, and dyes. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the fibers include glass fibers, carbon fibers, vinylon fibers, nylon fibers, aramid fibers, polypropylene fibers, acrylic fibers, polyester fibers, cellulose fibers, metal fibers such as steel fibers, and ceramic fibers such as alumina fibers. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the wax include paraffin wax and polar wax. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the thixotropic agent include inorganic thixotropic agents and organic thixotropic agents. Examples of the organic thixotropic agent include amide-based thixotropic agents such as hydrogenated castor oil and acrylamide, oxidized polyethylene, vegetable oil, polymer oil, surfactants, and combinations thereof. Examples of the inorganic thixotropic agent include silica and bentonite, and any of a hydrophobic inorganic thixotropic agent and a hydrophilic inorganic thixotropic agent can be used. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the additive is within a range not affecting the curing performance and storage stability of the thermosetting resin composition, and can be appropriately adjusted according to the desired physical properties of the cured product of the resin composition to be produced. The total content of the additives is preferably 0.1 to 700 parts by mass, more preferably 0.1 to 500 parts by mass, and still more preferably 0.1 to 300 parts by mass, based on 100 parts by mass of the total of the thermosetting resin (a) and the ethylenically unsaturated compound (B).
(method for producing thermosetting resin composition)
The thermosetting resin composition can be obtained by mixing and stirring the thermosetting resin (a), the ethylenically unsaturated compound (B), the thiol compound (C), the metal complex compound (D), the inorganic aggregate (E), and the water (F) by a known method. Further, as optional components, the above-mentioned additives and the like may be added. The order of addition and mixing of the components is not particularly limited. In the mixing and stirring, an appropriate solvent can be used from the viewpoint of uniformly mixing the respective blending components as described above.
In one embodiment, for example, the thermosetting resin (a), the ethylenically unsaturated compound (B), and the metal complex compound (D) are mixed, and then the thiol compound (C) is mixed. Then, mixing water (F) and finally mixing the inorganic aggregate (E). When produced by this method, the thiol compound (C) can be efficiently coordinated in the vicinity of the metal complex compound (D).
In another embodiment, the inorganic aggregate (E) is mixed with water (F) in advance, and the mixture of (a) to (D) is mixed therewith. When produced by this method, the water-soluble component segregated on the surface of the inorganic aggregate (E) can be efficiently dispersed, and the water resistance of the cured product can be further improved.
The mixing method in each step is not particularly limited, and may be performed by a known method. In addition, the temperature at the time of mixing is preferably 20 to 40 ℃ from the viewpoint of uniform mixing and from the viewpoint of suppressing deterioration of each component.
(viscosity of thermosetting resin composition)
The viscosity of the thermosetting resin composition is preferably 2.5 pas or less. By setting the viscosity of the thermosetting resin composition to 2.5 pas or less, the filling property into a space becomes good, and it is possible to fill a narrow space densely. The viscosity of the thermosetting resin composition is more preferably 2.0 pas or less, still more preferably 1.0 pas or less, and still more preferably 0.5 pas or less. The lower limit of the viscosity of the thermosetting resin composition may be in a range that does not impair the effects of the present invention, and the viscosity of the thermosetting resin composition may be, for example, 0.15Pa · s or more.
The viscosity of the thermosetting resin composition may be measured according to JIS K7117: 1999 "プラスチック -color sensing method of color capable of rendering による viscosity capable of dispersing は (plastic-liquid, opaque or dispersing resin-method of measuring apparent viscosity by using brookfield rotational viscometer)" measurement, which is described in detail in examples.
[ cured product of thermosetting resin composition ]
The present invention also provides a cured product of the thermosetting resin composition.
The thermosetting resin composition can be cured by the radical polymerization reaction described above, and can be cured in any state of a state in which the thermosetting resin composition contains water (F), a state in which the thermosetting resin composition is brought into contact with water, or a state in which the thermosetting resin composition is immersed in water.
By using the above radical polymerization initiator (G), the thermosetting resin composition can be cured at a temperature preferably of 5 ℃ or higher.
The "state in which the thermosetting resin composition contains water (F)" means a state in which water (F) is not removed from the thermosetting resin composition by drying or the like. The term "state in which the thermosetting resin composition is brought into contact with water" means a state in which all or a part of the thermosetting resin composition is brought into contact with water other than water (F), that is, water present in the environment surrounding the thermosetting resin composition. Further, the term "state in which the thermosetting resin composition is immersed in water" means a state in which all or a part of the thermosetting resin composition is immersed in water.
Since the thermosetting resin composition can be cured even in a water-containing state as described above, it can be cured even in a state of being in contact with water or in a state of being further immersed.
By the above-mentioned curing method, all or a part of the water (F) in the thermosetting resin composition is introduced into the cured product of the resin component without solid-liquid separation, so that the mechanical strength such as the elastic modulus and the elastic retention rate of the cured product becomes good, and further, even if the cured product is in contact with water for a long time, the reduction in the mechanical strength can be suppressed, and the water resistance of the cured product is improved.
[ uses and the like ]
The thermosetting resin composition of the present invention exhibits good curing performance under dry conditions, even under wet/underwater conditions, and can achieve excellent mechanical strength in the cured product, and therefore can be used for various applications such as pipe renovation, a caulking material in tunnel construction, an inorganic structure repair material for water stop of concrete, and a fiber-reinforced composite material. In particular, the thermosetting resin composition is useful as a space-filling material, and can be suitably used for a canal or a tunnel using the cured product.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
The raw materials used for the production of the thermosetting resin compositions of the following examples and comparative examples are as follows.
< thermosetting resin (A) >
[ production of unsaturated polyester resin A1 ]
191g of propylene glycol, 164g of diethylene glycol, 64g of isophthalic acid and 64g of terephthalic acid were charged into a 1L flask equipped with a stirrer, a fractional condenser, a thermometer and a nitrogen inlet, and reacted at 215 ℃ for 5 hours while heating and stirring, and then cooled to 120 ℃. 189g of maleic anhydride and 0.04g of tert-butylhydroquinone were added thereto, and the mixture was reacted at 215 ℃ with heating and stirring, cooled until the acid value became 20mgKOH/g, and added with 0.05g of hydroquinone, 0.02g of copper naphthenate and 400g of styrene monomer to obtain 609g of a mixture AB-1 containing 60 mass% of an unsaturated polyester resin A1 (weight-average molecular weight: 3,700, degree of unsaturation: 100 mol%).
< ethylenically unsaturated Compound (B) >
Styrene (total of styrene (content: 40% by mass) contained in the above-mentioned mixture AB-1 and styrene to be added separately.)
< thiol Compound (C) >
Cyanuric acid skeleton 3-functional Secondary thiol (manufactured by Showa Denko K.K., カレンズ MT (registered trademark) BD1, 1, 4-bis (3-mercaptobutyryloxy) butane)
< Metal Complex (D) >)
Cobalt octylate (manufactured by Togro chemical Co., Ltd., ヘキソエートコバルト, cobalt content in total amount of product 8 mass%, molecular weight 345.34)
< inorganic aggregate (E) >)
Aluminum hydroxide (manufactured by Nippon light Metal Co., Ltd., B103, center particle diameter 7 μm)
Silica sand (center particle size 80 μm)
< Water (F) >
Distilled water
< radical polymerization initiator (G) >)
Cumene hydroperoxide (manufactured by Nichiku corporation, パークミル (registered trademark) H-80)
< surfactant >
Sodium lauryl sulfate
< curing Accelerator >
N, N-dimethylaniline (DMA, Tokyo chemical industry Co., Ltd.)
[ production of thermosetting resin composition ]
(example 1)
To 80g of the mixture AB-1 (containing 48g of the unsaturated polyester resin A1 and 32g of styrene) and 20g of the ethylenically unsaturated compound (B) were added 0.9g (0.0002 mol) of the metal complex (D), and they were mixed with stirring at 25 ℃. To this, 0.5G (0.002 mol) of a thiol compound (C), 100G of aluminum hydroxide as an inorganic aggregate (E), 1.0G of water (F), and 0.1G of a curing accelerator were added, and stirred and mixed, and 1.0G of a radical polymerization initiator (G) was further added, and stirred and mixed, thereby obtaining a thermosetting resin composition.
(examples 2 to 4 and comparative examples 1 to 4)
Each thermosetting resin composition was obtained in the same manner as in example 1, with the compounding composition shown in table 1 below. In comparative example 4, the surfactant was added simultaneously with the water (F).
[ evaluation of thermosetting resin composition ]
The thermosetting resin compositions produced in the examples and comparative examples were evaluated for the following items.
The evaluation results are shown in table 1 below.
< Water resistance >
The thermosetting resin compositions produced in the examples and comparative examples were cured by curing at 23 ℃ for 3 days to obtain cured products of the thermosetting resin compositions. The resulting cured product was cut into a rectangular parallelepiped of 10mm × 80mm × 4mm to prepare a test piece.
(method of measuring initial flexural modulus)
Using the above test piece, the test piece was measured according to JIS K7171: 2016 "(determination of plastic-bending characteristics) of the め square (determination of plastic-bending characteristics) of the characteristics of プラスチック -koji, and the initial flexural modulus of elasticity was determined by measuring the flexural modulus of elasticity at 23 ℃ and 50% RH.
(method of measuring flexural modulus after 2 weeks)
The test piece was immersed in distilled water 300 times the mass of the test piece and stored at 60 ℃ for 2 weeks.
The immersed test piece was taken out of distilled water, and then the surface of the test piece was wiped off with a rag or the like, and after curing at 23 ℃ for 6 hours, the flexural modulus was measured under the same conditions as the initial flexural modulus, and the flexural modulus after 2 weeks was set.
(method of calculating the retention ratio of flexural modulus)
The retention ratio of flexural modulus is calculated by the following equation.
(modulus of elasticity after 2 weeks)/(modulus of elasticity at initial bending) × 100
< viscosity >
250mL of the thermosetting resin compositions prepared in the examples and comparative examples were put into a 300mL beaker in a thermostatic bath ("PH-102", manufactured by エスペック K.), and the volume ratio was adjusted in accordance with JIS K7117: 1999, "プラスチック -viscosity of resin による transparent to け (plastic-liquid, opaque or dispersed resin-method of measuring apparent viscosity using brookfield rotational viscometer)", viscosity was measured using brookfield B-type rotational viscometer ("TV-25", manufactured by eastern industries) under conditions of liquid temperature 23 ℃, rotational speed 60rpm, and spindle (rotor) No.3, and viscosity (Pa · s) of the thermosetting resin composition was determined.
[ Table 1]
From the results shown in table 1, it is also clear that the thermosetting resin compositions (examples 1 to 4) containing a specific amount of water have a higher retention of flexural modulus than comparative examples 1 to 4, and therefore the cured products have high water resistance.
Further, as is clear from comparison of examples 1 to 3 with comparative example 3 or comparative example 4, the content of water and the surfactant in the thermosetting resin composition is set to a specific range, whereby the flexural modulus and the flexural elasticity retention rate are excellent. Therefore, the cured product of the thermosetting resin composition of the present invention has good mechanical strength, and the decrease in mechanical strength can be suppressed even when the cured product is in contact with water for a long period of time.
Industrial applicability
The thermosetting resin composition of the present invention exhibits good curing performance under dry conditions, even under wet/underwater conditions, and can achieve excellent mechanical strength in the cured product, and therefore can be used for various applications such as pipe renovation, a caulking material in tunnel construction, an inorganic structure repair material for water stop of concrete, and a fiber-reinforced composite material.
Claims (10)
1. A thermosetting resin composition comprising: a thermosetting resin (A) having a plurality of ethylenically unsaturated bonds, an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex compound (D), an inorganic aggregate (E), and water (F),
a content of the surfactant is 0 part by mass or more and less than 0.05 part by mass with respect to 100 parts by mass of a total content of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F),
the content of the water (F) is 0.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (A) and the ethylenically unsaturated compound (B).
2. The thermosetting resin composition according to claim 1, wherein the viscosity at 25 ℃ is 2.5 Pa-s or less.
3. The thermosetting resin composition according to claim 1 or 2, the thermosetting resin (a) comprising 1 or more of any of an unsaturated polyester resin and a vinyl ester resin.
4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the metal complex compound (D) is a metal soap.
5. The thermosetting resin composition according to any one of claims 1 to 4, the inorganic aggregate (E) comprising any 1 or more of alumina, aluminum hydroxide, silica sand, glass powder, talc and fused silica.
6. The thermosetting resin composition according to any one of claims 1 to 5, wherein the inorganic aggregate (E) has a central particle diameter of 1 to 300 μm.
7. The thermosetting resin composition according to any one of claims 1 to 6, further comprising a radical polymerization initiator (G).
8. A space-filling material comprising the thermosetting resin composition described in any one of claims 1 to 7.
9. A cured product of the thermosetting resin composition according to any one of claims 1 to 7.
10. A canal or tunnel using the cured product according to claim 9.
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| JP2019213386A JP7358940B2 (en) | 2019-11-26 | 2019-11-26 | thermosetting resin composition |
| JP2019-213386 | 2019-11-26 |
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| EP3228637B1 (en) | 2015-04-21 | 2019-02-20 | Showa Denko K.K. | Radical-polymerizable resin composition, curing method thereof, method of producing same, use of radical-polymerizable resin composition, and use method of thereof |
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| CN112851874B (en) | 2023-09-26 |
| JP7358940B2 (en) | 2023-10-12 |
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