WO2024090516A1 - Composition d'agent de durcissement pour résine polymérisable par voie radicalaire, et composition de résine polymérisable par voie radicalaire - Google Patents

Composition d'agent de durcissement pour résine polymérisable par voie radicalaire, et composition de résine polymérisable par voie radicalaire Download PDF

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WO2024090516A1
WO2024090516A1 PCT/JP2023/038679 JP2023038679W WO2024090516A1 WO 2024090516 A1 WO2024090516 A1 WO 2024090516A1 JP 2023038679 W JP2023038679 W JP 2023038679W WO 2024090516 A1 WO2024090516 A1 WO 2024090516A1
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acid
compound
radical polymerizable
polymerizable resin
curing agent
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PCT/JP2023/038679
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English (en)
Japanese (ja)
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彬 宇佐美
的 山下
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株式会社レゾナック
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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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof

Definitions

  • the present invention relates to a curing agent composition for radical polymerizable resins, a radical polymerizable resin composition containing the curing agent composition for radical polymerizable resins, and a cured product of the radical polymerizable resin composition.
  • Non-Patent Document 1 discloses the use of a transition metal complex as a polymerization initiator.
  • Non-Patent Document 2 discloses that radical polymerization is possible by using trivalent manganese and a carboxylic acid in water.
  • Non-Patent Document 3 discloses that polymerization is possible at room temperature by using an ⁇ -hydroxy ester in addition to a transition metal complex.
  • Non-Patent Document 1 requires high heat energy for polymerization.
  • the method of Non-Patent Document 2 requires a post-process to remove water, and therefore has not yet been used for industrial purposes.
  • the method of Non-Patent Document 3 requires a long curing time.
  • the cured products obtained by the methods disclosed in the above-mentioned prior art documents have a problem in that they are inferior in mechanical properties such as hardness, compared to cured products obtained by using conventional organic peroxides as polymerization initiators.
  • the present invention has been made in consideration of these circumstances, and provides a curing agent composition for radical polymerizable resins that can be cured at room temperature of about 20°C to 40°C without using an organic peroxide and that provides good mechanical properties such as hardness of the cured product obtained; a radical polymerizable resin composition that contains the curing agent composition for radical polymerizable resins; and a cured product of the radical polymerizable resin composition.
  • a curing agent composition for radical polymerizable resins comprising: (A) an organometallic compound containing at least one of manganese and cobalt; (B) at least one compound selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone; and (C) an acidic compound.
  • a radically polymerizable resin composition comprising: (A) an organometallic compound containing at least one of manganese and cobalt; (B) at least one compound selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone; and (C) an acidic compound; and further comprising (D) a radically polymerizable resin.
  • the radical polymerizable resin composition according to the above [6] further comprising an ethylenically unsaturated compound (E).
  • the present invention provides a curing agent composition for radical polymerizable resins that can be cured at 20°C to 40°C without using an organic peroxide and that provides good mechanical properties such as hardness of the cured product obtained; a radical polymerizable resin composition that contains the curing agent composition for radical polymerizable resins; and a cured product of the radical polymerizable resin composition.
  • to means greater than or equal to the value before “to” and less than or equal to the value after “to”.
  • (Meth)acrylic is a general term for acrylic and methacrylic
  • (meth)acrylate means acrylate or methacrylate
  • (meth)acryloyl group means acryloyl group or methacryloyl group.
  • ethylenically unsaturated bond means a double bond formed between carbon atoms other than those forming an aromatic ring
  • ethylenically unsaturated compound means a monomer having an ethylenically unsaturated bond.
  • the curing agent composition for radical polymerizable resins of this embodiment (hereinafter, may be simply referred to as "curing agent composition") contains an organometallic compound (A) containing at least one metal of manganese and cobalt, a compound (B) which is at least one selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone, and an acidic compound (C).
  • the curing agent composition does not contain an organic peroxide.
  • the above-mentioned curing agent composition can be cured at 20°C to 40°C without using an organic peroxide, and a cured product of a radically polymerizable resin composition (hereinafter, may be simply referred to as a "resin composition") containing such a curing agent composition has excellent curability and mechanical properties such as hardness, specifically, the mechanical properties are equal to or greater than those of a cured product cured using an organic peroxide.
  • resin composition a cured product of a radically polymerizable resin composition
  • the organometallic compound (A) is a compound containing at least one of manganese and cobalt.
  • the organometallic compound (A) include manganese salts or cobalt salts of long-chain fatty acids or other organic acids, or organomanganese compounds or organocobalt compounds having a compound having a ⁇ -diketone skeleton as a ligand.
  • the organometallic compound (A) can function as a curing accelerator in the curing agent composition or resin composition.
  • the organometallic compound (A) contains at least one of manganese and cobalt, thereby improving the curing property of the curing agent composition of the present embodiment.
  • the organometallic compound (A) is a manganese salt or cobalt salt of a long-chain fatty acid or other organic acid
  • the long-chain fatty acid may be either a saturated fatty acid or an unsaturated fatty acid.
  • Manganese salts or cobalt salts of long-chain fatty acids or other organic acids are also acidic compounds (C), and when such compounds are used, one compound may be used as both the organometallic compound (A) and the acidic compound (C).
  • the number of carbon atoms in the long-chain fatty acid is not particularly limited, but from the viewpoint of the dispersibility or solubility of the organometallic compound (A) in the resin composition, it is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 16.
  • long-chain fatty acids examples include heptanoic acid, octanoic acid (caprylic acid, 2-ethylhexanoic acid, etc.), 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, naphthenic acid, and other linear saturated fatty acids or those having a cyclic structure in a partial structure; and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid.
  • long-chain fatty acids include rosin acid derived from other natural products, fatty acids extracted from linseed oil, fatty acids extracted from soybean oil, and fatty acids extracted from tall oil.
  • octanoic acid and naphthenic acid are preferred, 2-ethylhexanoic acid and naphthenic acid are more preferred, and 2-ethylhexanoic acid is even more preferred.
  • the other organic acid is preferably a weak acid having, for example, a carboxy group, a hydroxy group, an enol group, or the like, which is soluble in a solvent that may be contained in the curable composition or resin composition, as described below.
  • weak acids having a carboxy group include carboxylic acids such as formic acid, acetic acid, and oxalic acid, hydroxy acids such as citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, and folic acid, amino acids such as alanine and arginine, and aromatic acids such as benzoic acid and phthalic acid.
  • Examples of compounds having a hydroxy group or an enol group include ascorbic acid, ⁇ acid, imido acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, and phosphonic acid.
  • manganese or cobalt salts of long-chain fatty acids or other organic acids include manganese(II) 2-ethylhexanoate, cobalt(II) 2-ethylhexanoate, cobalt octoate, manganese octoate, cobalt naphthenate, and cobalt neodecanoate, with manganese(II) ethylhexanoate, cobalt(II) 2-ethylhexanoate, cobalt octoate, manganese octoate, and cobalt naphthenate being preferred from the standpoint of curing performance.
  • the organometallic compound (A) is an organomanganese compound or an organocobalt compound having a compound having a ⁇ -diketone skeleton as a ligand
  • the compound having a ⁇ -diketone skeleton means a compound having a structure represented by the following formula (i) in which one carbon is located between two carbonyl groups.
  • R1 and R2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms.
  • These groups may have a substituent, and examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, and an alkyl group having 1 to 10 carbon atoms.
  • Examples of compounds having a ⁇ -diketone skeleton include acetylacetone, ethyl acetoacetate, benzoylacetone, hexafluoroacetylacetone, 2,2,6,6-tetramethylheptane-3,5-dione, 2,6-dimethylheptane-3,5-dione, 2,2,6,6-tetramethyloctane-3,5-dione, etc.
  • acetylacetone or a derivative thereof is preferred, and acetylacetone is more preferred.
  • the organometallic compound (A) is preferably an organomanganese compound or an organocobalt compound having a compound with a ⁇ -diketone skeleton as a ligand.
  • Specific examples include manganese acetylacetonate (III), cobalt acetylacetonate (III), and ethyl acetoacetate cobalt. From the viewpoint of controlling the curing performance, manganese acetylacetonate (III) and cobalt acetylacetonate (III) are preferred.
  • the organometallic compound (A) may be used alone or in combination of two or more kinds.
  • the curing agent composition of the present embodiment may contain an organometallic compound other than the organometallic compound (A).
  • organometallic compounds may include metal salts of long-chain fatty acids or other organic acids containing metals other than manganese and cobalt, organometallic compounds having a compound having a ⁇ -diketone skeleton as a ligand, and organometallic compounds in other forms, within a range that does not impair the effects of the present invention.
  • examples of such other metals include vanadium, iron, copper, titanium, yttrium, tin, lead, bismuth, zirconium, and calcium.
  • the curing agent composition of the present embodiment contains a compound (B) which is at least one selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone, which are a type of 1,3-dioxo compound.
  • the compound (B) may be any one of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone, or may be a mixture of two or three selected from ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone k.
  • the 1,3-dioxo compound is a compound in which two carbonyl carbon atoms are bonded to one carbon atom.
  • the 1,3-dioxo compound has a coordinate bond with manganese or cobalt contained in the organometallic compound (A) and can change the electronic state of the metal.
  • the 1,3-dioxo compound include the above-mentioned compounds having a ⁇ -diketone skeleton, as well as ⁇ -ketolactones such as ⁇ -acetyllactones, such as ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone.
  • ⁇ -acetyllactones the ring structure tends to open more easily as the number of carbon atoms increases.
  • the curing agent composition of the present embodiment specifically exhibits the effects of the present invention by containing at least one compound (B) selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone from the viewpoint of stability.
  • the curing agent composition of the present embodiment may contain a 1,3-dioxo compound other than ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone, but the content is preferably 0.1 moles or less per mole of compound (B), which is at least one compound selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone.
  • compound (B) which is at least one compound selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone.
  • the acidic compound (C) examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, and hypophosphorous acid; organic sulfonic acids such as p-toluenesulfonic acid and trifluoromethanesulfonic acid; organic oxoacids described below; and synthetic organic acids such as terminal carboxylate polyesters.
  • the acidic compound (C) contributes to improving the curability.
  • Co(EHA) 2 cobalt (II) 2-ethylhexanoate
  • Mn(EHA) 2 manganese (II) 2-ethylhexanoate
  • organic oxoacids include saturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid (octylic acid), nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid, and metal salts thereof; hydroxy acids such as lactic acid, malic acid, and citric acid; aromatic carboxylic acids such as benzoic acid, orthophthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, and mellitic acid, and metal salts thereof; oxalic acid, malonic acid, and succinic acid.
  • saturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid,
  • Examples of the acidic compound (C) include saturated dicarboxylic acids such as glutaric acid and adipic acid, and their metal salts, and aliphatic polycarboxylic acids such as tricarboxylic acids such as aconitic acid, and their metal salts; compounds having a phenolic hydroxyl group such as phenol and its derivatives, catechol and its derivatives such as catechol, methylcatechol, ethylcatechol, propylcatechol, and butylcatechol; phosphonic acid derivatives such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, and phenylphosphonic acid; etc.
  • saturated dicarboxylic acids such as glutaric acid and adipic acid, and their metal salts
  • aliphatic polycarboxylic acids such as tricarboxylic acids such as aconitic acid, and their metal salts
  • compounds having a phenolic hydroxyl group such as
  • the acidic compound (C) does not include unsaturated carboxylic acids which also fall under the category of ethylenically unsaturated compounds (E).
  • unsaturated carboxylic acids which also fall under the category of ethylenically unsaturated compounds (E).
  • E ethylenically unsaturated compounds
  • the acidic compound (C) may be used alone or in combination of two or more kinds.
  • a commercially available product may be appropriately used, or a derivative of an organic oxoacid may be appropriately produced and used.
  • the curing agent composition of the present embodiment can be obtained by mixing and stirring the organometallic compound (A), at least one compound (B) selected from the group consisting of ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -valerolactone, and ⁇ -acetyl- ⁇ -caprolactone, and the acidic compound (C) by a known method.
  • the order of addition and mixing of each component is not particularly limited.
  • a solvent may be appropriately used from the viewpoint of uniformly mixing each compounded component.
  • the molar ratio of the compound (B) to the organometallic compound (A) ((B)/(A)) is preferably 1.0 to 42.0, more preferably 2.0 to 30.0, and even more preferably 3.0 to 20.0, from the viewpoint of exhibiting good curing performance and improving mechanical properties such as hardness of the cured product of the resin composition.
  • the organometallic compound (A) and the compound (B) may be used in the preparation of the curing agent composition in a state of being dissolved in a solvent described below.
  • the content of the organometallic compound (A) in the curing agent composition of the present embodiment is preferably 0.5 to 40.0 mass %, more preferably 1.0 to 30.0 mass %, based on the total mass of the curing agent composition.
  • the content of the compound (B) in the curing agent composition of the present embodiment is preferably 2.0 to 80.0 mass %, more preferably 4.0 to 75.0 mass %, based on the total mass of the curing agent composition.
  • the content of the acidic compound (C) in the curing agent composition of the present embodiment is preferably 1.0 to 90.0 mass %, more preferably 3.0 to 87.0 mass %, based on the total mass of the curing agent composition.
  • the mass ratio ((A):(B):(C)) of the contents of the organometallic compound (A), the compound (B), and the acidic compound (C) in the curing agent composition of the present embodiment is preferably 0.5-40.0:2.0-80.0:1.0-90.0, and more preferably 1.8-28.2:5.3-70.6:4.0-86.5.
  • the acid value of the curing agent composition of the present embodiment is preferably 10.0 to 600.0 mgKOH/g, more preferably 20.0 to 300.0 mgKOH/g, and further preferably 28.0 to 200.0 mgKOH/g.
  • the acid value of the curing agent composition is measured by the method described in the Examples below.
  • the resin composition of the present embodiment preferably contains each component of the curing agent composition described above, a radical polymerizable resin (D), and further contains an ethylenically unsaturated compound (E).
  • the resin composition preferably does not contain an organic peroxide.
  • the radically polymerizable resin (D) is a resin that has an ethylenically unsaturated hydrocarbon group in the molecule and undergoes a polymerization reaction by radicals.
  • the radical polymerizable resin (D) include vinyl ester resins such as epoxy (meth)acrylate resins, unsaturated polyester resins, polyester (meth)acrylate resins, urethane (meth)acrylate resins, (meth)acrylate resins, etc. These may be used alone or in combination of two or more.
  • vinyl ester resins and unsaturated polyester resins are more preferred from the viewpoint of improving the mechanical properties such as hardness of the cured product obtained by curing the resin composition containing the curing agent composition of this embodiment.
  • vinyl ester resins are compounds having a polymerizable unsaturated bond obtained by a ring-opening reaction between an epoxy group in an epoxy compound having two or more epoxy groups (hereinafter simply referred to as an "epoxy compound”) and a carboxy group in an unsaturated monobasic acid having a polymerizable unsaturated bond and a carboxy group (hereinafter simply referred to as an "unsaturated monobasic acid”).
  • epoxy compound an epoxy compound having two or more epoxy groups
  • an unsaturated monobasic acid hereinafter simply referred to as an "unsaturated monobasic acid”
  • the epoxy compound is not particularly limited as long as it has two or more epoxy groups.
  • at least one selected from bisphenol type epoxy compounds, hydrogenated bisphenol type epoxy compounds, and novolac phenol type epoxy compounds can be used.
  • Such epoxy compounds can further improve the mechanical properties and corrosion resistance of the cured product.
  • bisphenol type epoxy compounds include those obtained by reacting a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S, or tetrabromobisphenol A with epichlorohydrin or methylepichlorohydrin; and those obtained by reacting a glycidyl ether of bisphenol A, a condensate of the above bisphenol compound, and epichlorohydrin or methylepichlorohydrin.
  • Examples of hydrogenated bisphenol type epoxy compounds include those obtained by reacting a glycidyl ether of hydrogenated bisphenol A with a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S, or tetrabromobisphenol A.
  • Examples of novolak phenol type epoxy compounds include those obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin; and the like.
  • bisphenol A epoxy compounds are preferred from the viewpoint of chemical resistance.
  • the unsaturated monobasic acid is not particularly limited as long as it is a monocarboxylic acid having a polymerizable unsaturated bond, but acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. are preferred, acrylic acid and methacrylic acid are more preferred, and methacrylic acid is even more preferred.
  • the vinyl ester resin obtained by reacting methacrylic acid with an epoxy compound has high hydrolysis resistance against acids and alkalis, and can further improve the corrosion resistance of the cured product.
  • the amount of unsaturated monobasic acid used when the epoxy compound and the unsaturated monobasic acid are subjected to a ring-opening reaction is preferably 0.3 to 1.5 equivalents, more preferably 0.4 to 1.2 equivalents, and even more preferably 0.5 to 1.0 equivalents per equivalent of the epoxy group of the epoxy compound.
  • the amount of unsaturated monobasic acid used is in the range of 0.3 to 1.5 equivalents per equivalent of the epoxy group of the epoxy compound, a cured product with sufficient hardness can be obtained by the radical polymerization reaction of the resin composition.
  • the vinyl ester resin can be produced by a method in which an epoxy compound and an unsaturated monobasic acid are dissolved in a solvent as necessary in the presence of a known esterification catalyst such as a tertiary amine such as triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, or diazabicyclooctane; a phosphorus compound such as triphenylphosphine or benzyltriphenylphosphonium chloride; or diethylamine hydrochloride, and the like, and reacted at preferably 70 to 150° C., more preferably 80 to 140° C., and even more preferably 90 to 130° C.
  • a known esterification catalyst such as a tertiary amine such as triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, or diazabicyclooctane
  • a phosphorus compound such as trip
  • any unreacted unsaturated monobasic acid remaining after the production of the vinyl ester resin is regarded as an ethylenically unsaturated compound (E) described below. That is, although unsaturated monobasic acids such as acrylic acid, methacrylic acid, and cinnamic acid are also organic oxoacids, such unreacted unsaturated monobasic acids are not included in the acidic compound (C).
  • the unsaturated polyester resin is obtained by polycondensation of a polyhydric alcohol, an unsaturated polybasic acid, and, if necessary, at least one selected from a saturated polybasic acid and a monobasic acid, and is not particularly limited.
  • 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 polyhydric alcohol is not particularly limited as long as it is a compound having two or more hydroxyl groups.
  • the unsaturated polybasic acid is not particularly limited as long as it is a compound having an ethylenically unsaturated bond and two or more carboxy groups or an acid anhydride thereof, and examples thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, etc.
  • maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, etc. are preferred, and maleic anhydride and fumaric acid are more preferred.
  • the unsaturated polybasic acids may be used alone or in combination of two or more kinds.
  • the saturated polybasic acid is not particularly limited as long as it is a compound or an acid anhydride thereof that does not have an ethylenically unsaturated bond and has two or more carboxy groups, and 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, halogenated phthalic anhydride, oxalic acid, malonic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, etc.
  • phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, endomethylenetetrahydrophthalic anhydride, and tetrahydrophthalic anhydride are preferred, and phthalic anhydride, isophthalic acid, and terephthalic acid are more preferred.
  • Examples of monobasic acids include dicyclopentadiene maleate, benzoic acid and its derivatives, and cinnamic acid and its derivatives.
  • dicyclopentadiene maleate is preferred.
  • Dicyclopentadiene maleate can be synthesized from maleic anhydride and dicyclopentadiene by a known method. The use of a monobasic acid can reduce the viscosity of the unsaturated polyester resin.
  • Unsaturated polyester resins can be produced by known methods using the above raw materials.
  • Various conditions in the production of unsaturated polyester resins can be set appropriately depending on the raw materials used and their amounts, and generally, an esterification reaction can be applied in a stream of inert gas such as nitrogen gas at a temperature of 140 to 230°C under pressure or reduced pressure.
  • inert gas such as nitrogen gas
  • known esterification catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate can be used alone or in combination of two or more types, as necessary.
  • the weight average molecular weight (Mw) of the unsaturated polyester resin is not particularly limited, but is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 18,000. If the Mw is 3,000 to 25,000, the moldability of the resin composition of this embodiment will be better. Note that Mw is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the degree of unsaturation of the unsaturated polyester resin is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. When the degree of unsaturation is within the above range, the moldability of the resin composition of the present embodiment is better.
  • polyester resins include, for example, "Rigolac (registered trademark)” manufactured by Showa Denko K.K.
  • urethane (meth)acrylate resin for example, a resin obtained by reacting hydroxyl groups or isocyanato groups at both ends of a polyurethane obtained by reacting a polyisocyanate with a polyhydric alcohol with (meth)acrylic acid can be used.
  • the content of the radical polymerizable resin (D) is appropriately set depending on the intended use and application of the radical polymerizable resin (D), but from the viewpoint of efficiently obtaining a good cured product of the resin composition of this embodiment, it is preferably 10 to 99 parts by mass, more preferably 20 to 98 parts by mass, and even more preferably 50 to 98 parts by mass per 100 parts by mass of the radical polymerizable resin (D) and the ethylenically unsaturated compound combined.
  • the ethylenically unsaturated compound (E) contained in the resin composition of the present embodiment is a monomer compound having an ethylenically unsaturated hydrocarbon group in the molecule and undergoing a polymerization reaction by radicals, and is also called a reactive diluent.
  • the ethylenically unsaturated compound (E) may have one or more ethylenically unsaturated hydrocarbon groups.
  • Examples of the ethylenically unsaturated compound (E) include ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide, or ester derivatives of styrene compounds such as styrene, vinyltoluene, and t-butylstyrene; vinyl compounds such as methoxystyrene, divinylbenzene, vinylnaphthalene, and acenaphthylene; 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
  • styrene, vinyl toluene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate are preferred, and styrene, vinyl toluene, and methyl (meth)acrylate are more preferred. These may be used alone or in combination of two or more.
  • the resin composition of the present embodiment contains a radical polymerizable resin (D). From the viewpoint of obtaining a resin composition having better mechanical properties such as hardness of a cured product, the resin composition preferably contains both the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).
  • the total content of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E) in the resin composition of this embodiment is preferably 80 to 99 mass %, more preferably 90 to 99 mass %.
  • the content of the ethylenically unsaturated compound (E) is preferably 1 to 90 parts by mass, more preferably 2 to 80 parts by mass, and even more preferably 2 to 50 parts by mass, based on 100 parts by mass of the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).
  • the content of the ethylenically unsaturated compound (E) is 1 to 90 parts by mass based on the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E)
  • the mechanical properties such as hardness of the cured product can be further improved.
  • the content of the acidic compound (C) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1.0 to 10 parts by mass, per 100 parts by mass of the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E). If the content of the acidic compound (C) is within such a range, the curing of the resin composition is not excessively delayed, and the mechanical properties such as hardness of the obtained cured product can be further improved.
  • the resin composition of the present embodiment may further contain various additives, such as a solvent, a thixotropy-imparting agent, a thixotropy-imparting assistant agent, a thickener, a colorant, a plasticizer, and a wax, as necessary, depending on the purpose of use, application, and the like, within a range that does not affect the effects of the present invention or does not deteriorate the mechanical properties, etc., of the cured product.
  • additives such as a solvent, a thixotropy-imparting agent, a thixotropy-imparting assistant agent, a thickener, a colorant, a plasticizer, and a wax
  • the solvent is used as necessary from the viewpoint of uniformly mixing each component contained in the resin composition.
  • the content is not particularly limited, and can be appropriately adjusted depending on the handling property during use.
  • the type of solvent is appropriately selected within a range that does not affect the curing performance and storage stability of the resin composition depending on the type of resin and the use purpose, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, and chain carbonates. These may be used alone or in combination of two or more. Examples of aliphatic hydrocarbons include cyclohexane, n-hexane, white spirits, and mineral spirits such as odorless mineral spirits (OMS).
  • OMS odorless mineral spirits
  • aromatic hydrocarbons include naphthene, a mixture of naphthene and paraffin, benzene, toluene, and quinoline.
  • ethers include diethyl ether and diisopropyl ether.
  • ketones include acetone, methyl ethyl ketone, and cyclohexanone.
  • esters include ethyl acetate, butyl acetate, diethyl malonate, diethyl succinate, dibutyl succinate, dibutyl maleate, 2,2,4-trimethylpentanediol diisobutyrate, mono- and diesters of ketoglutaric acid, pyruvates, and mono- and diesters of ascorbic acid such as palmitate of ascorbic acid.
  • chain carbonate esters include dimethyl carbonate and diethyl carbonate.
  • 1,2-dioximes, N-methylpyrrolidone, N-ethylpyrrolidinone, dimethylformamide, and the like can also be used. These solvents may be contained in commercially available products of the organometallic compound (A), the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).
  • Examples of the thixotropic agent include inorganic powders such as silica and clay.
  • Examples of the thixotropy-imparting assistant include polyethylene glycol, glycerin, polyhydroxycarboxylic acid amide, organic quaternary ammonium salt, etc.
  • a specific example of the polyhydroxycarboxylic acid amide is BYK-R-605 (manufactured by BYK Japan KK).
  • the thickener include metal oxides such as magnesium oxide, calcium oxide, and zinc oxide; and metal hydroxides such as magnesium hydroxide and calcium hydroxide.
  • Examples of colorants include organic pigments, inorganic pigments, and dyes.
  • Examples of the plasticizer include chlorinated paraffin, phosphate ester, and phthalate ester. Waxes can be added for the purpose of improving the surface drying properties by blocking air on the surface of the cured product. Examples of such waxes include petroleum waxes, olefin waxes, polar waxes, and special
  • the content of the additives can be adjusted as appropriate according to the desired physical properties of the cured product of the resin composition to be produced, within a range that does not affect the curing performance and storage stability of the resin composition.
  • the total content of the additives is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).
  • the resin composition of this embodiment is obtained by mixing a curing agent composition containing an organometallic compound (A), a compound (B) and an acidic compound (C) with a radical polymerizable resin (D) and an ethylenically unsaturated compound (E) which is an optional component.
  • the resin composition of this embodiment can be obtained by mixing and stirring the curing agent composition with the radical polymerizable resin (D) and the ethylenically unsaturated compound (E) by a known method. It is not necessary to once prepare a composition of the organometallic compound (A), the compound (B), and the acidic compound (C).
  • the organometallic compound (A), the compound (B), and the acidic compound (C) may be individually mixed with the radical polymerizable resin (D) and the ethylenically unsaturated compound (E), respectively, or the organometallic compound (A), the compound (B), and the acidic compound (C) may be mixed at once. Furthermore, the above-mentioned additives may be added as optional components.
  • the order of adding and mixing each component is not particularly limited. When mixing, as described above, a solvent may be appropriately used from the viewpoint of uniformly mixing each compounding component.
  • the mixing method is not particularly limited and may be any known method.
  • the temperature during mixing is preferably 20 to 40° C. from the viewpoints of uniform mixing and suppressing deterioration of each component.
  • the content of the curing agent composition is 1.5 to 10.0 parts by mass relative to a total of 100 parts by mass of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E), and that the acid value of the prepared resin composition is 2.0 mgKOH/g or more.
  • the content of the curing agent composition is more preferably 1.5 to 9.0 parts by mass, and even more preferably 1.5 to 8.0 parts by mass, per 100 parts by mass in total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).
  • the acid value of the prepared resin composition is more preferably 2.0 to 20.0 mgKOH/g, and further preferably 2.0 to 15.0 mgKOH/g.
  • the acid value of the resin composition can be measured by the method described in the examples below.
  • the gelation time of the resin composition can be shortened and the amount of the remaining ethylenically unsaturated compound (E) in the cured product can be further reduced. If the content of the curing agent composition is 10.0 parts by mass or less per 100 parts by mass of the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E), the resin composition can be cured in an appropriate gelation time.
  • the resin composition can be cured within an appropriate gelation time.
  • gelation time refers to the time that will be explained in the Examples below.
  • the cured product can be obtained by curing the radical polymerizable resin composition of the present embodiment.
  • the method for curing the resin composition include a method of curing the prepared resin composition at room temperature or by heating, a method of adding a curing accelerator to the prepared resin composition, mixing the composition, and then curing the composition at room temperature or by heating, etc.
  • the specific temperature range for room temperature and heating can be, for example, about 15 to 200° C., and a range of 15 to 160° C. is more preferable.
  • the resin composition of this embodiment has excellent mechanical properties such as hardness of the cured product, and therefore can be used in a variety of applications such as adhesives, primers, paints, inorganic structure repair materials for concrete cross-section repair, crack injection, water stoppage, etc., and fiber-reinforced composite materials.
  • a colorant may be added to the resin composition
  • a filler may be added.
  • the resin composition may contain components necessary for function expression according to various applications, such as adding reinforcing fibers to use the resin composition as a fiber-reinforced composite material.
  • [Acidic Compound (C)] (C-1): Organic acid produced by the procedure of Synthesis Example 1 below [Synthesis Example 1] 315g of succinic anhydride, 49g of propylene glycol, and 446g of trimethylolpropane tripropyl ether were added to a four-neck flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser, and the mixture was heated to 120°C, stirred until the acid value was 215mgKOH/g or less, and then cooled. 190g of styrene was added to this reaction mixture at 100°C to obtain an organic acid composition (styrene content 19%).
  • the organic acid is a polyester polycarboxylic acid obtained by dehydration polycondensation of succinic anhydride and propylene glycol.
  • C-2) p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.)
  • C-3 Phosphoric acid (Tokyo Chemical Industry Co., Ltd.)
  • C-4) Hydrochloric acid (Tokyo Chemical Industry Co., Ltd.) [Organometallic Compound (A) and Acidic Compound (C)]
  • Co(EHA) 2 2-ethylhexanoate cobalt(II) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Mn(EHA)2 Manganese 2-ethylhexanoate (II) (Tokyo Chemical Industry Co., Ltd.)
  • Example 1 (1) In the formulation shown in Table 1 below, ABL (B-1) as compound (B) was added to Mn(acac) 3 as organometallic compound (A) at 23°C, and then (C-1) as acidic compound (C) was added at 23°C and mixed with stirring to prepare a curing agent composition for radical polymerizable resin. (2) In the formulation shown in Table 1 below, (D-1) as the radical polymerizable resin (D) and a styrene monomer as the ethylenically unsaturated compound (E) were mixed at 23°C, and then the curing agent composition for radical polymerizable resins prepared in (1) above was added at 25°C to obtain a radical polymerizable resin composition.
  • Examples 2 to 21, Comparative Examples 1 to 10 A radical polymerizable resin curing agent composition and a radical polymerizable resin composition were obtained in the same manner as in Example 1, except that the types and amounts of the components used were changed as shown in Tables 1 to 3. In Tables 1 to 3, blank spaces indicate no blend.
  • the acid value was measured using an "Autoburette UCB-2000 (product name, manufactured by Hiranuma Sangyo Co., Ltd.)" and a mixed indicator of bromothymol blue and phenol red.
  • the acid value of the radical polymerizable resin composition the “acid value of the curing agent composition for radical polymerizable resin” and the “acid values of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E)" were measured separately, and the acid value of the radical polymerizable resin composition was calculated from each measurement result.
  • the “minimum curing time” refers to the time (minutes) required for the temperature of the prepared radical polymerizable resin composition to reach the maximum heat generation temperature, assuming that the time from when the curing agent composition for radical polymerizable resins was added to the mixture of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E) is 0 minutes.
  • the “maximum heat generation temperature” refers to the maximum temperature (°C) reached during temperature measurement of the radical polymerizable resin composition after the addition of the curing agent composition.
  • the temperatures were measured by placing the radically polymerizable resin compositions prepared in each of the Examples and Comparative Examples in a test tube (outer diameter 18 mm, length 165 mm) previously set in a thermostatic water bath set at 25° C. to a depth of 100 mm, and measuring the temperature of the filled material with a thermocouple.
  • the radical polymerizable resin compositions obtained in each of the Examples and Comparative Examples were cured at 25° C. for 4 days, and the hardness of the cured products was measured at 23° C. using a hardness tester [Barbar-Colman Company's "Barcol Impressor (registered trademark) GYZJ-935" (product name)] in accordance with JIS K7060;1995.
  • the evaluation results are shown in Tables 1 to 3.
  • the curing agent composition for radically polymerizable resins of the present invention can be cured at 20°C to 40°C without using organic peroxides, and radically polymerizable resin compositions containing such a curing agent composition have excellent curing performance.
  • the resulting cured products have good mechanical properties such as hardness, and can be suitably used in a variety of fields such as adhesives, primers, paints, inorganic structure repair materials, and fiber-reinforced composite materials.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition d'agent de durcissement pour résine polymérisable par voie radicalaire qui contient : un composé organométallique (A) contenant à son tour au moins un métal parmi un manganèse et un cobalt ; au moins une sorte de composé (B) choisie dans un groupe constitué d'un α－acétyl－γ－butyrolactone, d'un α－acétyl－δ－valérolactone, et d'un α－acétyl－ε－caprolactone ; et un composé acide (C).
PCT/JP2023/038679 2022-10-28 2023-10-26 Composition d'agent de durcissement pour résine polymérisable par voie radicalaire, et composition de résine polymérisable par voie radicalaire WO2024090516A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11140384A (ja) * 1997-11-06 1999-05-25 Ooyama Tsusho:Kk 常温硬化型接着剤
WO2010146912A1 (fr) * 2009-06-18 2010-12-23 Dic株式会社 Composition de résine de polyester (méth)acrylate séchant à l'air, structure et procédé permettant de l'obtenir
DE102011078785A1 (de) * 2011-07-07 2013-01-10 Hilti Aktiengesellschaft Härterzusammensetzung, diese enthaltendes Mehrkomponenten-Mörtelsystem, dessen Verwendung sowie Patrone, Kartusche oder Folienbeutel enthaltend ein Mehrkomponenten - Mörtelsystem
JP2021021017A (ja) * 2019-07-29 2021-02-18 昭和電工株式会社 不飽和ポリエステル樹脂組成物及び該不飽和ポリエステル樹脂組成物を含む複合材料
JP2022516293A (ja) * 2019-01-02 2022-02-25 ポリント コンポジッツ ユーエスエイ インコーポレイテッド ラジカル重合性組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11140384A (ja) * 1997-11-06 1999-05-25 Ooyama Tsusho:Kk 常温硬化型接着剤
WO2010146912A1 (fr) * 2009-06-18 2010-12-23 Dic株式会社 Composition de résine de polyester (méth)acrylate séchant à l'air, structure et procédé permettant de l'obtenir
DE102011078785A1 (de) * 2011-07-07 2013-01-10 Hilti Aktiengesellschaft Härterzusammensetzung, diese enthaltendes Mehrkomponenten-Mörtelsystem, dessen Verwendung sowie Patrone, Kartusche oder Folienbeutel enthaltend ein Mehrkomponenten - Mörtelsystem
JP2022516293A (ja) * 2019-01-02 2022-02-25 ポリント コンポジッツ ユーエスエイ インコーポレイテッド ラジカル重合性組成物
JP2021021017A (ja) * 2019-07-29 2021-02-18 昭和電工株式会社 不飽和ポリエステル樹脂組成物及び該不飽和ポリエステル樹脂組成物を含む複合材料

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