Curing agent composition for radical-polymerizable resin, and radical-polymerizable resin composition

Abstract

A curing agent composition for radically polymerizable resins, which contains (A) an organometallic compound that contains at least one metal selected from manganese and cobalt, (B) at least one compound that is selected from the group consisting of alpha-acetyl-gamma-butyrolactone, alpha-acetyl-delta-valerolactone and alpha-acetyl-epsilon-caprolactone, and (C) an acidic compound.

Description

Technical Field

[0001] The present invention relates to a curing agent composition for a radical polymerizable resin, a radical polymerizable resin composition comprising the curing agent composition for a radical polymerizable resin, and a cured product of the radical polymerizable resin composition. Background Art

[0002] In the past, when curing free radical polymerizable resins such as unsaturated polyester resins, vinyl ester resins, and urethane (meth) acrylate resins, a thermal polymerization initiator containing an organic peroxide was generally used. Organic peroxides are known as self-reactive substances that thermally decompose at relatively low temperatures because they have peroxide bonds with low binding energy. Most of the organic peroxides are classified as Class 5 dangerous substances under the Fire Protection Act in Japan, and dangerous substance management is required during their manufacture / transport / storage / handling.

[0003] Therefore, methods for curing free radical polymerizable resins without using organic peroxides have been studied. For example, Non-Patent Document 1 discloses the use of a transition metal complex as a polymerization initiator. Non-Patent Document 2 discloses that free radical polymerization can be achieved by using trivalent manganese and carboxylic acid in water. Non-Patent Document 3 discloses that polymerization can be achieved at room temperature by using an α-hydroxy ester in addition to a transition metal complex.

[0004] Prior art literature

[0005] Non-patent literature

[0006] Non-patent document 1: Angew. Chem., Int. Ed. Engl. 1965, 4 (4), 322

[0007] Non-patent document 2: European Polymer Journal 1978, 14, 287

[0008] Non-patent literature 3: Macromolecules, 2018, 51, 6395 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, the polymerization initiator disclosed in Non-Patent Document 1 requires high heat energy for polymerization. The method of Non-Patent Document 2 is not used for industrial purposes because it requires a water removal step in the post-process. The method of Non-Patent Document 3 requires a long curing time.

[0011] Furthermore, it was revealed that the cured product obtained by the method disclosed in the above-mentioned prior art document has a problem of being inferior in mechanical properties such as hardness, compared with a cured product obtained by using a conventional organic peroxide as a polymerization initiator.

[0012] The present invention has been proposed in view of such actual conditions, and provides a curing agent composition for a radically polymerizable resin which can be cured at room temperature of about 20°C to 40°C without using an organic peroxide, and the obtained cured product has excellent mechanical properties such as hardness, a radically polymerizable resin composition containing the curing agent composition for a radically polymerizable resin, and a cured product of the radically polymerizable resin composition.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved by the following invention.

[0015] That is, the present disclosure relates to the following.

[0016] [1] A curing agent composition for a radical polymerizable resin, comprising:

[0017] an organometallic compound (A) containing at least one metal of manganese and cobalt,

[0018] at least one compound (B) selected from the group consisting of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and

[0019] Acidic compounds (C).

[0020] [2] The radical polymerizable resin curing agent composition according to [1] above, wherein the organometallic compound (A) is an organometallic compound containing a compound having a β-diketone skeleton as a ligand.

[0021] [3] The radical polymerizable resin curing agent composition according to [1] or [2] above, wherein the molar ratio of the compound (B) to the organometallic compound (A) ((B) / (A)) is 1.0 to 42.0.

[0022] [4] The radical polymerizable resin curing agent composition according to any one of [1] to [3] above, wherein the acid value is 10.0 to 600.0 mgKOH / g.

[0023] [5] According to any one of [1] to [4] above, the mass ratio of the content of the above-mentioned organic metal compound (A), the above-mentioned compound (B) and the above-mentioned acidic compound (C) ((A):(B):(C)) is 0.5-40.0:2.0-80.0:1.0-90.0.

[0024] [6] A radical polymerizable resin composition comprising: an organic metal compound (A) containing at least one metal selected from the group consisting of manganese and cobalt, a compound (B) of at least one selected from the group consisting of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and an acidic compound (C), and further comprising a radical polymerizable resin (D).

[0025] [7] The radically polymerizable resin composition according to [6] above, further comprising an ethylenically unsaturated compound (E).

[0026] [8] According to the free radical polymerizable resin composition described in [7] above, the content of the above-mentioned free radical polymerizable resin curing agent composition is 1.5 to 10.0 parts by mass relative to 100 parts by mass of the total of the above-mentioned free radical polymerizable resin (D) and the above-mentioned ethylenically unsaturated compound (E), and the acid value of the free radical polymerizable resin composition is greater than 2.0 mgKOH / g.

[0027] [9] According to the free radical polymerizable resin composition described in [7] or [8] above, the mass ratio of the total content of the above-mentioned organic metal compound (A), the above-mentioned compound (B) and the above-mentioned acidic compound (C) to the total content of the above-mentioned free radical polymerizable resin (D) and the above-mentioned ethylenically unsaturated compound (E) (((A)+(B)+(C)):((D)+(E))) is 1.5 to 10.0:100.

[0028]

[10] According to any one of the above-mentioned radical polymerizable resin composition [7] to [9], the mass ratio of the content of the above-mentioned ethylenically unsaturated compound (E) to the total content of the above-mentioned radical polymerizable resin (D) and the above-mentioned ethylenically unsaturated compound (E) ((E):((D)+(E)))) is 1 to 90:100.

[0029]

[11] A cured product of the radical polymerizable resin composition according to any one of [6] to

[10] above.

[0030] Effects of the Invention

[0031] According to the present invention, there can be provided a curing agent composition for a radically polymerizable resin which can be cured at 20°C to 40°C without using an organic peroxide and the obtained cured product has excellent mechanical properties such as hardness, a radically polymerizable resin composition containing the curing agent composition for a radically polymerizable resin, and a cured product of the radically polymerizable resin composition. DETAILED DESCRIPTION

[0032] Hereinafter, the present invention will be described in detail with reference to one embodiment.

[0033] In the present specification, “to” means a value greater than or equal to the value before the description “to” and a value less than or equal to the value after the description “to”.

[0034] The term “(meth)acrylic” is a general term for acrylic and methacrylic, the term “(meth)acrylate” refers to acrylate or methacrylate, and the term “(meth)acryloyl” refers to acryloyl or methacryloyl.

[0035] The term “ethylenically unsaturated bond” refers to a double bond formed between carbon atoms other than carbon atoms forming an aromatic ring, and the term “ethylenically unsaturated compound” refers to a monomer having an ethylenically unsaturated bond.

[0036] (Curing agent composition for radical polymerizable resin)

[0037] The curing agent composition for a radical polymerizable resin of the present embodiment (hereinafter, sometimes simply referred to as a "curing agent composition") comprises an organic metal compound (A) containing at least one metal of manganese and cobalt, a compound (B) selected from at least one of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and an acidic compound (C). Here, the curing agent composition preferably does not contain an organic peroxide.

[0038] The above-mentioned curing agent composition can be cured at 20°C to 40°C without using an organic peroxide, and the free radical polymerizable resin composition (hereinafter sometimes referred to as "resin composition") containing such a curing agent composition has excellent curability and excellent mechanical properties such as hardness. Specifically, the mechanical properties of the cured product are equal to or better than those of the cured product when cured using an organic peroxide.

[0039] Hereinafter, each component will be described.

[0040] [Organometallic compound (A)]

[0041] The organometallic compound (A) is a compound containing at least one metal of manganese and cobalt. As the organometallic compound (A), a manganese salt or cobalt salt of a long-chain fatty acid or other organic acid or an organic manganese compound or an organic cobalt compound containing a compound having a β-diketone skeleton as a ligand can be cited. The organometallic compound (A) can act as a curing accelerator in a curing agent composition or a resin composition. In addition, by containing at least one metal of manganese and cobalt in the organometallic compound (A), the curability of the curing agent composition of the present embodiment is improved.

[0042] When the organometallic compound (A) is a manganese salt or a cobalt salt of a long-chain fatty acid or other organic acid, the long-chain fatty acid may be any of a saturated fatty acid and an unsaturated fatty acid.

[0043] Manganese salts or cobalt salts of long-chain fatty acids or other organic acids are also acidic compounds (C). When such compounds are used, a single compound may be used as both the organometallic compound (A) and the acidic compound (C).

[0044] The number of carbon atoms in the long-chain fatty acid is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 16 from the viewpoint of dispersibility or solubility of the organometallic compound (A) in the resin composition.

[0045] As long-chain fatty acids, for example, heptanoic acid, octanoic acid (octanoic 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, cycloalkanoic acid, etc., chain saturated fatty acids having a ring structure in a partial structure; unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid. In addition, other rosin acids derived from natural products, linseed oil extracted fatty acids, soybean oil extracted fatty acids, tall oil extracted fatty acids, etc. can also be cited. Among them, octanoic acid and cycloalkanoic acid are preferred, 2-ethylhexanoic acid and cycloalkanoic acid are more preferred, and 2-ethylhexanoic acid is further preferred.

[0046] As other organic acids, for example, a weak acid having a carboxyl group, a hydroxyl group, an enol group, etc. and soluble in a solvent which may be contained in the curable composition or the resin composition described later is preferred.

[0047] Examples of weak acids having a carboxyl 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; aromatic acids such as benzoic acid and phthalic acid; etc. Examples of compounds having a hydroxyl group or an enol group include ascorbic acid, alpha acid, imidic acid, isoascorbic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, and phosphonic acid.

[0048] Specific examples of the manganese salt or cobalt salt of a long-chain fatty acid or other organic acid include manganese (II) 2-ethylhexanoate, cobalt (II) 2-ethylhexanoate, cobalt octylate, manganese octylate, cobalt naphthenate, and cobalt neodecanoate. From the viewpoint of curing performance, manganese (II) 2-ethylhexanoate, cobalt (II) 2-ethylhexanoate, cobalt octylate, manganese octylate, and cobalt naphthenate are preferred.

[0049] When the organometallic compound (A) is an organomanganese compound or an organocobalt compound containing a compound having a β-diketone skeleton as a ligand, the compound having a β-diketone skeleton refers to a compound having a structure having one carbon between two carbonyl groups as represented by the following formula (i).

[0050] R 1 -C(=O)-CH2-C(=O)-R 2 ···(i)

[0051] Here, R 1 and R 2 Each independently represents 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 alkoxy 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.

[0052] Examples of such compounds having a β-diketone skeleton include acetylacetone, ethyl acetylacetone, benzoylacetone, hexafluoroacetylacetone, 2,2,6,6-tetramethylheptane-3,5-dione, 2,6-dimethylheptane-3,5-dione, and 2,2,6,6-tetramethyloctane-3,5-dione. Among them, acetylacetone or a derivative thereof is preferred, and acetylacetone is more preferred.

[0053] In the curing agent composition of the present embodiment, the organometallic compound (A) is preferably an organomanganese compound or an organocobalt compound containing a compound having a β-diketone skeleton as a ligand. Specifically, manganese (III) acetylacetonate, cobalt (III) acetylacetonate, cobalt ethyl acetylacetonate, etc. can be cited. From the viewpoint of controlling the curing performance, manganese (III) acetylacetonate and cobalt (III) acetylacetonate are preferred.

[0054] The organometallic compound (A) may be used alone or in combination of two or more.

[0055] The curing agent composition of the present embodiment may contain an organometallic compound other than the organometallic compound (A). As such an organometallic compound, it may include, within the scope that does not impair the effect of the present invention: an organometallic compound containing other metals other than manganese and cobalt, a metal salt of a long-chain fatty acid or other organic acid, an organometallic compound containing a compound having a β-diketone skeleton as a ligand, and an organometallic compound in other forms. As such other metals, for example, vanadium, iron, copper, titanium, yttrium, tin, lead, bismuth, zirconium, calcium, etc. may be cited.

[0056] [Compound (B)]

[0057] The curing agent composition of the present embodiment contains at least one compound (B) selected from α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, which is a 1,3-dioxo compound. Compound (B) may be any one of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, or may be a mixture of two or three selected from α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone. 1,3-dioxo compounds are compounds in which two carbonyl carbon atoms are bonded to one carbon atom. 1,3-dioxo compounds have a coordination bonding property to manganese or cobalt possessed by the organometallic compound (A), and can change the electronic state of the metal. As 1,3-dioxo compounds, in addition to the above-mentioned compounds having a β-diketone skeleton, α-keto lactones represented by α-acetyl lactones such as α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone, and α-acetyl-ε-caprolactone can also be exemplified. In α-acetyl lactone, there is a tendency that the ring structure is easy to open as the number of carbon atoms it has increases. Therefore, among the above-mentioned 1,3-dioxo compounds, from the perspective of stability, the curing agent composition of the present embodiment contains at least one compound (B) selected from α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone, and α-acetyl-ε-caprolactone, thereby abnormally expressing the effect of the present invention. The curing agent composition of the present embodiment may contain 1,3-dioxo compounds other than α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and the content thereof is preferably 0.1 mol or less relative to 1 mol of at least one compound (B) selected from α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone. In addition, when calculating the molar ratio, the compound having a β-diketone skeleton as the organometallic compound (A) containing at least one metal of manganese and cobalt is not included in the calculation.

[0058] [Acidic compound (C)]

[0059] Examples of the acidic compound (C) 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 oxygen acids described below; synthetic organic acids such as terminal carboxylic acid polyesters; and the like.

[0060] The acidic compound (C) contributes to the improvement of curability.

[0061] In addition, both "Co(EHA)2:2-ethylhexanoic acid cobalt (II)" and "Mn(EHA)2:2-ethylhexanoic acid manganese (II)" are organic metal compounds (A) and acidic compounds (C). The masses of "Co(EHA)2:2-ethylhexanoic acid cobalt (II)" and "Mn(EHA)2:2-ethylhexanoic acid manganese (II)" are counted from both (A) and (C) when calculating the mass ratio of "(A):(B):(C)" described later. On the other hand, when calculating the mass ratio of "((A)+(B)+(C)):((D)+(E))" described later, both (A) and (C) are not counted repeatedly, but only one of (A) and (C) is counted.

[0062] Examples of the organic oxygen-containing acid include saturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, heptadecanoic 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, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, and mellitic acid; Acids and their metal salts; saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, 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 phenol and its derivatives, catechol, methyl catechol, ethyl catechol, propyl catechol, butyl catechol and their derivatives; phosphonic acid derivatives such as methyl phosphonic acid, ethyl phosphonic acid, propyl phosphonic acid, butyl phosphonic acid, phenyl phosphonic acid; etc. Here, the acidic compound (C) does not include unsaturated carboxylic acids which also correspond to the ethylenically unsaturated compound (E).

[0063] Among them, at least one selected from the group consisting of polycarboxylic acid, sulfonic acid, and phosphonic acid is preferred from the viewpoint of water resistance and chemical resistance. The acidic compound (C) may be used alone or in combination of two or more.

[0064] As the acidic compound (C), a commercially available product may be used as appropriate, or a derivative of an organic oxo acid may be produced as appropriate and used.

[0065] [Preparation of Curing Agent Composition]

[0066] The curing agent composition of the present embodiment can be obtained by mixing and stirring an organic metal compound (A), a compound (B) selected from at least one of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and an acidic compound (C) by a known method. The order of adding and mixing the components is not particularly limited. During the mixing and stirring, as described above, from the viewpoint of uniformly mixing the components, an appropriate solvent can be used.

[0067] The molar ratio of the compound (B) to the organometallic compound (A) ((B) / (A)) in the curing agent composition of the present embodiment 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 expressing good curing performance and improving mechanical properties such as hardness of the cured product of the resin composition.

[0068] The organometallic compound (A) and the compound (B) can be used for the preparation of the curing agent composition in a state of being dissolved in a solvent described later.

[0069] The content of the organometallic compound (A) in the curing agent composition of the present embodiment is preferably 0.5 to 40.0% by mass, more preferably 1.0 to 30.0% by mass, based on the total mass of the curing agent composition.

[0070] The content of the compound (B) in the curing agent composition of the present embodiment is preferably 2.0 to 80.0% by mass, more preferably 4.0 to 75.0% by mass, based on the total mass of the curing agent composition.

[0071] The content of the acidic compound (C) in the curing agent composition of the present embodiment is preferably 1.0 to 90.0% by mass, more preferably 3.0 to 87.0% by mass, based on the total mass of the curing agent composition.

[0072] The mass ratio of the content of the organometallic compound (A), the compound (B), and the acidic compound (C) in the curing agent composition of the present embodiment ((A):(B):(C)) is preferably 0.5 to 40.0:2.0 to 80.0:1.0 to 90.0, and more preferably 1.8 to 28.2:5.3 to 70.6:4.0 to 86.5.

[0073] 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. If the acid value of the curing agent composition is within the above range, the chemical resistance and water resistance of the cured product can be improved.

[0074] The acid value of the curing agent composition is measured by the method described in Examples below.

[0075] (Radical polymerizable resin composition)

[0076] The resin composition of the present embodiment preferably contains the components of the curing agent composition and the radical polymerizable resin (D), and further contains an ethylenically unsaturated compound (E). Here, the resin composition preferably does not contain an organic peroxide.

[0077] [Radical polymerizable resin (D)]

[0078] The radical polymerizable resin (D) is a resin having an ethylenically unsaturated hydrocarbon group in the molecule and undergoing polymerization reaction by radicals.

[0079] As free radical polymerizable resin (D), vinyl ester resins such as epoxy (meth) acrylate resins, unsaturated polyester resins, polyester (meth) acrylate resins, carbamate (meth) acrylate resins, (meth) acrylate resins, etc. can be cited. They can be used alone or in combination of two or more. Among the above-mentioned resins, from the viewpoint of good mechanical properties such as the hardness of the cured product obtained by curing the resin composition containing the curing agent composition of the present embodiment, vinyl ester resins and unsaturated polyester resins are more preferred.

[0080] <Vinyl ester resin>

[0081] Vinyl ester resin is generally a compound 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 referred to as an "epoxy compound") and a carboxyl group in an unsaturated monobasic acid having a polymerizable unsaturated bond and a carboxyl group (hereinafter referred to as an "unsaturated monobasic acid"). Such vinyl ester resins are described in, for example, Polyester Resin Handbook (Nikkan Kogyo Shimbun, published in 1988) and the like.

[0082] The epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups. For example, at least one selected from bisphenol epoxy compounds, hydrogenated bisphenol epoxy compounds, and novolac phenol epoxy compounds can be used. Such epoxy compounds can further improve the mechanical properties and corrosion resistance of the cured product.

[0083] Examples of bisphenol-type epoxy compounds include substances obtained by reacting bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin or methyl epichlorohydrin; substances obtained by reacting a condensate of a glycidyl ether of bisphenol A and the above-mentioned bisphenol compounds with epichlorohydrin or methyl epichlorohydrin; and the like.

[0084] Examples of the hydrogenated bisphenol-type epoxy compound include compounds obtained by reacting glycidyl ether of hydrogenated bisphenol A with a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S, or tetrabromobisphenol A.

[0085] Examples of the novolac phenol-type epoxy compound include compounds obtained by reacting phenol novolac or cresol novolac with epichlorohydrin or methyl epichlorohydrin; and the like.

[0086] Among epoxy compounds, bisphenol A epoxy compounds are preferred from the viewpoint of chemical resistance.

[0087] The unsaturated monocarboxylic acid is not particularly limited as long as it is a monocarboxylic acid having a polymerizable unsaturated bond, and is preferably acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc., more preferably acrylic acid, methacrylic acid, and even more preferably methacrylic acid. The vinyl ester resin obtained by the reaction of methacrylic acid and an epoxy compound has high hydrolysis resistance to acids and alkalis, and thus can further improve the corrosion resistance of the cured product.

[0088] The amount of the 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 relative to 1 equivalent of the epoxy group of the epoxy compound. If the amount of the unsaturated monobasic acid 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 cured product having sufficient hardness can be obtained by a free radical polymerization reaction of the resin composition.

[0089] Vinyl ester resins can be prepared, for example, by reacting tertiary amines such as triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, diazabicyclooctane, triphenylphosphine, benzyltriphenyl chloride, diethylamine hydrochloride; etc. in the presence of a known esterification catalyst, the epoxy compound and the unsaturated monobasic acid are dissolved in a solvent as needed, preferably at 70 to 150°C, more preferably at 80 to 140°C, and further preferably at 90 to 130°C.

[0090] Examples of commercially available products of vinyl ester resins include “LPOKISHI (registered trademark)” manufactured by Showa Denko K.K., and the like.

[0091] In addition, unreacted unsaturated monobasic acids that may remain after the production of the vinyl ester resin are regarded as ethylenically unsaturated compounds (E) described below. That is, although unsaturated monobasic acids such as acrylic acid, methacrylic acid, and cinnamic acid are also organic oxygen-containing acids, such unreacted unsaturated monobasic acids are not included in the acidic compound (C).

[0092] <Unsaturated polyester resin>

[0093] The unsaturated polyester resin is obtained by polycondensing a polyol with an unsaturated polybasic acid and at least one selected from a saturated polybasic acid and a monobasic acid as required, and is not particularly limited. The so-called unsaturated polybasic acid is a polybasic acid having an ethylenically unsaturated bond, and the so-called saturated polybasic acid is a polybasic acid not having an ethylenically unsaturated bond.

[0094] As long as the polyol is a compound having more than two hydroxyl groups, there is no particular restriction. Among them, preferably ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexylene glycol, neopentyl glycol, tetraethylene glycol, polyethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, bisphenol A, glycerol, ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A, from the viewpoints of heat resistance and mechanical properties of the cured product, more preferably ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A. Polyols can be used alone or in combination of two or more.

[0095] As unsaturated polyacid, as long as it has ethylenic unsaturated bond, and, has the compound or its anhydride of 2 or more carboxyl groups, there is no particular restriction, for example, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid etc. can be mentioned. Among them, from the viewpoint of heat resistance and mechanical properties of cured product, preferably maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, more preferably maleic anhydride, fumaric acid. Unsaturated polyacid can be used alone or in combination of 2 or more.

[0096] The saturated polyacid is not particularly limited as long as it is a compound having no ethylenically unsaturated bond and having two or more carboxyl groups or its anhydride, and examples thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endo methylene tetrahydrophthalic anhydride, nitrophthalic acid, tetrahydrophthalic anhydride, halogenated phthalic anhydride, oxalic acid, malonic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and the like. Among them, from the viewpoint of heat resistance and mechanical properties of the cured product, 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.

[0097] As the monoacid, for example, dicyclopentadiene maleate, benzoic acid and its derivatives, cinnamic acid and its derivatives, etc. can be cited. Among them, dicyclopentadiene maleate is preferred. Dicyclopentadiene maleate can be synthesized from maleic anhydride and dicyclopentadiene by a known method. If a monoacid is used, the viscosity of the unsaturated polyester resin can be reduced.

[0098] The unsaturated polyester resin can be produced by a known method using the above raw materials. Various conditions in the production of the unsaturated polyester resin can be appropriately set according to the raw materials used and their amounts. Generally, an esterification reaction under pressure or reduced pressure can be applied at a temperature of 140 to 230° C. in a stream of an inert gas such as nitrogen. In the esterification reaction, a known esterification catalyst such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate can be used alone or in combination of two or more as needed.

[0099] 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 further preferably 7,000 to 18,000. If Mw is 3,000 to 25,000, the moldability of the resin composition of the present embodiment becomes better. In addition, Mw is a standard polystyrene conversion value measured by gel permeation chromatography (GPC: gel permeation chromatography).

[0100] The unsaturation degree of the unsaturated polyester resin is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and further preferably 70 to 100 mol%. If the unsaturation degree is within the above range, the moldability of the resin composition of the present embodiment is better. The unsaturation degree of the unsaturated polyester resin can be calculated by the following formula using the molar number of the unsaturated polyacid and the saturated polyacid used as raw materials.

[0101] Unsaturation degree (mol %) = {(number of moles of unsaturated polyacid × number of unsaturated groups in unsaturated polyacid) / (number of moles of unsaturated polyacid + number of moles of saturated polyacid)} × 100

[0102] As a commercial item of an unsaturated polyester resin, "RIGOLRACK (registered trademark)" etc. are mentioned, for example, the Showa Denko K.K. manufacture.

[0103] <Urethane (meth)acrylate resin>

[0104] As the urethane (meth)acrylate resin, for example, a resin obtained by reacting (meth)acrylic acid with hydroxyl groups or isocyanate groups at both terminals of polyurethane obtained by reacting polyisocyanate with polyol can be used.

[0105] The content of the radical polymerizable resin (D) is appropriately set depending on the purpose of 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 the present 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, relative to 100 parts by mass of the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound.

[0106] [Ethylenically unsaturated compound (E)]

[0107] 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 polymerization reaction by free radicals, and is sometimes referred to as a reactive diluent. The ethylenically unsaturated hydrocarbon group contained in the ethylenically unsaturated compound (E) may be one or more.

[0108] Examples of the ethylenically unsaturated compound (E) include α-, o-, m-, p-alkyl, nitro, cyano, amide, or ester derivatives of styrene compounds such as styrene, vinyltoluene, and tert-butylstyrene; vinyl compounds such as 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, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and t-butyl (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, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, ethylene glycol monohexyl ether (meth)acrylate, ethylene glycol mono-2-ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate 1,3-Butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy 1,3-dimethacryloyloxypropane, 2,2-bis[4-(methacryloylethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxy / diethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxy / polyethylene]propane (Meth)acrylates such as (meth)acrylic acid esters, ...N-(meth)acryloylphthalimide; etc.;

[0109] Among them, from the viewpoint of mechanical properties such as hardness of the cured product and surface dryness, styrene, vinyltoluene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate are preferred, and styrene, vinyltoluene, and methyl (meth)acrylate are more preferred. One of these may be used alone, or two or more of them may be used in combination.

[0110] The resin composition of the present embodiment contains a radical polymerizable resin (D), but from the viewpoint of obtaining a resin composition having better mechanical properties such as hardness of a cured product, it is preferably a configuration containing both a radical polymerizable resin (D) and an ethylenically unsaturated compound (E).

[0111] The total content of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E) in the resin composition of the present embodiment is preferably 80 to 99% by mass, more preferably 90 to 99% by mass.

[0112] 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 still more preferably 2 to 50 parts by mass, relative to 100 parts by mass of the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E). If the content of the ethylenically unsaturated compound (E) is 1 to 90 parts by mass relative to the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E), the mechanical properties such as the hardness of the cured product can be further improved.

[0113] In addition, when the resin composition is prepared, for example, 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 further preferably 1.0 to 10 parts by mass relative to 100 parts by mass of the total of the free 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 can be prevented from being extremely delayed, and the mechanical properties such as the hardness of the obtained cured product can be further improved.

[0114] [Optional ingredients]

[0115] The resin composition of the present embodiment may further contain various additives such as a solvent, a thixotropy-imparting agent, a thixotropy-imparting auxiliary agent, a thickener, a colorant, a plasticizer, and a wax as needed, depending on the purpose of use, application, etc., within the range that does not affect the effects of the present invention or within the range that does not reduce the mechanical properties of the cured product.

[0116] From the viewpoint of uniformly mixing each containing component in the resin combination, solvent is used as required. Its content is not particularly limited, and can be appropriately adjusted according to operability during use, etc. The kind of solvent is appropriately selected in the scope that the curing property and storage stability of the resin combination are not affected according to the kind of resin, use purposes, etc., and for example aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, linear carbonates, etc. can be cited. They can be used alone 1 kind, or two or more kinds can be used in combination.

[0117] Examples of aliphatic hydrocarbons include cyclohexane, n-hexane, white spirit, odorless mineral spirits (OMS) and other mineral spirits. Examples of aromatic hydrocarbons include cycloalkanes, mixtures of cycloalkanes and paraffins, benzene, toluene, quinoline and the like. Examples of ethers include diethyl ether and diisopropyl ether. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone and the like. Examples of esters include ethyl acetate, butyl acetate, diethyl malonate, diethyl succinate, dibutyl succinate, dibutyl maleate, 2,2,4-trimethylpentanediol diisobutyrate, monoesters and diesters of ketoglutaric acid, pyruvic acid esters, monoesters and diesters of ascorbic acid such as palmitate of ascorbic acid and the like. Examples of chain carbonates include dimethyl carbonate and diethyl carbonate. In addition, 1,2-dioximes, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, and the like can also be used.

[0118] These solvents are also sometimes contained in commercially available preparations of the organometallic compound (A), the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).

[0119] Examples of the thixotropy-imparting agent include inorganic powders such as silica and clay.

[0120] Examples of the thixotropy-imparting auxiliary agent include polyethylene glycol, glycerin, polyhydroxycarboxylic acid amide, and organic quaternary ammonium salts. A specific example of the polyhydroxycarboxylic acid amide is BYK-R-605 (manufactured by Big Chemie Jaman Co., Ltd.).

[0121] Examples of the thickener include metal oxides such as magnesium oxide, calcium oxide, and zinc oxide; and metal hydroxides such as magnesium hydroxide and calcium hydroxide.

[0122] Examples of the colorant include organic pigments, inorganic pigments, and dyes.

[0123] Examples of the plasticizer include chlorinated paraffin, phosphoric acid ester, and phthalic acid ester.

[0124] Wax can be added for the purpose of improving the surface drying property by the air barrier effect on the surface of the cured product. Examples of such wax include petroleum wax, olefin wax, polar wax, and special wax.

[0125] The content of the additives can be appropriately adjusted according to the desired physical properties of the cured product of the resin composition, within the range that does not affect the curing performance and storage stability of the resin composition. The total content of the above-mentioned additives is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the free radical polymerizable resin (D) and the ethylenically unsaturated compound (E).

[0126] [Method for producing resin composition]

[0127] The resin composition of the present embodiment is obtained by mixing a curing agent composition containing an organometallic compound (A), a compound (B) and an acidic compound (C) with a free radical polymerizable resin (D) and an ethylenically unsaturated compound (E) as an optional component. Suitably, the resin composition of the present embodiment can be obtained by mixing and stirring the above-mentioned curing agent composition with a free radical polymerizable resin (D) and an ethylenically unsaturated compound (E) by a known method.

[0128] In addition, there is no need to temporarily prepare a composition of the organic metal compound (A), the compound (B) and the acidic compound (C), and the organic metal compound (A), the compound (B) and the acidic compound (C) can be separately mixed in the free radical polymerizable resin (D) and the ethylenically unsaturated compound (E), or the organic metal compound (A), the compound (B) and the acidic compound (C) can be mixed at once.

[0129] Furthermore, the above-mentioned additives and the like may be added as arbitrary components. The order of adding and mixing the components is not particularly limited. During mixing, as described above, an appropriate solvent may be used from the viewpoint of uniformly mixing the components.

[0130] The mixing method is not particularly limited and can be performed by a known method. In addition, from the viewpoint of uniform mixing and the viewpoint of suppressing the deterioration of each component, the temperature during each mixing is preferably 20 to 40°C.

[0131] In the resin composition of this embodiment, the content of the curing agent composition is preferably 1.5 to 10.0 parts by mass based on 100 parts by mass of the total of the radical polymerizable resin (D) and the above-mentioned ethylenically unsaturated compound (E), and the acid value of the prepared resin composition is 2.0 mgKOH / g or more.

[0132] 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, relative to 100 parts by mass of the total of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E).

[0133] The acid value of the prepared resin composition is more preferably 2.0 to 20.0 mgKOH / g, and even more preferably 2.0 to 15.0 mgKOH / g.

[0134] The acid value of the resin composition can be measured by the method described in Examples below.

[0135] If the content of the curing agent composition is 1.5 parts by mass or more relative to 100 parts by mass of the total of the free radical polymerizable resin (D) and the above-mentioned ethylenically unsaturated compound (E), the gelation time of the resin composition can be shortened, and the amount of the residual 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 relative to 100 parts by mass of the total of the free radical polymerizable resin (D) and the above-mentioned ethylenically unsaturated compound (E), the resin composition can be cured with an appropriate gelation time.

[0136] Furthermore, when the content of the curing agent composition is within the above range and the acid value of the prepared resin composition is 2.0 mgKOH / g or more, the resin composition can be cured with an appropriate gelation time.

[0137] In addition, the "gel time" refers to the time described in the Examples below.

[0138] [Cured product of radical polymerizable resin composition]

[0139] The cured product is obtained by curing the radical polymerizable resin composition of the present embodiment.

[0140] As a method for curing the resin composition, there can be mentioned 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, and curing at room temperature or by heating, etc. Here, the specific temperature range of room temperature and heating can be, for example, about 15 to 200°C, more preferably in the range of 15 to 160°C.

[0141] [Application, etc.]

[0142] The resin composition of this embodiment has excellent mechanical properties such as hardness of its cured product and can be used in various applications such as adhesives, primers, coatings, inorganic structure repair materials for concrete cross-section repair, crack injection, waterproofing, etc., and fiber-reinforced composite materials.

[0143] When the resin composition of the present embodiment is used as a coating, a colorant may be contained in the resin composition, and when used as an inorganic structure repair material, a filler may be contained. In addition, the resin composition may contain components required for functional performance according to various uses such as containing reinforcing fibers and using it as a fiber-reinforced composite material.

[0144] Example

[0145] Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[0146] 1. Details of each ingredient

[0147] The details of each component used for preparation of the composition are as follows.

[0148] [Organometallic compound (A)]

[0149] ·Mn(acac)3: Manganese(III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0150] · Co(acac)3: Cobalt(III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0151] ·Fe(acac)3: Iron(III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0152] Cr(acac)3: chromium(III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0153] · Zr(acac)4: Zirconium(IV) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0154] 〔1,3-dioxo compounds〕

[0155] <Compound (B)>

[0156] (B-1): α-acetyl-γ-butyrolactone (abbreviated as ABL, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0157] (B-2): α-acetyl-δ-valerolactone (abbreviated as AVL, manufactured by SAGECHEM LIMITED)

[0158] (B-3): α-acetyl-ε-caprolactone (abbreviated as ACL, manufactured by SAGECHEM LIMITED)

[0159] <Except compound (B)>

[0160] (B'-1): Ethylene glycol monoacetoacetate monomethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0161] 〔Acidic compounds (C)〕

[0162] (C-1): an organic acid produced by the steps of Synthesis Example 1 below

[0163] [Synthesis example 1]

[0164] In a four-necked flask equipped with a thermometer, a stirrer, a gas introduction tube and a reflux cooling tube, 315 g of succinic anhydride, 49 g of propylene glycol and 446 g of trimethylolpropane tripropyl ether were added and heated to 120°C. After stirring until the acid value became 215 mgKOH / g or less, the mixture was temporarily cooled. 190 g of styrene was added to the 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.

[0165] (C-2): p-Toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0166] (C-3): Phosphoric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0167] (C-4): Hydrochloric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0168] [Organometallic compound (A) and acidic compound (C)]

[0169] · Co(EHA)2: 2-ethylhexanoate cobalt(II) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0170] ·Mn(EHA)2: 2-ethylhexanoate manganese(II) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0171] [Free radical polymerizable resin (D)]

[0172] (D-1): Radically polymerizable resin produced by the steps of Synthesis Example 2 below

[0173] [Synthesis example 2]

[0174] In a flask equipped with a stirrer, a reflux cooler, a thermometer and a gas inlet tube, 51.8 g of bisphenol A epoxy resin and 18.2 g of acrylic acid were reacted at 120°C while blowing air. The mixture was cooled when the acid value became below 5 mgKOH / g, and 30 g of styrene was added at below 100°C to obtain a free radical polymerizable resin D-1 (styrene content: 30% by mass).

[0175] [Ethylenically unsaturated compound (E)]

[0176] Styrene monomer (NS styrene monomer system)

[0177] [Example 1]

[0178] (1) ABL (B-1) as a compound (B) was added to Mn (acac) 3 as an organometallic compound (A) at 23°C in the mixture shown in the following Table 1, and then (C-1) as an acidic compound (C) was added at 23°C and stirred and mixed to prepare a curing agent composition for a radical polymerizable resin.

[0179] (2) (D-1) as a free radical polymerizable resin (D) and a styrene monomer as an ethylenically unsaturated compound (E) are mixed at 23°C in the mixture shown in the following Table 1, and then the curing agent composition for the free radical polymerizable resin prepared in the above (1) is added at 25°C to obtain a free radical polymerizable resin composition.

[0180] [Examples 2 to 21, Comparative Examples 1 to 10]

[0181] Except having changed the kind and compounding amount of each component used as described in Tables 1 to 3, it carried out similarly to Example 1, and obtained the curing agent composition for radical polymerizable resin and the radical polymerizable resin composition.

[0182] In Tables 1 to 3, blank columns indicate that no compounding is performed.

[0183] 4. Evaluation

[0184] 4-1. Acid value

[0185] In accordance with JIS K6901:2021 "Partial acid value (indicator titration method)", the mass of potassium hydroxide required to neutralize the acid components contained in the radical polymerizable resin curing agent composition and the radical polymerizable resin composition prepared in each example and comparative example was measured, and the acid value of each radical polymerizable resin curing agent composition (a composition composed of an organic metal compound (A), a compound (B) and an acidic compound (C)) and each radical polymerizable resin composition (a composition composed of an organic metal compound (A), a compound (B), an acidic compound (C), a radical polymerizable resin (D) and an ethylenically unsaturated compound (E)) was determined.

[0186] In addition, as the measuring device of the acid value, "Auto Bureto UCB-2000 (trade name, manufactured by Hiranuma Sangyo Co., Ltd.)" was used, and as the indicator, a mixed indicator of bromothymol blue and phenol red was used.

[0187] In addition, regarding the acid value of the radical polymerizable resin composition, the "acid value of the radical polymerizable resin curing agent composition" and the "acid values ​​of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E)" were measured respectively, and the acid value of the radical polymerizable resin composition was calculated from the respective measurement results.

[0188] 4-2. Curability of Radical Polymerizable Resin Composition at 25°C

[0189] The curability at 25° C. of the radical polymerizable resin composition prepared in each of the Examples and Comparative Examples was measured in accordance with JIS K6901:2021 “Room-temperature curing characteristics (exothermic method)”.

[0190] The evaluation items described in Tables 1 to 3 are respectively shown as follows.

[0191] The so-called "gel time" is the time (minutes) required for the temperature of the prepared radical polymerizable resin composition to reach 30°C, with the time from adding the radical polymerizable resin curing agent composition to the mixture of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E) being set to 0 minutes.

[0192] The so-called "minimum curing time" is the time (minutes) required for the temperature of the prepared radical polymerizable resin composition to reach the maximum exothermic temperature, with the time from adding the radical polymerizable resin curing agent composition to the mixture of the radical polymerizable resin (D) and the ethylenically unsaturated compound (E) being set to 0 minutes.

[0193] Here, the "maximum exothermic temperature" refers to the highest temperature (°C) reached in the temperature measurement of the radical polymerizable resin composition after the curing agent composition is added.

[0194] In addition, the measurement of each temperature was carried out by placing the free radical polymerizable resin composition prepared in each example and comparative example into a test tube (outer diameter 18 mm, length 165 mm) in a constant temperature water bath pre-set at a set temperature of 25°C to a depth of 100 mm, and measuring the temperature of the filling with a thermocouple.

[0195] 4-3. Barcol hardness

[0196] In accordance with JIS K7060; 1995, the hardness of the cured product obtained by curing the radical polymerizable resin composition obtained in each Example and Comparative Example at 25°C for 4 days was measured at 23°C using a hardness meter [Barbar-Colman Company, "Barcol Impressor (registered trademark) GYZJ-935" (trade name)].

[0197] The evaluation results are shown in Tables 1 to 3.

[0198] Table 1

[0199]

[0200] Table 2

[0201]

[0202] Table 3

[0203]

[0204] From the results of Examples 1 to 21, it was confirmed that the radical resin composition containing the curing agent composition of the present invention has good curability and the obtained cured product has excellent hardness.

[0205] In contrast, it is understood that the Barcol hardness is low in Comparative Examples 1, 2 and 7 which do not contain the acidic compound (C), Comparative Example 4 which does not contain the organometallic compound (A), and Comparative Examples 8 to 10 which use an organometallic compound not containing manganese or cobalt, or the curing performance is poor in Comparative Examples 3, 5 and 6 which do not contain the compound (B). When other 1,3-dioxo compounds other than the compound (B) are contained, the effect of the present invention is not exhibited.

[0206] Industrial Availability

[0207] The curing agent composition for the radical polymerizable resin of the present invention can be cured at 20°C to 40°C without using an organic peroxide, and the radical polymerizable resin composition containing such a curing agent composition has excellent curing performance. Furthermore, the obtained cured product has good mechanical properties such as hardness, and can be suitably used in various fields such as adhesives, primers, coatings, inorganic structure repair materials, and fiber-reinforced composite materials.

Claims

1. A curing agent composition for a free radical polymerizable resin, comprising: an organometallic compound A containing at least one metal of manganese and cobalt, a compound B of at least one selected from the group consisting of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and Acidic compound C. 2 . The radical polymerizable resin curing agent composition according to claim 1 , wherein the organometallic compound A is an organometallic compound containing a compound having a β-diketone skeleton as a ligand. 3 . The radical polymerizable resin curing agent composition according to claim 1 , wherein a molar ratio of the compound B to the organometallic compound A (B / A) is 1.0 to 42.

0.

4. The curing agent composition for a radical polymerizable resin according to claim 1 or 2, which has an acid value of 10.0 to 600.0 mgKOH / g. 5 . The radical polymerizable resin curing agent composition according to claim 1 , wherein the mass ratio of the organic metal compound A to the compound B to the acidic compound C, i.e., A:B:C, is 0.5 to 40.0:2.0 to 80.0:1.0 to 90.

0.

6. A free radical polymerizable resin composition comprising: an organometallic compound A containing at least one metal of manganese and cobalt, a compound B of at least one selected from the group consisting of α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone and α-acetyl-ε-caprolactone, and Acidic compound C, And further includes a radical polymerizable resin D. The radically polymerizable resin composition according to claim 6 , further comprising an ethylenically unsaturated compound (E).

8. The radical polymerizable resin composition according to claim 7, wherein the content of the radical polymerizable resin curing agent composition is 1.5 to 10.0 parts by mass relative to 100 parts by mass of the total of the radical polymerizable resin D and the ethylenically unsaturated compound E, and the acid value of the radical polymerizable resin composition is 2.0 mgKOH / g or more.

9. According to the free radical polymerizable resin composition according to claim 7 or 8, the mass ratio of the total content of the organic metal compound A, the compound B and the acidic compound C to the total content of the free radical polymerizable resin D and the ethylenically unsaturated compound E, i.e. (A+B+C):(D+E), is 1.5 to 10.0:

100. 10 . The radical polymerizable resin composition according to claim 7 , wherein the mass ratio of the content of the ethylenically unsaturated compound E to the total content of the radical polymerizable resin D and the ethylenically unsaturated compound E, namely, E:(D+E), is 1 to 90:

100.

11. A cured product of the radical polymerizable resin composition according to claim 6 or 7.

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