Curing accelerator for oxidatively polymerized unsaturated resins and curable resin composition

Abstract

To provide a curing accelerator for oxidative polymerizable unsaturated resin having excellent dryability and stability over time.SOLUTION: A curing accelerator for oxidative polymerizable unsaturated resin comprises non-cobalt metallic soap, a diamine compound, an amino alcohol compound, and a fatty acid. The diamine compound has at least one of two amines being a primary amine, the two amines being linked through two carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curing accelerator for oxidatively polymerized unsaturated resins and a curable resin composition. [Background technology]

[0002] In fields that use oxidative polymerization resins, such as printing inks and paints, driers are added as curing accelerators to dry the resins. The driers used in such inks and paints are generally metal salts of cobalt and carboxylic acids (hereinafter, metal salts of metals and carboxylic acids may be abbreviated as "metal soaps").

[0003] While cobalt metal soaps have excellent drying properties, the cobalt compounds themselves are carcinogenic substances of concern, listed in Group 2B of the International Agency for Research on Cancer's carcinogenic risk index, which states that they are "suspected of being carcinogenic to humans." In addition to this concern about carcinogenicity, metallic cobalt is a rare metal, and its supply is unstable and expensive. Therefore, various non-cobalt metal soaps that do not use cobalt have been proposed (for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2013 / 077267A1 [Patent Document 2] WO2015 / 005121A1 Summary of the Invention [Problem to be solved by the invention]

[0005] The non-cobalt metal soap of Patent Document 1 has insufficient drying performance, and the non-cobalt soap of Patent Document 2 has the problem of poor stability over time.

[0006] The problem to be solved by the present invention is to provide a curing accelerator for oxidatively polymerized unsaturated resins which has excellent drying performance and stability over time. [Means for solving the problem]

[0007] As a result of extensive research to solve the above problems, the inventors discovered that excellent drying performance and stability over time can be achieved by using a non-cobalt metal soap in combination with a specific diamine compound, an amino alcohol compound, and a fatty acid, and thus completed the present invention.

[0008] That is, the present invention relates to a curing accelerator for oxidatively polymerized unsaturated resins, which contains a non-cobalt metal soap, a diamine compound, an aminoalcohol compound, and a fatty acid, wherein the diamine compound is a diamine compound having a structure in which at least one of the diamine compounds is a primary amine and two nitrogen atoms are linked via two carbon atoms. [Effects of the Invention]

[0009] According to the present invention, a curing accelerator for oxidatively polymerized unsaturated resins having excellent drying performance and stability over time can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention.

[0011] [Curing accelerator for oxidative polymerization unsaturated resins] The curing accelerator for oxidatively polymerized unsaturated resins of the present invention (hereinafter sometimes simply referred to as "the curing accelerator of the present invention") contains a non-cobalt metal soap, a diamine compound, an aminoalcohol compound, and a fatty acid.

[0012] In the present invention, the use of a specific diamine compound and amino alcohol compound provides the metal soap with excellent drying performance and stability over time of the drying performance, and the use of a fatty acid further enhances the stability over time of the curing accelerator itself. In other words, the "stability over time" in the present invention has two meanings: the curing accelerator itself does not crystallize over time, and when added to an oxidatively polymerized unsaturated resin to form a composition, the curing accelerator effect does not decrease over time. Each component of the curing accelerator of the present invention will be described below.

[0013] (Non-cobalt metal soap) Non-cobalt metal soaps include, for example, M(X) n It is a metal salt represented by the formula: Here, M is manganese, iron, bismuth, zirconium, barium, calcium, strontium, nickel, copper, zinc, cerium, or vanadium. X is F - , Cl - , Br - , I - , PF6 - , SbF6 - , AsF6 - , BF4 - , B(C6F5)4 - , ClO4 - , ClO3 - , CO2 - , ClO - , H2PO4 - , H2PO3 - , H2PO2 - , HCO3 - , NO3 - , NO2 - , (CH3CO)2CH - , R.C.O.O. - (R is a hydrocarbon group having 1 to 22 carbon atoms), O 2- , S 2- , SO4 2- , SO3 2- , CO3 2- It is one or more selected from the following. n is an integer of 1 or greater.

[0014] The non-cobalt metal soap is preferably a fatty acid metal salt of a fatty acid having 1 to 22 carbon atoms, and more preferably a metal salt represented by the following general formula (A).

[0015] [ka] (In the general formula (A), R 11 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, n is an integer ranging from 1 to 4, M is manganese, iron, bismuth, zirconium, barium, calcium, strontium, nickel, copper, zinc, cerium, or vanadium.

[0016] In the general formula (A), when n is an integer of 2 or more, a plurality of R 11 may be the same as or different from each other.

[0017] R 11 The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure.

[0018] R 11 The alkyl group having 1 to 21 carbon atoms is used in the production of fatty acid metal salts. 11 It corresponds to a carboxylic acid residue obtained by removing the carboxyl group (COOH) from a carboxylic acid having 1 to 22 carbon atoms, represented by COOH. Examples of the carboxylic acid residue include acetic acid residue, propionic acid residue, butanoic acid residue, pentanoic acid residue, acrylic acid residue, methacrylic acid residue, octylic acid residue (2-ethylhexanoic acid residue), neodecanoic acid residue, naphthenic acid residue, isononanoic acid residue, tung oil acid residue, tall oil fatty acid residue, coconut oil fatty acid residue, soybean oil fatty acid residue, linseed oil fatty acid residue, safflower oil fatty acid residue, dehydrated castor oil fatty acid residue, tung oil fatty acid residue, lauric acid residue, myristic acid residue, palmitic acid residue, stearic acid residue, isostearic acid residue, and oleic acid residue.

[0019] R11 The alkyl group having 1 to 21 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 11 carbon atoms, and even more preferably an acetic acid residue, a propionic acid residue, a butanoic acid residue, a pentanoic acid residue, a 2-ethylhexanoic acid residue, an isononanoic acid residue, a neodecanoic acid residue, or a naphthenic acid residue.

[0020] n is a number corresponding to the ionic valence of the metal atom of M.

[0021] The non-cobalt metal soap contained in the curing accelerator of the present invention may be one type alone or two or more types in combination.

[0022] The non-cobalt metal soap contained in the curing accelerator of the present invention can be divided into two types: a main non-cobalt metal soap and an auxiliary non-cobalt metal soap (auxiliary drier). The main non-cobalt metal soap is preferably a manganese soap and / or an iron soap. The auxiliary drier can use a non-cobalt metal soap other than a manganese soap or an iron soap. In the definitions of the amounts of diamine compounds, amino alcohol compounds and fatty acids described below, the term "non-cobalt metal soap" refers to the main non-cobalt metal soap, which is manganese soap and / or iron soap.

[0023] When an auxiliary dryer is used, the amount of the auxiliary dryer is, for example, 100 to 2,000 parts by mass per 100 parts by mass of the main non-cobalt metal soap. The amount of the auxiliary dryer is, for example, in the range of 1 to 60 mol, and preferably in the range of 5 to 50 mol, per mol of metal atoms in the main non-cobalt metal soap.

[0024] The non-cobalt metal soap can be produced by a known method, and commercially available products may also be used.

[0025] (diamine compounds) The diamine compound is a diamine compound having a structure in which at least one of the nitrogen atoms is a primary amine and two nitrogen atoms are linked via two carbon atoms, and is preferably a diamine compound represented by the following general formula (B):

[0026] [ka] (In the general formula (B), R 21 and R 22 are each independently an alkyl group having 1 to 9 carbon atoms or an oxo group, R 23 and R 24 are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a phenyl group, R 21 and R 22 may be bonded to each other to form an alicyclic structure or an aromatic ring structure, R 21 and R 24 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure, R 22 and R 23 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure, R 23 and R 24 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure.

[0027] The diamine compound contained in the curing accelerator of the present invention has a structure in which two nitrogen atoms, at least one of which is a primary amine, are linked via two carbon atoms. This structure is thought to form a metal complex with the non-cobalt metal soap, imparting excellent drying performance to the metal soap.

[0028] R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 9 carbon atoms may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure. R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 9 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms.

[0029] R 21 , R 22 , R 23 and R 24 Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an isoheptyl group, and a tert-heptyl group.

[0030] R 23 and R 24 Preferably, at least one of is a hydrogen atom, and more preferably, both are hydrogen atoms.

[0031] R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 9 carbon atoms may have a substituent, and examples of the substituent include a hydroxyl group, an oxo group (═O), and a phenyl group. Also, R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 9 carbon atoms may have one or more ether bonds (—O—) between carbon atoms.

[0032] R 21 and R 22 may be bonded to each other to form an alicyclic structure or an aromatic ring structure, The alicyclic structure may be a cyclohexane ring, and the aromatic ring structure may be a benzene ring.

[0033] R 21 and R 24may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure. R 22 and R 23 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure. R 23 and R 24 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure. Examples of the nitrogen-containing alicyclic structure include a pyrrolidine ring, a piperidine ring, and an azepane ring, and examples of the nitrogen-containing aromatic ring structure include a pyrrole ring and a pyridine ring.

[0034] Specific examples of the diamine compound include the following compounds, of which 1,2-cyclohexanediamine, 1,2-diaminopropane and 2-picolylamine are preferred.

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] TIFF0007726005000006.tif92163

[0039] The diamine compound contained in the curing accelerator of the present invention may be one type alone or two or more types in combination.

[0040] The content of the diamine compound is, for example, in the range of 0.1 to 20 mol, preferably in the range of 0.2 to 10 mol, and more preferably in the range of 0.5 to 8 mol, per 1 mol of metal atoms in the non-cobalt metal soap.

[0041] The diamine compound can be produced by a known method, or a commercially available product may be used.

[0042] (amino alcohol compounds) An amino alcohol compound is a compound having a hydroxy group and an amino group in an alkane skeleton, and it is believed that the nitrogen atom in the amino alcohol coordinates with the non-cobalt metal soap, giving the metal soap excellent drying performance and stability over time.

[0043] The amino alcohol is preferably a compound represented by the following general formula (C).

[0044] [ka] (In the general formula (C), R 31 and R 32 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X 1 and X 2 are each independently an alkylene group having 1 to 6 carbon atoms, Y is an ether bond or -NR 33 - (R 33 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0045] R 31 , R 32 and R 33 The alkyl group having 1 to 6 carbon atoms may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure.

[0046] X 1 and X 2 The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 2 to 3 carbon atoms.

[0047] Specific examples of the amino alcohol compound include 2-[(2-dimethylaminoethyl)methylamino]ethanol, 2-(2-aminoethyl)aminoethanol, 1-(2-aminoethyl)amino-2-propanol, 2-(3-aminopropylamino)ethanol, and 2-(2-dimethylaminoethoxy)ethanol.

[0048] The amino alcohol compound contained in the curing accelerator of the present invention may be one type alone or two or more types in combination.

[0049] The content of the amino alcohol compound is, for example, in the range of 0.1 to 20 mol, preferably in the range of 0.2 to 15 mol, more preferably in the range of 0.5 to 12 mol, and even more preferably in the range of 0.5 to 10 mol, per 1 mol of metal atoms in the non-cobalt metal soap.

[0050] The amino alcohol compound can be produced by a known method, or a commercially available product may be used.

[0051] (fatty acid) It is believed that the curing accelerator of the present invention further contains a fatty acid in addition to the non-cobalt metal soap, diamine compound, and aminoalcohol compound, thereby increasing the solubility of the metal complex formed by the non-cobalt metal soap.

[0052] The fatty acid is preferably an aliphatic carboxylic acid having 1 to 22 carbon atoms, and examples thereof include acetic acid, propionic acid, butanoic acid, pentanoic acid, acrylic acid, methacrylic acid, octylic acid (2-ethylhexanoic acid), neodecanoic acid, naphthenic acid, isononanoic acid, tung oil fatty acid, tall oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid.

[0053] The fatty acids are preferably octylic acid, isononanoic acid, neodecanoic acid and naphthenic acid.

[0054] When the non-cobalt metal soap contained in the hardening accelerator is a fatty acid metal salt, the fatty acid may be the same as or different from the fatty acid constituting the non-cobalt metal soap.

[0055] The fatty acids contained in the curing accelerator of the present invention may be used alone or in combination of two or more.

[0056] The content of the fatty acid is, for example, in the range of 0.1 to 10 mol, and preferably in the range of 0.5 to 4 mol, per 1 mol of metal atoms in the non-cobalt metal soap.

[0057] (diluent) The curing accelerator of the present invention is usually used by diluting the non-cobalt metal soap, diamine compound, aminoalcohol compound, and fatty acid with a diluent.

[0058] Known diluents can be used, and examples thereof include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; alcohol solvents such as methanol, ethanol, propanol, cyclohexanol, 1-methoxy-2-propanol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, glycerin, diethylene glycol, ethylene glycol, dipropylene glycol, 2-methyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, and benzyl alcohol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; fatty acid esters such as methyl caproate, methyl caprate, and methyl laurate; and vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil.

[0059] The diluent contained in the curing accelerator of the present invention may be one type alone or two or more types in combination.

[0060] The content of the diluent may be set appropriately, and the ratio (total mass of non-cobalt metal soap, diamine compound, amino alcohol compound, and fatty acid) / (mass of diluent) is, for example, in the range of 10 / 90 to 95 / 5, preferably in the range of 20 / 80 to 90 / 10, and more preferably in the range of 40 / 60 to 80 / 20. The ratio of the diluent to the total curing accelerator is preferably in the range of 25 to 50 mass%.

[0061] The curing accelerator of the present invention may contain a non-cobalt metal soap, a diamine compound, an aminoalcohol compound, a fatty acid, and optionally a diluent, or may consist essentially of these components. Here, "consist essentially of" means that the total proportion of the non-cobalt metal soap, diamine compound, aminoalcohol compound, fatty acid, and diluent in the curing accelerator of the present invention is, for example, 80 mass % or more, 90 mass % or more, or 95 mass % or more. The upper limit of the total mass of the non-cobalt metal soap, diamine compound, amino alcohol compound, fatty acid and diluent is not particularly limited, but is, for example, 100 mass %. The curing accelerator of the present invention may contain other components within the range that does not impair the effects of the present invention.

[0062] [Curable resin composition] The curable resin composition of the present invention contains the curing accelerator of the present invention and an oxidatively polymerizable unsaturated resin. The oxidatively polymerizable unsaturated resin may be any resin as long as it has an unsaturated bond in its molecular structure and the unsaturated bond can be oxidatively polymerized by oxygen in the air.

[0063] The content of the curing accelerator of the present invention in the curable resin composition of the present invention is, for example, 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the oxidatively polymerized unsaturated resin.

[0064] Specific examples of oxidatively polymerized unsaturated resins for use in printing inks include rosin-modified phenolic resins, unsaturated group-containing polyester resins, alkyd resins, petroleum resins, polymerized oils, etc., and for use in paints include alkyd resins, unsaturated group-containing urethane resins, unsaturated group-containing epoxy resins, unsaturated group-containing polyester resins, polymerized oils, etc. Similar effects can also be expected with diene rubbers including natural rubber.

[0065] The oxidatively polymerizable unsaturated resin contained in the curable resin composition of the present invention may be one type alone or two or more types in combination.

[0066] The curable resin composition of the present invention can be suitably used as a printing ink or a coating material, and the oxidatively polymerizable unsaturated resin and other components contained in the curable resin composition of the present invention can be appropriately selected depending on the application. The use of the curable resin composition of the present invention as a printing ink and as a paint will be described below.

[0067] (printing ink) When the curable resin composition of the present invention is used for printing ink applications, the printing ink contains, in addition to the curing accelerator for oxidative polymerization type unsaturated resins and the oxidative polymerization type unsaturated resins, a pigment or dye, a gelling agent, a surface modifier, a drying inhibitor, vegetable oil, various organic solvents, and the like. The blending ratio of these components and the types of blended materials are appropriately adjusted depending on the printing method. The curable resin composition of the present invention can be suitably used for printing inks of any type, such as lithographic offset ink, lithographic waterless ink, and letterpress ink.

[0068] The content of the curing accelerator of the present invention in the printing ink is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the printing ink, since this results in an ink that has a short drying time and is less prone to skinning.

[0069] Examples of pigments that can be used include organic pigments for printing inks listed in the "Organic Pigments Handbook" (author: Isao Hashimoto, publisher: Color Office, first edition 2006), and examples of usable pigments include soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments.

[0070] Inorganic pigments can also be used as the pigment, and examples thereof include inorganic coloring pigments such as titanium oxide, graphite, and zinc oxide, as well as inorganic body pigments such as lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, baryte powder, and abrasive powder, silicone, and glass beads.

[0071] The pigments used may be one type alone or two or more types in combination. The content of the pigment varies depending on the type of printing ink to be used, but is usually in the range of 5 to 55 parts by mass per 100 parts by mass of the printing ink.

[0072] The gelling agent is used for the purpose of adjusting the viscoelasticity of the printing ink, and examples thereof include organoaluminum compounds, organotitanate compounds, organozinc compounds, and organocalcium compounds. More specifically, the organoaluminum compound includes aluminum alcoholates and aluminum chelate compounds, and specific examples of the aluminum chelate compound include aluminum diisopropoxide monoethylacetoacetate, aluminum di-n-butoxide monomethylacetoacetate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-butoxide monomethylacetoacetate, aluminum di-sec-butoxide monoethylacetoacetate, aluminum tris(acetylacetonate), aluminum tris(ethylacetonate), aluminum mono-acetylacetonate bis(ethylacetonate), and the like.

[0073] The gelling agent used may be one type alone or two or more types in combination. The content of the gelling agent varies depending on the type of printing ink to be produced, but is usually in the range of 0.1 to 5 parts by mass per 100 parts by mass of the printing ink.

[0074] Surface modifiers are added for the purpose of improving the abrasion resistance, anti-blocking properties, smoothness, scratch resistance, etc. of the ink coating film, and examples thereof include natural waxes such as carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, and microcrystalline wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compounds.

[0075] The surface modifiers used may be one type alone or two or more types in combination. The content of the gelling agent varies depending on the type of printing ink to be produced, but is usually in the range of 0.1 to 7 parts by mass per 100 parts by mass of the printing ink.

[0076] The drying inhibitor is added for the purpose of improving the storage stability of the printing ink and suppressing skinning, and examples thereof include hydroquinone, methoquinone, tert-butylhydroquinone, and methylhydroquinone.

[0077] The drying inhibitors used may be one type alone or two or more types in combination. The content of the drying inhibitor varies depending on the type of printing ink to be used, but is usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of the printing ink.

[0078] Examples of vegetable oils include linseed oil, tung oil, rice bran oil, safflower oil, soybean oil, tall oil, rapeseed oil, palm oil, castor oil, and coconut oil; recycled vegetable oils obtained by recycling these vegetable oils after using them for food processing, etc.; and vegetable oil fatty acid monoesters such as linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, and soybean oil fatty acid butyl. Among these, vegetable oils having unsaturated bonds in the molecule, such as linseed oil, tung oil, and soybean oil, are preferred because they are used for printing inks with excellent drying properties, and soybean oil and its recycled oil are more preferred because they have a small environmental impact.

[0079] The vegetable oils used may be one type alone or two or more types in combination.

[0080] Commercially available organic solvents can be used, including "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphtesol H," and "Alkene 56NT" (all manufactured by Eneos Corporation), "Diadol 13," and "Dialene 168" (all manufactured by Mitsubishi Chemical Corporation); "F Oxocol" and "F Oxocol 180" manufactured by JX Corporation; "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" (all manufactured by Nissan Chemical Industries, Ltd.); and "Sol Examples include "Bent H" and "N-Paraffin C14-C18" (all manufactured by IS Chemical Co., Ltd.); "Supersol LA35" and "Supersol LA38" (all manufactured by Idemitsu Kosan Co., Ltd.); "Exsor D80", "Exsor D110", "Exsor D120", "Exsor D130", "Exsor D160", "Exsor D100K", "Exsor D120K", "Exsor D130K", "Exsor D280", "Exsor D300", and "Exsor D320" (all manufactured by Exxon Mobil Corporation).

[0081] The organic solvents used may be one type alone or two or more types in combination.

[0082] The total content of the vegetable oil and organic solvent varies depending on the type of printing ink to be produced, but is usually in the range of 20 to 80 parts by mass per 100 parts by mass of the printing ink.

[0083] The printing ink can be produced, for example, by using a refining machine such as a triple-roll mill to mill a mixture of an oxidatively polymerized unsaturated resin, a pigment, a vegetable oil, an organic solvent, various additives, etc. When a rosin-modified phenolic resin, which is particularly versatile, is used as the oxidatively polymerized unsaturated resin, a method may be used in which the rosin-modified phenolic resin, vegetable oil, organic solvent, gelling agent, etc. are previously made into a varnish, and the resulting varnish is then milled using a refining machine such as a triple-roll mill to mill a mixture of the pigment, vegetable oil, organic solvent, various additives, etc. The hardening accelerator of the present invention may be added during or after the kneading. The hardening accelerator of the present invention may be added by adding a pre-blended mixture of the components constituting the hardening accelerator of the present invention, or by adding the components constituting the hardening accelerator of the present invention separately.

[0084] (paint) When the curable resin composition of the present invention is used for a coating material, the coating material contains, in addition to the curing accelerator for an oxidatively polymerizable unsaturated resin and the oxidatively polymerizable unsaturated resin, a pigment, a pigment dispersant, a drying inhibitor, a surface conditioner, an ultraviolet absorber, an antifoaming agent, a thickener, an anti-settling agent, vegetable oil, various organic solvents, and the like. The types and blending ratios of these components are adjusted appropriately depending on the application and desired performance of the paint.

[0085] The content of the curing accelerator of the present invention in the paint is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the paint, since this results in an ink that has a short drying time and is less prone to skinning.

[0086] As mentioned above, examples of oxidatively polymerized unsaturated resins used in coating applications include alkyd resins, unsaturated group-containing urethane resins, unsaturated group-containing epoxy resins, etc. Among these, alkyd resins, which are particularly versatile, are a type of polyester resin whose main raw materials are polybasic acid compounds, polyhydric alcohol compounds, and oil fatty acids.

[0087] The polybasic acid compounds mainly used include dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, and maleic anhydride, and lower alkyl esters of these acids. If necessary, trivalent or higher polybasic acids such as trimellitic anhydride, methylcyclohexene tricarboxylic acid, and pyromellitic anhydride, sulfophthalic acid, sulfoisophthalic acid, and their ammonium salts, sodium salts, and lower alkyl esters can also be used. In addition to the polybasic acid compounds, monobasic acids such as benzoic acid, crotonic acid, and pt-butylbenzoic acid can be used in combination as acid components for the purpose of adjusting the molecular weight.

[0088] Examples of the polyhydric alcohol compound include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, etc. If necessary, trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc.; polyhydric alcohols having a polyoxyethylene group, etc. may be used in combination.

[0089] A part of the above-mentioned acid components and alcohol components can be replaced with oxyacid components such as dimethylolpropionic acid, oxypivalic acid, paraoxybenzoic acid, etc.; lower alkyl esters of these acids; lactones such as ε-caprolactone, etc.

[0090] Examples of the oil fatty acids include coconut oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, safflower oil fatty acids, tall oil fatty acids, dehydrated castor oil fatty acids, and tung oil fatty acids.

[0091] Epoxy-modified alkyd resins using an epoxy compound as part of the raw material, and vinyl-modified alkyd resins graft-polymerized with vinyl monomers such as styrene and (meth)acrylic acid esters can also be used as the oxidatively polymerized unsaturated resin.

[0092] Polyester resins (hereinafter referred to as "recycled PES") whose main raw material is terephthalic acid are recycled from polyethylene terephthalate (e.g., PET bottles) collected for resource recycling, industrial waste polyethylene terephthalate, and scraps generated during the production of polyester products (films, fibers, automobile parts, electronic parts, etc.) such as polyethylene terephthalate and polybutylene terephthalate, which are made primarily from terephthalic acid. The recycled PES is dissolved in a mixture of the alcohol component and polybasic acid component described above, and depolymerized and esterified to obtain recycled PES-modified alkyd resins, which can also be used as oxidatively polymerized unsaturated resins.

[0093] Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, and carbon black; and organic pigments such as azo pigments, diazo pigments, condensed azo pigments, thioindigo pigments, indanthrones, quinacridone pigments, anthraquinone pigments, benzimidazolone pigments, perylene pigments, perinone pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthrapyridine pigments, and dioxazine pigments.

[0094] The pigments used may be one type alone or two or more types in combination. The content of the pigment varies depending on the application of the paint and the desired performance, but is usually in the range of 20 to 70 parts by mass per 100 parts by mass of the paint.

[0095] The drying inhibitor, vegetable oil and organic solvent used in the paint can be the same as the drying inhibitor, vegetable oil and organic solvent used in the printing ink described above, and the content can be in the same range.

[0096] The paint can be produced, for example, by mixing a compound of an oxidatively polymerized unsaturated resin, a pigment, an organic solvent, various additives, etc., in a mixer such as a paint shaker. The curing accelerator of the present invention may be added during or after this mixing. The curing accelerator of the present invention may be added by adding a mixture of the components constituting the curing accelerator of the present invention in advance, or by adding the components constituting the curing accelerator of the present invention separately.

[0097] The coating material of the present invention can be applied to a substrate by a conventional method, followed by drying and curing to obtain a coating film. Examples of substrates (substrates) to which the coating material of the present invention can be applied include steel. The drying conditions (curing conditions) after application include room temperature drying. The coating material of the present invention is particularly useful as a thick coating material because it can exhibit excellent curing properties even when the coating film is thick, and specifically, the thickness of the cured coating film can be set in the range of 1 to 500 μm. Therefore, the coating material of the present invention is useful as an architectural coating material. [Example]

[0098] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[0099] (Preparation Examples 1-4 and Comparative Preparation Examples 1-5: Preparation of Curing Accelerators) The components shown in Table 1 were mixed in the amounts shown in Table 1 at 70°C for 30 minutes with stirring to prepare curing accelerators 1-4 and 1'-5', respectively.

[0100] [Table 1]

[0101] The metal soaps and amino alcohols used in the preparation of the curing accelerators of the Preparation Examples and Comparative Examples are as follows. Manganese soap: Manganese neodecanoate (manganese content 6.84% by mass) Amino alcohol: 2-[(2-dimethylaminoethyl)methylamino]ethanol

[0102] The diamine compounds of the comparative preparation examples, 1,4-diazabicyclo[2.2.2]octane and 2-aminobenzamide, are compounds having the following structures, respectively.

[0103] [ka]

[0104] The cyclohexanediamine and aminoalcohol used in the preparation of the curing accelerators in the Preparation Examples and Comparative Examples were both commercially available products. The cyclohexanediamine was "1,2-Cyclohexanediamine (cis and trans-mixture)" manufactured by Tokyo Ohka Kogyo Co., Ltd., and the aminoalcohol was "JEFFCAT Z-110" manufactured by Huntsman Corporation.

[0105] (Examples 1-4 and Comparative Examples 1-5: Preparation and Evaluation of Paints for Evaluation) A base paint was obtained by kneading 77.7 parts by mass of titanium white pigment ("Ti-Pure R-960" manufactured by Chemours Inc.), 33.3 parts by mass of calcium carbonate ("NS♯200" manufactured by Nitto Funka Kogyo Co., Ltd.), 158.1 parts by mass of an alkyd resin having an unsaturated fatty acid group in the molecule ("Beckosol P-470-70" manufactured by DIC Corporation), 30.0 parts by mass of mineral spirits ("Oxazol LA" manufactured by Oxalis Chemicals Inc.), 0.3 parts by mass of a thickener ("Bentone 34" manufactured by Toshin Kasei Co., Ltd.), and 0.6 parts by mass of an anti-skinning agent ("Methyl Ethyl Ketoxime" manufactured by Ube Industries, Ltd.) in a paint shaker using glass beads.

[0106] The curing accelerators shown in Table 2 were added to the resulting paints to prepare paints for evaluation. The metal soaps used in preparing the coating materials for evaluation are as follows: Calcium soap: A mixture of calcium neodecanoate and calcium 2-ethylhexanoate (DICNATE Ca 5% manufactured by DIC Corporation) Zirconium soap: Zirconium 2-ethylhexanoate (DIC Corporation "12% Zr-DICNATE")

[0107] The resulting paint for evaluation was subjected to the following evaluations, and the results are shown in Table 2. (Initial drying test) The newly obtained evaluation paint was left overnight at room temperature, and after leaving overnight, the evaluation paint was applied to a glass substrate to form a coating film with a wet film thickness of 152 μm. After application, the coating film was touched with a fingertip every 30 minutes to check its dryness. The time when the evaluation paint no longer adheres to the fingertip was taken as the drying time and evaluated. (Drying test after storage) The evaluation paints that had just been obtained were stored in a storage cabinet at 50° C. for 2 weeks. After storage, the evaluation paints were used to evaluate the drying time in the same manner as in the initial drying test.

[0108] In addition to the evaluation of the paint, the stability of the curing accelerator used in the preparation of the paint was also evaluated. Specifically, the curing accelerator immediately after preparation was stored at room temperature in a storage cabinet for two weeks, and the properties of the curing accelerator after storage were visually evaluated according to the following criteria. Good: No crystals are observed in the hardening accelerator. Bad: Crystals are found in the hardening accelerator.

[0109] [Table 2]

[0110] From Tables 1 and 2, it was confirmed that the combination of a specific diamine compound, amino alcohol, and fatty acid provides excellent initial drying performance and drying performance after storage, and improves the stability of the curing accelerator itself over time. On the other hand, Comparative Examples 1 and 3, which did not contain at least one of a fatty acid and an amino alcohol, showed poor drying performance stability and storage stability of the curing accelerator itself, and Comparative Examples 2, 4, and 5, which did not contain a specific diamine compound, showed poor initial drying performance.

Claims

1. A curing accelerator for oxidatively polymerized unsaturated resins, comprising a non-cobalt metal soap, a diamine compound, an aminoalcohol compound, and a fatty acid, The diamine compound is a curing accelerator for oxidatively polymerized unsaturated resins, which is a diamine compound represented by the following general formula (B): 【Chemical 1】 (In the general formula (B), R 21 and R 22 each independently represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms; R 23 and R 24 each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a phenyl group; R 21 and R 22 may be bonded to each other to form an alicyclic structure or an aromatic ring structure; R 21 and R 24 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure; R 22 and R 23 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure; R 23 and R 24 may be bonded to each other to form a nitrogen-containing alicyclic structure or a nitrogen-containing aromatic ring structure.

2. A curing accelerator for oxidatively polymerized unsaturated resins, comprising a non-cobalt metal soap, a diamine compound, an aminoalcohol compound, and a fatty acid, The diamine compound is a curing accelerator for oxidatively polymerized unsaturated resins, which is one or more of the following compounds: 【Chemical 1】

3. 2. The curing accelerator for oxidatively polymerized unsaturated resins according to claim 1, wherein the diamine compound is at least one selected from the group consisting of 1,2-cyclohexanediamine, 1,2-diaminopropane, and 2-picolylamine.

4. The curing accelerator for oxidatively polymerized unsaturated resins according to any one of claims 1 to 3, wherein the non-cobalt metal soap is a fatty acid metal salt of a fatty acid having 1 to 22 carbon atoms, and the metal of the fatty acid metal salt is manganese, iron, bismuth, zirconium, barium, calcium, strontium, nickel, copper, zinc, cerium, or vanadium.

5. 5. The curing accelerator for oxidatively polymerized unsaturated resins according to claim 1, wherein the non-cobalt metal soap comprises manganese soap and / or iron soap.

6. 6. The curing accelerator for oxidatively polymerized unsaturated resins according to claim 1, wherein the amino alcohol compound is a compound represented by the following general formula (C): 【Chemistry 2】 (In the general formula (C), R ３１ and R ３２ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X １ and X ２ are each independently an alkylene group having 1 to 6 carbon atoms, Y is an ether bond or —NR ３３ A linking group represented by - (R ３３ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

7. 7. The curing accelerator for oxidatively polymerized unsaturated resins according to claim 1, wherein the fatty acid is at least one selected from the group consisting of octylic acid, isononanoic acid, neodecanoic acid, and naphthenic acid.

8. A curable resin composition comprising the curing accelerator for oxidatively polymerized unsaturated resins according to any one of claims 1 to 7 and an oxidatively polymerized unsaturated resin.

9. The curable resin composition according to claim 8, which is a printing ink or a paint.

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