WO2013084824A1 - Drier for paint and paint using same - Google Patents
Drier for paint and paint using same Download PDFInfo
- Publication number
- WO2013084824A1 WO2013084824A1 PCT/JP2012/081117 JP2012081117W WO2013084824A1 WO 2013084824 A1 WO2013084824 A1 WO 2013084824A1 JP 2012081117 W JP2012081117 W JP 2012081117W WO 2013084824 A1 WO2013084824 A1 WO 2013084824A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paint
- acid
- fatty acid
- dryer
- resin
- Prior art date
Links
- 239000003973 paint Substances 0.000 title claims abstract description 54
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 34
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 229930195729 fatty acid Natural products 0.000 claims abstract description 34
- -1 fatty acid manganese salt Chemical class 0.000 claims abstract description 29
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- KUHJJSKJQLIHBS-UHFFFAOYSA-N 1,4-diaminobutan-1-ol Chemical compound NCCCC(N)O KUHJJSKJQLIHBS-UHFFFAOYSA-N 0.000 claims description 2
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 2
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 claims description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 2
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 2
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 claims 1
- SNJOHDZPYHMEKF-UHFFFAOYSA-N 1-(3-aminopropylamino)ethanol Chemical compound CC(O)NCCCN SNJOHDZPYHMEKF-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 39
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- 229910017052 cobalt Inorganic materials 0.000 abstract description 15
- 239000010941 cobalt Substances 0.000 abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004904 shortening Methods 0.000 abstract description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- 238000001035 drying Methods 0.000 description 24
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- 239000004215 Carbon black (E152) Substances 0.000 description 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- 230000000711 cancerogenic effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 231100000315 carcinogenic Toxicity 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- TVQGDYNRXLTQAP-UHFFFAOYSA-N ethyl heptanoate Chemical compound CCCCCCC(=O)OCC TVQGDYNRXLTQAP-UHFFFAOYSA-N 0.000 description 1
- BYEVBITUADOIGY-UHFFFAOYSA-N ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC BYEVBITUADOIGY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- OVFMRFMJVFDSAA-UHFFFAOYSA-N propyl decanoate Chemical compound CCCCCCCCCC(=O)OCCC OVFMRFMJVFDSAA-UHFFFAOYSA-N 0.000 description 1
- FTBUKOLPOATXGV-UHFFFAOYSA-N propyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCC FTBUKOLPOATXGV-UHFFFAOYSA-N 0.000 description 1
- HTUIWRWYYVBCFT-UHFFFAOYSA-N propyl hexanoate Chemical compound CCCCCC(=O)OCCC HTUIWRWYYVBCFT-UHFFFAOYSA-N 0.000 description 1
- HCMSDHYNNJTLRW-UHFFFAOYSA-N propyl nonanoate Chemical compound CCCCCCCCC(=O)OCCC HCMSDHYNNJTLRW-UHFFFAOYSA-N 0.000 description 1
- IDHBLVYDNJDWNO-UHFFFAOYSA-N propyl octanoate Chemical compound CCCCCCCC(=O)OCCC IDHBLVYDNJDWNO-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000005314 unsaturated fatty acid group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F9/00—Compounds to be used as driers, i.e. siccatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a dryer which is a drying accelerator for a paint using an oxidation polymerization type resin, and a paint using the dryer.
- a drying accelerator (dryer) for drying the paint is added to the paint containing the oxidation polymerization type resin.
- the dryer used is generally a metal salt of a heavy metal such as cobalt, manganese, lead, iron or zinc and various carboxylic acids (hereinafter sometimes abbreviated as “metal soap”).
- metal soaps cobalt metal soap has been used as a main dryer so far because of its excellent drying performance.
- Cobalt metal soap has excellent drying performance, but is listed in Group 2B, which is listed as “suspected to be carcinogenic to humans” in the list of carcinogenic risks of the International Cancer Institute. There is a point that there is a concern, the supply of metal cobalt is unstable because it is a rare metal, the cost of cobalt metal soap is expensive, etc., while reducing the amount of cobalt metal soap used, it is high There has been a demand for a dryer having curing performance.
- cobalt metal soap in order to achieve a smaller amount of cobalt metal soap used, cobalt metal soap, manganese metal soap, and at least one amino alcohol selected from diethanolamine, diethylethanolamine, dibutylethanolamine, and n-butyldiethanolamine are contained.
- the dryer which performs is proposed (for example, refer patent document 1).
- cobalt metal soap since cobalt metal soap is still used, it has not solved the above-mentioned carcinogenic concerns, raw material supply anxiety and high cost problems.
- Patent Document 2 As a dryer that does not use cobalt metal, a dryer using manganese soap and bipyridyl in combination has already been proposed before the disclosure of Patent Document 1 (for example, see Patent Document 2).
- the problem to be solved by the present invention is to provide a paint drier that does not use cobalt metal soap, which is likely to be affected by the human body, and that can shorten the coating interval during repeated coating.
- the present invention relates to a paint dryer comprising a fatty acid manganese salt (A) and an amino alcohol (B) represented by the following general formula (1), and a paint using the same.
- R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- X 1 and X 2 each independently represents an alkylene group having 2 to 6 carbon atoms
- Y Is —NR 3 — wherein R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an oxygen atom.
- the paint dryer of the present invention can provide a paint capable of shortening the interval between coating times while solving the problems of carcinogenicity, uneasy supply of raw materials, and high cost.
- the paint dryer of the present invention contains a fatty acid manganese salt (A) and an amino alcohol (B) represented by the following general formula (1).
- R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- X 1 and X 2 each independently represents an alkylene group having 2 to 6 carbon atoms
- Y Is —NR 3 — wherein R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an oxygen atom.
- the fatty acid manganese salt (A) is a manganese salt of a fatty acid, and as the fatty acid, octylic acid, naphthenic acid, neodecanoic acid, isononanoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid Etc. These fatty acid manganese salts (A) can be used alone or in combination of two or more.
- the fatty acid manganese salt (A) is obtained by dissolving a fatty acid in water as a water-soluble salt, usually a sodium salt, and adding water-soluble manganese salt thereto to carry out an ion exchange reaction called metathesis, and washing with water. It can be obtained by dehydration and filtration.
- the amino alcohol (B) is a compound represented by the following general formula (1).
- an amino alcohol having the structure represented by the following general formula (1) it is possible to exhibit excellent drying performance such that drying time is short and wrinkles and shrinkage due to skinning can be prevented.
- R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- X 1 and X 2 each independently represents an alkylene group having 2 to 6 carbon atoms
- Y Is —NR 3 — wherein R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an oxygen atom.
- X 1 and X 2 are each an alkylene having 2 to 3 carbon atoms. What is group is preferable.
- amino alcohol (B) examples include 2-[(2-dimethylaminoethyl) methylamino] ethanol, 2- (2-aminoethyl) aminoethanol, 1- (2-aminoethyl) amino-2- Examples include propanol, 2- (3-aminopropylamino) ethanol, 2- (2-dimethylaminoethoxy) ethanol and the like. These amino alcohols (B) can be used alone or in combination of two or more.
- the mixing ratio (a) / (B) on the mass basis of the manganese metal (a) and the amino alcohol (B) in the fatty acid manganese salt (A) is 1 /
- the range is preferably 0.1 to 1/30, more preferably 1 / 0.3 to 1/20, and even more preferably 1 / 0.5 to 1/10. .
- the nitrogen atom in the amino alcohol (B) coordinates to the metal (manganese), changes the electronic state of the metal, enhances the activity and promotes the oxidation catalytic action of the manganese soap,
- the present inventors consider that the recoating property and the gloss of the coating film are improved by promoting the drying of the coating film and uniformly curing from the surface of the coating film to the inside, thereby improving the internal drying property. .
- the paint dryer of the present invention is preferably used as a solution with good handling properties by diluting the fatty acid manganese salt (A) and the amino alcohol (B) with a diluent (C).
- a diluent examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; alcohol solvents such as methanol, ethanol, propanol, and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol; fatty acid esters such as caproic acid methyl ester, capric acid methyl ester, lauric acid methyl ester; soybean oil, linseed oil, rapeseed oil, safflower Vegetable oils such as oil; the following general formula (2)
- R 4 is an alkyl group having 5 to 11 carbon atoms
- R 5 is an alkyl group having 1 to 3 carbon atoms.
- the fatty acid ester (C1) is obtained by esterifying a carboxylic acid having 6 to 12 carbon atoms and an alcohol having 1 to 3 carbon atoms.
- the carbon chain of the carboxylic acid and the alcohol is It may be linear or branched.
- Examples of the fatty acid ester (C1) include caproic acid methyl ester, enanthic acid methyl ester, caprylic acid methyl ester, pelargonic acid methyl ester, capric acid methyl ester, lauric acid methyl ester, caproic acid ethyl ester, and enanthic acid ethyl ester.
- These fatty acid esters can be used alone or in combination of two or more.
- caproic acid methyl ester, capric acid methyl ester, and lauric acid methyl ester are preferred because of their low odor.
- lauric acid methyl ester is preferable because it can achieve both a reduction in viscosity and a reduction in odor in a printing ink dryer.
- the mixing ratio of the total amount of the fatty acid manganese salt (A) and amino alcohol (B) and the diluent (C) on a mass basis [ (A) + (B)] / (C) is preferably in the range of 10/90 to 95/5, more preferably in the range of 40/60 to 80/20, and 20/80 to 90. More preferably, the range is / 10.
- the paint of the present invention is characterized by containing the paint dryer of the present invention and an oxidative polymerization type unsaturated resin.
- oxidative polymerization type unsaturated resin examples include an oxidative polymerization curable alkyd resin, an oxidative polymerization curable urethane resin, and an oxidative polymerization curable modified epoxy resin.
- oxidative polymerization curable alkyd resin examples include ester resins mainly composed of a polybasic acid component, a polyhydric alcohol component, and an oil fatty acid.
- polybasic acid component examples 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 esterified products of these acids are mainly used. Furthermore, if necessary, tribasic or higher polybasic acids such as trimellitic anhydride, methylcyclohexenic carboxylic acid, pyromellitic anhydride; sulfophthalic acid, sulfoisophthalic acid and ammonium salts thereof, sodium salts, lower alkyl esterified products, etc. Can be used.
- monobasic acids such as benzoic acid, crotonic acid, and pt-butylbenzoic acid can be used in combination for the purpose of adjusting the molecular weight.
- polyhydric alcohol component examples include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and the like.
- a dihydric alcohol is mentioned.
- trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol; polyhydric alcohols having a polyoxyethylene group, and the like can be used in combination. These polyhydric alcohols can be used alone or in admixture of two or more.
- a part of the acid component and alcohol component may be replaced with dimethylolpropionic acid, oxypivalic acid, paraoxybenzoic acid, etc .; lower alkyl esters of these acids; oxyacid components such as lactones such as ⁇ -caprolactone. it can.
- oil fatty acid examples include coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, and kiri oil fatty acid.
- the oil length of the alkyd resin is preferably in the range of 5 to 80% by mass, particularly 20 to 70% by mass, from the viewpoints of the curability, toughness, feeling of feeling of the coating film, and the like.
- an epoxy-modified alkyd resin obtained by partially esterifying an epoxy compound using an epoxy compound as part of an alcohol component a maleated alkyd resin obtained by introducing maleic anhydride into an alkyd resin; a maleated alkyd resin and a hydroxyl group-containing alkyd Grafted alkyd resins obtained by adding a resin; vinyl-modified alkyd resins obtained by graft-polymerizing vinyl monomers such as styrene and (meth) acrylic acid ester to alkyd resins can also be used.
- polyethylene terephthalate for example, PET bottles
- polyester products such as polyethylene terephthalate and polybutylene terephthalate that use terephthalic acid as the main raw material (films, fibers, automotive parts)
- regenerated PES polyester resin mainly made of terephthalic acid regenerated from scraps, etc. generated during the manufacture of electronic components, etc.
- the regenerated PES is dissolved, depolymerized, and esterified to obtain an alkyd resin, a maleated alkyd resin obtained by reacting the alkyd resin with maleic anhydride, the alkyd Resin and ethylenically unsaturated groups Etc. are modified alkyd resins obtained by reacting an acid anhydride having no may also be used.
- the oxidative polymerization curable alkyd resin described in detail above preferably has a Gardner viscosity (25 ° C.) of 15 to 60 Stokes from the viewpoint of good curability and coating film properties.
- the urethane resin is not particularly limited, and for example, a urethane, a urethane resin obtained by reacting a polyol, an oil and fat with a polyhydric alcohol, and a polyisocyanate can be used.
- polyisocyanate examples include aliphatic isocyanates such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,8-diisocyanate methyl caproate.
- Alicyclic disissocyanates such as 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate and methylcyclohexyl-2,4-diisocyanate; toluylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthene diisocyanate, diphenylmethyl Aromatic dii such as methane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4-dibenzyl diisocyanate, 1,3-phenylene diisocyanate Cyanates; chlorinated diisocyanates include brominated diisocyanates etc., can be used as these alone, or two or more thereof.
- polystyrene resins examples include various polyols commonly used in the production of urethane resins, such as diethylene glycol, butanediol, hexanediol, neopentyl glycol, bisphenol A, cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, and polyethylene glycol.
- Examples of the polyol obtained by esterifying the fat and the polyhydric alcohol include those obtained by esterifying a fat and oil having an iodine value of 7 to 200 and a polyhydric alcohol such as trimethylolpropane and pentaerythritol.
- a polyhydric alcohol such as trimethylolpropane and pentaerythritol.
- Mitsui Chemicals, Inc Commercially available products such as “XP1076E”, “XP1077E”, “XP1580E”, “FB20-50XB” manufactured by the company can also be used.
- Examples of the oxidative polymerization curable modified epoxy resin include resins obtained by reacting an epoxy resin with an unsaturated fatty acid component and an acid group-containing acrylic component as raw materials.
- the resin raw material composition is 30 to 50% by weight of the epoxy resin, 25 to 40% by weight of the unsaturated fatty acid component, and 10 to 45% by weight of the acid group-containing acrylic component with respect to the total weight of the raw material of 100% by weight, It is preferable from the viewpoint of excellent physical properties.
- the iodine value of the oxidative polymerization curable modified epoxy resin is preferably from 30 to 100, particularly preferably from 35 to 90, from the viewpoint of obtaining good curability.
- the epoxy resin that can be used as a raw material is not particularly limited, but is bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol from the viewpoint of easy modification and excellent performance of the resulting cured coating film.
- Bisphenol type epoxy resins such as F type epoxy resins are preferred. These may be used alone or in combination of two or more.
- any natural or synthetic unsaturated fatty acid can be used.
- it can be obtained from tung oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, tall oil, soybean oil, coconut oil.
- Unsaturated fatty acids can be used.
- the acid group-containing acrylic component for example, a mixture of (meth) acrylic acid and an acrylic monomer containing no acid group such as styrene or (meth) acrylic acid ester can be used.
- an acrylic monomer containing no acid group such as styrene or (meth) acrylic acid ester
- styrene is preferable because excellent coating film hardness can be obtained.
- the oxidation polymerization curable modified epoxy resin can be obtained as follows. First, an epoxy ester resin is produced from an epoxy resin and an unsaturated fatty acid component. For example, an epoxy resin and an unsaturated fatty acid component are used in a suitable solvent such as toluene and xylene, using a condensation catalyst, and if necessary, at 150 to 250 ° C. in an inert gas atmosphere such as nitrogen gas, An epoxy ester resin is obtained by reacting until a desired acid value is obtained.
- the condensation catalyst for example, dibutyltin oxide, tetra n-butylammonium bromide and the like can be used.
- the obtained epoxy ester resin is reacted with the acid group-containing acrylic component to obtain an oxidative polymerization curable modified epoxy resin.
- the reaction between the epoxy ester resin and the acid group-containing acrylic component can be carried out in the temperature range of 80 to 150 ° C. in the presence of a polymerization initiator and in an inert gas atmosphere such as nitrogen gas.
- a polymerization initiator various substances such as peroxides and azo compounds can be used.
- “Kayabutyl B (alkyl perester type)” manufactured by Kayaku Akzo is used in an amount of 0. It can be used at a ratio of 1 to 20 parts by mass.
- an oxidative polymerization curable alkyd resin is preferable because it is inexpensive and easily available in the present invention and is excellent in the drying property (practicality) of the paint.
- the paint of the present invention preferably further contains an organic solvent.
- organic solvent examples include the hydrocarbon solvents, alcohol solvents, ketone solvents, and ether solvents.
- the paint of the present invention may further include a colorant, a diluent, a pigment dispersant, a surface conditioner, an ultraviolet absorber, an antifoaming agent, a thickener, an antisettling agent, etc.
- a colorant e.g., a diluent, a pigment dispersant, a surface conditioner, an ultraviolet absorber, an antifoaming agent, a thickener, an antisettling agent, etc.
- examples of the colorant include carbon black, phthalocyanine pigment, dial, azo pigment, quinacridone pigment and the like.
- examples of the diluent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirit; alcohol solvents such as methanol, ethanol, propanol, and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol; fatty acid esters such as caproic acid methyl ester, capric acid methyl ester, lauric acid methyl ester; soybean oil, linseed oil, rapeseed oil, sa And vegetable oils such as flower oil.
- the blending amount of the dryer of the present invention with respect to the paint is not particularly limited, but the total mass of the metal components in the dryer is in the range of 0.005 to 1.5 parts by mass with respect to 100 parts by mass of the oxidation polymerization type unsaturated resin. It is preferable.
- the coating material of the present invention described in detail above can be applied to an object to be coated, dried and cured by a conventional method to obtain a coating film.
- a base material (object to be coated) on which the paint of the present invention can be applied for example, steel and the like can be mentioned.
- drying conditions (curing conditions) after coating there is a normal drying.
- the coating material of the present invention can exhibit excellent curability even when the coating film is thick, it is particularly useful as a coating material for thick coatings.
- the range may be 500 ⁇ m. Therefore, the paint of the present invention is useful as an architectural paint.
- Comparative Example 1 (Preparation of a comparative paint dryer) 12 parts of cobalt naphthenate and 38 parts of zirconium octylate were dissolved in 50 parts of mineral spirit to obtain a comparative coating dryer 1 '. This dryer was made to demonstrate the average level of performance of prior art metal soaps including cobalt metal soaps.
- Comparative Example 2 (same as above) 56 parts of manganese naphthenate and 18 parts of 2,2′-bipyridyl were dissolved in 26 parts of mineral spirit to obtain a comparative paint dryer 2 ′.
- Example 6 (Preparation of paint) 1960 g of titanium white pigment (“JR-701” manufactured by Teika Co., Ltd.), resin for paint “Beccosol P-470-70” (manufactured by DIC Co., Ltd., alkyd resin having an oxidation-polymerized unsaturated fatty acid group in the molecule) 3340 g, 280 g of mineral spirit, and 20 g of anti-skinning agent (methyl ethyl ketoxime) in 40 g of the mixture obtained by kneading with three rolls, the ratio of manganese metal content to 0.06% of the coating dryer 1 for 100 parts of resin non-volatile content It added so that the coating material 1 of this invention might be prepared.
- the drying test of the paint 1, the glossiness of the coating film obtained, and the test of overcoating were conducted by the following methods. The evaluation results are shown in Table 2.
- ⁇ Testing method for drying properties of paint> ⁇ Method for measuring drying time>
- the coating material was applied on a glass plate using a 3 mil applicator, and then tested using a drying time recorder (“Model No. 404” manufactured by Dazai Equipment Co., Ltd.). The measurement was performed in a constant temperature and humidity chamber (25 ° C., 50% RH).
- the drying time of the coating material was the time until the coating material was completely dried and disappeared after the coating material was applied on the glass plate and the coating material was completely dried by the needle of the drying time recorder ( Unit: hours).
- ⁇ Multi-layer coating test> Using an applicator on a glass plate, draw a 152 ⁇ m coating film and use the applicator after a certain time (4 hours, 8 hours, 1 day, 2 days, and 3 days) at a temperature of 25 degrees and a humidity of 50%. The coating film with a thickness of 152 ⁇ m was applied again at a temperature of 25 ° C. and a humidity of 50%, and after drying for 7 days, the state of the coating film surface was visually observed.
- Comparative Example 3 A comparison was made in the same manner as in Example 6 except that the paint dryer 1 'for comparison was added so that the ratio of the cobalt metal content to 100 parts of the resin non-volatile content was 0.06% instead of using the paint dryer 1 A control paint 1 'was obtained. The drying time was measured in the same manner as in Example 6, and the results are shown in Table 3.
- Comparative Example 4 A comparison was made in the same manner as in Example 6 except that instead of using the paint dryer 1, a comparative paint dryer 2 'was added so that the ratio of manganese metal content to 100 parts of the resin non-volatile content was 0.06%. A control paint 2 'was obtained. The drying time was measured in the same manner as in Example 6, and the results are shown in Table 3.
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Abstract
The purpose of the present invention is to provide: a drier for paint that does not use cobalt metal soap for which there are concerns about the impact thereof on the human body, said drier being capable of shortening the coating interval when recoating; and a paint using same. Provided are: a drier for paint, containing a fatty acid manganese salt (A) and an amino alcohol (B) indicated by general formula (1) (in the formula, R1 and R2 each independently indicate a hydrogen atom or a C1-6 alkyl group; X1 and X2 each independently indicate a C2-6 alkylene group; and Y indicates -NR3- (R3 indicates a hydrogen atom or a C1-6 alkyl group) or an oxygen atom); and a paint containing said drier for paint.
Description
本発明は、酸化重合型樹脂を用いる塗料の乾燥促進剤であるドライヤー及びそれを用いた塗料に関する。
The present invention relates to a dryer which is a drying accelerator for a paint using an oxidation polymerization type resin, and a paint using the dryer.
酸化重合型樹脂を含む塗料には、塗料を乾燥させるための乾燥促進剤（ドライヤー）が添加される。用いられるドライヤーとしては、コバルト、マンガン、鉛、鉄、亜鉛等の重金属と種々のカルボン酸との金属塩（以下、「金属石鹸」と略記することがある。）が一般的である。これらの金属石鹸の中でも、コバルト金属石鹸は、優れた乾燥性能を有しているため、これまで主要なドライヤーとして用いられてきた。
A drying accelerator (dryer) for drying the paint is added to the paint containing the oxidation polymerization type resin. The dryer used is generally a metal salt of a heavy metal such as cobalt, manganese, lead, iron or zinc and various carboxylic acids (hereinafter sometimes abbreviated as “metal soap”). Among these metal soaps, cobalt metal soap has been used as a main dryer so far because of its excellent drying performance.
コバルト金属石鹸は、優れた乾燥性能を有しているが、国際がん研究機関の発ガン性リスク一覧において「ヒトに対する発癌性が疑われる」とされるグループ２Ｂにリストアップされており発ガン性が懸念される点、金属コバルトは希少金属であるため供給が不安定であり、コバルト金属石鹸はコスト的に高価である点などがあり、コバルト金属石鹸の使用量をより低減しつつ、高い硬化性能を有するドライヤーが求められていた。
Cobalt metal soap has excellent drying performance, but is listed in Group 2B, which is listed as “suspected to be carcinogenic to humans” in the list of carcinogenic risks of the International Cancer Institute. There is a point that there is a concern, the supply of metal cobalt is unstable because it is a rare metal, the cost of cobalt metal soap is expensive, etc., while reducing the amount of cobalt metal soap used, it is high There has been a demand for a dryer having curing performance.
そこで、より少ないコバルト金属石鹸の使用量を達成する為に、コバルト金属石鹸、マンガン金属石鹸及び、ジエタノールアミン、ジエチルエタノールアミン、ジブチルエタノールアミン、ｎ－ブチルジエタノールアミンから選ばれる少なくとも１種のアミノアルコールを含有するドライヤーが提案されている（例えば、特許文献１参照。）。しかしながら、依然コバルト金属石鹸を使用しているため、上記の発ガン性の懸念、原料の供給不安及びコスト高の問題を解決するものではなかった。
Therefore, in order to achieve a smaller amount of cobalt metal soap used, cobalt metal soap, manganese metal soap, and at least one amino alcohol selected from diethanolamine, diethylethanolamine, dibutylethanolamine, and n-butyldiethanolamine are contained. The dryer which performs is proposed (for example, refer patent document 1). However, since cobalt metal soap is still used, it has not solved the above-mentioned carcinogenic concerns, raw material supply anxiety and high cost problems.
コバルト金属を用いないドライヤーとして、マンガン石鹸とビピリジルとを併用したドライヤーが、前記特許文献１が開示される以前にすでに提案されている（例えば、特許文献２参照。）。
As a dryer that does not use cobalt metal, a dryer using manganese soap and bipyridyl in combination has already been proposed before the disclosure of Patent Document 1 (for example, see Patent Document 2).
一般に塗料を塗装する場合、塗りムラの発生を防ぐために、塗膜形成成分の濃度が薄い塗料を重ね塗りすることが通常行われている。重ね塗りする際は、塗布する間隔をあけないと塗り重ねた後の塗膜に皺、縮みが発生する。その為、前記特許文献１や特許文献２に開示されたドライヤーを含む塗料は塗り重ねする際には１日程度の間隔をあけなければならず、塗装効率が悪い問題があった。また、塗膜表面の光沢も十分でない問題があった。
In general, when coating a paint, it is common practice to repeatedly apply a paint having a low concentration of coating film forming component in order to prevent the occurrence of uneven coating. When overcoating, wrinkles and shrinkage occur in the coated film unless the coating interval is left. For this reason, the paint including the dryer disclosed in Patent Document 1 and Patent Document 2 has to have an interval of about one day when it is repeatedly applied, which has a problem of poor coating efficiency. There is also a problem that the gloss of the coating surface is not sufficient.
本発明が解決しようとする課題は、人体への影響が懸念されるコバルト金属石鹸を使用せず、更に、重ね塗りする際の塗装間隔を短くできる塗料用ドライヤーを提供することである。
The problem to be solved by the present invention is to provide a paint drier that does not use cobalt metal soap, which is likely to be affected by the human body, and that can shorten the coating interval during repeated coating.
本発明者らは、鋭意研究を重ねた結果、脂肪酸金属塩として、非コバルトの脂肪酸マンガン塩を用い、特定のアミノアルコールを併用することで上記課題を解決できることを見出し、本発明を完成した。
As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a non-cobalt fatty acid manganese salt as a fatty acid metal salt and using a specific amino alcohol in combination, thereby completing the present invention.
すなわち、本発明は、脂肪酸マンガン塩（Ａ）及び下記一般式（１）で表されるアミノアルコール（Ｂ）を含有することを特徴とする塗料用ドライヤー及びそれを用いた塗料に関する。
That is, the present invention relates to a paint dryer comprising a fatty acid manganese salt (A) and an amino alcohol (B) represented by the following general formula (1), and a paint using the same.
本発明の塗料用ドライヤーは、発ガン性の懸念、原料の供給不安及びコスト高の問題を解決しつつ、塗り重ねの時間の間隔を短くできる塗料を提供できる。
The paint dryer of the present invention can provide a paint capable of shortening the interval between coating times while solving the problems of carcinogenicity, uneasy supply of raw materials, and high cost.
本発明の塗料用ドライヤーは、脂肪酸マンガン塩（Ａ）及び下記一般式（１）で表されるアミノアルコール（Ｂ）を含有するものである。
The paint dryer of the present invention contains a fatty acid manganese salt (A) and an amino alcohol (B) represented by the following general formula (1).
前記脂肪酸マンガン塩（Ａ）は、脂肪酸のマンガン塩であり、前記脂肪酸としては、オクチル酸、ナフテン酸、ネオデカン酸、イソノナン酸、桐油酸、アマニ油酸、大豆油酸、樹脂酸、トール油脂肪酸等が挙げられる。これらの脂肪酸マンガン塩（Ａ）は、単独で用いることも２種以上併用することもできる。
The fatty acid manganese salt (A) is a manganese salt of a fatty acid, and as the fatty acid, octylic acid, naphthenic acid, neodecanoic acid, isononanoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid Etc. These fatty acid manganese salts (A) can be used alone or in combination of two or more.
前記脂肪酸マンガン塩（Ａ）は、脂肪酸を水に可溶な塩、通常はナトリウム塩として水に溶解し、これに水に可溶なマンガン塩を加え、複分解といわれるイオン交換反応を行い、水洗、脱水、ろ過することによって得ることができる。
The fatty acid manganese salt (A) is obtained by dissolving a fatty acid in water as a water-soluble salt, usually a sodium salt, and adding water-soluble manganese salt thereto to carry out an ion exchange reaction called metathesis, and washing with water. It can be obtained by dehydration and filtration.
前記アミノアルコール（Ｂ）は、下記一般式（１）で表される化合物である。本発明では、この下記一般式（１）の構造を有するアミノアルコールを用いることで、乾燥時間が短く、かつ皮張りによるシワや縮みを防止できるという優れた乾燥性能を発揮することができる。
The amino alcohol (B) is a compound represented by the following general formula (1). In the present invention, by using an amino alcohol having the structure represented by the following general formula (1), it is possible to exhibit excellent drying performance such that drying time is short and wrinkles and shrinkage due to skinning can be prevented.
前記一般式（１）で表されるアミノアルコール（Ｂ）の中でも、よりシワや縮みを防止しつつ、より乾燥時間を短くできることから、Ｘ１及びＸ２がそれぞれ炭素原子数２～３のアルキレン基であるものが好ましい。
Among the amino alcohols (B) represented by the general formula (1), since the drying time can be further reduced while preventing wrinkles and shrinkage, X 1 and X 2 are each an alkylene having 2 to 3 carbon atoms. What is group is preferable.
前記アミノアルコール（Ｂ）の具体例としては、２－［（２－ジメチルアミノエチル）メチルアミノ］エタノール、２－（２－アミノエチル）アミノエタノール、１－（２－アミノエチル）アミノ－２－プロパノール、２－（３－アミノプロピルアミノ）エタノール、２-（２－ジメチルアミノエトキシ）エタノール等が挙げられる。なお、これらのアミノアルコール（Ｂ）は、単独で用いることも２種以上併用することもできる。
Specific examples of the amino alcohol (B) include 2-[(2-dimethylaminoethyl) methylamino] ethanol, 2- (2-aminoethyl) aminoethanol, 1- (2-aminoethyl) amino-2- Examples include propanol, 2- (3-aminopropylamino) ethanol, 2- (2-dimethylaminoethoxy) ethanol and the like. These amino alcohols (B) can be used alone or in combination of two or more.
乾燥性能をより向上するためには、前記脂肪酸マンガン塩（Ａ）中のマンガン金属（ａ）と前記アミノアルコール（Ｂ）との質量基準での配合比（ａ）／（Ｂ）は、１／０．１～１／３０の範囲であることが好ましく、１／０．３～１／２０の範囲であることがより好ましく、１／０．５～１／１０の範囲であることがさらに好ましい。
In order to further improve the drying performance, the mixing ratio (a) / (B) on the mass basis of the manganese metal (a) and the amino alcohol (B) in the fatty acid manganese salt (A) is 1 / The range is preferably 0.1 to 1/30, more preferably 1 / 0.3 to 1/20, and even more preferably 1 / 0.5 to 1/10. .
尚、本発明において、上記アミノアルコール（Ｂ）中の窒素原子が、金属(マンガン)へ配位し、金属の電子状態を変化させ、活性を高めてマンガン石鹸の酸化触媒作用を促進し、塗料の乾燥を促進すると共に、塗膜表面から内部に渡って均一に硬化し、結果的に内部乾燥性を向上させることにより、リコート性及び塗膜の光沢が良くなると本発明者らは考えている。
In the present invention, the nitrogen atom in the amino alcohol (B) coordinates to the metal (manganese), changes the electronic state of the metal, enhances the activity and promotes the oxidation catalytic action of the manganese soap, The present inventors consider that the recoating property and the gloss of the coating film are improved by promoting the drying of the coating film and uniformly curing from the surface of the coating film to the inside, thereby improving the internal drying property. .
本発明の塗料用ドライヤーは、前記脂肪酸マンガン塩（Ａ）及び前記アミノアルコール（Ｂ）を希釈剤（C）で希釈することにより、ハンドリング性の良い溶液として用いることが好ましい。前記希釈剤としては、例えば、トルエン、キシレン、ヘプタン、ヘキサン、ミネラルスピリット等の炭化水素系溶媒；メタノール、エタノール、プロパノール、シクロヘキサノール等のアルコール系溶媒；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；プロピルエーテル、メチルセロソルブ、セロソルブ、ブチルセロソルブ、メチルカルビトール等のエーテル系溶媒；カプロン酸メチルエステル、カプリン酸メチルエステル、ラウリン酸メチルエステル等の脂肪酸エステル；大豆油、亜麻仁油、菜種油、サフラワー油等の植物油脂；下記一般式（２）
The paint dryer of the present invention is preferably used as a solution with good handling properties by diluting the fatty acid manganese salt (A) and the amino alcohol (B) with a diluent (C). Examples of the diluent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; alcohol solvents such as methanol, ethanol, propanol, and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol; fatty acid esters such as caproic acid methyl ester, capric acid methyl ester, lauric acid methyl ester; soybean oil, linseed oil, rapeseed oil, safflower Vegetable oils such as oil; the following general formula (2)
で表される脂肪酸エステル（C１）等を例示することができる、これらの希釈剤は、１種類のみで用いることも２種以上併用することもできる。
These diluents can be used alone or in combination of two or more kinds.
前記脂肪酸エステル（C１）は、炭素原子数６～１２のカルボン酸と、炭素原子数１～３のアルコールとをエステル化反応することにより得られるもので、前記カルボン酸及びアルコールの炭素鎖は、直鎖状でも分岐状でも構わない。
The fatty acid ester (C1) is obtained by esterifying a carboxylic acid having 6 to 12 carbon atoms and an alcohol having 1 to 3 carbon atoms. The carbon chain of the carboxylic acid and the alcohol is It may be linear or branched.
前記脂肪酸エステル（C１）としては、例えば、カプロン酸メチルエステル、エナント酸メチルエステル、カプリル酸メチルエステル、ペラルゴン酸メチルエステル、カプリン酸メチルエステル、ラウリン酸メチルエステル、カプロン酸エチルエステル、エナント酸エチルエステル、カプリル酸エチルエステル、ペラルゴン酸エチルエステル、カプリン酸エチルエステル、ラウリン酸エチルエステル、カプロン酸プロピルエステル、エナント酸プロピルエステル、カプリル酸プロピルエステル、ペラルゴン酸プロピルエステル、カプリン酸プロピルエステル、ラウリン酸プロピルエステル等が挙げられる。これらの脂肪酸エステルは、単独で用いることも２種以上併用することもできる。また、これらの脂肪酸エステルの中でも、カプロン酸メチルエステル、カプリン酸メチルエステル、ラウリン酸メチルエステルは、臭気が少ないため好ましい。特に、ラウリン酸メチルエステルは、印刷インキ用ドライヤーの粘度低下と臭気の低減との両立を図ることができるため好ましい。
Examples of the fatty acid ester (C1) include caproic acid methyl ester, enanthic acid methyl ester, caprylic acid methyl ester, pelargonic acid methyl ester, capric acid methyl ester, lauric acid methyl ester, caproic acid ethyl ester, and enanthic acid ethyl ester. , Caprylic acid ethyl ester, pelargonic acid ethyl ester, capric acid ethyl ester, lauric acid ethyl ester, caproic acid propyl ester, enanthic acid propyl ester, caprylic acid propyl ester, pelargonic acid propyl ester, capric acid propyl ester, lauric acid propyl ester Etc. These fatty acid esters can be used alone or in combination of two or more. Among these fatty acid esters, caproic acid methyl ester, capric acid methyl ester, and lauric acid methyl ester are preferred because of their low odor. In particular, lauric acid methyl ester is preferable because it can achieve both a reduction in viscosity and a reduction in odor in a printing ink dryer.
また、より低粘度でハンドリング性に優れたドライヤーとするために、前記脂肪酸マンガン塩（Ａ）、アミノアルコール（Ｂ）の合計量と、前記希釈剤（C）との質量基準での配合比［（Ａ）＋（Ｂ）］／（C）は、１０／９０～９５／５の範囲であることが好ましく、４０／６０～８０／２０の範囲であることがより好ましく、２０／８０～９０／１０の範囲であることがさらに好ましい。
Further, in order to obtain a dryer having lower viscosity and excellent handling properties, the mixing ratio of the total amount of the fatty acid manganese salt (A) and amino alcohol (B) and the diluent (C) on a mass basis [ (A) + (B)] / (C) is preferably in the range of 10/90 to 95/5, more preferably in the range of 40/60 to 80/20, and 20/80 to 90. More preferably, the range is / 10.
本発明の塗料は、本発明の塗料用ドライヤーと酸化重合型不飽和樹脂を含有することを特徴とする。
The paint of the present invention is characterized by containing the paint dryer of the present invention and an oxidative polymerization type unsaturated resin.
前記酸化重合型不飽和樹脂としては、例えば、酸化重合硬化型アルキッド樹脂、酸化重合硬化型ウレタン樹脂、酸化重合硬化型変性エポキシ樹脂等が挙げられる。
Examples of the oxidative polymerization type unsaturated resin include an oxidative polymerization curable alkyd resin, an oxidative polymerization curable urethane resin, and an oxidative polymerization curable modified epoxy resin.
上記酸化重合硬化型アルキッド樹脂としては、多塩基酸成分、多価アルコール成分及び油脂肪酸を主たる原料成分とするエステル系樹脂が挙げられる、
Examples of the oxidative polymerization curable alkyd resin include ester resins mainly composed of a polybasic acid component, a polyhydric alcohol component, and an oil fatty acid.
上記多塩基酸成分としては、例えば、無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、コハク酸、フマル酸、アジピン酸、セバシン酸、無水マレイン酸等の二塩基酸；及びこれらの酸の低級アルキルエステル化物が主として用いられる。更に必要に応じて、無水トリメリット酸、メチルシクロヘキセントリカルボン酸、無水ピロメリット酸等の３価以上の多塩基酸；スルホフタル酸、スルホイソフタル酸及びこれらのアンモニウム塩、ナトリウム塩や低級アルキルエステル化物等を使用することができる。また、酸成分として、安息香酸、クロトン酸、ｐ－ｔ－ブチル安息香酸等の一塩基酸を分子量調整等の目的で併用することができる。
Examples of the polybasic acid component 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 esterified products of these acids are mainly used. Furthermore, if necessary, tribasic or higher polybasic acids such as trimellitic anhydride, methylcyclohexenic carboxylic acid, pyromellitic anhydride; sulfophthalic acid, sulfoisophthalic acid and ammonium salts thereof, sodium salts, lower alkyl esterified products, etc. Can be used. As the acid component, monobasic acids such as benzoic acid, crotonic acid, and pt-butylbenzoic acid can be used in combination for the purpose of adjusting the molecular weight.
前記多価アルコール成分としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、３－メチルペンタンジオール、１，４－ヘキサンジオール、１，６－ヘキサンジオール等の二価アルコールが挙げられる。更に必要に応じて、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール等の３価以上の多価アルコール；ポリオキシエチレン基を有する多価アルコール等を併用することができる。これらの多価アルコールは単独で、又は２種以上を混合して使用することができる。また、前記酸成分、アルコール成分の一部をジメチロールプロピオン酸、オキシピバリン酸、パラオキシ安息香酸等；これらの酸の低級アルキルエステル；ε－カプロラクトン等のラクトン類等のオキシ酸成分に置き換えることもできる。
Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and the like. A dihydric alcohol is mentioned. If necessary, trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol; polyhydric alcohols having a polyoxyethylene group, and the like can be used in combination. These polyhydric alcohols can be used alone or in admixture of two or more. In addition, a part of the acid component and alcohol component may be replaced with dimethylolpropionic acid, oxypivalic acid, paraoxybenzoic acid, etc .; lower alkyl esters of these acids; oxyacid components such as lactones such as ε-caprolactone. it can.
前記油脂肪酸としては、例えば、ヤシ油脂肪酸、大豆油脂肪酸、アマニ油脂肪酸、サフラワー油脂肪酸、トール油脂肪酸、脱水ヒマシ油脂肪酸、キリ油脂肪酸等を挙げることができる。アルキッド樹脂の油長は５～８０質量％、特に２０～７０質量％の範囲内であることが、得られる塗膜の硬化性、強靭性、肉持ち感等の面から好適である。
Examples of the oil fatty acid include coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, and kiri oil fatty acid. The oil length of the alkyd resin is preferably in the range of 5 to 80% by mass, particularly 20 to 70% by mass, from the viewpoints of the curability, toughness, feeling of feeling of the coating film, and the like.
また、アルコール成分の一部としてエポキシ化合物を使用してエポキシ化合物を部分エステル化したエポキシ変性アルキッド樹脂；アルキッド樹脂に無水マレイン酸を導入してなるマレイン化アルキッド樹脂；マレイン化アルキッド樹脂と水酸基含有アルキッド樹脂とを付加してなるグラフト化アルキッド樹脂；アルキッド樹脂にスチレン、（メタ）アクリル酸エステル等のビニルモノマーをグラフト重合させたビニル変性アルキッド樹脂等も使用することができる。
In addition, an epoxy-modified alkyd resin obtained by partially esterifying an epoxy compound using an epoxy compound as part of an alcohol component; a maleated alkyd resin obtained by introducing maleic anhydride into an alkyd resin; a maleated alkyd resin and a hydroxyl group-containing alkyd Grafted alkyd resins obtained by adding a resin; vinyl-modified alkyd resins obtained by graft-polymerizing vinyl monomers such as styrene and (meth) acrylic acid ester to alkyd resins can also be used.
更に、資源のリサイクルのために回収されたポリエチレンテレフタレート（例えば、ＰＥＴボトル）、産業廃棄物ポリエチレンテレフタレート、テレフタル酸を主原料とするポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステル製品（フィルム、繊維、自動車部品、電子部品等）の製造に際して発生する屑等から再生されたテレフタル酸を主原料とするポリエステル樹脂（以下、「再生ＰＥＳ」と略す。）を利用して、上述のアルコール成分と多塩基酸成分との混合物中に、この再生ＰＥＳを溶解させ、解重合するとともに、エステル化反応させることにより得られるアルキッド樹脂や、該アルキッド樹脂を無水マレイン酸と反応させて得られるマレイン化アルキッド樹脂、該アルキッド樹脂とエチレン性不飽和基を有さない酸無水物とを反応させて得られる変性アルキッド樹脂等も使用することができる。
In addition, polyethylene terephthalate (for example, PET bottles) collected for resource recycling, industrial waste polyethylene terephthalate, and polyester products such as polyethylene terephthalate and polybutylene terephthalate that use terephthalic acid as the main raw material (films, fibers, automotive parts) The above-mentioned alcohol component and polybasic acid component using a polyester resin (hereinafter, abbreviated as “regenerated PES”) mainly made of terephthalic acid regenerated from scraps, etc. generated during the manufacture of electronic components, etc. In the mixture, the regenerated PES is dissolved, depolymerized, and esterified to obtain an alkyd resin, a maleated alkyd resin obtained by reacting the alkyd resin with maleic anhydride, the alkyd Resin and ethylenically unsaturated groups Etc. are modified alkyd resins obtained by reacting an acid anhydride having no may also be used.
以上詳述した酸化重合硬化型アルキッド樹脂は、硬化性及び塗膜物性が良好となる点からガードナー粘度（２５℃）が１５～６０ストークスのものが好ましい。
The oxidative polymerization curable alkyd resin described in detail above preferably has a Gardner viscosity (25 ° C.) of 15 to 60 Stokes from the viewpoint of good curability and coating film properties.
前記ウレタン樹脂としては、特に限定されるものではないが、例えば、ポリオール、油脂と多価アルコールをウムエステル化したポリオール、及びポリイソシアネートとを反応させて得られるウレタン樹脂を使用することができる。
The urethane resin is not particularly limited, and for example, a urethane, a urethane resin obtained by reacting a polyol, an oil and fat with a polyhydric alcohol, and a polyisocyanate can be used.
上記ポリイソシアネートとしては、例えば、１，４－テトラメチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，８－ジイソシアネートメチルカプロエート等の脂肪族イソシアネート類；３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート、メチルシクロヘキシル－２，４－ジイソシアネート等の脂環族ジシソシアネート類；トルイレンジイソシアネート、ジフェニルメタンジイソシアネート、１，５－ナフテンジイソシアネート、ジフェニルメチルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソサネート、４，４－ジベンジルジイソシアネート、１，３－フェニレンジイソシアネート等の芳香族ジイソシアネート類；塩素化ジイソシアネート類、臭素化ジイソシアネート類等が挙げられ、これらを単独で、又は２種以上の混合物として用いることができる。
Examples of the polyisocyanate include aliphatic isocyanates such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,8-diisocyanate methyl caproate. Alicyclic disissocyanates such as 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate and methylcyclohexyl-2,4-diisocyanate; toluylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthene diisocyanate, diphenylmethyl Aromatic dii such as methane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4-dibenzyl diisocyanate, 1,3-phenylene diisocyanate Cyanates; chlorinated diisocyanates include brominated diisocyanates etc., can be used as these alone, or two or more thereof.
前記ポリオールとしては、通常ウレタン樹脂の製造に使用される種々のポリオール、例えば、ジエチレングリコール、ブタンジオール、ヘキサンジオール、ネオペンチルグリコール、ビスフェノールＡ、シクロヘキサンジメタノール、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ポリエチレングリコール、ポリプロピレングリコール、ポリエステルポリオール、ポリカプロラクトン、ポリテトラメチレンエーテルグリコール、ポリチオエーテルポリオール、ポリアセタールポリオール、ポリブタジエンポリオール、フランジメタノール等が挙げられ、これらを単独で、又は２種以上の混合物として用いることができる。
Examples of the polyol include various polyols commonly used in the production of urethane resins, such as diethylene glycol, butanediol, hexanediol, neopentyl glycol, bisphenol A, cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, and polyethylene glycol. , Polypropylene glycol, polyester polyol, polycaprolactone, polytetramethylene ether glycol, polythioether polyol, polyacetal polyol, polybutadiene polyol, flange methanol, and the like, and these can be used alone or as a mixture of two or more.
前記油脂と多価アルコールをエステル化したポリオールとしては、例えば、ヨウ素価が７～２００の油脂とトリメチロールプロパン、ペンタエリスリトール等の多価アルコールとをエステル化したものが挙げられ、例えば三井化学株式会社製「ＸＰ１０７６Ｅ」、「ＸＰ１０７７Ｅ」、「ＸＰ１５８０Ｅ」、「ＦＢ２０－５０ＸＢ」等の市販品も使用できる。
Examples of the polyol obtained by esterifying the fat and the polyhydric alcohol include those obtained by esterifying a fat and oil having an iodine value of 7 to 200 and a polyhydric alcohol such as trimethylolpropane and pentaerythritol. For example, Mitsui Chemicals, Inc. Commercially available products such as “XP1076E”, “XP1077E”, “XP1580E”, “FB20-50XB” manufactured by the company can also be used.
前記酸化重合硬化型変性エポキシ樹脂としては、例えば、エポキシ樹脂を不飽和脂肪酸成分と酸基含有アクリル成分を原料として、これらを反応させることにより得られる樹脂が挙げられる。樹脂原料配合が、原料の合計重量１００重量％に対し、エポキシ樹脂３０～５０重量％、不飽和脂肪酸成分２５～４０重量％及び酸基含有アクリル成分１０～４５重量％であると、硬化塗膜の物性に優れる点から好ましい。
Examples of the oxidative polymerization curable modified epoxy resin include resins obtained by reacting an epoxy resin with an unsaturated fatty acid component and an acid group-containing acrylic component as raw materials. When the resin raw material composition is 30 to 50% by weight of the epoxy resin, 25 to 40% by weight of the unsaturated fatty acid component, and 10 to 45% by weight of the acid group-containing acrylic component with respect to the total weight of the raw material of 100% by weight, It is preferable from the viewpoint of excellent physical properties.
また、酸化重合硬化型変性エポキシ樹脂のヨウ素価は、良好な硬化性が得られる点から、３０～１００が好ましく、特に３５～９０が好ましい。
The iodine value of the oxidative polymerization curable modified epoxy resin is preferably from 30 to 100, particularly preferably from 35 to 90, from the viewpoint of obtaining good curability.
原料として使用できるエポキシ樹脂としては、特に限定されるものではないが、変性が容易で且つ得られる硬化塗膜の性能に優れる点から、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂が好ましい。これらは、単独で用いてもよく又は２種以上を併用してもよい。
The epoxy resin that can be used as a raw material is not particularly limited, but is bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol from the viewpoint of easy modification and excellent performance of the resulting cured coating film. Bisphenol type epoxy resins such as F type epoxy resins are preferred. These may be used alone or in combination of two or more.
不飽和脂肪酸成分としては、天然または合成系の不飽和脂肪酸がいずれも使用でき、例えば、桐油、アマニ油、ヒマシ油、脱水ヒマシ油、サフラワー油、トール油、大豆油、ヤシ油から得られる不飽和脂肪酸等が使用できる。
As the unsaturated fatty acid component, any natural or synthetic unsaturated fatty acid can be used. For example, it can be obtained from tung oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, tall oil, soybean oil, coconut oil. Unsaturated fatty acids can be used.
また、酸基含有アクリル成分としては、例えば、（メタ）アクリル酸と、スチレンや（メタ）アクリル酸エステル類等の酸基を含有しないアクリルモノマーとの混合物等を用いることができる。後者の酸基を含有しないアクリルモノマーとしては、優れた塗膜硬度が得られる点から、スチレンが好ましい。
As the acid group-containing acrylic component, for example, a mixture of (meth) acrylic acid and an acrylic monomer containing no acid group such as styrene or (meth) acrylic acid ester can be used. As the latter acrylic monomer containing no acid group, styrene is preferable because excellent coating film hardness can be obtained.
酸化重合硬化型変性エポキシ樹脂は、以下のようにして得ることができる。まずエポキシ樹脂と不飽和脂肪酸成分とからエポキシエステル樹脂を製造する。例えば、エポキシ樹脂と不飽和脂肪酸成分とを、トルエン、キシレン等の適当な溶媒中で、縮合触媒を用い、必要に応じて、窒素ガス等の不活性ガス雰囲気下において、１５０～２５０℃で、所望の酸価となるまで反応させることによりエポキシエステル樹脂を得る。縮合触媒としては、例えば、ジブチル錫オキサイド、テトラｎ－ブチルアンモニウムブロマイド等が使用できる。
The oxidation polymerization curable modified epoxy resin can be obtained as follows. First, an epoxy ester resin is produced from an epoxy resin and an unsaturated fatty acid component. For example, an epoxy resin and an unsaturated fatty acid component are used in a suitable solvent such as toluene and xylene, using a condensation catalyst, and if necessary, at 150 to 250 ° C. in an inert gas atmosphere such as nitrogen gas, An epoxy ester resin is obtained by reacting until a desired acid value is obtained. As the condensation catalyst, for example, dibutyltin oxide, tetra n-butylammonium bromide and the like can be used.
次に、得られたエポキシエステル樹脂を、前記酸基含有アクリル成分と反応させて、酸化重合硬化型変性エポキシ樹脂を得る。エポキシエステル樹脂と酸基含有アクリル成分との反応は、重合開始剤の存在下、窒素ガス等の不活性ガス雰囲気下において、８０～１５０℃の温度範囲で行うことができる。重合開始剤としては、過酸化物、アゾ化合物等の種々のものが使用でき、例えば、化薬アクゾ製「カヤブチルＢ（アルキルパーエステル系）」等を、使用するモノマー合計量に対して０．１～２０質量部％の割合で使用できる。
Next, the obtained epoxy ester resin is reacted with the acid group-containing acrylic component to obtain an oxidative polymerization curable modified epoxy resin. The reaction between the epoxy ester resin and the acid group-containing acrylic component can be carried out in the temperature range of 80 to 150 ° C. in the presence of a polymerization initiator and in an inert gas atmosphere such as nitrogen gas. As the polymerization initiator, various substances such as peroxides and azo compounds can be used. For example, “Kayabutyl B (alkyl perester type)” manufactured by Kayaku Akzo is used in an amount of 0. It can be used at a ratio of 1 to 20 parts by mass.
以上詳述した酸化重合型不飽和樹脂のなかでも特に本発明では安価で、入手が容易であり、また、塗料の乾燥性(実用性)に優れる点から酸化重合硬化型アルキッド樹脂が好ましい。
Among the oxidative polymerization type unsaturated resins described in detail above, an oxidative polymerization curable alkyd resin is preferable because it is inexpensive and easily available in the present invention and is excellent in the drying property (practicality) of the paint.
本発明の塗料は、更に、有機溶剤を含有することが好ましい。ここで使用し得る有機溶剤としては、例えば、前記炭化水素系溶剤、アルコール系溶剤、ケトン系溶剤、エーテル系溶剤が挙げられる。
The paint of the present invention preferably further contains an organic solvent. Examples of the organic solvent that can be used here include the hydrocarbon solvents, alcohol solvents, ketone solvents, and ether solvents.
本発明の塗料は、上記した各成分に加え、更に必要に応じて、着色剤、希釈剤、顔料分散剤、表面調整剤、紫外線吸収剤、消泡剤、増粘剤、沈降防止剤等の各種塗料用添加剤を含有させることができる。
In addition to the above-described components, the paint of the present invention may further include a colorant, a diluent, a pigment dispersant, a surface conditioner, an ultraviolet absorber, an antifoaming agent, a thickener, an antisettling agent, etc. Various paint additives can be contained.
前記着色剤としては、カーボンブラック、フタロシアニン顔料、弁柄、アゾ顔料、キナクリドン顔料等が挙げられる。さらに、希釈剤としては、例えば、トルエン、キシレン、ヘプタン、ヘキサン、ミネラルスピリット等の炭化水素系溶媒；メタノール、エタノール、プロパノール、シクロヘキサノール等のアルコール系溶媒；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；プロピルエーテル、メチルセロソルブ、セロソルブ、ブチルセロソルブ、メチルカルビトール等のエーテル系溶媒；カプロン酸メチルエステル、カプリン酸メチルエステル、ラウリン酸メチルエステル等の脂肪酸エステル；大豆油、亜麻仁油、菜種油、サフラワー油等の植物油脂などが挙げられる。
Examples of the colorant include carbon black, phthalocyanine pigment, dial, azo pigment, quinacridone pigment and the like. Furthermore, examples of the diluent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirit; alcohol solvents such as methanol, ethanol, propanol, and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents: ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol; fatty acid esters such as caproic acid methyl ester, capric acid methyl ester, lauric acid methyl ester; soybean oil, linseed oil, rapeseed oil, sa And vegetable oils such as flower oil.
前記塗料に対する本発明のドライヤーの配合量は、特に限定されないが、酸化重合型不飽和樹脂１００質量部に対する、ドライヤー中の金属成分の合計質量が０．００５～１．５質量部の範囲となることが好ましい。
The blending amount of the dryer of the present invention with respect to the paint is not particularly limited, but the total mass of the metal components in the dryer is in the range of 0.005 to 1.5 parts by mass with respect to 100 parts by mass of the oxidation polymerization type unsaturated resin. It is preferable.
以上詳述した本発明の塗料は、常法により被塗物に塗布、乾燥・硬化させることにより塗膜を得ることができる。ここで、本発明の塗料を塗工することが可能な基材（被塗物）としては、例えば、鉄鋼等が挙げられる。また、塗布後の乾燥条件（硬化条件）としては常乾が挙げあれる。更に、本発明の塗料は塗膜を厚くしても優れた硬化性を発現させることができることから、厚塗り用塗料としてとりわけ有用であり、具体的には、硬化塗膜の膜厚を１～５００μｍの範囲とすることができる。従って、本発明の塗料は建築用塗料として有用である。
The coating material of the present invention described in detail above can be applied to an object to be coated, dried and cured by a conventional method to obtain a coating film. Here, as a base material (object to be coated) on which the paint of the present invention can be applied, for example, steel and the like can be mentioned. Further, as drying conditions (curing conditions) after coating, there is a normal drying. Furthermore, since the coating material of the present invention can exhibit excellent curability even when the coating film is thick, it is particularly useful as a coating material for thick coatings. The range may be 500 μm. Therefore, the paint of the present invention is useful as an architectural paint.
実施例１～５（塗料用ドライヤーの調製）
第１表に示す割合（質量部）で脂肪酸マンガン塩（Ａ）、アミノアルコール（Ｂ）及び希釈剤（Ｃ）を配合し、塗料用ドライヤー１～５を得た。 Examples 1 to 5 (Preparation of paint dryer)
Fatty acid manganese salt (A), amino alcohol (B) and diluent (C) were blended in the proportions (parts by mass) shown in Table 1 to obtain coating dryers 1-5.
第１表に示す割合（質量部）で脂肪酸マンガン塩（Ａ）、アミノアルコール（Ｂ）及び希釈剤（Ｃ）を配合し、塗料用ドライヤー１～５を得た。 Examples 1 to 5 (Preparation of paint dryer)
Fatty acid manganese salt (A), amino alcohol (B) and diluent (C) were blended in the proportions (parts by mass) shown in Table 1 to obtain coating dryers 1-5.
比較例１（比較対照用塗料用ドライヤーの調製）
ナフテン酸コバルト１２部及びオクチル酸ジルコニウム３８部をミネラルスピリット５０部に溶解させて、比較対照用塗料用ドライヤー１´を得た。このドライヤーは、コバルト金属石鹸を含む従来技術の金属石鹸の平均水準の性能を示す目的で作成したものである。 Comparative Example 1 (Preparation of a comparative paint dryer)
12 parts of cobalt naphthenate and 38 parts of zirconium octylate were dissolved in 50 parts of mineral spirit to obtain a comparative coating dryer 1 '. This dryer was made to demonstrate the average level of performance of prior art metal soaps including cobalt metal soaps.
ナフテン酸コバルト１２部及びオクチル酸ジルコニウム３８部をミネラルスピリット５０部に溶解させて、比較対照用塗料用ドライヤー１´を得た。このドライヤーは、コバルト金属石鹸を含む従来技術の金属石鹸の平均水準の性能を示す目的で作成したものである。 Comparative Example 1 (Preparation of a comparative paint dryer)
12 parts of cobalt naphthenate and 38 parts of zirconium octylate were dissolved in 50 parts of mineral spirit to obtain a comparative coating dryer 1 '. This dryer was made to demonstrate the average level of performance of prior art metal soaps including cobalt metal soaps.
比較例２（同上）
ナフテン酸マンガン５６部及び２，２’－ビピリジル１８部をミネラルスピリット２６部に溶解させて、比較対照用塗料用ドライヤー２´を得た。 Comparative Example 2 (same as above)
56 parts of manganese naphthenate and 18 parts of 2,2′-bipyridyl were dissolved in 26 parts of mineral spirit to obtain a comparative paint dryer 2 ′.
ナフテン酸マンガン５６部及び２，２’－ビピリジル１８部をミネラルスピリット２６部に溶解させて、比較対照用塗料用ドライヤー２´を得た。 Comparative Example 2 (same as above)
56 parts of manganese naphthenate and 18 parts of 2,2′-bipyridyl were dissolved in 26 parts of mineral spirit to obtain a comparative paint dryer 2 ′.
実施例６（塗料の調製）
チタンホワイト顔料（テイカ株式会社製「ＪＲ－７０１」）１９６０ｇ、塗料用樹脂「ベッコゾールＰ－４７０－７０」（ＤＩＣ株式会社製の、分子内に酸化重合型不飽和脂肪酸基を有するアルキッド系樹脂）３３４０ｇ、ミネラルスピリット２８０ｇ、皮張防止剤（メチルエチルケトオキシム）２０ｇを３本ロールで混練して得た混合物４０ｇに、塗料用ドライヤー１を樹脂不揮発分１００部に対するマンガン金属分の割合が０．０６％になるように添加して、本発明の塗料１を調製した。塗料１の乾燥試験、得られる塗膜の光沢度及び重ね塗りの試験を下記の方法で行った。評価結果を第２表に示す。 Example 6 (Preparation of paint)
1960 g of titanium white pigment (“JR-701” manufactured by Teika Co., Ltd.), resin for paint “Beccosol P-470-70” (manufactured by DIC Co., Ltd., alkyd resin having an oxidation-polymerized unsaturated fatty acid group in the molecule) 3340 g, 280 g of mineral spirit, and 20 g of anti-skinning agent (methyl ethyl ketoxime) in 40 g of the mixture obtained by kneading with three rolls, the ratio of manganese metal content to 0.06% of the coating dryer 1 for 100 parts of resin non-volatile content It added so that the coating material 1 of this invention might be prepared. The drying test of the paint 1, the glossiness of the coating film obtained, and the test of overcoating were conducted by the following methods. The evaluation results are shown in Table 2.
チタンホワイト顔料（テイカ株式会社製「ＪＲ－７０１」）１９６０ｇ、塗料用樹脂「ベッコゾールＰ－４７０－７０」（ＤＩＣ株式会社製の、分子内に酸化重合型不飽和脂肪酸基を有するアルキッド系樹脂）３３４０ｇ、ミネラルスピリット２８０ｇ、皮張防止剤（メチルエチルケトオキシム）２０ｇを３本ロールで混練して得た混合物４０ｇに、塗料用ドライヤー１を樹脂不揮発分１００部に対するマンガン金属分の割合が０．０６％になるように添加して、本発明の塗料１を調製した。塗料１の乾燥試験、得られる塗膜の光沢度及び重ね塗りの試験を下記の方法で行った。評価結果を第２表に示す。 Example 6 (Preparation of paint)
1960 g of titanium white pigment (“JR-701” manufactured by Teika Co., Ltd.), resin for paint “Beccosol P-470-70” (manufactured by DIC Co., Ltd., alkyd resin having an oxidation-polymerized unsaturated fatty acid group in the molecule) 3340 g, 280 g of mineral spirit, and 20 g of anti-skinning agent (methyl ethyl ketoxime) in 40 g of the mixture obtained by kneading with three rolls, the ratio of manganese metal content to 0.06% of the coating dryer 1 for 100 parts of resin non-volatile content It added so that the coating material 1 of this invention might be prepared. The drying test of the paint 1, the glossiness of the coating film obtained, and the test of overcoating were conducted by the following methods. The evaluation results are shown in Table 2.
＜塗料の乾燥性の試験方法＞
＜乾燥時間の測定方法＞
塗料を、ガラス板上に３ミルのアプリケーターを使用して塗付した後、ドライングタイムレコーダー（太佑機材株式会社製「型式Ｎｏ．４０４」）を用いて試験を行った。測定は、恒温恒湿室（２５℃、５０％ＲＨ）内で行った。なお、塗料の乾燥時間は、ガラス板上に塗料を塗布後、ドライングタイムレコーダーの針により塗料の乾燥が始まると見られるキズが、塗料が完全に乾燥して見られなくなるまでの時間とした（単位：時間）。 <Testing method for drying properties of paint>
<Method for measuring drying time>
The coating material was applied on a glass plate using a 3 mil applicator, and then tested using a drying time recorder (“Model No. 404” manufactured by Dazai Equipment Co., Ltd.). The measurement was performed in a constant temperature and humidity chamber (25 ° C., 50% RH). In addition, the drying time of the coating material was the time until the coating material was completely dried and disappeared after the coating material was applied on the glass plate and the coating material was completely dried by the needle of the drying time recorder ( Unit: hours).
＜乾燥時間の測定方法＞
塗料を、ガラス板上に３ミルのアプリケーターを使用して塗付した後、ドライングタイムレコーダー（太佑機材株式会社製「型式Ｎｏ．４０４」）を用いて試験を行った。測定は、恒温恒湿室（２５℃、５０％ＲＨ）内で行った。なお、塗料の乾燥時間は、ガラス板上に塗料を塗布後、ドライングタイムレコーダーの針により塗料の乾燥が始まると見られるキズが、塗料が完全に乾燥して見られなくなるまでの時間とした（単位：時間）。 <Testing method for drying properties of paint>
<Method for measuring drying time>
The coating material was applied on a glass plate using a 3 mil applicator, and then tested using a drying time recorder (“Model No. 404” manufactured by Dazai Equipment Co., Ltd.). The measurement was performed in a constant temperature and humidity chamber (25 ° C., 50% RH). In addition, the drying time of the coating material was the time until the coating material was completely dried and disappeared after the coating material was applied on the glass plate and the coating material was completely dried by the needle of the drying time recorder ( Unit: hours).
＜塗膜の光沢度の測定方法＞
ガラス板上にアプリケータを用いて乾燥膜厚が１５２μｍの塗膜をひき、温度２５度、湿度５０％で７日間乾燥させた後、ＪＩＳ Ｋ５６００中の６０°、２０°鏡面光沢度試験に準じ、試験を行った。 <Measurement method of glossiness of coating film>
Using an applicator on a glass plate, draw a coating film with a dry film thickness of 152 μm, and after drying for 7 days at a temperature of 25 ° C. and a humidity of 50%, according to the 60 °, 20 ° specular gloss test in JIS K5600 The test was conducted.
ガラス板上にアプリケータを用いて乾燥膜厚が１５２μｍの塗膜をひき、温度２５度、湿度５０％で７日間乾燥させた後、ＪＩＳ Ｋ５６００中の６０°、２０°鏡面光沢度試験に準じ、試験を行った。 <Measurement method of glossiness of coating film>
Using an applicator on a glass plate, draw a coating film with a dry film thickness of 152 μm, and after drying for 7 days at a temperature of 25 ° C. and a humidity of 50%, according to the 60 °, 20 ° specular gloss test in JIS K5600 The test was conducted.
＜重ね塗り試験＞
ガラス板上にアプリケータを用いて１５２μｍの塗膜をひき、温度２５度、湿度５０％で一定時間（４時間後、８時間後、１日後、２日後及び３日後）後に更にアプリケータを用いて１５２μｍの塗膜を塗り重ね、温度２５度、湿度５０％で、塗り重ねて後に７日間乾燥させた後、塗膜表面の状態を目視で観察した。
・判定方法
◎：異常無し
○：塗面に皺が発生するが、塗面に縮みは発生していない。
×：塗面に皺が発生すると共に塗面に塗膜に縮みも発生する。 <Multi-layer coating test>
Using an applicator on a glass plate, draw a 152 μm coating film and use the applicator after a certain time (4 hours, 8 hours, 1 day, 2 days, and 3 days) at a temperature of 25 degrees and a humidity of 50%. The coating film with a thickness of 152 μm was applied again at a temperature of 25 ° C. and a humidity of 50%, and after drying for 7 days, the state of the coating film surface was visually observed.
-Judgment method ◎: No abnormality ○: Wrinkles occur on the paint surface, but no shrinkage occurs on the paint surface.
X: Wrinkles occur on the coated surface and shrinkage occurs on the coated surface.
ガラス板上にアプリケータを用いて１５２μｍの塗膜をひき、温度２５度、湿度５０％で一定時間（４時間後、８時間後、１日後、２日後及び３日後）後に更にアプリケータを用いて１５２μｍの塗膜を塗り重ね、温度２５度、湿度５０％で、塗り重ねて後に７日間乾燥させた後、塗膜表面の状態を目視で観察した。
・判定方法
◎：異常無し
○：塗面に皺が発生するが、塗面に縮みは発生していない。
×：塗面に皺が発生すると共に塗面に塗膜に縮みも発生する。 <Multi-layer coating test>
Using an applicator on a glass plate, draw a 152 μm coating film and use the applicator after a certain time (4 hours, 8 hours, 1 day, 2 days, and 3 days) at a temperature of 25 degrees and a humidity of 50%. The coating film with a thickness of 152 μm was applied again at a temperature of 25 ° C. and a humidity of 50%, and after drying for 7 days, the state of the coating film surface was visually observed.
-Judgment method ◎: No abnormality ○: Wrinkles occur on the paint surface, but no shrinkage occurs on the paint surface.
X: Wrinkles occur on the coated surface and shrinkage occurs on the coated surface.
実施例７～１０（同上）
第２表に示す塗料用ドライヤーを用いた以外は実施例６と同様にして塗料２～５を得た。実施例６と同様に塗料の評価を行い、その結果を第２表に示す。 Examples 7 to 10 (same as above)
Paints 2 to 5 were obtained in the same manner as in Example 6 except that the paint dryer shown in Table 2 was used. The paint was evaluated in the same manner as in Example 6, and the results are shown in Table 2.
第２表に示す塗料用ドライヤーを用いた以外は実施例６と同様にして塗料２～５を得た。実施例６と同様に塗料の評価を行い、その結果を第２表に示す。 Examples 7 to 10 (same as above)
Paints 2 to 5 were obtained in the same manner as in Example 6 except that the paint dryer shown in Table 2 was used. The paint was evaluated in the same manner as in Example 6, and the results are shown in Table 2.
比較例３
塗料用ドライヤー１を用いるかわりに比較対象用塗料用ドライヤー１´を、樹脂不揮発分１００部に対するコバルト金属分の割合が０．０６％になるように添加した以外は実施例６と同様にして比較対照用塗料１´を得た。実施例６と同様に乾燥時間を測定し、その結果を第３表に示す。 Comparative Example 3
A comparison was made in the same manner as in Example 6 except that the paint dryer 1 'for comparison was added so that the ratio of the cobalt metal content to 100 parts of the resin non-volatile content was 0.06% instead of using the paint dryer 1 A control paint 1 'was obtained. The drying time was measured in the same manner as in Example 6, and the results are shown in Table 3.
塗料用ドライヤー１を用いるかわりに比較対象用塗料用ドライヤー１´を、樹脂不揮発分１００部に対するコバルト金属分の割合が０．０６％になるように添加した以外は実施例６と同様にして比較対照用塗料１´を得た。実施例６と同様に乾燥時間を測定し、その結果を第３表に示す。 Comparative Example 3
A comparison was made in the same manner as in Example 6 except that the paint dryer 1 'for comparison was added so that the ratio of the cobalt metal content to 100 parts of the resin non-volatile content was 0.06% instead of using the paint dryer 1 A control paint 1 'was obtained. The drying time was measured in the same manner as in Example 6, and the results are shown in Table 3.
比較例４
塗料用ドライヤー１を用いるかわりに比較対象用塗料用ドライヤー２´を、樹脂不揮発分１００部に対するマンガン金属分の割合が０．０６％になるように添加した以外は実施例６と同様にして比較対照用塗料２´を得た。実施例６と同様に乾燥時間を測定し、その結果を第３表に示す。 Comparative Example 4
A comparison was made in the same manner as in Example 6 except that instead of using the paint dryer 1, a comparative paint dryer 2 'was added so that the ratio of manganese metal content to 100 parts of the resin non-volatile content was 0.06%. A control paint 2 'was obtained. The drying time was measured in the same manner as in Example 6, and the results are shown in Table 3.
塗料用ドライヤー１を用いるかわりに比較対象用塗料用ドライヤー２´を、樹脂不揮発分１００部に対するマンガン金属分の割合が０．０６％になるように添加した以外は実施例６と同様にして比較対照用塗料２´を得た。実施例６と同様に乾燥時間を測定し、その結果を第３表に示す。 Comparative Example 4
A comparison was made in the same manner as in Example 6 except that instead of using the paint dryer 1, a comparative paint dryer 2 'was added so that the ratio of manganese metal content to 100 parts of the resin non-volatile content was 0.06%. A control paint 2 'was obtained. The drying time was measured in the same manner as in Example 6, and the results are shown in Table 3.
Claims (4)
- 脂肪酸マンガン塩（Ａ）及び下記一般式（１）で表されるアミノアルコール（Ｂ）を含有することを特徴とする塗料用ドライヤー。
- 前記アミノアルコール（Ｂ）が、２－［（２－ジメチルアミノエチル）メチルアミノ］エタノール、２－（２－アミノエチル）アミノエタノール、１－（２－アミノエチル）アミノ－２－プロパノール、２－（３－アミノプロピルアミノ）エタノール及び２-（２－ジメチルアミノエトキシ）エタノールからなる群から選ばれる少なくとも１種である請求項１記載の塗料用ドライヤー。 The amino alcohol (B) is 2-[(2-dimethylaminoethyl) methylamino] ethanol, 2- (2-aminoethyl) aminoethanol, 1- (2-aminoethyl) amino-2-propanol, 2- The paint dryer according to claim 1, which is at least one selected from the group consisting of (3-aminopropylamino) ethanol and 2- (2-dimethylaminoethoxy) ethanol.
- 前記脂肪酸マンガン塩（Ａ）の脂肪酸が、オクチル酸、ネオデカン酸、イソノナン酸及びナフテン酸からなる群から選ばれる少なくとも１種である脂肪酸である請求項１又は２記載の塗料用ドライヤー。 The paint dryer according to claim 1 or 2, wherein the fatty acid manganese salt (A) is at least one fatty acid selected from the group consisting of octylic acid, neodecanoic acid, isononanoic acid and naphthenic acid.
- 請求項１～３のいずれか１項記載の塗料用ドライヤーを含有することを特徴とする塗料。 A paint comprising the paint dryer according to any one of claims 1 to 3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011266763 | 2011-12-06 | ||
| JP2011-266763 | 2011-12-06 |
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| WO2013084824A1 true WO2013084824A1 (en) | 2013-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2012/081117 WO2013084824A1 (en) | 2011-12-06 | 2012-11-30 | Drier for paint and paint using same |
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| JP (1) | JPWO2013084824A1 (en) |
| TW (1) | TW201331279A (en) |
| WO (1) | WO2013084824A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9896603B2 (en) | 2013-07-08 | 2018-02-20 | Dic Corporation | Curing accelerator for oxidative polymerization-type unsaturated resin, printing ink, and coating material |
| US10738203B2 (en) | 2015-09-08 | 2020-08-11 | Dic Corporation | Curing accelerator for oxidatively polymerizable unsaturated resin, printing ink and coating material |
| JP7183461B1 (en) | 2022-03-15 | 2022-12-05 | 中国塗料株式会社 | Modified (meth)acrylic resin coating composition, laminated coating film, substrate with coated film, and method for producing the same |
| WO2024057813A1 (en) * | 2022-09-13 | 2024-03-21 | Dic株式会社 | Curing promoter for oxidative-polymerization-type unsaturated resin, and curable resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049102A (en) * | 1999-06-03 | 2001-02-20 | Dainippon Ink & Chem Inc | Curing promoter and resin composition |
| JP2003201424A (en) * | 2001-10-26 | 2003-07-18 | Dainippon Ink & Chem Inc | Dryer for printing ink and printing ink containing the dryer |
| JP2007119619A (en) * | 2005-10-28 | 2007-05-17 | Dainippon Ink & Chem Inc | Hardening promoter for aqueous coating |
| WO2011158694A1 (en) * | 2010-06-14 | 2011-12-22 | Dic株式会社 | Printing ink drying agent and printing ink using same |
-
2012
- 2012-11-30 WO PCT/JP2012/081117 patent/WO2013084824A1/en active Application Filing
- 2012-11-30 JP JP2013519887A patent/JPWO2013084824A1/en active Pending
- 2012-12-04 TW TW101145378A patent/TW201331279A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049102A (en) * | 1999-06-03 | 2001-02-20 | Dainippon Ink & Chem Inc | Curing promoter and resin composition |
| JP2003201424A (en) * | 2001-10-26 | 2003-07-18 | Dainippon Ink & Chem Inc | Dryer for printing ink and printing ink containing the dryer |
| JP2007119619A (en) * | 2005-10-28 | 2007-05-17 | Dainippon Ink & Chem Inc | Hardening promoter for aqueous coating |
| WO2011158694A1 (en) * | 2010-06-14 | 2011-12-22 | Dic株式会社 | Printing ink drying agent and printing ink using same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9896603B2 (en) | 2013-07-08 | 2018-02-20 | Dic Corporation | Curing accelerator for oxidative polymerization-type unsaturated resin, printing ink, and coating material |
| US10738203B2 (en) | 2015-09-08 | 2020-08-11 | Dic Corporation | Curing accelerator for oxidatively polymerizable unsaturated resin, printing ink and coating material |
| JP7183461B1 (en) | 2022-03-15 | 2022-12-05 | 中国塗料株式会社 | Modified (meth)acrylic resin coating composition, laminated coating film, substrate with coated film, and method for producing the same |
| JP2023135579A (en) * | 2022-03-15 | 2023-09-28 | 中国塗料株式会社 | Modified (meth)acrylic resin coating composition, laminated coating film, substrate with coating film, and method for producing the same |
| WO2024057813A1 (en) * | 2022-09-13 | 2024-03-21 | Dic株式会社 | Curing promoter for oxidative-polymerization-type unsaturated resin, and curable resin composition |
| JP7574973B2 (en) | 2022-09-13 | 2024-10-29 | Dic株式会社 | Curing accelerator for oxidatively polymerized unsaturated resins and curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201331279A (en) | 2013-08-01 |
| JPWO2013084824A1 (en) | 2015-04-27 |
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