JP5688523B1 - Two-component paint composition - Google Patents
Two-component paint composition Download PDFInfo
- Publication number
- JP5688523B1 JP5688523B1 JP2014119360A JP2014119360A JP5688523B1 JP 5688523 B1 JP5688523 B1 JP 5688523B1 JP 2014119360 A JP2014119360 A JP 2014119360A JP 2014119360 A JP2014119360 A JP 2014119360A JP 5688523 B1 JP5688523 B1 JP 5688523B1
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- Prior art keywords
- group
- coating composition
- coating film
- copolymer
- fatty acid
- Prior art date
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- 239000003973 paint Substances 0.000 title description 11
- 239000000203 mixture Substances 0.000 title description 10
- 238000000576 coating method Methods 0.000 claims abstract description 92
- 239000011248 coating agent Substances 0.000 claims abstract description 88
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 62
- 239000008199 coating composition Substances 0.000 claims abstract description 59
- 229920000180 alkyd Polymers 0.000 claims abstract description 55
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 50
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 46
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 38
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 36
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 125000000524 functional group Chemical group 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 9
- -1 trimethoxysilyl group Chemical group 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- 239000011630 iodine Substances 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 34
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- 230000000052 comparative effect Effects 0.000 description 18
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- 125000003545 alkoxy group Chemical group 0.000 description 6
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- 239000003513 alkali Substances 0.000 description 5
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- 230000018044 dehydration Effects 0.000 description 5
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- 229910052710 silicon Inorganic materials 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 235000008753 Papaver somniferum Nutrition 0.000 description 3
- 240000001090 Papaver somniferum Species 0.000 description 3
- 229920000263 Rubber seed oil Polymers 0.000 description 3
- 235000019485 Safflower oil Nutrition 0.000 description 3
- 235000019486 Sunflower oil Nutrition 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 description 3
- 240000006365 Vitis vinifera Species 0.000 description 3
- 235000014787 Vitis vinifera Nutrition 0.000 description 3
- 235000019498 Walnut oil Nutrition 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 239000002285 corn oil Substances 0.000 description 3
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- 235000012343 cottonseed oil Nutrition 0.000 description 3
- 239000002385 cottonseed oil Substances 0.000 description 3
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 3
- 235000021323 fish oil Nutrition 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 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
- 239000010460 hemp oil Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical group O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 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
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
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- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- IKRMQEUTISXXQP-UHFFFAOYSA-N tetrasulfane Chemical compound SSSS IKRMQEUTISXXQP-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
【課題】塗装作業性が良好であり、形成される塗膜が光沢を帯びて肉持ち感がある上に、予め錆止め塗料組成物を塗装しなくても防錆性の高い塗膜を形成することが可能な二液混合型塗料組成物を提供すること。【解決手段】金属基材の表面を被覆する塗膜を形成するために用いられる、主剤(I)及び強化剤(II)からなる二液混合型塗料組成物であって、前記主剤(I)は、酸化重合可能な不飽和脂肪酸(a−1)及び酸化重合性基を有するアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、水酸基及びアルコキシシリル基の少なくとも一方を有するシリコーン(a−4)と、の共重合体(A)を含み、前記強化剤(II)は、ポリイソシアネート(B−1)と、同一分子内に異なる2種の官能基を有するシランカップリング剤(B−2)と、を含む。【選択図】なしAn object of the present invention is to provide a coating film with good coating workability, a glossy coating film and a feeling of fleshiness, and also to form a coating film having high rust prevention properties without applying a rust-preventive coating composition in advance. To provide a two-component coating composition capable of being mixed. A two-component mixed coating composition comprising a main agent (I) and a reinforcing agent (II), which is used for forming a coating film covering the surface of a metal substrate, the main agent (I) Is an oxidatively polymerizable unsaturated fatty acid (a-1) and an alkyd resin (a-2) having an oxidatively polymerizable group, an acrylic copolymer (a-3), a hydroxyl group and an alkoxysilyl group. Including a copolymer (A) of silicone (a-4) having at least one, and the reinforcing agent (II) has two different functional groups in the same molecule as the polyisocyanate (B-1). Having a silane coupling agent (B-2). [Selection figure] None
Description
本発明は、二液混合型塗料組成物に関する。 The present invention relates to a two-component mixed coating composition.
従来、金属基材の表面を被覆するために用いられる塗料組成物が知られている。このような金属基材の表面を被覆する塗膜を形成するための塗料組成物として、アルキッド樹脂をバインダー成分とする塗料組成物が広く用いられている(例えば、特許文献1参照)。アルキッド樹脂をバインダー成分とする塗料組成物は、油性調合ペイントよりも乾燥が早く、形成される塗膜が光沢を帯びている。更に、アルキッド樹脂をバインダー成分とする塗料組成物は、刷毛等を用いての塗装作業性が良好である上に、形成される塗膜に肉持ち感がある。
なお、木質建材の表面を被覆する塗膜を形成するためにも、アルキッド樹脂をバインダー成分とする塗料組成物が用いられる場合もある(例えば、特許文献2参照)。
Conventionally, the coating composition used in order to coat | cover the surface of a metal base material is known. As a coating composition for forming a coating film covering the surface of such a metal substrate, a coating composition containing an alkyd resin as a binder component is widely used (for example, see Patent Document 1). A coating composition containing an alkyd resin as a binder component dries faster than an oil-based blended paint, and the formed coating film is glossy. Furthermore, a coating composition containing an alkyd resin as a binder component has good workability in painting using a brush and the like, and the formed coating film has a feeling of life.
In addition, in order to form the coating film which coat | covers the surface of a wooden building material, the coating composition which uses an alkyd resin as a binder component may be used (for example, refer patent document 2).
一方、アルキッド樹脂をバインダー成分とする塗料組成物は、上記のように油性調合ペイントよりは乾燥が早いが、酸化重合反応により自然硬化して塗膜を形成するため、速乾性(初期乾燥性)が十分高いとは言えず、形成される塗膜がべたつくばあいがある。また、アルキッド樹脂をバインダー成分とする塗料組成物によって形成される塗膜は、耐候性及び塗膜強度が低い。アルキッド樹脂をバインダー成分とする塗料組成物を用いた場合に想定されるこれらの問題を克服するために、アルキッド樹脂をシリコーン等によって変性した上で、塗料組成物に用いる方法が提案されている(例えば、特許文献3参照)。 On the other hand, the coating composition containing an alkyd resin as a binder component dries faster than the oil-based blended paint as described above, but since it spontaneously cures by an oxidative polymerization reaction to form a coating film, quick drying (initial drying) Cannot be said to be sufficiently high, and the formed coating film may be sticky. Moreover, the coating film formed with the coating composition which uses an alkyd resin as a binder component has low weather resistance and coating film strength. In order to overcome these problems assumed when using a coating composition containing an alkyd resin as a binder component, a method of modifying the alkyd resin with silicone or the like and then using it in the coating composition has been proposed ( For example, see Patent Document 3).
ところで、変性アルキッド樹脂をバインダー成分とする塗料組成物をもってしても、十分な防錆性を確保するのは難しい。金属基材の防錆性を向上させるためには、金属基材を、変性アルキッド樹脂をバインダー成分とする塗料組成物で塗装する前に、錆止め塗料組成物を塗装しておく必要がある。 By the way, even if it has a coating composition which uses modified alkyd resin as a binder component, it is difficult to ensure sufficient rust prevention. In order to improve the rust prevention property of the metal substrate, it is necessary to apply the rust-preventing coating composition before coating the metal substrate with a coating composition containing a modified alkyd resin as a binder component.
また、近年、金属基材であるトタン屋根や鋼板屋根の表面を被覆した塗膜の塗り替え用の塗料には、形成される塗膜の酸性雨に対する耐性が求められているが、アルキッド樹脂が酸化重合反応することによって形成される塗膜は、時間の経過とともに塗膜強度が低下し、酸性雨に対する耐性も低下しやすい傾向にある。 In recent years, paints for repainting coatings covering the surface of metallic roofs such as tin roofs and steel sheet roofs have been required to have resistance against acid rain of the formed coatings. The coating film formed by the polymerization reaction has a tendency that the coating film strength decreases with time and the resistance to acid rain tends to decrease.
本発明は、上記課題に鑑みてなされたものであり、塗装作業性が良好であり、形成される塗膜が光沢を帯びて肉持ち感がある上に、予め錆止め塗料組成物を塗装しなくても防錆性の高い塗膜を形成することが可能な二液混合型塗料組成物を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems, has good coating workability, the formed coating film is glossy and has a feeling of fleshiness, and does not previously apply a rust-preventing coating composition. However, an object of the present invention is to provide a two-component mixed coating composition capable of forming a coating film having high antirust properties.
本発明は、金属基材の表面を被覆する塗膜を形成するために用いられる、主剤(I)及び強化剤(II)からなる二液混合型塗料組成物であって、前記主剤(I)は、酸化重合可能な不飽和脂肪酸(a−1)及び酸化重合性基を有するアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、水酸基及びアルコキシシリル基の少なくとも一方を有するシリコーン(a−4)と、の共重合体(A)を含み、前記強化剤(II)は、ポリイソシアネート(B−1)と、同一分子内に異なる2種の官能基を有するシランカップリング剤(B−2)と、を含み、前記共重合体(A)は、固形ヨウ素価が5〜80であり、重量平均分子量が10,000〜150,000である二液混合型塗料組成物に関する。 The present invention is a two-component mixed coating composition comprising a main agent (I) and a reinforcing agent (II), which is used to form a coating film that covers the surface of a metal substrate, the main agent (I) Is an oxidatively polymerizable unsaturated fatty acid (a-1) and an alkyd resin (a-2) having an oxidatively polymerizable group, an acrylic copolymer (a-3), a hydroxyl group and an alkoxysilyl group. Including a copolymer (A) of silicone (a-4) having at least one, and the reinforcing agent (II) has two different functional groups in the same molecule as the polyisocyanate (B-1). The copolymer (A) has a solid iodine value of 5 to 80 and a weight average molecular weight of 10,000 to 150,000. The present invention relates to a mold coating composition.
また、前記シランカップリング剤(B−2)は、異なる2種の官能基の一方の官能基として、トリメトキシシリル基又はトリエトキシシリル基を有することが好ましい。 Moreover, it is preferable that the said silane coupling agent (B-2) has a trimethoxysilyl group or a triethoxysilyl group as one functional group of two different types of functional groups.
また、前記シランカップリング剤(B−2)は、異なる2種の官能基の他方の官能基として、イソシアネート基、イソシアヌレート基又はエポキシ基を有することが好ましい。 Moreover, it is preferable that the said silane coupling agent (B-2) has an isocyanate group, an isocyanurate group, or an epoxy group as the other functional group of two different types of functional groups.
また、前記ポリイソシアネート(B−1)に由来するイソシアネート基と前記共重合体(A)に由来する水酸基の当量比(NCO当量/OH当量)は、0.5〜1.5であることが好ましい。 Moreover, the equivalent ratio (NCO equivalent / OH equivalent) of the isocyanate group derived from the polyisocyanate (B-1) and the hydroxyl group derived from the copolymer (A) is 0.5 to 1.5. preferable.
また、前記主剤(I)及び強化剤(II)の全固形分における前記シランカップリング剤(B−2)の含有量は、0.1〜10質量%であることが好ましい。 Moreover, it is preferable that content of the said silane coupling agent (B-2) in the total solid of the said main ingredient (I) and reinforcement | strengthening agent (II) is 0.1-10 mass%.
本発明によれば、塗装作業性が良好であり、形成される塗膜が光沢を帯びて肉持ち感がある上に、予め錆止め塗料組成物を塗装しなくても防錆性の高い塗膜を形成することが可能な二液混合型塗料組成物を提供することができる。 According to the present invention, the coating workability is good, the coating film to be formed is glossy and has a feeling of fleshiness, and the coating film has high rust prevention properties even without previously applying a rust-preventing coating composition. It is possible to provide a two-component mixed coating composition capable of forming
以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。
本実施形態に係る二液混合型塗料組成物は、金属基材の表面を被覆する塗膜を形成するために用いられる。本実施形態にける金属基材は、特に限定されないが、屋外に設置される構造物に配置される金属基材を挙げることができる。このような金属基材としては、表面に形成される塗膜に、高い強度、耐酸性雨性及び防錆性の求められるトタン屋根や鋼板屋根を好ましく挙げることができる。これらの屋根材は、熱伝導性が高く結露しやすいことから長時間に亘って水が付着する場合があるので、表面に形成される塗膜には特に高い防錆性が求められる。
Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.
The two-component mixed coating composition according to this embodiment is used to form a coating film that covers the surface of a metal substrate. Although the metal base material in this embodiment is not specifically limited, The metal base material arrange | positioned at the structure installed outdoors can be mentioned. As such a metal base material, a tin roof or a steel plate roof, which is required to have high strength, acid rain resistance and rust resistance, can be preferably mentioned in the coating film formed on the surface. Since these roofing materials have high thermal conductivity and are likely to condense, water may adhere for a long time, and therefore, a coating film formed on the surface is required to have particularly high rust prevention.
また、トタン屋根や鋼板屋根は、表面に形成された塗膜を塗り替えることがあるが、塗り替えの際に、本実施形態に係る二液混合型塗料組成物を用いてもよい。この場合、基材の表面に当初から形成されていた塗膜や錆は、除去してから塗膜の塗り替えを行ってもよいし、除去せずに塗膜の塗り替えを行ってもよい。なお、基材の表面の錆は、除去してから塗り替える方が好ましい。 Moreover, although the tin roof and the steel plate roof may repaint the coating film formed on the surface, the two-component mixed coating composition according to the present embodiment may be used when repainting. In this case, the coating film and rust formed on the surface of the substrate from the beginning may be removed and then the coating film may be repainted, or the coating film may be repainted without being removed. The rust on the surface of the substrate is preferably removed and then repainted.
本実施形態に係る二液混合型塗料組成物は、主剤(I)及び強化剤(II)からなる。 The two-component mixed coating composition according to this embodiment comprises a main agent (I) and a reinforcing agent (II).
[主剤(I)]
主剤(I)は、共重合体(A)を含む。
[Main agent (I)]
Main agent (I) contains a copolymer (A).
<共重合体(A)>
共重合体(A)は、酸化重合可能な不飽和脂肪酸(a−1)及び酸化重合性基を有するアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、水酸基及びアルコキシシリル基の少なくとも一方を有するシリコーン(a−4)と、が共重合した構造を有する。
<Copolymer (A)>
The copolymer (A) includes at least one of an oxidatively polymerizable unsaturated fatty acid (a-1) and an alkyd resin (a-2) having an oxidative polymerizable group, an acrylic copolymer (a-3), It has a structure in which silicone (a-4) having at least one of a hydroxyl group and an alkoxysilyl group is copolymerized.
<酸化重合可能な不飽和脂肪酸(a−1)>
酸化重合可能な不飽和脂肪酸(a−1)(以下、単に「不飽和脂肪酸(a−1)」と言う場合がある)は、分子内に少なくとも1つの不飽和炭素結合を有する脂肪酸であれば、特に限定されない。不飽和脂肪酸(a−1)の代表例としては、魚油脂肪酸、脱水ヒマシ油脂肪酸、サフラワー油脂肪酸、アマニ油脂肪酸、ダイズ油脂肪酸、ゴマ油脂肪酸、ケシ油脂肪酸、エノ油脂肪酸、麻実油脂肪酸、ブドウ核油脂肪酸、トウモロコシ油脂肪酸、トール油脂肪酸、ヒマワリ油脂肪酸、綿実油脂肪酸、クルミ油脂肪酸、ゴム種油脂肪酸等が挙げられる。
<Oxidatively polymerizable unsaturated fatty acid (a-1)>
The oxidatively polymerizable unsaturated fatty acid (a-1) (hereinafter sometimes simply referred to as “unsaturated fatty acid (a-1)”) is a fatty acid having at least one unsaturated carbon bond in the molecule. There is no particular limitation. Representative examples of unsaturated fatty acid (a-1) include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, Examples include grape kernel oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, and rubber seed oil fatty acid.
<酸化重合性基を有するアルキッド樹脂(a−2)>
酸化重合性基を有するアルキッド樹脂(a−2)(以下、単に「アルキッド樹脂(a−2)」と言う場合がある)は、ポリエステル樹脂の一種であり、多価アルコールと多塩基酸とを縮合させることによって得られる。本実施形態においては、アルキッド樹脂の中でも、酸化重合性基を有するアルキッド樹脂が用いられる。
<Alkyd Resin Having Oxidatively Polymerizable Group (a-2)>
The alkyd resin (a-2) having an oxidatively polymerizable group (hereinafter may be simply referred to as “alkyd resin (a-2)”) is a kind of polyester resin, and contains a polyhydric alcohol and a polybasic acid. Obtained by condensation. In the present embodiment, among the alkyd resins, alkyd resins having an oxidative polymerizable group are used.
アルキッド樹脂が有する酸化重合性基は、例えば、不飽和脂肪酸に由来する不飽和炭素結合(炭素二重結合又は炭素三重結合)である。例えば、アルキッド樹脂(a−2)は、アルキッド樹脂に不飽和脂肪酸を導入することによって得られる。アルキッド樹脂に導入される不飽和脂肪酸としては、固形ヨウ素価が高い、すなわち不飽和炭素結合を多く有するものが好ましい。このような不飽和脂肪酸としては、例えば、乾性油脂肪酸及び半乾性油脂肪酸が挙げられる。乾性油脂肪酸及び半乾性油脂肪酸は、厳密に区別できるものではないが、通常、乾性油脂肪酸は固形ヨウ素価が130以上の不飽和脂肪酸であり、半乾性油脂肪酸は固形ヨウ素価が100以上且つ130未満の不飽和脂肪酸である。なお、不乾性油脂肪酸は、通常、固形ヨウ素価が100未満の脂肪酸である。乾性油脂肪酸及び半乾性油脂肪酸としては、例えば、魚油脂肪酸、脱水ヒマシ油脂肪酸、サフラワー油脂肪酸、亜麻仁油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油脂肪酸、エノ油脂肪酸、麻実油脂肪酸、ブドウ核油脂肪酸、トウモロコシ油脂肪酸、トール油脂肪酸、ヒマワリ油脂肪酸、綿実油脂肪酸、クルミ油脂肪酸、ゴム種油脂肪酸、ハイジェン酸脂肪酸等が挙げられる。これらの乾性油脂肪酸及び半乾性油脂肪酸は、必要に応じて不乾性油脂肪酸(例えば、ヤシ油脂肪酸、水添ヤシ油脂肪酸、パーム油脂肪酸等)、カプロン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等と併用してもよい。 The oxidative polymerizable group possessed by the alkyd resin is, for example, an unsaturated carbon bond (carbon double bond or carbon triple bond) derived from an unsaturated fatty acid. For example, the alkyd resin (a-2) can be obtained by introducing an unsaturated fatty acid into the alkyd resin. As the unsaturated fatty acid introduced into the alkyd resin, those having a high solid iodine value, that is, having many unsaturated carbon bonds are preferable. Examples of such unsaturated fatty acids include dry oil fatty acids and semi-dry oil fatty acids. Although dry oil fatty acids and semi-dry oil fatty acids are not strictly distinguishable, usually dry oil fatty acids are unsaturated fatty acids having a solid iodine value of 130 or more, and semi-dry oil fatty acids have a solid iodine value of 100 or more and Less than 130 unsaturated fatty acids. The non-drying oil fatty acid is usually a fatty acid having a solid iodine value of less than 100. Examples of the dry oil fatty acid and semi-dry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, grape Examples include nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, hyogenic acid fatty acid and the like. These dry oil fatty acids and semi-dry oil fatty acids may be non-dry oil fatty acids (for example, coconut oil fatty acid, hydrogenated coconut oil fatty acid, palm oil fatty acid, etc.), caproic acid, capric acid, lauric acid, myristic acid as necessary. , Palmitic acid, stearic acid and the like may be used in combination.
更に、本実施形態では、アルキッド樹脂に不飽和脂肪酸とともに、あるいは不飽和脂肪酸の代わりに、油脂(グリセリド)を導入してもよい。このような油脂としては、不飽和炭素結合を有する油脂であって、例えば、魚油、脱水ヒマシ油、サフラワー油、亜麻仁油、大豆油、ゴマ油、ケシ油、エノ油、麻実油、ブドウ核油、トウモロコシ油、トール油、ヒマワリ油、綿実油、クルミ油、ゴム種油等の乾性油又は半乾性油が挙げられる。不飽和脂肪酸は、酸化硬化形の重合性不飽和基をもつ脂肪酸であって、アルキッド樹脂に酸化重合性基を付与するものである。 Furthermore, in this embodiment, you may introduce fats and oils (glyceride) into an alkyd resin with an unsaturated fatty acid or instead of an unsaturated fatty acid. Such fats and oils are those having unsaturated carbon bonds, such as fish oil, dehydrated castor oil, safflower oil, linseed oil, soybean oil, sesame oil, poppy oil, eno oil, hemp seed oil, grape kernel oil. Corn oil, tall oil, sunflower oil, cottonseed oil, walnut oil, rubber seed oil and the like. The unsaturated fatty acid is a fatty acid having an oxidatively curing type polymerizable unsaturated group, and imparts an oxidizable polymerizable group to the alkyd resin.
共重合体(A)は、アルキッド樹脂(a−2)と、アクリル共重合体(a−3)と、水酸基及びアルコキシシリル基の少なくとも一方を有するシリコーン(a−4)と、が共重合体した構造を有することが好ましい。共重合体(A)がアルキッド樹脂(a−2)に由来する構造を有することで、共重合体(A)のアルキッド樹脂(a−2)に由来する水酸基と、後段で詳述するポリイソシアネート(B−1)のイソシアネート基とのウレタン反応が進行し、によって形成される塗膜のべたつきを抑えることができる。また、共重合体(A)がアルキッド樹脂(a−2)に由来する構造を有することで、共重合体(A)のアルキッド樹脂(a−2)に由来する水酸基あるいはアクリル共重合体(a−3)に由来するカルボニル基と、後段で詳述するシランカップリング剤(B−2)との反応(酸エポキシ反応あるいはウレタン反応)が進行し、塗膜と金属基材との付着性を向上させることができる。塗膜と金属基材との付着性が向上すると、塗膜の防錆性がより向上する。 The copolymer (A) is a copolymer of an alkyd resin (a-2), an acrylic copolymer (a-3), and a silicone (a-4) having at least one of a hydroxyl group and an alkoxysilyl group. It is preferable to have such a structure. Since the copolymer (A) has a structure derived from the alkyd resin (a-2), the hydroxyl group derived from the alkyd resin (a-2) of the copolymer (A) and the polyisocyanate described in detail later The urethane reaction with the isocyanate group of (B-1) proceeds, and the stickiness of the coating film formed can be suppressed. In addition, since the copolymer (A) has a structure derived from the alkyd resin (a-2), a hydroxyl group or an acrylic copolymer derived from the alkyd resin (a-2) of the copolymer (A) (a -3) and the silane coupling agent (B-2) described later in detail (acid-epoxy reaction or urethane reaction) proceed to improve adhesion between the coating film and the metal substrate. Can be improved. When the adhesion between the coating film and the metal substrate is improved, the rust prevention property of the coating film is further improved.
<アクリル共重合体(a−3)>
本実施形態において用いられるアクリル共重合体(a−3)としては、アクリルモノマーを含む重合性不飽和モノマーの共重合体を挙げることができる。
重合性不飽和モノマーとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸n−オクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸シクロヘキシル等のアクリル酸又はメタクリル酸の炭素数1〜24のアルキルエステル;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、3−ヒドロキシブチル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート等の如きα,β−エチレン性不飽和カルボン酸のヒドロキシアルキルエステル類や、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレートの如きアルキレンオキシド鎖と水酸基を有するα,β−エチレン性不飽和カルボン酸エステル等の水酸基含有モノマー;(メタ)アクリル酸イソボロニル、(メタ)アクリル酸1,2,2,6,6−ペンタメチルピペリジル、(メタ)アクリル酸2,2,6,6−テトラメチルピペリジニル、2−(2′−ヒドロキシ−5′−メタアクリルオキシフェニル)−2H−ベンゾトリアゾール、スチレン等を挙げることができる。
<Acrylic copolymer (a-3)>
Examples of the acrylic copolymer (a-3) used in the present embodiment include a copolymer of a polymerizable unsaturated monomer containing an acrylic monomer.
Examples of the polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, ( Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid C1-C24 alkyl ester of acrylic acid or methacrylic acid such as cyclohexyl; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acryl , Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as 4-hydroxybutyl (meth) acrylate, and alkylene oxides such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate Hydroxyl group-containing monomers such as α, β-ethylenically unsaturated carboxylic acid ester having a chain and a hydroxyl group; (meth) acrylic acid isobornyl, (meth) acrylic acid 1,2,2,6,6-pentamethylpiperidyl, (meta ) 2,2,6,6-tetramethylpiperidinyl acrylate, 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, styrene and the like.
<水酸基及びアルコキシ基の少なくとも一方を有するシリコーン(a−4)>
本実施形態において用いられる水酸基及びアルコキシ基の少なくとも一方を有するシリコーン(a−4)(以下、単に「シリコーン(a−4)」と言う場合がある)は、例えば、シロキサン結合(−Si−O−Si−)を主鎖とし、側鎖にアルキル基、アリール基、水酸基、アルコキシ基等の置換基が存在する分岐構造を有するポリシロキサンである。本実施形態において用いられるシリコーンは、水酸基及びアルコキシ基の少なくとも一方を有するシリコーンであれば、特に限定されない。水酸基又はアルコキシ基の少なくとも1つは、シリコーン分子内の少なくとも1つのケイ素原子に、直接結合していることが好ましい。
<Silicone (a-4) having at least one of hydroxyl group and alkoxy group>
Silicone (a-4) having at least one of a hydroxyl group and an alkoxy group used in the present embodiment (hereinafter sometimes simply referred to as “silicone (a-4)”) is, for example, a siloxane bond (—Si—O). -Si-) is a polysiloxane having a branched structure in which a main chain is present and a substituent such as an alkyl group, an aryl group, a hydroxyl group or an alkoxy group is present in the side chain. The silicone used in this embodiment is not particularly limited as long as it has at least one of a hydroxyl group and an alkoxy group. It is preferable that at least one of the hydroxyl group or the alkoxy group is directly bonded to at least one silicon atom in the silicone molecule.
シリコーン(a−4)の構造は、例えば、下記の式(1)で示される
[化1]
R1 m(R2O)nSiO(4−m−n)/2 ・・・(1)
(式中、R1及びR2は、それぞれ同一又は異なって、水素原子、炭素数が1〜8のアルキル基、又は炭素数が6〜12のアリール基を表し、mは0≦m≦3.5を満足し、nは0.0005≦n<4を満足する)。
シリコーン(a−4)は、重合度や官能基の置換度が異なる分子の混合物であるため、上記の式におけるmやnの値は必ずしも整数とはならない。
The structure of silicone (a-4) is represented by, for example, the following formula (1):
R 1 m (R 2 O) n SiO (4-mn) / 2 (1)
Wherein R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and m is 0 ≦ m ≦ 3. .5 and n satisfies 0.0005 ≦ n <4).
Since silicone (a-4) is a mixture of molecules having different degrees of polymerization and substitution of functional groups, the values of m and n in the above formula are not necessarily integers.
シリコーン(a−4)としては、水酸基又はアルコキシ基に加えて、フェニル基を更に有するシリコーンが好ましく、フェニル基は、ケイ素原子に直接結合していることがより好ましい。フェニル基を有するシリコーン(a−4)を用いると、溶剤(特に後述する弱溶剤)への溶解性がより高くなる。その結果、塗料の粘度を適度に下げることができるため、作業性をより向上させることができる。また塗膜の屈折率が向上するため、初期光沢値が向上する。更に、アルキル基を有するシリコーン(a−4)が好ましく、アルキル基は、ケイ素原子に直接結合していることがより好ましい。ケイ素原子に直接結合するフェニル基とケイ素原子に直接結合するプロピル基(n−プロピル基又はイソプロピル基)とを有するシリコーン(a−4)が特に好ましい。 Silicone (a-4) is preferably a silicone further having a phenyl group in addition to a hydroxyl group or an alkoxy group, and the phenyl group is more preferably directly bonded to a silicon atom. When silicone (a-4) having a phenyl group is used, solubility in a solvent (particularly a weak solvent described later) is further increased. As a result, since the viscosity of the paint can be lowered appropriately, workability can be further improved. Further, since the refractive index of the coating film is improved, the initial gloss value is improved. Further, silicone (a-4) having an alkyl group is preferable, and the alkyl group is more preferably directly bonded to a silicon atom. Silicone (a-4) having a phenyl group directly bonded to a silicon atom and a propyl group (n-propyl group or isopropyl group) bonded directly to a silicon atom is particularly preferable.
シリコーン(a−4)の分子量は特に限定されない。本実施形態においては、好ましくは200〜5,500の数平均分子量を有するシリコーン(a−4)、より好ましくは1,400〜3,000の数平均分子量を有するシリコーン(a−4)が用いられる。
このようなシリコーン(a−4)の代表的な市販品としては、3037 INTERMEDIATE、3074 INTERMEDIATE、Z−6018、217 FLAKE、220 FLAKE、233 FLAKE、249 FLAKE、QP8−5314、SR2402、AY 42−163(いずれも東レ・ダウコーニング株式会社製);TSR160、TSR165、TSR3168(いずれもモメンティブ・パフォーマンス・マテリアルズ社製);KR−211、KR−216、KR−213、KR−9218(いずれも信越化学工業株式会社製);SILRES SY 231、SILRES SY 300、SILRES SY 409、SILRES IC368(いずれも旭化成ワッカーシリコーン株式会社製)等が挙げられる。
The molecular weight of silicone (a-4) is not particularly limited. In the present embodiment, a silicone (a-4) having a number average molecular weight of preferably 200 to 5,500, more preferably a silicone (a-4) having a number average molecular weight of 1,400 to 3,000 is used. It is done.
Typical examples of such commercially available silicone (a-4) include 3037 INTERMEDIATE, 3074 INTERMEDIATE, Z-6018, 217 FLAKE, 220 FLAKE, 233 FLAKE, 249 FLAKE, QP8-5314, SR2402, AY 42-163. (All manufactured by Toray Dow Corning Co., Ltd.); TSR160, TSR165, TSR3168 (all manufactured by Momentive Performance Materials); KR-211, KR-216, KR-213, KR-9218 (all manufactured by Shin-Etsu Chemical) SILRES SY 231, SILRES SY 300, SILRES SY 409, SILRES IC 368 (all manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like.
上記共重合体(A)において、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)と、アクリル共重合体(a−3)との共重合比率は、得られる共重合体(A)の溶剤への溶解性等の点から、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−3)の合計が、3〜70質量%であり、アクリル共重合体(a−3)が30〜97質量%であることが好ましい。また、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−3)の合計が5〜40重量%であり、アクリル共重合体(a−3)が60〜95質量%であることがより好ましい。 In the copolymer (A), the copolymerization ratio between the unsaturated fatty acid (a-1) and the alkyd resin (a-2) and the acrylic copolymer (a-3) is determined by the copolymer (A ) In terms of solubility in a solvent, etc., the total of unsaturated fatty acid (a-1) and alkyd resin (a-3) is 3 to 70% by mass, and acrylic copolymer (a-3) is It is preferable that it is 30-97 mass%. Moreover, it is more preferable that the sum total of unsaturated fatty acid (a-1) and alkyd resin (a-3) is 5 to 40 weight%, and acrylic copolymer (a-3) is 60 to 95 mass%. .
共重合体(A)におけるアクリル共重合体(a−3)のモノマーとして水酸基含有モノマーを使用する場合、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方とアクリル共重合体(a−3)との反応におけるゲル化や、シリコーン(a−4)との反応の際のゲル化が起こらないように、水酸基含有モノマーの使用量を決定すべきである。通常、水酸基含有モノマーの使用量は、共重合体(A)の原料となる不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方とアクリル共重合体(a−3)の合計質量中、50質量部以下であることが好ましい。 When a hydroxyl group-containing monomer is used as the monomer of the acrylic copolymer (a-3) in the copolymer (A), at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) and acrylic copolymer The amount of the hydroxyl group-containing monomer used should be determined so that gelation in the reaction with the union (a-3) or gelation in the reaction with the silicone (a-4) does not occur. Usually, the usage-amount of a hydroxyl-containing monomer is the at least one of the unsaturated fatty acid (a-1) used as the raw material of a copolymer (A), an alkyd resin (a-2), and an acrylic copolymer (a-3). The total mass is preferably 50 parts by mass or less.
共重合体(A)を得るための共重合方法は、とくに限定されるものではないが、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、シリコーン(a−4)と、の反応のさせやすさ等の観点から、有機溶剤中にてラジカル重合開始剤存在下で行う、溶液重合法が好適である。 The copolymerization method for obtaining the copolymer (A) is not particularly limited, but at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) and an acrylic copolymer ( From the viewpoint of easiness of reaction between a-3) and silicone (a-4), a solution polymerization method performed in the presence of a radical polymerization initiator in an organic solvent is preferable.
上記の溶液重合による合成に際して使用されるラジカル重合開始剤としては、例えば、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス(2,4−ジメチルバレロニトリル)等のアゾ系重合開始剤;ラウリルパーオキサイド、t−ブチルパーオキシ−2−エチルヘキサノエート、ベンゾイルパーオキサイド等の過酸化物系重合開始剤等を挙げることができる。 Examples of the radical polymerization initiator used in the synthesis by the solution polymerization include azo series such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile). Polymerization initiators: peroxide polymerization initiators such as lauryl peroxide, t-butylperoxy-2-ethylhexanoate, and benzoyl peroxide can be used.
上記溶液重合による合成に際して使用される有機溶剤としては、例えばn−ヘキサン、n−オクタン、2,2,2−トリメチルペンタン、イソオクタン、n−ノナン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶剤;ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素系溶剤;ミネラルスピリット、「スワゾール1000」(コスモ石油株式会社製)、石油エーテル、石油ベンジン、石油ナフサ等の石油系溶剤;メチルイソブチルケトン等のケトン系溶剤;酢酸イソブチル等のエステル系溶剤;イソプロパノール等のアルコール系溶剤等を挙げることができる。これらは、必要に応じて単独で、あるいは2種以上を混合して用いることができる。 Examples of the organic solvent used in the synthesis by solution polymerization include aliphatic hydrocarbon solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane, and methylcyclohexane. Aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; mineral spirits, "Swazole 1000" (manufactured by Cosmo Oil Co., Ltd.), petroleum ethers such as petroleum ether, petroleum benzine and petroleum naphtha; methyl isobutyl ketone, etc. Ketone solvents; ester solvents such as isobutyl acetate; alcohol solvents such as isopropanol; These may be used alone or in admixture of two or more as required.
本発明に用いる共重合体(A)を製造するための、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、シリコーン(a−4)との反応順序は、特に制限されるものではない。共重合体(A)は、上記(a−1)から(a−4)を同時に反応させることもできるが、上記不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、を反応させて得られる酸化硬化型アクリル共重合体に、シリコーン(a−4)を反応させることによって得られる。この、酸化硬化型アクリル共重合体にシリコーン(a−4)を反応させることによって共重合体(A)を得る方法が、反応の制御のし易さ等の観点から好ましい。 At least one of unsaturated fatty acid (a-1) and alkyd resin (a-2), acrylic copolymer (a-3), silicone (for producing copolymer (A) used in the present invention, The reaction order with a-4) is not particularly limited. The copolymer (A) can be reacted with (a-1) to (a-4) at the same time, but with at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) It is obtained by reacting silicone (a-4) with an oxidatively curable acrylic copolymer obtained by reacting acrylic copolymer (a-3). This method of obtaining the copolymer (A) by reacting the oxidatively curable acrylic copolymer with the silicone (a-4) is preferable from the viewpoint of easy control of the reaction.
上記不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)との反応は、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方の中の水酸基とアクリル共重合体(a−3)中のカルボキシル基とのエステル化反応に基づくものである。この反応によって通常、2級水酸基が生成する。この反応に際しては、必要に応じて、N,N−ジメチルアミノエタノール等の3級アミン;臭化テトラブチルアンモニウム等の4級アンモニウム塩等の反応触媒を用いることができる。反応触媒を使用する場合には、その使用量は、不飽和脂肪酸(a−1)、アルキッド樹脂(a−2)及びアクリル共重合体(a−3)の合計100質量部に対して0.01〜100重量部の範囲内が適当である。 The reaction of at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) with the acrylic copolymer (a-3) is carried out by reacting the unsaturated fatty acid (a-1) and the alkyd resin (a- It is based on the esterification reaction between the hydroxyl group in at least one of 2) and the carboxyl group in the acrylic copolymer (a-3). This reaction usually produces a secondary hydroxyl group. In this reaction, a reaction catalyst such as a tertiary amine such as N, N-dimethylaminoethanol; a quaternary ammonium salt such as tetrabutylammonium bromide can be used as necessary. When using a reaction catalyst, the amount of use is 0.00 with respect to a total of 100 mass parts of unsaturated fatty acid (a-1), alkyd resin (a-2), and an acrylic copolymer (a-3). A range of 01 to 100 parts by weight is appropriate.
不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)との反応条件は、ゲル化等の反応上の問題を起こすことなく、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方とアクリル共重合体(a−3)中のカルボキシル基とが反応できる条件であればよい。通常、100〜170℃で、2〜10時間加熱する条件で反応させることが適当である。 The reaction conditions of at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) and the acrylic copolymer (a-3) are not affected without causing a reaction problem such as gelation. What is necessary is just the conditions which can react at least one of saturated fatty acid (a-1) and alkyd resin (a-2), and the carboxyl group in an acrylic copolymer (a-3). Usually, it is suitable to make it react on the conditions heated at 100-170 degreeC for 2 to 10 hours.
上記不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、を反応させて得られる酸化硬化型アクリル共重合体にシリコーン(a−4)を反応させる方法は、必要に応じて、反応触媒の存在下において加熱して、脱水又は脱アルコール縮合反応させることによって行うことができる。脱水又は脱アルコール縮合反応は、酸化硬化型アクリル共重合体中の水酸基あるいはカルボキシル基とシリコーン(a−4)中の水酸基又はアルコキシシリル基との反応によるものである。上記重合体(A)中の水酸基あるいはカルボキシル基には、不飽和脂肪酸(a−1)あるいはアルキッド樹脂(a−2)中にはじめから存在する水酸基、アクリル共重合体(a−3)中にはじめから存在するカルボキシル基、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)との反応によって生成する水酸基あるいはカルボキシル基がある。 An oxidation-curable acrylic copolymer obtained by reacting at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) with an acrylic copolymer (a-3) is added to silicone (a The method of reacting -4) can be carried out by heating in the presence of a reaction catalyst, if necessary, to cause dehydration or dealcohol condensation reaction. The dehydration or dealcoholization condensation reaction is based on the reaction between the hydroxyl group or carboxyl group in the oxidatively curable acrylic copolymer and the hydroxyl group or alkoxysilyl group in the silicone (a-4). The hydroxyl group or carboxyl group in the polymer (A) includes a hydroxyl group present in the unsaturated fatty acid (a-1) or alkyd resin (a-2) from the beginning, and the acrylic copolymer (a-3). There are a hydroxyl group or a carboxyl group generated by a reaction of at least one of a carboxyl group, an unsaturated fatty acid (a-1) and an alkyd resin (a-2) present from the beginning with an acrylic copolymer (a-3).
上記脱水、脱アルコール縮合反応における反応触媒としては、金属アルコキシド化合物、金属キレート化合物、金属エステル化合物等が用いられる。金属アルコキシド化合物としては、例えば、アルミニウムトリメトキシド、アルミニウムトリエトキシド、アルミニウムトリn−プロポキシド、アルミニウムトリイソプロポキシド、アルミニウムトリ−n−ブトキシド、アルミニウムトリイソブトキシド、アルミニウムトリ−sec−ブトキシド、アルミニウムトリ−tert−ブトキシド等のアルミニウムアルコキシド;テトラメチルチタネート、テトラエチルチタネート、テトラ−n−プロピルチタネート、テトライソプロピルチタネート、テトラ−n−ブチルチタネート、テトライソブチルチタネート、テトラ−tert−ブチルチタネート、テトラ−n−ヘキシルチタネート、テトライソオクチルチタネート、テトラ−n−ラウリルチタネート等のチタニウムアルコキシド;テトラエチルジルコネート、テトラ−n−プロピルジルコネート、テトライソプロピルジルコネート、テトラ−n−ブチルジルコネート、テトラ−sec−ブチルジルコネート、テトラ−tert−ブチルジルコネート、テトラ−n−ペンチルジルコネート、テトラ−tert−ペンチルジルコネート、テトラ−tert−ヘキシルジルコネート、テトラ−n−ヘプチルジルコネート、テトラ−n−オクチルジルコネート、テトラ−n−ステアリルジルコネート等のジルコニウムアルコキシド;ジブチルスズジブトキシド等が挙げられ、金属キレート化合物としては、例えば、トリス(エチルアセトアセテート)アルミニウム、トリス(n−プロピルアセトアセテート)アルミニウム、トリス(イソプロピルアセトアセテート)アルミニウム、トリス(n−ブチルアセトアセテート)アルミニウム、イソプロポキシビス(エチルアセトアセテート)アルミニウム、トリス(アセチルアセトナト)アルミニウム、トリス(プロポニルアセトナト)アルミニウム、ジイソプロポキシプロピオニルアセトナトアルミニウム、アセチルアセトナト・ビス(プロピオニルアセトナト)アルミニウム、モノエチルアセトアセテート・ビス(アセチルアセトナト)アルミニウム、アセチルアセトナトアルミニウム・ジsec−ブチレート、メチルアセトアセテートアルミニウム・ジtert−ブチレート、ビス(アセチルアセトナト)アルミニウム・モノsec−ブチレート、ジ(メチルアセトアセテート)アルミニウム・モノtert−ブチレート等のアルミニウムキレート化合物;ジイソプロポキシ・ビス(エチルアセトアセテート)チタネート、ジイソプロポキシ・ビス(アセチルアセトナト)チタネート、ジn−ブトキシ・ビス(アセチルアセトナト)チタネート等のチタニウムキレート化合物;テトラキス(アセチルアセトナト)ジルコニウム、テトラキス(n−プロピルアセトアセテート)ジルコニウム、テトラキス(エチルアセトアセテート)ジルコニウム等のジルコニウムキレート化合物;ジブチル錫ビス(アセチルアセトネート)等が挙げられ、金属エステル化合物としては、例えば、ジブチル錫ジアセテート、ジブチル錫ジ(2−エチルへキシレート)、ジベンジル錫ジ(2−エチルヘキシレート)、ジブチル錫ジラウレート、ジブチル錫ジイソオクチルマレエート等の錫エステル化合物等が挙げられる。これらの反応触媒は1種又は2種以上を組み合わせて用いることができる。 As a reaction catalyst in the dehydration and dealcoholization condensation reaction, a metal alkoxide compound, a metal chelate compound, a metal ester compound, or the like is used. Examples of the metal alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide, Aluminum alkoxide such as aluminum tri-tert-butoxide; tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetra-n -Titanium alkoxides such as hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate; Til zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert -Zirconium alkoxides such as pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate; dibutyltin dibutoxide, etc., metal Examples of the chelate compound include tris (ethyl acetoacetate) aluminum, tris (n-propyl acetoacetate) aluminum, tris (isopropyl acetoacetate) aluminum, (N-butylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonato bis ( Propionylacetonato) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, acetylacetonatoaluminum disec-butyrate, methylacetoacetate aluminum ditert-butyrate, bis (acetylacetonato) aluminum monosec- Aluminum chelate compounds such as butyrate, di (methylacetoacetate) aluminum mono-tert-butyrate; diisopropoxy Titanium chelate compounds such as bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate, di-n-butoxy bis (acetylacetonato) titanate; tetrakis (acetylacetonato) zirconium, tetrakis (n- Zirconium chelate compounds such as propylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; dibutyltin bis (acetylacetonate) and the like. Examples of metal ester compounds include dibutyltin diacetate and dibutyltin di (2 -Ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate, dibutyltin diisooctyl maleate, and the like. These reaction catalysts can be used alone or in combination of two or more.
上記反応触媒は、反応の促進効果の観点から、酸化硬化型アクリル共重合体及びシリコーン(a−3)の合計100質量部に対して、0.001〜5質量部用いることが好ましく、0.005〜1質量部用いることがより好ましい。 The reaction catalyst is preferably used in an amount of 0.001 to 5 parts by mass with respect to a total of 100 parts by mass of the oxidatively curable acrylic copolymer and silicone (a-3), from the viewpoint of the effect of promoting the reaction. It is more preferable to use 005 to 1 parts by mass.
上記不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、を反応させて得られる酸化硬化型アクリル共重合体にシリコーン(a−3)を反応させる条件は、脱水、脱アルコール縮合反応が進行する条件であれば、特に限定されるものではない。通常、反応温度は、60〜250℃、好ましくは80℃〜200℃、更に好ましくは100〜180℃であり、反応時間は、0.5〜24時間、好ましくは1〜12時間である。また、上記反応において、反応により生成する水、アルコールを系から除去することにより反応を円滑に進行させることができる。 An oxidation-curable acrylic copolymer obtained by reacting at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) with an acrylic copolymer (a-3) is added to silicone (a The condition for reacting -3) is not particularly limited as long as the dehydration and dealcohol condensation reaction proceeds. Usually, the reaction temperature is 60 to 250 ° C., preferably 80 to 200 ° C., more preferably 100 to 180 ° C., and the reaction time is 0.5 to 24 hours, preferably 1 to 12 hours. Moreover, in the said reaction, reaction can be advanced smoothly by removing the water and alcohol which are produced | generated by reaction from a system.
上記反応においては、得られる樹脂が塗料用樹脂としての性能を発揮できるまで脱水、脱アルコール縮合反応が進行すればよく、水酸基の一部が反応していてもよいし、実質的に水酸基の全てが反応していてもよい。反応の進行程度は、赤外線吸収スペクトル(IR)測定によって水酸基に起因する吸収強度を求める方法、あるいは反応により生成する水、アルコール量を測定する方法、系の粘度上昇を測定する方法等により知ることができる。 In the above reaction, the dehydration and dealcohol condensation reaction may proceed until the obtained resin can exhibit the performance as a coating resin, and a part of the hydroxyl groups may be reacted, or substantially all of the hydroxyl groups may be reacted. May react. The degree of progress of the reaction can be known by the method of obtaining the absorption intensity due to the hydroxyl group by infrared absorption spectrum (IR) measurement, the method of measuring the amount of water and alcohol produced by the reaction, the method of measuring the increase in viscosity of the system, etc. Can do.
本実施形態の共重合体(A)は、好ましくは5〜80の固形ヨウ素価を有する。固形ヨウ素価がこのような範囲の場合、得られる塗膜は、耐候性に加えて耐水性及び耐アルカリ性も良好となり、強度や肉持ち感も良好となる。更に、共重合体の製造中にゲル化することも少なく、弱溶剤への溶解性も低下しにくくなる。本実施形態の共重合体(A)は、より好ましくは20〜60、の固形ヨウ素価を有する。固形ヨウ素価は、JIS K 0070(化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法)に準拠して測定することができる。 The copolymer (A) of this embodiment preferably has a solid iodine value of 5 to 80. When the solid iodine value is in such a range, the obtained coating film has good water resistance and alkali resistance in addition to weather resistance, and good strength and fleshiness. Furthermore, it hardly causes gelation during the production of the copolymer, and the solubility in a weak solvent is hardly lowered. The copolymer (A) of the present embodiment more preferably has a solid iodine value of 20 to 60. The solid iodine value can be measured according to JIS K 0070 (Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products).
更に、上記共重合体(A)の重量平均分子量は、10,000〜150,000である。共重合体(A)の重量平均分子量がこのような範囲に属することで、得られる塗膜は、耐候性に加えて耐水性及び耐アルカリ性が良好となり、より光沢が得られるようになる。更に、塗料の粘度が高くなりすぎず、塗装する際の作業性もより良好になる。共重合体(A)の重量平均分子量は、好ましくは20,000〜100,000、よりに好ましくは30,000〜80,000である。重量平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー(GPC)により測定される。 Further, the copolymer (A) has a weight average molecular weight of 10,000 to 150,000. When the weight average molecular weight of the copolymer (A) falls within such a range, the resulting coating film has good water resistance and alkali resistance in addition to weather resistance, and more gloss can be obtained. Furthermore, the viscosity of the paint does not become too high, and the workability during coating becomes better. The weight average molecular weight of the copolymer (A) is preferably 20,000 to 100,000, more preferably 30,000 to 80,000. The weight average molecular weight is measured by, for example, gel permeation chromatography (GPC).
主剤(I)は、共重合体(A)を、溶剤、顔料、ドライヤー、更に必要に応じて他の添加剤(レベリング剤、タレ防止剤等)と混合して調製される。
溶剤としては、不飽和脂肪酸(a−1)及びアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、を反応させて酸化硬化型アクリル共重合体を得る工程及び、酸化硬化型アクリル共重合体とシリコーン(a−4)とを反応させる工程において、必要に応じて使用されるものと同様のものが使用できる。
顔料としては、二酸化チタン、カーボンブラック、酸化カルシウム、硫酸バリウム、シリカ、クレー、タルク、ケイ砂等の無機顔料や、フタロシアニンブルー等の有機顔料が挙げられる。
ドライヤーとしては、ナフテン酸又はオクチル酸のコバルト塩、マンガン塩、鉛塩、ジルコニウム塩、カルシウム塩等が挙げられる。
The main agent (I) is prepared by mixing the copolymer (A) with a solvent, a pigment, a dryer, and, if necessary, other additives (leveling agent, sagging inhibitor, etc.).
As the solvent, a step of obtaining an oxidatively curable acrylic copolymer by reacting at least one of the unsaturated fatty acid (a-1) and the alkyd resin (a-2) with the acrylic copolymer (a-3). In the step of reacting the oxidatively curable acrylic copolymer and silicone (a-4), those similar to those used as necessary can be used.
Examples of the pigment include inorganic pigments such as titanium dioxide, carbon black, calcium oxide, barium sulfate, silica, clay, talc, and silica sand, and organic pigments such as phthalocyanine blue.
Examples of the dryer include cobalt salts, manganese salts, lead salts, zirconium salts, and calcium salts of naphthenic acid or octylic acid.
主剤(I)中における共重合体(A)の含有量は、10〜90質量%であることが好ましく、40〜70質量%であることがより好ましい。 The content of the copolymer (A) in the main agent (I) is preferably 10 to 90% by mass, and more preferably 40 to 70% by mass.
[強化剤(II)]
強化剤(II)は、ポリイソシアネート(B−1)と、同一分子内に異なる2種の官能基を有するシランカップリング剤(B−2)と、を含む。
[Strengthening agent (II)]
The reinforcing agent (II) contains polyisocyanate (B-1) and a silane coupling agent (B-2) having two different functional groups in the same molecule.
<ポリイソシアネート(B−1)>
ポリイソシアネート(B−1)は、分子中に2個以上のイソシアネート基を有する限り特に限定されない。ポリイソシアネート(B−1)としては、例えば、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート等の低分子量ポリイソシアネート、これらのポリイソシアネートのプレポリマー、これらのポリイソシアネートのイソシアヌレート体、これらのポリイソシアネートのトリオン体及びこれらのポリイソシアネートの誘導体や変性体等が挙げられる。
<Polyisocyanate (B-1)>
The polyisocyanate (B-1) is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples of the polyisocyanate (B-1) include low molecular weight polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates, prepolymers of these polyisocyanates, and isocyanurates of these polyisocyanates. , Trione bodies of these polyisocyanates, and derivatives and modified bodies of these polyisocyanates.
なお、「ポリイソシアネート」とは、分子中に複数のイソシアネート基を有する化合物の総称であり、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート等の低分子ポリイソシアネート及びこれらのポリイソシアネートから得られる誘導体、変性物、プレポリマー等を含む。「ポリイソシアネート誘導体」とは、低分子ポリイソシアネートから得られる化合物の総称であり、変性物、プレポリマー等を含む。「ポリイソシアネート変性体」とは、低分子ポリイソシアネートやプレポリマーを変性した反応物を意味する。 “Polyisocyanate” is a general term for compounds having a plurality of isocyanate groups in the molecule, and low molecular polyisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and derivatives obtained from these polyisocyanates, Includes modified products, prepolymers and the like. The “polyisocyanate derivative” is a general term for compounds obtained from low-molecular polyisocyanates, and includes modified products, prepolymers, and the like. The “polyisocyanate modified product” means a reaction product obtained by modifying a low molecular polyisocyanate or a prepolymer.
脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、1,2−プロピレンジイソシアネート、テトラメチレンジイソシアネート、1,2−ブチレンジイソシアネート、2,3−ブチレンジイソシアネート、1,3−ブチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、2,4,4−又は2,2,4−トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネートや、リジンエステルトリイソシアネート、1,4,8−トリイソシアナトオクタン、1,6,11−トリイソシアナトウンデカン、1,8−ジイソシアナト−4−イソシアナトメチルオクタン、1,3,6−トリイソシアナトヘキサン、2,5,7−トリメチル−1,8−ジイソシアナト−5−イソシアナトメチルオクタン等の脂肪族ポリイソシアネートが挙げられる。 Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene diisocyanate, and pentane. Aliphatic diisocyanates such as methylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-tri Isocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-i Cyanatophenyl include aliphatic polyisocyanates methyl octane.
脂環族ポリイソシアネートとしては、例えば、1,3−シクロペンタンジイソシアネート、1,4−シクロヘキサンジイソシアネート、1,3−シクロヘキサンジイソシアネート、3−イソシアナトメチル−3,5,5−トリメチルシクロヘキシルイソシアネート(イソホロンジイソシアネート)、4,4’−メチレンビス(シクロヘキシルイソシアネート)、メチル−2,4−シクロヘキサンジイソシアネート、メチル−2,6−シクロヘキサンジイソシアネート、1,3−又は1,4−ビス(イソシアナトメチル)シクロヘキサン等の脂環族ジイソシアネートや、例えば、1,3,5−トリイソシアナトシクロヘキサン、1,3,5−トリメチルイソシアナトシクロヘキサン、2−(3−イソシアナトプロピル)−2,5−ジ(イソシアナトメチル)−ビシクロ[2.2.1]ヘプタン、2−(3−イソシアナトプロピル)−2,6−ジ(イソシアナトメチル)−ビシクロ(2.2.1)ヘプタン、3−(3−イソシアナトプロピル)−2,5−ジ(イソシアナトメチル)−ビシクロ[2.2.1]ヘプタン、5−(2−イソシアナトエチル)−2−イソシアナトメチル−3−(3−イソシアナトプロピル)−ビシクロ[2.2.1]ヘプタン、6−(2−イソシアナトエチル)−2−イソシアナトメチル−3−(3−イソシアナトプロピル)−ビシクロ[2.2.1]ヘプタン、5−(2−イソシアナトエチル)−2−イソシアナトメチル−2−(3−イソシアナトプロピル)−ビシクロ[2.2.1]−ヘプタン、6−(2−イソシアナトエチル)−2−イソシアナトメチル−2−(3−イソシアナトプロピル)−ビシクロ[2.2.1]ヘプタン等の脂環族ポリイソシアネートが挙げられる。 Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate). ), 4,4′-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane Cyclic diisocyanates such as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanate) Tomethyl) -bicyclo [2.2.1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanate Natopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -Bicyclo [2.2.1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 5- ( 2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2.2.1] -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethi 2- (3-isocyanatopropyl) - bicyclo [2.2.1], and aromatic polyisocyanates such as heptane.
芳香族ポリイソシアネートとしては、m−フェニレンジイソシアネート、p−フェニレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、1,5−ナフタレンジイソシアネート、2,4’−又は4,4’−ジフェニルメタンジイソシアネートもしくはその混合物、2,4−又は2,6−トリレンジイソシアネートもしくはその混合物、4,4’−トルイジンジイソシアネート、4,4’−ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネートや、トリフェニルメタン−4,4’,4’’−トリイソシアネート、1,3,5−トリイソシアネートベンゼン、2,4,6−トリイソシアネートトルエン、4,4’−ジフェニルメタン−2,2’,5,5’−テトライソシアネート等の芳香族ポリイソシアネートが挙げられる。 Aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate or mixtures thereof. , 4- or 2,6-tolylene diisocyanate or mixtures thereof, aromatic diisocyanates such as 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and triphenylmethane-4,4 ', 4' '- Aromatic polyisocyanates such as triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate It is below.
ポリイソシアネートの誘導体としては、例えば、上記のポリイソシアネートのダイマー、トリマー(イソシアヌレート環含有ポリイソシアネート)、ビウレット、アロファネート、炭酸ガスと上記ポリイソシアネート単量体との反応により得られる2,4,6−オキサジアジントリオン環を有するポリイソシアネート、カルボジイミド、ウレットジオン、ポリメチレンポリフェニルポリイソシアネート等が挙げられる。 Examples of the polyisocyanate derivative include dimer, trimer (isocyanurate ring-containing polyisocyanate), biuret, allophanate, carbon dioxide gas obtained by the reaction of the polyisocyanate monomer with 2,4,6. -Polyisocyanate having an oxadiazine trione ring, carbodiimide, uretdione, polymethylene polyphenyl polyisocyanate and the like.
更に、ポリイソシアネートの変性体としては、例えば、上記のポリイソシアネートやポリイソシアネートの誘導体と、ポリオール又はポリアミンとを、ポリイソシアネートのイソシアネート基が、ポリオールのヒドロキシル基又はポリアミンのアミノ基よりも過剰となるような当量比で反応させることによって得られる、ポリオール変性体やポリアミン変性体等が挙げられる。これらポリイソシアネート(B−1)は、単独で用いてもよく、2種以上を併用してもよい。 Furthermore, as a modified polyisocyanate, for example, the above polyisocyanate or a polyisocyanate derivative and a polyol or polyamine, the isocyanate group of the polyisocyanate is in excess of the hydroxyl group of the polyol or the amino group of the polyamine. Examples include polyol modified products and polyamine modified products obtained by reacting at such an equivalent ratio. These polyisocyanate (B-1) may be used independently and may use 2 or more types together.
このようなポリイソシアネート(B−1)の代表的な市販品としては、TSA−100、TSR−100、TSS−100、TSE−100(旭化成ケミカルズ株式会社製)、タケネートD−170N、177N(三井化学株式会社製)、バーノック DN−990、DN−992(DIC株式会社製)、コロネート HX、HXR、HXLV(日本ポリウレタン株式会社製)等を挙げることができる。 As typical commercial products of such polyisocyanate (B-1), TSA-100, TSR-100, TSS-100, TSE-100 (manufactured by Asahi Kasei Chemicals Corporation), Takenate D-170N, 177N (Mitsui) Chemical Co., Ltd.), Vernock DN-990, DN-992 (DIC Corporation), Coronate HX, HXR, HXLV (Nihon Polyurethane Co., Ltd.), and the like.
<シランカップリング剤(B−2)>
シランカップリング剤(B−2)は、同一分子内に異なる2種の官能基を有する限り、特に限定されない。
シランカップリング剤(B−2)は、異なる2種の官能基の一方の官能基として、アルコキシシリル基を有する。シランカップリング剤(B−2)は、異なる2種の官能基の一方の官能基として、トリメトキシシリル基又はトリエトキシシリル基を有する。このように、シランカップリング剤(B−2)がトリメトキシシリル基又はトリエトキシシリル基のような、三置換のアルコキシシリル基を有することで、金属基材と形成される塗膜との密着性が向上し、形成される塗膜の防錆性が向上する傾向にある。
<Silane coupling agent (B-2)>
The silane coupling agent (B-2) is not particularly limited as long as it has two different functional groups in the same molecule.
The silane coupling agent (B-2) has an alkoxysilyl group as one functional group of two different functional groups. The silane coupling agent (B-2) has a trimethoxysilyl group or a triethoxysilyl group as one functional group of two different functional groups. In this way, the silane coupling agent (B-2) has a trisubstituted alkoxysilyl group such as a trimethoxysilyl group or a triethoxysilyl group, so that adhesion between the metal substrate and the coating film to be formed is achieved. Tend to be improved, and the rust prevention property of the formed coating film tends to be improved.
シランカップリング剤(B−2)の、異なる2種の官能基の他方の官能基としては、イソシアネート基、イソシアヌレート基、エポキシ基、アミノ基、アクリロイル基、メタクリロイル基、ビニル基、メルカプト基等を挙げることができる。シランカップリング剤(B−2)は、異なる2種の官能基の他方の官能基として、イソシアネート基、イソシアヌレート基又はエポキシ基を有することが好ましい。シランカップリング剤(B−2)がこれらの官能基を有することで、金属基材と形成される塗膜との密着性が向上し、形成される塗膜の防錆性が向上する傾向にある。つまり、シランカップリング剤(B−2)がイソシアネート基又はイソシアヌレート基を有する場合は、これらの官能基が、共重合体(A)のアルキッド部分の水酸基と結合する。また、シランカップリング剤(B−2)がエポキシ基を有する場合は、エポキシ基がアクリル部分のカルボキシル基と酸エポキシ反応によって結合する。このように、シランカップリング剤(B−2)がイソシアネート基、イソシアヌレート基又はエポキシ基を有することで、形成される塗膜中にシランカップリング剤(B−2)が取り込まれやすく、結果的に金属基材と形成される塗膜との密着性が向上することになる。 As the other functional group of two different functional groups of the silane coupling agent (B-2), an isocyanate group, an isocyanurate group, an epoxy group, an amino group, an acryloyl group, a methacryloyl group, a vinyl group, a mercapto group, etc. Can be mentioned. The silane coupling agent (B-2) preferably has an isocyanate group, an isocyanurate group, or an epoxy group as the other functional group of two different functional groups. By having these functional groups in the silane coupling agent (B-2), the adhesion between the metal substrate and the formed coating film is improved, and the rust prevention property of the formed coating film tends to be improved. is there. That is, when the silane coupling agent (B-2) has an isocyanate group or an isocyanurate group, these functional groups are bonded to the hydroxyl group of the alkyd part of the copolymer (A). Moreover, when a silane coupling agent (B-2) has an epoxy group, an epoxy group couple | bonds with the carboxyl group of an acrylic part by acid epoxy reaction. Thus, since the silane coupling agent (B-2) has an isocyanate group, an isocyanurate group or an epoxy group, the silane coupling agent (B-2) is easily taken into the formed coating film, and the result In particular, the adhesion between the metal substrate and the coating film to be formed is improved.
シランカップリング剤(B−2)の具体例としては、γ−イソシアネートプロピルトリメトキシシラン、γ−イソシアネートプロピルトリエトキシシラン、γ−イソシアネートプロピルメチルジエトキシシラン、γ−イソシアネートプロピルメチルジメトキシシラン等のイソシアネート基含有シラン類;γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン等のエポキシ基含有シラン類;γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−(2−アミノエチル)アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジメトキシシラン、γ−(2−アミノエチル)アミノプロピルトリエトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジエトキシシラン、γ−(2−アミノエチル)アミノプロピルトリイソプロポキシシラン、γ−ウレイドプロピルトリメトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン、N−ベンジル−γ−アミノプロピルトリメトキシシラン、N−ビニルベンジル−γ−アミノプロピルトリエトキシシラン等のアミノ基含有シラン類;γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン等のメルカプト基含有シラン類;β−カルボキシエチルトリエトキシシラン、β−カルボキシエチルフェニルビス(2−メトキシエトキシ)シラン、N−β−(カルボキシメチル)アミノエチル−γ−アミノプロピルトリメトキシシラン等のカルボキシシラン類;ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロイルオキシプロピルメチルジメトキシシラン、γ−アクロイルオキシプロピルメチルトリエトキシシラン等のビニル型不飽和基含有シラン類;γ−クロロプロピルトリメトキシシラン等のハロゲン含有シラン類;トリス(トリメトキシシリル)イソシアヌレート等のイソシアヌレートシラン類;ビス(3−トリエトキシシリルプロピル)テトラスルファン等のポリスルファン類等を挙げることができる。 Specific examples of the silane coupling agent (B-2) include isocyanates such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatepropylmethyldimethoxysilane. Group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Epoxy group-containing silanes such as β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxy Orchid, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- ( 2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N Amino group-containing silanes such as phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane , Γ-mercap Mercapto group-containing silanes such as topropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) Carboxysilanes such as silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxy Vinyl-type unsaturated group-containing silanes such as propylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurates such as tris (trimethoxysilyl) isocyanurate Toshiran like; and bis (3-triethoxysilylpropyl) polysulfane such as tetrasulfane like.
このようなシランカップリング剤(B−2)の代表的な市販品としては、KBM−403(3−グリシドキシプロピルトリメトキシシラン)、KBE−403(3−グリシドキシプロピルトリエトキシシラン)、KBM−9659(トリス−(トリメトキシシリルプロピル)イソシアヌレート)、KBE−9007(3−イソシアネートプロピルトリエトキシシラン)、KBE−402(3−グリシドキシプロピルメチルジメトキシシラン)、KBM−303(2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン)、KBE−903(3−アミノプロピルトリエトキシシラン)等(以上、全て信越化学工業株式会社製)を挙げることができる。 Representative commercial products of such silane coupling agents (B-2) include KBM-403 (3-glycidoxypropyltrimethoxysilane) and KBE-403 (3-glycidoxypropyltriethoxysilane). , KBM-9659 (tris- (trimethoxysilylpropyl) isocyanurate), KBE-9007 (3-isocyanatopropyltriethoxysilane), KBE-402 (3-glycidoxypropylmethyldimethoxysilane), KBM-303 (2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane), KBE-903 (3-aminopropyltriethoxysilane) and the like (all are manufactured by Shin-Etsu Chemical Co., Ltd.).
強化剤(II)は、ポリイソシアネート(B−1)及びシランカップリング剤(B−2)を、溶剤と混合して調製される。
溶剤としては、主剤(I)に使用される溶剤と同様のものが使用できる。
また、場合によっては主剤(I)ではなく強化剤(II)に、顔料や、他の添加剤(レベリング剤、タレ防止剤等)を含有させてもよい。
The reinforcing agent (II) is prepared by mixing the polyisocyanate (B-1) and the silane coupling agent (B-2) with a solvent.
As the solvent, the same solvents as those used for the main agent (I) can be used.
In some cases, not the main agent (I) but the reinforcing agent (II) may contain pigments and other additives (leveling agents, sagging inhibitors, etc.).
強化剤(II)中におけるポリイソシアネート(B−1)及びシランカップリング剤(B−2)の含有量は、10〜90質量%であることが好ましく、40〜70質量%であることがより好ましい。 The content of the polyisocyanate (B-1) and the silane coupling agent (B-2) in the reinforcing agent (II) is preferably 10 to 90% by mass, and more preferably 40 to 70% by mass. preferable.
主剤(I)及び強化剤(II)の調製方法としては、特別の方法を必要とせず、当業者において通常用いられる方法を使用することができる。主剤(I)及び強化剤(II)は、例えば、各成分をディスパー、ボールミル、S.G.ミル、ロールミル等の分散機で溶剤中に分散することにより調製する方法を挙げることができる。 As a method for preparing the main agent (I) and the reinforcing agent (II), a special method is not required, and methods usually used by those skilled in the art can be used. The main agent (I) and the reinforcing agent (II) are, for example, dispersers, ball mills, S. G. The method of preparing by disperse | distributing in a solvent with dispersers, such as a mill and a roll mill, can be mentioned.
[塗膜形成方法]
本実施形態に係る塗膜形成方法は、混合工程と、塗装工程と、硬化工程と、を有する。
混合工程では、上記実施形態に係る二液混合型塗料組成物の主剤(I)及び強化剤(II)を混合して混合塗料組成物を得る。
[Coating film forming method]
The coating film forming method according to the present embodiment includes a mixing process, a painting process, and a curing process.
In the mixing step, the main component (I) and the reinforcing agent (II) of the two-component mixed coating composition according to the above embodiment are mixed to obtain a mixed coating composition.
混合工程における混合方法は特に限定されない。混合方法としては、主剤(I)及び強化剤(II)を配合し、ハンドミキサーやスタティックミキサーで混合する方法が挙げられる。 The mixing method in the mixing step is not particularly limited. Examples of the mixing method include a method in which the main agent (I) and the reinforcing agent (II) are blended and mixed with a hand mixer or a static mixer.
主剤(I)及び強化剤(II)の配合比は、全固形分換算で70/30〜95/5とすることが好ましい。このような配合比とすることで、塗膜の形成が円滑に進行する。
また、強化剤(II)中のポリイソシアネート(B−1)に由来するイソシアネート基と、主剤(I)中の酸共重合体(A)に由来する水酸基の当量比(NCO当量/OH当量)は、0.5〜1.5であることが好ましい。二液混合型塗料組成物における上記当量比(NCO当量/OH当量)の値が上記範囲外となると、形成される塗膜がべたつきやすくなる傾向にある。
The mixing ratio of the main agent (I) and the reinforcing agent (II) is preferably 70/30 to 95/5 in terms of total solids. By setting it as such a compounding ratio, formation of a coating film advances smoothly.
Moreover, the equivalent ratio (NCO equivalent / OH equivalent) of the isocyanate group derived from the polyisocyanate (B-1) in the reinforcing agent (II) and the hydroxyl group derived from the acid copolymer (A) in the main agent (I) Is preferably 0.5 to 1.5. When the value of the equivalent ratio (NCO equivalent / OH equivalent) in the two-component mixed coating composition is out of the above range, the formed coating film tends to be sticky.
更に、主剤(I)及び強化剤(II)(二液混合型塗料組成物)の全固形分における、強化剤(II)中のシランカップリング剤(B−2)の含有量は、0.1〜10質量%であることが好ましい。主剤(I)及び強化剤(II)の全固形分におけるシランカップリング剤(B−2)の含有量が、0.1質量%未満であると形成される塗膜の防錆性が低下する傾向にあり、10質量%よりも多いと強化剤(II)の貯蔵安定性が低下し、二液混合型塗料組成物の取り扱い性も低下する傾向にある。主剤(I)及び強化剤(II)(二液混合型塗料組成物)の全固形分における、強化剤(II)中のシランカップリング剤(B−2)の含有量は、0.5〜3.0質量%であることがより好ましい。 Furthermore, the content of the silane coupling agent (B-2) in the reinforcing agent (II) in the total solid content of the main agent (I) and the reinforcing agent (II) (two-component mixed coating composition) is 0.00. It is preferable that it is 1-10 mass%. When the content of the silane coupling agent (B-2) in the total solid content of the main agent (I) and the reinforcing agent (II) is less than 0.1% by mass, the rust prevention property of the formed coating film is lowered. If the amount is more than 10% by mass, the storage stability of the reinforcing agent (II) is lowered, and the handleability of the two-component mixed coating composition tends to be lowered. The content of the silane coupling agent (B-2) in the reinforcing agent (II) in the total solid content of the main agent (I) and the reinforcing agent (II) (two-component mixed coating composition) is 0.5 to It is more preferable that it is 3.0 mass%.
混合塗料組成物の全固形分濃度は、30〜70質量%であることが好ましい。混合塗料組成物の全固形分濃度が、上記範囲外であると、混合塗料組成物の取扱いが難しくなる傾向にある。 The total solid content of the mixed coating composition is preferably 30 to 70% by mass. When the total solid concentration of the mixed coating composition is outside the above range, the mixed coating composition tends to be difficult to handle.
塗装工程では、混合塗料組成物を、刷毛、ローラー、スプレー等を用いて、金属基材の表面に塗装する。
塗装工程では、形成される塗膜の膜厚(硬化後の膜厚)が10〜100μmとなるように塗装することが好ましい。硬化後の膜厚が10μm未満となるように塗装した場合、金属基材の保護効果が低くなってしまう。一方、混合塗料組成物を、硬化後の膜厚が100μmを超えるように塗装した場合、塗膜の形成のために使用する塗料組成物の量が多くなるのでコストが高くなる傾向にあるうえ、塗料流れや乾燥性不良が生じるおそれがある。
In the coating process, the mixed coating composition is applied to the surface of the metal substrate using a brush, a roller, a spray, or the like.
In the coating process, it is preferable that the coating film to be formed is coated so that the film thickness (film thickness after curing) is 10 to 100 μm. When it coats so that the film thickness after hardening may be less than 10 micrometers, the protective effect of a metal base material will become low. On the other hand, when the mixed coating composition is applied so that the film thickness after curing exceeds 100 μm, the amount of the coating composition used for forming the coating film tends to increase, and the cost tends to increase. There is a risk of paint flow and drying failure.
硬化工程における、混合塗料組成物の硬化方法は特に限定されないが、通常、金属基材を自然条件で放置することにより塗膜を形成させる。 The method for curing the mixed coating composition in the curing step is not particularly limited, but usually a coating film is formed by leaving the metal substrate under natural conditions.
以上説明した本実施形態に係る二液混合型塗料組成物によれば、以下の効果が奏される。
本実施形態では、金属基材の表面を被覆する塗膜を形成するために用いられる、主剤(I)及び強化剤(II)からなる二液混合型塗料組成物において、主剤(I)が共重合体(A)を含み、強化剤(II)が、ポリイソシアネート(B−1)とシランカップリング剤(B−2)とを含むものとした。
これにより、塗膜の形成において下記の(1)〜(3)の反応が進行する。
(1)共重合体(A)の酸化重合可能な不飽和脂肪酸(a−1)及び酸化重合性基を有するアルキッド樹脂(a−2)の少なくとも一方に由来する部分同士の酸化重合。
(2)共重合体(A)のシリコーン部分同士のシロキサン反応。
(3)シランカップリング剤(B−2)のケイ素官能基が加水分解されて生成するシラノール基の、金属基材への配位。
According to the two-component mixed coating composition according to the present embodiment described above, the following effects are exhibited.
In this embodiment, in the two-component mixed coating composition comprising the main agent (I) and the reinforcing agent (II) used for forming a coating film that covers the surface of the metal substrate, the main agent (I) The reinforcing agent (II) contains the polymer (A) and the polyisocyanate (B-1) and the silane coupling agent (B-2).
Thereby, reaction of following (1)-(3) advances in formation of a coating film.
(1) Oxidative polymerization of portions derived from at least one of unsaturated fatty acid (a-1) capable of oxidative polymerization of copolymer (A) and alkyd resin (a-2) having an oxidizable polymerizable group.
(2) Siloxane reaction between silicone parts of the copolymer (A).
(3) Coordination of the silanol group produced by hydrolysis of the silicon functional group of the silane coupling agent (B-2) to the metal substrate.
上記(1)及び(2)は、共重合体(A)自身による塗膜の形成反応である。上記(1)及び(2)によって、強度の高い塗膜を形成することができる。また、上記(1)及び(2)によって、光沢を帯びて肉持ち感がある塗膜を形成できる。
そして、上記(3)によって、塗膜と金属基材との付着性を向上させることができることから、塗膜の防錆性がより向上する。
以上のように、本実施形態に係る二液混合型塗料組成物は、塗装作業性が良好であり、形成される塗膜が光沢を帯びて肉持ち感がある上に、予め錆止め塗料組成物を塗装しなくても防錆性の高い塗膜を形成することが可能である。
Said (1) and (2) are the formation reaction of the coating film by copolymer (A) itself. A coating film having high strength can be formed by the above (1) and (2). Moreover, the said (1) and (2) can form the coating film which is glossy and has a feeling of flesh.
And since said (3) can improve the adhesiveness of a coating film and a metal base material, the rust prevention property of a coating film improves more.
As described above, the two-component mixed coating composition according to the present embodiment has good coating workability, and the formed coating film is glossy and has a feeling of fleshiness. Even without coating, it is possible to form a coating film having a high rust prevention property.
なお、本発明は上記実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれる。 It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within a scope that can achieve the object of the present invention are included in the present invention.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、特に断りのない限り「部」及び「%」は、質量基準である。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
[主剤(I)]
実施例及び比較例に係る二液混合型塗料組成物の主剤(I)としては、後述する合成例(1)〜(3)によってそれぞれ得られる共重合体(A)を用いた。
[Main agent (I)]
As the main component (I) of the two-component mixed coating composition according to Examples and Comparative Examples, the copolymers (A) obtained by Synthesis Examples (1) to (3) described later were used.
[強化剤(II)]
実施例及び比較例に係る二液混合型塗料組成物の強化剤(II)は、表1に示すポリイソシアネート及びシランカップリング剤が、表1に示す固形分質量比(単位:質量部)となるように混合した。
[Strengthening agent (II)]
The reinforcing agent (II) of the two-component mixed coating composition according to the example and the comparative example has a polyisocyanate and a silane coupling agent shown in Table 1 and a solid content mass ratio (unit: parts by mass) shown in Table 1. It mixed so that it might become.
なお、ポリイソシアネートとしては、以下のものを使用した。
ポリイソシアネート:デュラネートTSA−100、HDIヌレートタイプ、NCO%:20.6%、固形分100%、旭化成ケミカルズ株式会社製
In addition, the following were used as polyisocyanate.
Polyisocyanate: Duranate TSA-100, HDI nurate type, NCO%: 20.6%, solid content 100%, manufactured by Asahi Kasei Chemicals Corporation
また、シランカップリング剤としては、以下のものを使用した(以下、全て信越化学工業株式会社製)。
3−グリシドキシプロピルトリメトキシシラン:KBM−403
3−グリシドキシプロピルトリエトキシシラン:KBE−403
トリス−(トリメトキシシリルプロピル)イソシアヌレート:KBM−9659
3−イソシアネートプロピルトリエトキシシラン:KBE−9007
3−グリシドキシプロピルメチルジメトキシシラン:KBE−402
3−アミノプロピルトリエトキシシラン:KBE−903
In addition, the following were used as silane coupling agents (hereinafter all manufactured by Shin-Etsu Chemical Co., Ltd.).
3-Glycidoxypropyltrimethoxysilane: KBM-403
3-Glycidoxypropyltriethoxysilane: KBE-403
Tris- (trimethoxysilylpropyl) isocyanurate: KBM-9659
3-isocyanatopropyltriethoxysilane: KBE-9007
3-Glycidoxypropylmethyldimethoxysilane: KBE-402
3-aminopropyltriethoxysilane: KBE-903
[酸化硬化型アルキド樹脂の合成]
大豆油650質量部、ペンタエリスリトール137質量部及び水酸化リチウム0.15質量部を反応容器に仕込み、250℃まで昇温した。1時間のエステル交換後、200℃にて脂肪酸240質量部及びキシレン30質量部を加え、更に240℃まで昇温した。次いで、キシレンにて還流しながら、同温度にて酸価6となるまで約5時間反応させた後、不揮発分が60質量%となるように溶剤としてソルベッソ100(芳香族系炭化水素溶剤、東燃ゼネラル石油株式会社製)を670質量部加え、数平均分子量2,500、酸価44、脂肪酸62%の酸化硬化型アルキッド樹脂を得た。
[Synthesis of oxidation-curing alkyd resin]
650 parts by mass of soybean oil, 137 parts by mass of pentaerythritol and 0.15 parts by mass of lithium hydroxide were charged into a reaction vessel, and the temperature was raised to 250 ° C. After transesterification for 1 hour, 240 parts by mass of fatty acid and 30 parts by mass of xylene were added at 200 ° C., and the temperature was further raised to 240 ° C. Next, the reaction was continued for about 5 hours at the same temperature while refluxing with xylene until an acid value of 6 was reached, and then Solvesso 100 (aromatic hydrocarbon solvent, Tonen as a solvent so that the non-volatile content was 60% by mass. 670 parts by mass of General Petroleum Co., Ltd. was added to obtain an oxidatively curable alkyd resin having a number average molecular weight of 2,500, an acid value of 44, and a fatty acid of 62%.
[酸化硬化型アクリル共重合体の合成]
上記で得られた酸化硬化型アルキッド樹脂667質量部及び溶剤としてのソルベッソ100を410質量部、反応容器に仕込み120℃に昇温した。ついで下記に示すモノマー混合物を4時間かけて反応容器に滴下した。
(モノマー混合物)
メタクリル酸2−ヒドロキシエチル:100質量部
アクリル酸2−エチルヘキシル:35質量部
tert−ブチルパーオキシ(2−エチルエキサノエート):8質量部
tert−ブチルパーオキシベンゾエート:5質量部
ソルベッソ100:150質量部
次いで、120℃を保持しながら、不揮発分が50質量%となるように溶剤としてソルベッソ100を182質量部加えることにより、酸化硬化型アルキド樹脂に由来する構造及びアクリル共重合体に由来する構造を有し且つ水酸基を有する酸化硬化型アクリル共重合体(X)を得た。
[Synthesis of oxidation-curing acrylic copolymer]
The reaction vessel was charged with 667 parts by mass of the above-obtained oxidative curable alkyd resin and 410 parts by mass of Solvesso 100 as a solvent, and the temperature was raised to 120 ° C. Then, the monomer mixture shown below was dropped into the reaction vessel over 4 hours.
(Monomer mixture)
2-hydroxyethyl methacrylate: 100 parts by mass 2-ethylhexyl acrylate: 35 parts by mass tert-butyl peroxy (2-ethylexanoate): 8 parts by mass tert-butyl peroxybenzoate: 5 parts by mass Solvesso 100: 150 Next, 182 parts by mass of Solvesso 100 is added as a solvent so that the non-volatile content is 50% by mass while maintaining 120 ° C., and the structure derived from the oxidation-curable alkyd resin and the acrylic copolymer are derived. An oxidatively curable acrylic copolymer (X) having a structure and having a hydroxyl group was obtained.
[共重合体(A)の合成例(1)]
上記で得られた酸化硬化型アクリル共重合体(X)を2013部、シリコーン樹脂としてZ−6018(東レ・ダウコーニング株式会社製)を164質量部、溶剤としてソルベッソ100を115質量部及びキシレンを50質量部並びに反応触媒としてテトラ−n−ブチルチタネート0.8質量部を全て反応容器に仕込み、165℃まで昇温した。次いで、キシレン還流下、同温度にて5時間反応させた。不揮発分が60質量%、重量平均分子量73,000、水酸基価50、脂肪酸に由来する部分の含有量20質量%、ヨウ素価28、シリコーン樹脂に由来する部分の含有量14質量%の共重合体(A)を得た。
[Synthesis Example of Copolymer (A) (1)]
2013 parts of the oxidation curable acrylic copolymer (X) obtained above, 164 parts by mass of Z-6018 (manufactured by Toray Dow Corning Co., Ltd.) as a silicone resin, 115 parts by mass of Solvesso 100 as a solvent and xylene 50 parts by mass and all 0.8 parts by mass of tetra-n-butyl titanate as a reaction catalyst were charged in a reaction vessel and heated to 165 ° C. Subsequently, it was made to react at the same temperature for 5 hours under xylene reflux. A copolymer having a nonvolatile content of 60% by mass, a weight average molecular weight of 73,000, a hydroxyl value of 50, a content derived from a fatty acid of 20% by mass, an iodine value of 28, and a content derived from a silicone resin of 14% by mass (A) was obtained.
[共重合体(A)の合成例(2)]
上記で得られた酸化硬化型アクリル共重合体(X)を2013部、シリコーン樹脂としてZ−6018(東レ・ダウコーニング株式会社製)を82質量部、溶剤としてソルベッソ100を57質量部及びキシレンを25質量部並びに反応触媒としてテトラ−n−ブチルチタネート0.8質量部を全て反応容器に仕込み、165℃まで昇温した。次いで、キシレンにて還流しながら、同温度にて5時間反応させた。不揮発分が50質量%、重量平均分子量59,000、水酸基価55、脂肪酸に由来する部分の含有量22質量%、ヨウ素価31、シリコーン樹脂に由来する部分の含有量7質量%の共重合体(A)を得た。
[Synthesis Example of Copolymer (A) (2)]
2013 parts of the oxidation-curable acrylic copolymer (X) obtained above, 82 parts by mass of Z-6018 (manufactured by Toray Dow Corning Co., Ltd.) as a silicone resin, 57 parts by mass of Solvesso 100 as a solvent and xylene 25 parts by mass and 0.8 parts by mass of tetra-n-butyl titanate as a reaction catalyst were charged in a reaction vessel, and the temperature was raised to 165 ° C. Next, the mixture was reacted at the same temperature for 5 hours while refluxing with xylene. A copolymer having a nonvolatile content of 50% by mass, a weight average molecular weight of 59,000, a hydroxyl value of 55, a content of 22 parts by mass derived from fatty acids, an iodine value of 31 and a content of 7 parts by mass of parts derived from silicone resin (A) was obtained.
[共重合体(A)の合成例(3)]
上記で得られた酸化硬化型アクリル共重合体(X)を2013部、シリコーン樹脂としてZ−6018(東レ・ダウコーニング株式会社製)を41質量部、溶剤としてソルベッソ100を29質量部及びキシレンを12質量部並びに反応触媒としてテトラ−n−ブチルチタネート0.8質量部を全て反応容器に仕込み、165℃まで昇温した。次いで、キシレンにて還流しながら、同温度にて5時間反応させた。不揮発分が50質量%、重量平均分子量44,000、水酸基価57、脂肪酸に由来する部分の含有量23質量%、ヨウ素価57、シリコーン樹脂に由来する部分の含有量に由来する部分の含有量4%の共重合体(A)を得た。
[Synthesis Example of Copolymer (A) (3)]
2013 parts of the oxidation curable acrylic copolymer (X) obtained above, Z-6018 (manufactured by Toray Dow Corning Co., Ltd.) as a silicone resin, 41 parts by mass, 29 parts by mass of Solvesso 100 as a solvent, and xylene All 12 parts by mass and 0.8 parts by mass of tetra-n-butyl titanate as a reaction catalyst were charged in a reaction vessel, and the temperature was raised to 165 ° C. Next, the mixture was reacted at the same temperature for 5 hours while refluxing with xylene. Nonvolatile content is 50% by mass, weight average molecular weight 44,000, hydroxyl value 57, content of part derived from fatty acid 23% by mass, iodine value 57, content of part derived from content of part derived from silicone resin 4% of copolymer (A) was obtained.
[混合型塗料組成物の調製]
[実施例1から13及び比較例1から3]
上記主剤(I)及び強化剤(II)を、各成分が表1に示した固形分含有量(単位:質量部)となるように混合し、十分に撹拌して得られた混合型塗料組成物を得た。
[Preparation of mixed coating composition]
[Examples 1 to 13 and Comparative Examples 1 to 3]
A mixed paint composition obtained by mixing the main component (I) and the reinforcing agent (II) so that each component has a solid content (unit: part by mass) shown in Table 1 and stirring sufficiently. I got a thing.
[評価用試験板の作製]
評価用試験板の基材としては、みがき鋼板(150×70×0.8mm)を用いた。まず、みがき鋼板表面の防錆油を溶剤(キシレン)で洗浄し、溶剤をウエスでふき取った。そして、溶剤をふき取ったみがき鋼板の裏面に錆止め塗料組成物(ファインプライマーII、日本ペイント株式会社製)を塗装し、裏面をバックシールした。みがき鋼板の裏面の錆止め塗料が乾燥した後、みがき鋼板の表面に、混合塗料組成物を、刷毛を用いて塗布量が100〜120g/m2なるように塗装した。混合塗料組成物は、上記の実施例又は比較例の、主剤(I)及び強化剤(II)のそれぞれの成分が表1に示すような固形分質量比(単位:質量部)となるように混合することで得た。
続いて、混合塗料組成物を塗装したみがき鋼板を、室温にて24時間放置後、試験板の側面(端面)を上述の錆止め塗料組成物にて塗装し、側面をサイドシールした。更に、みがき鋼板を室温にて6日間放置乾燥することで、実施例及び比較例の評価用試験板を得た。
[Preparation of test plate for evaluation]
A polished steel plate (150 × 70 × 0.8 mm) was used as the base material for the test plate for evaluation. First, the rust preventive oil on the surface of the polished steel plate was washed with a solvent (xylene), and the solvent was wiped off with a waste cloth. Then, a rust-preventive paint composition (Fine Primer II, manufactured by Nippon Paint Co., Ltd.) was applied to the back surface of the polished steel plate after wiping off the solvent, and the back surface was back-sealed. After the rust preventive coating on the back surface of the polished steel plate was dried, the mixed coating composition was applied to the surface of the polished steel plate with a brush so that the coating amount was 100 to 120 g / m 2 . In the mixed coating composition, the respective components of the main agent (I) and the reinforcing agent (II) in the above Examples or Comparative Examples have a solid content mass ratio (unit: parts by mass) as shown in Table 1. Obtained by mixing.
Subsequently, the polished steel plate coated with the mixed coating composition was allowed to stand at room temperature for 24 hours, and then the side surface (end surface) of the test plate was coated with the above-mentioned rust-preventing coating composition, and the side surface was side-sealed. Furthermore, the test plate for evaluation of an Example and a comparative example was obtained by leaving and drying a polished steel plate at room temperature for 6 days.
<塩水噴霧(SST)試験>
実施例及び比較例の試験板の表面(混合塗料組成物を塗装した面)に、ユーティリティナイフで基材に達するようにクロスカット傷を入れた。次いで、試験板のクロスカット傷を入れた表面に対して、JIS Z 2371に準拠する塩水噴霧試験を48時間行った。その後、平面部における点錆及びふくれ(ブリスター)の発生を観察し、クロスカット部において発生した錆の幅及びクロスカット傷からの塗膜の膨れ幅(片側)の最大値を測定し、下記評価基準により評価を行った。「B」以上の評価を以って合格とした。結果を表1に示す。
<Salt spray (SST) test>
Crosscut scratches were made on the surface of the test plates of Examples and Comparative Examples (surface coated with the mixed coating composition) so as to reach the substrate with a utility knife. Next, a salt spray test in accordance with JIS Z 2371 was performed for 48 hours on the surface of the test plate with the cross cut wound. Then, the occurrence of spot rust and blisters (blisters) in the flat part was observed, and the maximum value of the width of the rust generated in the crosscut part and the swollen width (one side) of the coating film from the crosscut flaw was measured, and the following evaluation was performed. Evaluation was performed according to criteria. An evaluation of “B” or higher was accepted. The results are shown in Table 1.
<サイクル腐食(CCT)試験>
実施例及び比較例の試験板の表面(混合塗料組成物を塗装した面)に、ユーティリティナイフで基材に達するようにクロスカット傷を入れた。次いで、試験板のクロスカット傷を入れた表面に対して、35℃に保温した5質量%NaCl水溶液を2時間連続で噴霧した後、60℃、湿度20〜30%の条件下で4時間乾燥した。その後、50℃、湿度95%以上の湿潤雰囲気下で試験板を2時間静置した。NaCl水溶液の2時間連続での噴霧及び2時間の静置を1サイクルとして、36サイクル繰り返した。その後、平面部における点錆及びふくれ(ブリスター)の発生を観察し、クロスカット部において発生した錆の幅及びクロスカット傷からの塗膜の膨れ幅(片側)の最大値を測定し、下記評価基準により評価を行った。「B」以上の評価を以って合格とした。結果を表1に示す。
<Cycle corrosion (CCT) test>
Crosscut scratches were made on the surface of the test plates of Examples and Comparative Examples (surface coated with the mixed coating composition) so as to reach the substrate with a utility knife. Next, after spraying a 5 mass% NaCl aqueous solution kept at 35 ° C. for 2 hours continuously on the surface of the test plate with the cross-cut scratches, it was dried for 4 hours under conditions of 60 ° C. and humidity 20-30%. did. Thereafter, the test plate was allowed to stand for 2 hours in a humid atmosphere of 50 ° C. and humidity of 95% or more. Spraying of the NaCl aqueous solution for 2 hours continuously and standing for 2 hours was taken as 1 cycle, and 36 cycles were repeated. Then, the occurrence of spot rust and blisters (blisters) in the flat part was observed, and the maximum value of the width of the rust generated in the crosscut part and the swollen width (one side) of the coating film from the crosscut flaw was measured, and the following evaluation was performed. Evaluation was performed according to criteria. An evaluation of “B” or higher was accepted. The results are shown in Table 1.
<SST試験及びCCT試験の評価基準>
平面部点錆の評価(ASTM D610−68 A法に準拠)
A:錆発生面積が0.03%未満
B:錆発生面積が0.03〜1%
C:錆発生面積が1〜3%
D:錆発生面積が3〜10%
E:錆発生面積が10%以上
<Evaluation criteria for SST test and CCT test>
Evaluation of flat point rust (conforms to ASTM D610-68 A method)
A: Rust generation area is less than 0.03% B: Rust generation area is 0.03 to 1%
C: Rust generation area is 1 to 3%
D: Rust generation area is 3 to 10%
E: Rust generation area is 10% or more
平面部ふくれの評価(ASTM D714−56に準拠)
A:10点(ふくれ無し)
B:8点
C:6点
D:4点
E:3点以下
Flat surface blister evaluation (according to ASTM D714-56)
A: 10 points (no blister)
B: 8 points C: 6 points D: 4 points E: 3 points or less
クロスカット部の錆幅の評価
A:錆の最大幅がカット部より0mm(両側) (発生がない)
B:錆の最大幅がカット部より0mm以上0.5mm未満(両側)
C:錆の最大幅がカット部より0.5mm以上1mm未満(両側)
D:錆の最大幅がカット部より1mmを超える
Evaluation of rust width of cross cut part A: The maximum width of rust is 0 mm from the cut part (both sides) (No occurrence)
B: The maximum width of rust is 0 mm or more and less than 0.5 mm from the cut part (both sides)
C: The maximum width of rust is 0.5 mm or more and less than 1 mm from the cut part (both sides)
D: The maximum width of rust exceeds 1 mm from the cut part
クロスカット部のふくれ幅の評価
A:ふくれの最大幅がカット部より0mm(両側) (発生がない)
B:ふくれの最大幅がカット部より0mm以上0.5mm未満(両側)
C:ふくれの最大幅がカット部より0.5mm以上1mm未満(両側)
D:ふくれの最大幅がカット部より1mmを超える
Evaluation of bulge width of cross cut part A: Maximum width of bulge is 0mm from cut part (both sides) (No occurrence)
B: The maximum width of the blister is 0 mm or more and less than 0.5 mm from the cut part (both sides)
C: The maximum width of the blister is 0.5 mm or more and less than 1 mm from the cut part (both sides)
D: The maximum width of the blister exceeds 1 mm from the cut part
<耐水性試験>
実施例及び比較例の試験板を、20℃の水に16時間浸漬して引き上げた。引き上げ直後に塗膜表面のふくれを観察した。塗膜ふくれの判定基準は、ASTM D714−56に準拠して、下記評価基準により評価を行った。「B」以上の評価を以って合格とした。結果を表1に示す。
平面部ふくれの評価
A:10点(ふくれ無し)
B:8点
C:6点
D:4点
E:3点以下
<Water resistance test>
The test plates of Examples and Comparative Examples were pulled up by dipping in 20 ° C. water for 16 hours. Immediately after the lifting, the surface of the coating film was observed to bulge. The criteria for coating blistering were evaluated according to the following criteria based on ASTM D714-56. An evaluation of “B” or higher was accepted. The results are shown in Table 1.
Flat part blister evaluation A: 10 points (no blister)
B: 8 points C: 6 points D: 4 points E: 3 points or less
<耐アルカリ性試験>
JPMS 27.7.12 耐アルカリ性(社団法人日本塗料工業会規格)に準じる。
具体的には、実施例及び比較例の試験板を、JIS K 8575に規定する、水酸化カルシウムを脱イオン水で溶解した飽和水溶液に浸漬し、評価面に発生したふくれ(ブリスター)の大きさと発生密度を目視にて評価した。浸せき温度は23.2℃、浸せき時間は168時間(7日間)とした。下記の判定基準に従って評価し、「B」以上の評価を以って合格とした。結果を表1に示す。
平面部ふくれの評価(ASTM D714−56に準拠)
A:10点(ふくれ無し)
B:8点
C:6点
D:4点
E:3点以下
<Alkali resistance test>
According to JPMS 27.7.12. Alkali resistance (Japan Paint Manufacturers Association standard).
Specifically, the test plates of Examples and Comparative Examples are immersed in a saturated aqueous solution in which calcium hydroxide is dissolved in deionized water as defined in JIS K 8575, and the size of blisters generated on the evaluation surface is measured. The generation density was evaluated visually. The immersion temperature was 23.2 ° C., and the immersion time was 168 hours (7 days). The evaluation was made according to the following criteria, and the evaluation was “B” or higher to be accepted. The results are shown in Table 1.
Flat surface blister evaluation (according to ASTM D714-56)
A: 10 points (no blister)
B: 8 points C: 6 points D: 4 points E: 3 points or less
<耐酸性試験>
JPMS 27.7.11 耐酸性(社団法人日本塗料工業会規格)に準じる。
具体的には、実施例及び比較例の試験板を、JIS K 8951に規定する、硫酸を脱イオン水で5g/Lに調製した酸性溶液に浸漬し、評価面に発生したふくれ(ブリスター)の大きさと発生密度を目視にて評価した。浸せき時間は168時間(7日間)とした。下記の判定基準に従って評価し、「B」以上の評価を以って合格とした。結果を表1に示す。
平面部ふくれの評価(ASTM D714−56に準拠)
A:10点(ふくれ無し)
B:8点
C:6点
D:4点
E:3点以下
<Acid resistance test>
It conforms to JPMS 27.7.11 acid resistance (Japan Paint Manufacturers Association standard).
Specifically, the test plates of Examples and Comparative Examples were immersed in an acidic solution prepared in deionized water to 5 g / L as defined in JIS K 8951, and blisters (blisters) generated on the evaluation surface. The size and density were evaluated visually. The immersion time was 168 hours (7 days). The evaluation was made according to the following criteria, and the evaluation was “B” or higher to be accepted. The results are shown in Table 1.
Flat surface blister evaluation (according to ASTM D714-56)
A: 10 points (no blister)
B: 8 points C: 6 points D: 4 points E: 3 points or less
<耐結露性試験>
上記の実施例又は比較例の、主剤(I)及び強化剤(II)のそれぞれの成分が表1に示すような固形分質量比(単位:質量部)となるように混合することで得た混合塗料組成物を、18L石油缶(以下、単に石油缶という)の側面(縦15cm×横5cm)に刷毛を用いて、塗布量が100〜120g/m2となるように塗装した。続いて、石油缶を23℃で所定時間放置することで塗膜を乾燥し、得られた石油缶を耐結露性試験に供した。耐結露性試験は、室温23℃、湿度50%の恒温恒湿室にて実施した。
まず、石油缶内に氷水を半分程度入れ、氷水を撹拌し(撹拌条件:ラボミキサー(プライミックス株式会社製)、500回転/分にて30分間撹拌)、塗膜表面に結露水が着いたのを確認したら翌日まで放置した。翌日、塗膜表面の結露水が乾燥したのを確認後、缶内の水を抜き取り、光沢計(コニカミノルタ株式会社製の光沢計、品番:MULTI GLOSS 268plus)を用い、測定角度20度にて結露部(GR1)と未結露部(GR2)の光沢を測定し、グロスリテンションGR2/GR1を百分率で算出した。このグロスリテンションGR2/GR1を下記の判定基準に従って評価し、「B」以上の評価を以って合格とした。結果を表1に示す。
耐結露性判定基準
A:グロスリテンションGR2/GR1が90%を超える
B:グロスリテンションGR2/GR1が80%以上90%以下
C:グロスリテンションGR2/GR1が70%以上80%未満
D:グロスリテンションGR2/GR1が70%未満
<Condensation resistance test>
It obtained by mixing so that each component of main ingredient (I) and reinforcement | strengthening agent (II) of said Example or a comparative example might become solid content mass ratio (unit: mass part) as shown in Table 1. The mixed coating composition was applied on the side surface (15 cm long × 5 cm wide) of an 18 L oil can (hereinafter simply referred to as “oil can”) using a brush so that the coating amount was 100 to 120 g / m 2 . Subsequently, the coating film was dried by allowing the oil can to stand at 23 ° C. for a predetermined time, and the obtained oil can was subjected to a condensation resistance test. The dew condensation resistance test was performed in a constant temperature and humidity room at a room temperature of 23 ° C. and a humidity of 50%.
First, about half of the ice water was put in an oil can, and the ice water was stirred (stirring conditions: lab mixer (manufactured by Primix Co., Ltd.), stirring for 30 minutes at 500 rpm), and condensed water was deposited on the surface of the coating film. After confirming, I left it until the next day. The next day, after confirming that the condensed water on the surface of the coating film has dried, the water in the can is removed, and a gloss meter (Gloss meter manufactured by Konica Minolta Co., Ltd., product number: MULTI GLOSS 268plus) is used at a measurement angle of 20 degrees. The gloss of the dew condensation part (GR1) and the non-condensation part (GR2) was measured, and the gloss retention GR2 / GR1 was calculated as a percentage. The gloss retention GR2 / GR1 was evaluated according to the following criteria, and the evaluation was “B” or higher to be accepted. The results are shown in Table 1.
Criteria for determination of condensation resistance A: Gloss retention GR2 / GR1 exceeds 90% B: Gloss retention GR2 / GR1 is 80% or more and 90% or less C: Gloss retention GR2 / GR1 is 70% or more and less than 80% D: Gloss retention GR2 / GR1 is less than 70%
<初期乾燥性試験>
ガラス板上に、上記の実施例又は比較例の、主剤(I)及び強化剤(II)のそれぞれの成分が表1に示すような固形分質量比(単位:質量部)となるように混合することで得た混合塗料組成物を塗装した。塗装は、フィルムアプリケータ(大佑機材株式会社製)を用いて行い、膜厚が300μmとなるようにした。塗装後、20℃、75%RHの室内に6時間放置して、塗膜の指触乾燥性を調べ、下記の判定基準に従って評価した。
A:全く指紋がつかない
B:わずかに指紋がつく
C:指紋がつく
D:塗膜が指に付着する
<Initial drying test>
On the glass plate, mixing so that each component of the main agent (I) and the reinforcing agent (II) in the above examples or comparative examples has a solid content mass ratio (unit: parts by mass) as shown in Table 1. The mixed coating composition obtained was applied. The coating was performed using a film applicator (manufactured by Otsugi Equipment Co., Ltd.) so that the film thickness was 300 μm. After coating, it was left in a room at 20 ° C. and 75% RH for 6 hours to examine the dryness to touch of the coating film, and evaluated according to the following criteria.
A: No fingerprint at all B: Slight fingerprint is attached C: Fingerprint is attached D: Film is attached to the finger
実施例1〜13と、比較例2との比較から、実施例1〜13の塗膜の方が比較例2の塗膜よりも、防錆性が高いことが分かった。この結果から、強化剤(II)が同一分子内に異なる2種の官能基を有するシランカップリング剤(B−2)を含有することで、金属基材と形成される塗膜との付着性が向上し、塗膜の防錆性が高まることが明らかになった。 From a comparison between Examples 1 to 13 and Comparative Example 2, it was found that the coating films of Examples 1 to 13 had higher rust prevention properties than the coating film of Comparative Example 2. From this result, the reinforcing agent (II) contains the silane coupling agent (B-2) having two different functional groups in the same molecule, so that the adhesion between the metal substrate and the coating film to be formed is improved. It became clear that the rust prevention property of the coating film increased.
実施例3、12及び13と、比較例3との比較から、実施例3、12及び13の塗膜の方が、比較例3の塗膜よりも、防錆性、耐水性、耐アルカリ性、耐酸性、耐結露性及び初期乾燥性に優れることが分かった。この結果から、主剤(I)が酸化重合可能な不飽和脂肪酸(a−1)及び酸化重合性基を有するアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、水酸基及びアルコキシシリル基の少なくとも一方を有するシリコーン(a−4)と、の共重合体(A)を含有することによって、形成される塗膜の物性が向上することが明らかになった。 From the comparison between Examples 3, 12 and 13 and Comparative Example 3, the coating films of Examples 3, 12 and 13 were more resistant to rust, water and alkali than the coating film of Comparative Example 3. It was found to be excellent in acid resistance, condensation resistance and initial drying. From this result, at least one of the unsaturated fatty acid (a-1) in which the main agent (I) is oxidatively polymerizable and the alkyd resin (a-2) having an oxidatively polymerizable group, an acrylic copolymer (a-3), It became clear that the physical property of the coating film formed improves by containing the copolymer (A) with silicone (a-4) which has at least one of a hydroxyl group and an alkoxy silyl group.
実施例3と、比較例1との比較から、実施例3の塗膜の方が、比較例1の塗膜よりも、耐水性、耐結露性及び初期乾燥性に優れることが分かった。この結果から、強化剤(II)がポリイソシアネート(B−1)を含有することで、形成される塗膜のべたつきを抑えることができることが明らかになった。 From a comparison between Example 3 and Comparative Example 1, it was found that the coating film of Example 3 was superior to the coating film of Comparative Example 1 in water resistance, condensation resistance and initial drying property. From this result, it became clear that stickiness of the coating film formed can be suppressed because reinforcing agent (II) contains polyisocyanate (B-1).
Claims (5)
前記主剤(I)は、酸化重合可能な不飽和脂肪酸(a−1)及び酸化重合性基を有するアルキッド樹脂(a−2)の少なくとも一方と、アクリル共重合体(a−3)と、水酸基及びアルコキシシリル基の少なくとも一方を有するシリコーン(a−4)と、の共重合体(A)を含み、
前記強化剤(II)は、ポリイソシアネート(B−1)と、同一分子内に異なる2種の官能基を有するシランカップリング剤(B−2)と、を含み、
前記共重合体(A)は、固形ヨウ素価が5〜80であり、重量平均分子量が10,000〜150,000である二液混合型塗料組成物。 A two-component mixed coating composition comprising a main agent (I) and a reinforcing agent (II) used for forming a coating film covering the surface of a metal substrate,
The main agent (I) comprises at least one of an oxidatively polymerizable unsaturated fatty acid (a-1) and an alkyd resin (a-2) having an oxidatively polymerizable group, an acrylic copolymer (a-3), and a hydroxyl group. And a copolymer (A) with silicone (a-4) having at least one of alkoxysilyl groups,
The reinforcing agent (II) includes polyisocyanate (B-1) and a silane coupling agent (B-2) having two different functional groups in the same molecule,
The copolymer (A) is a two-component mixed coating composition having a solid iodine value of 5 to 80 and a weight average molecular weight of 10,000 to 150,000.
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CN105505193A (en) * | 2015-12-26 | 2016-04-20 | 上海巴德士化工新材料有限公司 | Environment-friendly smell purifying PU white finish with good weather resistance and high edge covering performance, whiteness and gloss |
CN107858090A (en) * | 2017-09-30 | 2018-03-30 | 合众(佛山)化工有限公司 | A kind of net taste type polyurethane varnish of high solid |
CN107858091A (en) * | 2017-09-30 | 2018-03-30 | 合众(佛山)化工有限公司 | A kind of net taste type alcohol acid and polyurethane white finish paint of high solid |
CN109504254A (en) * | 2018-11-06 | 2019-03-22 | 长安大学 | Concrete anticorrosive material and preparation method thereof |
CN111019511A (en) * | 2019-12-25 | 2020-04-17 | 东莞大宝化工制品有限公司 | PU transparent primer for preventing 'catheter bulge' and preparation method thereof |
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