JP6644597B2 - Powder coating composition - Google Patents
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- JP6644597B2 JP6644597B2 JP2016055862A JP2016055862A JP6644597B2 JP 6644597 B2 JP6644597 B2 JP 6644597B2 JP 2016055862 A JP2016055862 A JP 2016055862A JP 2016055862 A JP2016055862 A JP 2016055862A JP 6644597 B2 JP6644597 B2 JP 6644597B2
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- 239000000843 powder Substances 0.000 title claims description 81
- 239000008199 coating composition Substances 0.000 title claims description 61
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 92
- 229920005989 resin Polymers 0.000 claims description 76
- 239000011347 resin Substances 0.000 claims description 76
- 238000000576 coating method Methods 0.000 claims description 63
- 239000011248 coating agent Substances 0.000 claims description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 45
- 239000011701 zinc Substances 0.000 claims description 41
- 229910052725 zinc Inorganic materials 0.000 claims description 41
- 229920001225 polyester resin Polymers 0.000 claims description 28
- 239000004645 polyester resin Substances 0.000 claims description 28
- 239000004925 Acrylic resin Substances 0.000 claims description 27
- 229920000178 Acrylic resin Polymers 0.000 claims description 27
- 229920001187 thermosetting polymer Polymers 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001153 fluoro group Chemical class F* 0.000 claims 1
- 239000010410 layer Substances 0.000 description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 15
- 239000000049 pigment Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229940105570 ornex Drugs 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- VOAMNTKOJLSJCP-UHFFFAOYSA-N [Ca].[Zn].NC#N Chemical compound [Ca].[Zn].NC#N VOAMNTKOJLSJCP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- -1 dibutyltin compound Chemical class 0.000 description 2
- YMNMFUIJDSASQW-UHFFFAOYSA-N distrontium;oxygen(2-);vanadium Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[V].[V].[Sr+2].[Sr+2] YMNMFUIJDSASQW-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 2
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、金属部材の腐食を防止するために部材表面に塗装して防食性を付与する粉体塗料組成物に関する。 TECHNICAL FIELD The present invention relates to a powder coating composition that imparts anticorrosion properties by coating a metal member surface to prevent corrosion of the metal member.
金属部材で構成される工業製品などは、使用環境により腐食を受け、特性変化および強度劣化などが生じる。このような腐食を防止するために、金属部材の表面にはめっきによる被膜や塗料による塗膜を設けている。 Industrial products composed of metal members are subject to corrosion depending on the use environment, causing characteristic changes, strength deterioration, and the like. In order to prevent such corrosion, a coating by plating or a coating by paint is provided on the surface of the metal member.
腐食は、金属部材表面の金属原子がイオン化して部材表面から脱離することによって生じる。金属部材の表面に部材を構成する金属よりもイオン化傾向の大きい金属が存在すると、腐食環境下で金属部材よりも先にイオン化傾向が大きい金属がイオン化して金属部材の腐食を防止できる。このような防食は犠牲防食と呼ばれ、鉄部材の場合には犠牲材として主に亜鉛を用いる。 Corrosion occurs when metal atoms on the surface of a metal member are ionized and desorbed from the surface of the member. When a metal having a higher ionization tendency than the metal constituting the member is present on the surface of the metal member, the metal having a higher ionization tendency is ionized earlier than the metal member in a corrosive environment, so that corrosion of the metal member can be prevented. Such anticorrosion is called sacrificial anticorrosion. In the case of iron members, zinc is mainly used as a sacrificial material.
亜鉛によって鉄部材の表面を覆うために亜鉛を含む塗料を部材表面に塗布して亜鉛リッチの塗膜を形成する。特許文献１，２には、ジンクリッチプライマまたはジンクリッチペイントの代わりに使用され、エポキシ樹脂、硬化剤、亜鉛粉末を含有する粉体塗料が記載されている。特許文献３には、ディスクブレーキ装置の部材表面に塗装され、亜鉛からなる金属フィラーと熱硬化性樹脂とを含む粉体塗料が記載されている。特許文献４には、エポキシ樹脂、硬化剤、粒度が異なる２種の亜鉛粉末、防錆顔料を含む粉体塗料が記載されている。 A coating containing zinc is applied to the surface of the member to cover the surface of the iron member with zinc to form a zinc-rich coating. Patent Literatures 1 and 2 disclose a powder coating which is used instead of a zinc-rich primer or a zinc-rich paint and contains an epoxy resin, a curing agent, and zinc powder. Patent Literature 3 describes a powder coating that is applied to a member surface of a disc brake device and includes a metal filler made of zinc and a thermosetting resin. Patent Document 4 describes a powder coating containing an epoxy resin, a curing agent, two kinds of zinc powders having different particle sizes, and a rust preventive pigment.
鉄部材の腐食を防止するには、亜鉛を鉄に接触させる必要があり、なるべく多くの亜鉛を含有した粉体塗料を１度の塗装工程で一層塗布（１コート）するか、亜鉛を多く含む粉体塗料を鉄部材表面に塗布した後、さらに粉体塗料を塗布（２コート）している。 In order to prevent corrosion of iron members, it is necessary to bring zinc into contact with iron, and apply a powder coating containing as much zinc as possible in a single coating process (one coat) or contain a lot of zinc After the powder coating is applied to the surface of the iron member, the powder coating is further applied (two coats).
１コートでは、樹脂に対する亜鉛の含有量が非常に多く、塗装作業性が悪くなる。また塗装作業性を考慮して亜鉛の含有量を減らすと防食性が低下してしまう。 In one coat, the content of zinc in the resin is very large, and the coating workability is deteriorated. In addition, when the zinc content is reduced in consideration of the workability of coating, the anticorrosion property is reduced.
２コートでは、２種類の粉体塗料を塗布するために２度の塗布工程が必須となり、２つの粉体塗料塗膜の間で剥離などが生じやすい。 With two coats, two application steps are required to apply two types of powder coatings, and peeling or the like is likely to occur between the two powder coatings.
本発明の目的は、１度の塗装工程で防食性と耐候性に優れる粉体塗料組成物を提供することである。 An object of the present invention is to provide a powder coating composition having excellent corrosion resistance and weather resistance in a single coating step.
本発明は、熱硬化性樹脂（Ａ）と、亜鉛粉末（Ｂ）とを含む粉体塗料組成物であって、
前記亜鉛粉末（Ｂ）の含有量が、粉体塗料組成物全体に対して３０〜８０質量％であることを特徴とする粉体塗料組成物である。
The present invention is a powder coating composition comprising a thermosetting resin (A) and a zinc powder (B),
The powder coating composition, wherein the content of the zinc powder (B) is 30 to 80% by mass based on the whole powder coating composition.
また本発明は、被塗物の表面に塗装したときに、前記熱硬化性樹脂（Ａ）よりも前記亜鉛粉末（Ｂ）を多く含む亜鉛含有層、ならびに前記亜鉛粉末（Ｂ）よりも前記熱硬化性樹脂（Ａ）を多く含む樹脂含有層を有する塗膜を形成することを特徴とする。 Further, the present invention provides a zinc-containing layer containing more zinc powder (B) than the thermosetting resin (A) when coated on the surface of the object to be coated, and the above-described thermosetting resin more than the zinc powder (B). A coating film having a resin-containing layer containing a large amount of the curable resin (A) is formed.
また、熱硬化性樹脂（Ａ）の成分として、水酸基含有ポリエステル樹脂、水酸基含有フッ素樹脂、カルボキシ基含有ポリエステル樹脂、水酸基含有アクリル樹脂、グリシジル基含有アクリル樹脂、からなる群から選択される少なくとも１種の樹脂成分を使用することができる。 Further, as a component of the thermosetting resin (A), at least one selected from the group consisting of a hydroxyl group-containing polyester resin, a hydroxyl group-containing fluororesin, a carboxy group-containing polyester resin, a hydroxyl group-containing acrylic resin, and a glycidyl group-containing acrylic resin. Can be used.
さらに、熱硬化性樹脂（Ａ）の成分として、エポキシ樹脂を使用しないことにより、耐候性をさらに向上させることができる。 Furthermore, weather resistance can be further improved by not using an epoxy resin as a component of the thermosetting resin (A).
本発明によれば、塗膜中で亜鉛が被塗物表面側に偏在するので、従来技術に比較して亜鉛粉末の含有量が少なくても、被塗物と亜鉛とが十分に接触し防食性を発揮する。 According to the present invention, zinc is unevenly distributed on the surface side of the object to be coated in the coating film, so that even when the content of zinc powder is small as compared with the prior art, the object to be coated and the zinc sufficiently contact and prevent corrosion. Demonstrate the nature.
また、塗膜中で樹脂成分は塗膜の表層側に偏在し、２コートと同様の膜構造が１度の塗装工程で得られる。 In the coating film, the resin component is unevenly distributed on the surface side of the coating film, and a film structure similar to that of the two coatings can be obtained in one coating step.
さらに本発明によれば、亜鉛が多く含まれる層と樹脂成分が多く含まれる層との間で層間剥離することがない。 Further, according to the present invention, delamination does not occur between a layer containing a large amount of zinc and a layer containing a large amount of a resin component.
熱硬化性樹脂（Ａ）の成分としては、水酸基含有ポリエステル樹脂、水酸化含有フッ素樹脂、カルボキシ基含有ポリエステル樹脂、水酸基含有アクリル樹脂、グリシジル基含有アクリル樹脂、からなる群から選択される少なくとも１種の樹脂を使用できる。 The component of the thermosetting resin (A) is at least one selected from the group consisting of a hydroxyl-containing polyester resin, a hydroxyl-containing fluororesin, a carboxy-containing polyester resin, a hydroxyl-containing acrylic resin, and a glycidyl-containing acrylic resin. Resin can be used.
さらに、熱硬化性樹脂（Ａ）の成分として、エポキシ樹脂を使用しないことにより、耐候性が向上する。 Furthermore, weather resistance is improved by not using an epoxy resin as a component of the thermosetting resin (A).
本発明は、熱硬化性樹脂（Ａ）と、亜鉛粉末（Ｂ）と、を含む粉体塗料組成物である。これらの組成であって、亜鉛粉末（Ｂ）の含有量が、粉体塗料組成物全体に対して３０〜８０質量％である。 The present invention is a powder coating composition containing a thermosetting resin (A) and a zinc powder (B). In these compositions, the content of the zinc powder (B) is 30 to 80% by mass based on the entire powder coating composition.
熱硬化性樹脂（Ａ）と亜鉛粉末（Ｂ）とを含み、各成分が上記のような含有量であることによって、本発明の粉体塗料組成物を被塗物表面に塗布して得られる塗膜が、亜鉛粉末を相対的に多く含む亜鉛含有層と樹脂成分を相対的に多く含む樹脂含有層とを有することになる。 It contains the thermosetting resin (A) and the zinc powder (B), and is obtained by applying the powder coating composition of the present invention to the surface of the object to be coated, because each component has the above content. The coating film has a zinc-containing layer containing a relatively large amount of zinc powder and a resin-containing layer containing a relatively large amount of a resin component.
また、熱硬化性樹脂（Ａ）の成分としては、水酸基含有ポリエステル樹脂、水酸化含有フッ素樹脂、カルボキシ基含有ポリエステル樹脂、水酸基含有アクリル樹脂、グリシジル基含有アクリル樹脂、からなる群から選択される少なくとも１種の樹脂を使用できる。さらに、熱硬化性樹脂（Ａ）の成分としてエポキシ樹脂を使用しないことにより、樹脂含有層の成分に由来の性能の中で、特に耐候性がさらに向上する。 The component of the thermosetting resin (A) is at least selected from the group consisting of a hydroxyl group-containing polyester resin, a hydroxyl group-containing fluororesin, a carboxy group-containing polyester resin, a hydroxyl group-containing acrylic resin, and a glycidyl group-containing acrylic resin. One type of resin can be used. Furthermore, by not using an epoxy resin as a component of the thermosetting resin (A), in particular, weather resistance among properties derived from components of the resin-containing layer is further improved.
粉体塗料組成物の状態では、樹脂成分と亜鉛粉末とは偏ることなく分散しており、粉体塗料組成物としては従来の粉体塗料と同様に取り扱うことができる。また、塗装方法も従来と同様に静電塗装方法を用いることができ、従来と同様の取り扱いが可能である。すなわち、粉体塗料組成物としては、従来のものと何ら変わることなく、これまでと同様に取り扱うことができる。 In the state of the powder coating composition, the resin component and the zinc powder are dispersed without bias, and the powder coating composition can be handled in the same manner as a conventional powder coating. Further, the coating method can be the electrostatic coating method as in the past, and the same handling as the conventional method is possible. That is, the powder coating composition can be handled as before without any difference from the conventional one.
その一方で、防食性を付与したい被塗物の表面に本発明の粉体塗料組成物を塗装し、被塗物の表面に塗膜が形成されると、その塗膜では、被塗物の表面側に亜鉛粉末が偏り、表層側に樹脂成分が偏り、特性の異なる２つの層が形成される。 On the other hand, when the powder coating composition of the present invention is applied to the surface of an object to be provided with anticorrosion properties and a coating film is formed on the surface of the object, The zinc powder is biased toward the surface and the resin component is biased toward the surface, so that two layers having different characteristics are formed.
鉄材料からなる被塗物の表面側に形成される、亜鉛粉末（Ｂ）を相対的に多く含む亜鉛含有層は、被塗物表面を亜鉛粉末で被覆し、鉄材料に対する亜鉛の犠牲防食効果が発揮される。亜鉛粉末（Ｂ）が亜鉛含有層に濃縮されるので、粉体塗料組成物全体に対する亜鉛粉末（Ｂ）の含有量が比較的少なくしても十分に防食性を発揮する。亜鉛粉末（Ｂ）の含有量を少なくできるので、従来の過剰な亜鉛量の粉体塗料組成物よりも取り扱いが簡単で、塗装作業性が良好である。塗膜表層側には熱硬化性樹脂（Ａ）成分が偏在し、亜鉛粉末（Ｂ）が存在しないので、表面の平滑性が容易に得られる。また粉体塗料組成物に顔料などの着色剤を含む場合には、顔料も樹脂含有層側に多く含まれることになり、亜鉛粉末が存在しないので、塗膜表層での発色性が向上する。亜鉛含有層と樹脂含有層とは、１コートで一体的に形成され、亜鉛含有層と樹脂含有層との間には明確な界面が形成されないので、これらの層間で剥離することもない。 The zinc-containing layer formed on the surface side of the substrate made of an iron material and containing a relatively large amount of zinc powder (B) covers the surface of the substrate with the zinc powder, and has a sacrificial anticorrosion effect of zinc on the iron material. Is exhibited. Since the zinc powder (B) is concentrated in the zinc-containing layer, even if the content of the zinc powder (B) relative to the entire powder coating composition is relatively small, the anticorrosion property is sufficiently exhibited. Since the content of the zinc powder (B) can be reduced, it is easier to handle than the conventional powder coating composition having an excessive amount of zinc, and the coating workability is good. Since the thermosetting resin (A) component is unevenly distributed on the surface side of the coating film and the zinc powder (B) does not exist, smoothness of the surface can be easily obtained. When a colorant such as a pigment is contained in the powder coating composition, the pigment is also contained in a large amount on the resin-containing layer side, and since there is no zinc powder, the color developability on the surface layer of the coating film is improved. The zinc-containing layer and the resin-containing layer are integrally formed with one coat, and since no clear interface is formed between the zinc-containing layer and the resin-containing layer, there is no separation between these layers.
本発明は、熱硬化性樹脂（Ａ）と、亜鉛粉末（Ｂ）との組合せであって、かつ、亜鉛粉末（Ｂ）の含有量が、粉体塗料組成物全体に対して３０〜８０質量％であるときに、塗膜に層分離が生じて亜鉛含有層と樹脂含有層とを有するのである。 The present invention is a combination of a thermosetting resin (A) and a zinc powder (B), and the content of the zinc powder (B) is 30 to 80 mass based on the whole powder coating composition. %, The coating film undergoes layer separation to have a zinc-containing layer and a resin-containing layer.
各特許文献には、亜鉛粉末含有の粉体塗料組成物が記載されており、樹脂成分や亜鉛粉末の含有量なども記載されているが、塗膜が層分離し、被塗物表面側に亜鉛粉末が偏在することは記載されていない。特許文献の実施例には、水酸基含有ポリエステル樹脂、水酸基含有フッ素樹脂、カルボキシ基含有ポリエステル樹脂、水酸基含有アクリル樹脂、グリシジル基含有アクリル樹脂、からなる群から選択される少なくとも１種の樹脂と、亜鉛粉末との組合せという本発明の粉体塗料組成物における成分の特定の組合せおよび各成分の含有量は記載されていない。 In each patent document, a powder coating composition containing zinc powder is described, and the resin component and the content of zinc powder are also described.However, the coating film is separated into layers, and on the surface side of the object to be coated. It is not described that the zinc powder is unevenly distributed. Examples of the patent document include a hydroxyl group-containing polyester resin, a hydroxyl group-containing fluororesin, a carboxy group-containing polyester resin, a hydroxyl group-containing acrylic resin, a glycidyl group-containing acrylic resin, at least one resin selected from the group consisting of: The specific combination of components and the content of each component in the powder coating composition of the present invention in combination with powder are not described.
亜鉛粉末を用いた従来の塗料では、被塗物表面に形成された塗膜が亜鉛含有層と樹脂含有層とを有することは、知られていない。 With a conventional paint using zinc powder, it is not known that the coating film formed on the surface of the article to be coated has a zinc-containing layer and a resin-containing layer.
（粉体塗料組成物）
以下では本発明の粉体塗料組成物を構成する各成分について説明する。
(Powder coating composition)
Hereinafter, each component constituting the powder coating composition of the present invention will be described.
＜水酸基含有ポリエステル樹脂＞
本発明に用いる水酸基含有ポリエステル樹脂としては、主として常温で固形の水酸基含有ポリエステル樹脂を例示することができる。軟化点が８０〜１５０℃好ましくは１１０〜１４０℃であることが好適である。軟化点が８０℃未満であると、粉体塗料組成物のブロッキングが発生するために好ましくなく、１５０℃を超えると溶融混練を行う際に、粘度が高すぎて分散が十分に行われず、塗膜性能が発揮されない。また水酸基含有ポリエステル樹脂の水酸基価は２０〜１００ｍｇＫＯＨ／ｇ、好ましくは３０〜５０ｍｇＫＯＨ／ｇであることが好適である。水酸基含有ポリエステル樹脂を具体的に例示すると日本ユピカ株式会社製ＧＶ１１０、ＧＶ１２６、ＧＶ５００、ＧＶ７１０、ＤＩＣ株式会社製Ｍ−８０１０、Ｍ−８０２０、Ｍ−８１００、ダイセル・オルネクス株式会社製ＣＣ２８６８−０、ＣＣ２８３９−０等が挙げられる。
<Hydroxyl-containing polyester resin>
As the hydroxyl group-containing polyester resin used in the present invention, a hydroxyl group-containing polyester resin which is mainly solid at ordinary temperature can be exemplified. It is suitable that the softening point is 80 to 150 ° C, preferably 110 to 140 ° C. When the softening point is less than 80 ° C, it is not preferable because blocking of the powder coating composition occurs. When the softening point is higher than 150 ° C, when the melt-kneading is performed, the viscosity is too high and the dispersion is not sufficiently performed. Film performance is not exhibited. The hydroxyl value of the hydroxyl group-containing polyester resin is preferably from 20 to 100 mgKOH / g, and more preferably from 30 to 50 mgKOH / g. Specific examples of the hydroxyl group-containing polyester resin include GV110, GV126, GV500, GV710 manufactured by Nippon Yupika Co., Ltd., M-8010, M-8020, M-8100 manufactured by DIC Corporation, CC2868-0, CC2839 manufactured by Daicel Ornex Co., Ltd. −0 and the like.
＜水酸基含有フッ素樹脂＞
本発明に用いる水酸基含有フッ素樹脂としては、主として常温で固形の水酸基含有フッ素樹脂を例示することができる。軟化点が８０〜１５０℃好ましくは１１０〜１４０℃であることが好適である。軟化点が８０℃未満であると、粉体塗料組成物のブロッキングが発生するために好ましくなく、１５０℃を超えると溶融混練を行う際に、粘度が高すぎて分散が十分に行われず、塗膜性能が発揮されない。また水酸基含有フッ素樹脂の水酸基価は２０〜１００ｍｇＫＯＨ／ｇ、好ましくは３０〜５０ｍｇＫＯＨ／ｇであることが好適である。水酸基含有フッ素樹脂を具体的に例示すると旭硝子株式会社製ＬＦ−７１０Ｆ等が挙げられる。
<Hydroxy group-containing fluororesin>
Examples of the hydroxyl group-containing fluororesin used in the present invention include mainly those hydroxyl group-containing fluororesins which are solid at normal temperature. It is suitable that the softening point is 80 to 150 ° C, preferably 110 to 140 ° C. If the softening point is less than 80 ° C., it is not preferable because blocking of the powder coating composition occurs, and if it exceeds 150 ° C., when performing the melt kneading, the viscosity is too high and the dispersion is not sufficiently performed. Film performance is not exhibited. The hydroxyl value of the hydroxyl group-containing fluororesin is preferably from 20 to 100 mgKOH / g, more preferably from 30 to 50 mgKOH / g. Specific examples of the hydroxyl group-containing fluororesin include LF-710F manufactured by Asahi Glass Co., Ltd.
本発明の粉体塗料組成物における、水酸基含有ポリエステル樹脂、および、または、水酸基含有フッ素樹脂、および、または、水酸基含有アクリル樹脂の硬化剤としては、ブロックイソシアネート樹脂が好適に使用できる。ブロックイソシアネート樹脂を具体的に例示するとエボニック社製Ｂ−１５３０、バイエル社製クレランＵ−１等が挙げられる。ブロックイソシアネート樹脂の含有量は、水酸基含有ポリエステル樹脂、および、または、水酸基含有フッ素樹脂の水酸基価とブロックイソシアネート樹脂のイソシアネート当量によるが、水酸基含有ポリエステル樹脂、および、または、水酸基含有フッ素樹脂の含有量とブロックイソシアネート樹脂の含有量との和を１００質量部としたときに、５〜２０質量部とすることが好ましい。 As a curing agent for the hydroxyl group-containing polyester resin and / or the hydroxyl group-containing fluororesin and / or the hydroxyl group-containing acrylic resin in the powder coating composition of the present invention, a blocked isocyanate resin can be suitably used. Specific examples of the blocked isocyanate resin include B-1530 manufactured by Evonik and Cleran U-1 manufactured by Bayer. The content of the blocked isocyanate resin depends on the hydroxyl value of the hydroxyl group-containing polyester resin and / or the hydroxyl value of the hydroxyl group-containing fluororesin and the isocyanate equivalent of the blocked isocyanate resin. When the sum of the content of the resin and the content of the blocked isocyanate resin is 100 parts by mass, the content is preferably 5 to 20 parts by mass.
＜カルボキシ基含有ポリエステル樹脂＞
本発明に用いるカルボキシ基含有ポリエステル樹脂は、通常の粉体塗料組成物において使用されるものであれば、特に制限はない。カルボキシ基含有ポリエステル樹脂を具体的に例示するとダイセル・オルネクス株式会社製ＣＲＹＬＣＯＡＴ（ＣＣ）１５７３−０、２６９５−０、２４４１−２などが挙げられる。
<Carboxy group-containing polyester resin>
The carboxy group-containing polyester resin used in the present invention is not particularly limited as long as it is used in a usual powder coating composition. Specific examples of the carboxy group-containing polyester resin include CRYLCOAT (CC) 1573-0, 2695-0, and 2441-2 manufactured by Daicel Ornex.
本発明の粉体塗料組成物における、カルボキシ基含有ポリエステル樹脂の硬化剤としては、β−ヒドロキシアルキルアミド樹脂、および、または、トリグリシジルイソシアヌレートが好適に使用できる。β−ヒドロキシアルキルアミド樹脂を具体的に例示するとエムスケミー株式会社製ＸＬ−５５２、トリグリシジルイソシアヌレートを具体的に例示すると日産化学工業株式会社製ＴＥＰＩＣ−Ｇ等が挙げられる。 As the curing agent for the carboxy group-containing polyester resin in the powder coating composition of the present invention, a β-hydroxyalkylamide resin and / or triglycidyl isocyanurate can be suitably used. Specific examples of the β-hydroxyalkylamide resin include XL-552 manufactured by Ms. Chemie Corporation, and specific examples of triglycidyl isocyanurate include TEPIC-G manufactured by Nissan Chemical Industries, Ltd.
本発明の粉体塗料組成物におけるβ−ヒドロキシアルキルアミド樹脂の含有量は、カルボキシ基含有ポリエステル樹脂とβ−ヒドロキシアルキルアミド樹脂の含有量との和を１００質量部としたときに、３〜１０質量部とすることが好ましい。 The content of the β-hydroxyalkylamide resin in the powder coating composition of the present invention is 3 to 10 when the sum of the content of the carboxy group-containing polyester resin and the content of the β-hydroxyalkylamide resin is 100 parts by mass. It is preferred to be parts by mass.
本発明の粉体塗料組成物におけるトリグリシジルイソシアヌレートの含有量は、カルボキシ基含有ポリエステル樹脂とトリグリシジルイソシアヌレートの含有量との和を１００質量部としたときに、３〜１０質量部とすることが好ましい。 The content of triglycidyl isocyanurate in the powder coating composition of the present invention is 3 to 10 parts by mass when the sum of the content of the carboxy group-containing polyester resin and the content of triglycidyl isocyanurate is 100 parts by mass. Is preferred.
＜水酸基含有アクリル樹脂＞
本発明に用いる水酸基含有アクリル樹脂は、常温で固形の水酸基含有アクリル樹脂を例示することができる。軟化点が８０〜１５０℃好ましくは１００〜１４０℃であることが好適である。軟化点が８０℃未満であると、粉体塗料組成物のブロッキングが発生するために好ましくなく、１５０℃を超えると溶融混練を行う際に、粘度が高すぎて分散が十分に行われず、塗膜性能が発揮されない。また水酸基含有アクリル樹脂の水酸基価は２０〜２００ｍｇＫＯＨ／ｇ、好ましくは４０〜１１０ｍｇＫＯＨ／ｇであることが好適である。水酸基含有アクリル樹脂を具体的に例示するとＤＩＣ株式会社製Ａ−２５１等が挙げられる。
<Hydroxy group-containing acrylic resin>
Examples of the hydroxyl group-containing acrylic resin used in the present invention include a hydroxyl group-containing acrylic resin which is solid at normal temperature. It is suitable that the softening point is 80 to 150 ° C, preferably 100 to 140 ° C. When the softening point is less than 80 ° C, it is not preferable because blocking of the powder coating composition occurs. When the softening point is higher than 150 ° C, when the melt-kneading is performed, the viscosity is too high and the dispersion is not sufficiently performed. Film performance is not exhibited. The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably from 20 to 200 mgKOH / g, and more preferably from 40 to 110 mgKOH / g. Specific examples of the hydroxyl group-containing acrylic resin include A-251 manufactured by DIC Corporation.
＜グリシジル基含有アクリル樹脂＞
本発明に用いるグリシジル基含有アクリル樹脂は、常温で固形のグリシジル基含有アクリル樹脂を例示することができる。軟化点が８０〜１５０℃好ましくは１００〜１４０℃であることが好適である。軟化点が８０℃未満であると、粉体塗料組成物のブロッキングが発生するために好ましくなく、１５０℃を超えると溶融混練を行う際に、粘度が高すぎて分散が十分に行われず、塗膜性能が発揮されない。またグリシジル基含有アクリル樹脂のエポキシ当量は１００〜９００ｇ／ｅｑ、好ましくは４００〜６００ｇ／ｅｑであることが好適である。水酸基含有アクリル樹脂を具体的に例示するとＤＩＣ株式会社製Ａ−２６１等が挙げられる。
<Acrylic resin containing glycidyl group>
The glycidyl group-containing acrylic resin used in the present invention can be exemplified by a glycidyl group-containing acrylic resin that is solid at room temperature. It is suitable that the softening point is 80 to 150 ° C, preferably 100 to 140 ° C. If the softening point is less than 80 ° C., it is not preferable because blocking of the powder coating composition occurs, and if it exceeds 150 ° C., when performing the melt kneading, the viscosity is too high and the dispersion is not sufficiently performed. Film performance is not exhibited. The epoxy equivalent of the glycidyl group-containing acrylic resin is preferably 100 to 900 g / eq, and more preferably 400 to 600 g / eq. Specific examples of the hydroxyl group-containing acrylic resin include A-261 manufactured by DIC Corporation.
本発明の粉体塗料組成物における、グリシジル基含有アクリル樹脂の硬化剤としては、ジカルボン酸が好適に使用できる。ジカルボン酸を具体的に例示すると岡村製油株式会社製ＳＬ−１２等が挙げられる。 As a curing agent for the glycidyl group-containing acrylic resin in the powder coating composition of the present invention, dicarboxylic acid can be suitably used. Specific examples of dicarboxylic acids include SL-12 manufactured by Okamura Oil Co., Ltd.
本発明の粉体塗料組成物におけるジカルボン酸の含有量は、グリシジル基含有アクリル樹脂とジカルボン酸の含有量との和を１００質量部としたときに、１０〜３０質量部とすることが好ましい。 The content of the dicarboxylic acid in the powder coating composition of the present invention is preferably 10 to 30 parts by mass, when the sum of the glycidyl group-containing acrylic resin and the content of the dicarboxylic acid is 100 parts by mass.
＜亜鉛粉末＞
本発明に用いる亜鉛粉末としては、通常の粉体塗料組成物において使用されるものであれば、特に制限はない。たとえば、中位粒度１〜３０μｍ、好ましくは４〜１５μｍの亜鉛粉末を用いることができる。このような亜鉛粉末としては、本荘ケミカル株式会社製亜鉛末Ｆ−５００（中位粒度７．５μｍ）、Ｆ−１０００（中位粒度４．９μｍ）、Ｆ−３０００（中位粒度３．７μｍ）、堺化学工業株式会社製亜鉛末＃１（中位粒度５，０μｍ）、＃３（中位粒度４．０μｍ）、＃４０（中位粒度約５０．０μｍ）、エカルト社製Ｚｉｎｋ Ｆｌａｋｅ ＧＴＴ（中位粒度１３μｍ）、ＡＴ（中位粒度２０μｍ）などが挙げられる。亜鉛粉末は、中位粒度が異なる複数種類を混合して用いてもよい。なお、亜鉛粉末の中位粒度とは、日機装株式会社製マイクロトラック等のレーザー式粒度分布測定機などを用いて測定した粒度分布における、積算値５０％での粒径を意味する。
<Zinc powder>
The zinc powder used in the present invention is not particularly limited as long as it is used in a usual powder coating composition. For example, zinc powder having a median particle size of 1 to 30 μm, preferably 4 to 15 μm can be used. Examples of such zinc powder include zinc powder F-500 (medium particle size 7.5 μm), F-1000 (medium particle size 4.9 μm), and F-3000 (medium particle size 3.7 μm) manufactured by Honjo Chemical Co., Ltd. Zinc Powder # 1 (medium particle size: 5.0 μm), # 3 (medium particle size: 4.0 μm), # 40 (medium particle size: about 50.0 μm) manufactured by Sakai Chemical Industry Co., Ltd., Zink Flake GTT (Ecart Corporation) Median particle size 13 μm), AT (medium particle size 20 μm) and the like. As the zinc powder, a plurality of types having different median particle sizes may be mixed and used. The median particle size of the zinc powder means a particle size at an integrated value of 50% in a particle size distribution measured using a laser type particle size distribution measuring device such as a Microtrack manufactured by Nikkiso Co., Ltd.
本発明の粉体塗料組成物における亜鉛粉末の含有量は、粉体塗料組成物全体に対して３０〜８０質量％であり、好ましくは５５〜８０質量％であり、最も好ましくは６０〜７０質量％である。亜鉛粉末として上記のように粒径が異なる亜鉛粉末を混合して用いる場合は、その合計量が上記の範囲内であればよい。 The content of the zinc powder in the powder coating composition of the present invention is 30 to 80% by mass, preferably 55 to 80% by mass, and most preferably 60 to 70% by mass based on the whole powder coating composition. %. When zinc powders having different particle diameters are mixed and used as described above, the total amount may be within the above range.
亜鉛粉末の含有量は、粉体塗料組成物全体に対して３０〜８０質量％であると塗膜が、亜鉛含有層と樹脂含有層とを有するように層分離する。さらに含有量が、５５〜８０質量％であれば、防錆顔料を含まなくとも粉体塗料組成物が十分な防食性を発揮する。 When the content of the zinc powder is 30 to 80% by mass with respect to the entire powder coating composition, the coating film undergoes layer separation so as to have a zinc-containing layer and a resin-containing layer. Further, when the content is 55 to 80% by mass, the powder coating composition exhibits a sufficient anticorrosive property without containing a rust-preventive pigment.
＜防錆顔料＞
本発明の粉体塗料組成物は、上記各成分に加えて防錆顔料を含んでいてもよい。本発明に用いる防錆顔料としては、リン酸アルミニウム等のリン酸塩誘導体、モリブデン酸亜鉛、リンモリブデン酸アルミニウムなどのモリブデン酸誘導体、シアナミドカルシウム亜鉛、硼酸バリウムなどの硼酸塩誘導体、バナジン酸ストロンチウムなどのバナジン酸塩誘導体、水酸化ビスマス等が挙げられ、好ましくはリン酸アルミニウム、リン酸亜鉛、モリブデン酸亜鉛、リンモリブデン酸アルミニウム、シアナミドカルシウム亜鉛、硼酸バリウム、バナジン酸ストロンチウムが挙げられる。このような防錆顔料としては、ＰＭ−３００（リンモリブデン酸アルミニウム、キクチカラー株式会社製）、ＬＦボウセイＣＰ−Ｚ（リン酸亜鉛、キクチカラー株式会社製）、Ｋ−ＷＨＩＴＥ（トリポリリン酸アルミニウム、テイカ株式会社製）、ビューサン１１Ｍ−１（硼酸バリウム、堺化学工業株式会社）などが挙げられる。
<Rust prevention pigment>
The powder coating composition of the present invention may contain a rust preventive pigment in addition to the above components. Examples of the rust preventive pigment used in the present invention include phosphate derivatives such as aluminum phosphate, molybdate derivatives such as zinc molybdate and aluminum phosphomolybdate, borate derivatives such as cyanamide calcium zinc and barium borate, and strontium vanadate. And bismuth hydroxide, and the like, preferably, aluminum phosphate, zinc phosphate, zinc molybdate, aluminum phosphomolybdate, calcium zinc cyanamide, barium borate, and strontium vanadate. Examples of such rust preventive pigments include PM-300 (aluminum phosphomolybdate, manufactured by Kikuchi Color Co., Ltd.), LF Bosei CP-Z (zinc phosphate, manufactured by Kikuchi Color Co., Ltd.), and K-WHITE (aluminum tripolyphosphate, Teica Co., Ltd.) and Beusan 11M-1 (barium borate, Sakai Chemical Industry Co., Ltd.).
本発明の粉体塗料組成物における防錆顔料の含有量は、粉体塗料組成物全体に対して０〜７０質量％であり、好ましくは１０〜５０質量％である。 The content of the rust-preventive pigment in the powder coating composition of the present invention is 0 to 70% by mass, and preferably 10 to 50% by mass, based on the entire powder coating composition.
＜その他の添加剤＞
本発明の粉体塗料組成物は、上記各成分に加えてさらに通常の粉体塗料組成物に用いられる着色顔料、体質顔料、流動性調整剤、ブロッキング防止剤、表面調整剤、ワキ防止剤、帯電制御剤、硬化促進剤等のその他の添加剤を含有してもよい。
<Other additives>
The powder coating composition of the present invention, in addition to the above components, a coloring pigment used in a normal powder coating composition, an extender pigment, a fluidity regulator, an anti-blocking agent, a surface conditioning agent, an anti-bake agent, Other additives such as a charge control agent and a curing accelerator may be contained.
（粉体塗料組成物の製造方法）
粉体塗料組成物の製造方法は、たとえば、粉砕法などの公知の製造方法を用いることができる。粉砕法では、水酸基含有ポリエステル樹脂、水酸基含有フッ素樹脂、カルボキシ基含有ポリエステル樹脂、水酸基含有アクリル樹脂、グリシジル基含有アクリル樹脂、ブロックイソシアネート樹脂、β−ヒドロキシアルキルアミド樹脂、トリグリシジルイソシアヌレート、ジカルボン酸、亜鉛粉末および必要により防錆顔料、その他添加剤などの混合物を、タンブラーミキサ、ヘンシェルミキサなどの混合機で乾式混合し、混練機によって溶融混練する。混練機としては、たとえば、１軸または２軸のエクストルーダ、三本ロール、ラボブラストミルなどの一般的な混練機を使用できる。
(Production method of powder coating composition)
As a method for producing the powder coating composition, for example, a known production method such as a pulverization method can be used. In the pulverization method, hydroxyl group-containing polyester resin, hydroxyl group-containing fluororesin, carboxy group-containing polyester resin, hydroxyl group-containing acrylic resin, glycidyl group-containing acrylic resin, block isocyanate resin, β-hydroxyalkylamide resin, triglycidyl isocyanurate, dicarboxylic acid, A mixture of zinc powder and, if necessary, a rust-preventive pigment and other additives is dry-mixed by a mixer such as a tumbler mixer and a Henschel mixer, and melt-kneaded by a kneader. As the kneading machine, for example, a general kneading machine such as a single-screw or twin-screw extruder, a three-roll mill, and a lab blast mill can be used.
混練物を冷却固化し、固化物を粗粉砕および微粉砕して粉砕物を得る。粉砕機としては、たとえば、超音速ジェット気流を利用して粉砕するジェット式粉砕機、および高速で回転する回転子（ロータ）と固定子（ライナ）との間に形成される空間に固化物を導入して粉砕する衝撃式粉砕機が挙げられる。また必要により粉砕物に後添加剤（外添剤）を添加してもよい。 The kneaded material is cooled and solidified, and the solidified material is roughly pulverized and finely pulverized to obtain a pulverized material. As the pulverizer, for example, a jet pulverizer that pulverizes using a supersonic jet stream, and a solidified material in a space formed between a rotor (rotor) rotating at a high speed and a stator (liner). An impact-type pulverizer for introducing and pulverizing may be used. If necessary, a post-additive (external additive) may be added to the pulverized material.
粉砕物を分級して粉体を所望の粒子径および所望の粒径分布に調整して粉体塗料組成物を得る。分級には、遠心力および風力による分級により過粉砕トナー母粒子を除去できる公知の分級機を使用でき、たとえば、旋回式風力分級機（ロータリー式風力分級機）などを使用できる。 The pulverized material is classified to adjust the powder to a desired particle size and a desired particle size distribution to obtain a powder coating composition. For the classification, a known classifier capable of removing excessively pulverized toner base particles by classification by centrifugal force and wind force can be used, and for example, a revolving air classifier (rotary air classifier) or the like can be used.
なお、粉体塗料組成物の製造方法は上記の粉砕法に限らず、各成分が均一に分散した粉体塗料組成物を得ることができる製造方法であればよい。 The method for producing the powder coating composition is not limited to the above-mentioned pulverization method, but may be any production method capable of obtaining a powder coating composition in which each component is uniformly dispersed.
（塗装方法）
本発明の粉体塗料組成物を用いた塗装方法は、公知の静電粉体塗装方法を用いることができる。たとえば、コロナ帯電方式、摩擦帯電方式などである。コロナ帯電方式、摩擦帯電方式いずれの方式でも先端筒状のガンユニットを用いて塗装を行う。コロナ帯電方式の場合、ガンユニットの先端に配置したコロナ電極に高電圧を印加してコロナ放電を起こし、発生したイオンでコロナ電極近傍の塗料粉体を帯電させる。被塗物を接地電位としてコロナ電極と被塗物との間に電界を形成し、帯電した塗料粉体を電界によって被塗物に付着させる。
(Painting method)
As a coating method using the powder coating composition of the present invention, a known electrostatic powder coating method can be used. For example, a corona charging method, a friction charging method, and the like are used. In both the corona charging method and the friction charging method, coating is performed using a gun unit having a cylindrical tip. In the case of the corona charging method, a high voltage is applied to the corona electrode disposed at the tip of the gun unit to cause corona discharge, and the generated ions charge the paint powder near the corona electrode. An electric field is formed between the corona electrode and the object to be coated with the object to be grounded, and the charged paint powder is adhered to the object by the electric field.
摩擦帯電方式の場合、ガンユニットの内部を移動する塗料粉体をガンユニットの内面で摩擦させて帯電させる。被塗物を接地電位とすることで、帯電した塗料粉体をガンユニットから射出して被塗物に付着させる。コロナ帯電方式での放電による荷電量および摩擦帯電方式の射出量は、それぞれ粉体塗料組成物を塗布しようとする被塗物に応じて適宜設定すればよい。 In the case of the triboelectric charging method, the paint powder moving inside the gun unit is charged by friction with the inner surface of the gun unit. By setting the object to be grounded to ground, the charged paint powder is ejected from the gun unit and adheres to the object to be coated. The charge amount due to the discharge in the corona charging method and the injection amount in the triboelectric charging method may be appropriately set according to the object to be coated with the powder coating composition.
被塗物に塗布された粉体塗料組成物の硬化方法は、一般的な粉体塗料の焼付け硬化方法と同様で、それぞれの粉体塗料組成物に適した焼付け温度、焼付け時間に合わせて設定するが、たとえば、好ましい焼付け温度は１６０〜２００℃、好ましい焼付け時間は２０〜４０分間である。焼付け後の膜厚は、２０〜３００μｍの範囲が好適である。 The method of curing the powder coating composition applied to the object to be coated is the same as the general baking and curing method of powder coating, and is set according to the baking temperature and baking time suitable for each powder coating composition. However, for example, a preferable baking temperature is 160 to 200 ° C., and a preferable baking time is 20 to 40 minutes. The thickness after baking is preferably in the range of 20 to 300 μm.
被塗物の材質は、亜鉛によって防食効果が発揮される金属であれば特に限定されない。本発明の粉体塗料組成物によって形成された塗膜による防食効果は、いわゆる犠牲防食によるものであり、素地金属よりもイオン化傾向が大きい卑の金属を用いて素地金属の腐食を防止する。本発明の粉体塗料組成物は、亜鉛粉末を含むので、被塗物の材質としては、亜鉛よりもイオン化傾向が小さい貴の金属であればよく、たとえば鉄、ニッケル、銅などを用いることができ、鉄素材が好適である。 The material of the object to be coated is not particularly limited as long as it is a metal that exhibits an anticorrosion effect by zinc. The anti-corrosion effect of the coating film formed by the powder coating composition of the present invention is due to so-called sacrificial anti-corrosion, and the base metal is prevented from corroding by using a base metal having a higher ionization tendency than the base metal. Since the powder coating composition of the present invention contains zinc powder, the material of the object to be coated may be any precious metal having a smaller ionization tendency than zinc, such as iron, nickel, or copper. Yes, iron material is preferred.
（塗膜）
本発明の粉体塗料組成物を用いた塗装を行い、焼き付けによって硬化させ、被塗物の表面に塗膜を形成する。形成される塗膜は、焼付け後の膜厚が２０〜３００μｍであり、好ましくは３０〜１００μｍであり、最も好ましくは４０〜８０μｍである。
(Coating)
The coating using the powder coating composition of the present invention is performed and cured by baking to form a coating film on the surface of the object to be coated. The coating film to be formed has a film thickness after baking of 20 to 300 μm, preferably 30 to 100 μm, and most preferably 40 to 80 μm.
被塗物の表面に形成された塗膜は、亜鉛粉末を相対的に多く含む亜鉛含有層と樹脂成分を相対的に多く含む樹脂含有層とを有する。亜鉛含有層は、被塗物表面に近い側に形成され、樹脂含有層は、塗膜の表層側に形成される。 The coating film formed on the surface of the article to be coated has a zinc-containing layer containing a relatively large amount of zinc powder and a resin-containing layer containing a relatively large amount of a resin component. The zinc-containing layer is formed on the side closer to the surface of the article to be coated, and the resin-containing layer is formed on the surface side of the coating film.
被塗物は、材質が上記のような金属であれば、形状や大きさなどは特に限定されないが、使用環境により腐食を受けやすい工業製品が特に好ましい。鉄系金属製の枠部材、壁面部材、ばね部材などの表面塗装に本発明の粉体塗料組成物が好適である。 The shape and size of the object to be coated are not particularly limited as long as the material is the above-mentioned metal, but industrial products that are susceptible to corrosion depending on the use environment are particularly preferable. The powder coating composition of the present invention is suitable for surface coating of frame members, wall members, spring members, and the like made of an iron-based metal.
次に、本発明の粉体塗料組成物について実施例および比較例を挙げてさらに詳細に説明するが、本発明はこれらに限定されるものではない。なお、表中の配合量は特別な記載がない限り、質量部を表す。
表１〜表６に示す配合の実施例１〜３０および比較例１〜１５の粉体塗料を、前記の製造方法で製造し、被塗物としてサンドブラスト処理の１．６ｍｍ厚ＳＳ−４００を用い、塗装膜厚が５０μｍになるように静電塗装し、１８０℃、２０分間の焼き付けによって試験片を作製した。次に、この試験片を用いて性能評価した。
Next, the powder coating composition of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the compounding quantity in a table | surface expresses a mass part unless there is particular description.
The powder coatings of Examples 1 to 30 and Comparative Examples 1 to 15 having the formulations shown in Tables 1 to 6 were produced by the above-described production method, and 1.6 mm thick SS-400 sandblasted as an object to be coated. Then, electrostatic coating was performed so that the coating film thickness became 50 μm, and a test piece was prepared by baking at 180 ° C. for 20 minutes. Next, performance evaluation was performed using this test piece.
＜評価方法＞
・樹脂含有層の形成
塗膜に層分離が生じているかどうかを評価した。塗膜を切断して切断面を光学顕微鏡および電子顕微鏡（ＳＥＭ）にて確認、またＥＰＭＡ（ＺＮマッピング)にて亜鉛の密度を目視で観察し、樹脂成分を相対的に多く含む樹脂含有層が形成されていれば評価を「あり」とし、樹脂含有層が形成されていなければ評価を「なし」とした。
<Evaluation method>
-Formation of resin-containing layer It was evaluated whether layer separation occurred in the coating film. After cutting the coating film, the cut surface is confirmed with an optical microscope and an electron microscope (SEM), and the density of zinc is visually observed with EPMA (ZN mapping). If the resin-containing layer was formed, the evaluation was “absent”. If the resin-containing layer was not formed, the evaluation was “absent”.
・外観
塗膜の外観状態を評価した。塗膜表面にブツが多い、亜鉛粒子が一部露出しているなど試験片を目視および指触して明らかに不具合が生じている場合は×とし、それ以外は２段階で評価し◎(良好)または○(◎よりは劣るが良好)とした。
-Appearance The appearance of the coating film was evaluated. When the test specimen was clearly visually or touched, such as a lot of bumps on the surface of the coating film, or some of the zinc particles were exposed, and there was a clear problem, it was evaluated as ×, and the other evaluations were evaluated in two steps. ) Or ((poor but better than ◎).
・耐おもり落下性
ＪＩＳ Ｋ５６００−５−３に準拠する試験方法（デュポン式：撃ち型φ１／２インチ、錘重さ５００ｇ、落下高さ３０〜５０ｃｍ）により評価した。落下高さを３０ｃｍ、４０ｃｍ、５０ｃｍとし、それぞれの高さで目視によるひび割れなどなければ良好とした。たとえば、落下高さが３０ｃｍおよび４０ｃｍでひび割れがなく、落下高さ５０ｃｍでひび割れが生じた場合は、表中に「４０ｃｍ○」と記載した。落下高さ３０ｃｍでもひび割れが生じた場合は、表中に「３０ｃｍ×」と記載した。
-Weight drop resistance Evaluated by a test method (DuPont type: shooting type 1/2 inch, weight of weight 500 g, drop height 30 to 50 cm) in accordance with JIS K5600-5-3. The drop heights were set to 30 cm, 40 cm, and 50 cm, and it was determined that there was no visual cracking at each height, and that it was good. For example, when there were no cracks at drop heights of 30 cm and 40 cm and cracks occurred at a drop height of 50 cm, "40 cm ○" was described in the table. In the case where cracking occurred even at a falling height of 30 cm, "30 cm ×" was described in the table.
・初期錆色
上記の耐中性塩水噴霧性試験中において、塩水噴霧時間が２４時間、４８時間、７２時間の状態で発生する錆色を目視で評価した。白色であれば、酸化亜鉛の色が表出しており、塗膜による犠牲防食効果が機能している。赤白色であれば、酸化亜鉛の白色に加えて一部に酸化鉄の赤色が表出しており、塗膜による犠牲防食効果が弱まっている。赤色であれば、全面が酸化鉄に覆われており塗膜による犠牲防食効果が見られない。
-Initial rust color In the above-mentioned neutral salt spray resistance test, the rust color generated when the salt spray time was 24 hours, 48 hours, and 72 hours was visually evaluated. If it is white, the color of zinc oxide is revealed, and the sacrificial anticorrosion effect of the coating film functions. In the case of red-white, in addition to the white color of the zinc oxide, the red color of the iron oxide is partially expressed, and the sacrificial anticorrosion effect of the coating film is weakened. If it is red, the entire surface is covered with iron oxide, and the sacrificial anticorrosion effect of the coating film is not seen.
・耐中性塩水噴霧性
ＪＩＳ Ｋ５６００−７−１に準拠する試験方法（液温３５℃の５％塩化ナトリウム水溶液を８４０時間噴霧、２４０時間で中間確認）により評価した。表には錆幅およびフクレ幅の数値を記載した。錆幅、フクレ幅ともに３ｍｍ以下を良好な評価としているが、数値が小さい方がより良好である。
-Neutral salt water spray resistance Evaluation was made by a test method in accordance with JIS K5600-7-1 (spraying with a 5% aqueous solution of sodium chloride at a liquid temperature of 35 ° C for 840 hours, and intermediate confirmation in 240 hours). The table shows the values of rust width and blister width. Although the rust width and blister width are both 3 mm or less as a good evaluation, the smaller the numerical value, the better.
・促進耐候性
サンシャインウェザーメーター３００時間試験後の光沢保持率を評価した。３００時間試験後の光沢値の初期光沢値に対する割合を記載した。数値が大きい方がより良好である。
-Accelerated weather resistance The gloss retention after a 300-hour sunshine weather meter test was evaluated. The ratio of the gloss value after the test for 300 hours to the initial gloss value was described. The higher the value, the better.
＜樹脂種の影響および亜鉛粉末量の影響＞
熱硬化性樹脂（Ａ）の種類を変化させたときの実施例１〜７、実施例２２〜２８を表１と表４に示す。塗膜に亜鉛が多く含まれる層と樹脂成分が多く含まれる層とが形成され、評価結果はすべて良好であった。
<Effect of resin type and effect of zinc powder amount>
Tables 1 and 4 show Examples 1 to 7 and Examples 22 to 28 when the type of the thermosetting resin (A) was changed. A layer containing a large amount of zinc and a layer containing a large amount of a resin component were formed in the coating film, and all the evaluation results were good.
熱硬化性樹脂（Ａ）の種類を実施例１〜７と同じとし、亜鉛末含有量を増やした実施例８〜１４を表２に示す。塗膜に亜鉛が多く含まれる層と樹脂成分が多く含まれる層とが形成されたが、実施例１〜７よりは外観、耐おもり落下性が劣る結果であった。 Table 2 shows Examples 8 to 14 in which the type of the thermosetting resin (A) was the same as Examples 1 to 7 and the content of zinc dust was increased. Although a layer containing a large amount of zinc and a layer containing a large amount of a resin component were formed in the coating film, the results were inferior to Examples 1 to 7 in appearance and weight drop resistance.
熱硬化性樹脂（Ａ）の種類を実施例１〜７と同じとし、亜鉛末含有量をさらに増やした比較例１〜７を表５に示す。亜鉛粉末含有量が多すぎたためか、塗膜に亜鉛が多く含まれる層と樹脂成分が多く含まれる層とが形成されなかった。外観も悪く、耐おもり落下性も３０ｃｍで割れが発生した。 Table 5 shows Comparative Examples 1 to 7 in which the type of the thermosetting resin (A) was the same as Examples 1 to 7 and the content of zinc dust was further increased. The layer containing a large amount of zinc and the layer containing a large amount of the resin component were not formed, probably because the content of the zinc powder was too large. The appearance was poor, and the weight drop resistance was 30 cm, and cracks occurred.
熱硬化性樹脂（Ａ）の種類を実施例１〜７と同じとし、亜鉛末含有量が少ないが防錆顔料を使用している実施例１５〜２１を表３に示す。塗膜に亜鉛が多く含まれる層と樹脂成分が多く含まれる層とが形成された。外観、耐おもり落下性は実施例１〜７と同等であるが、耐中性塩水噴霧性では２４０時間の錆幅、８４０時間の錆幅は実施例１〜７と比較すると大きく、耐食性がやや劣る結果であった。 Table 3 shows Examples 15 to 21 in which the type of the thermosetting resin (A) was the same as in Examples 1 to 7, and the content of zinc dust was small but the rust preventive pigment was used. A layer containing a large amount of zinc and a layer containing a large amount of a resin component were formed in the coating film. The appearance and the weight drop resistance are equivalent to those of Examples 1 to 7, but the rust width of 240 hours and the rust width of 840 hours are larger in the neutral salt spray resistance than in Examples 1 to 7, and the corrosion resistance is slightly higher. The results were inferior.
熱硬化性樹脂（Ａ）の種類を実施例１〜７と同じとし、亜鉛末含有量をさらに減らした比較例８〜１４を表６に示す。亜鉛粉末含有量が少なすぎたために塩水噴霧試験４８時間で赤錆が見られた。 Table 6 shows Comparative Examples 8 to 14 in which the type of the thermosetting resin (A) was the same as Examples 1 to 7 and the content of zinc dust was further reduced. Red rust was observed at 48 hours in the salt spray test due to too little zinc powder content.
実施例２２からエポキシ樹脂を除いた実施例２９を表４に示す。耐中性塩水噴霧性では２４０時間の錆幅、８４０時間の錆幅が大きく耐食性が劣る結果であったが、耐候性は向上した。 Table 4 shows Example 29 in which the epoxy resin was omitted from Example 22. In the neutral salt spray resistance, the rust width of 240 hours and the rust width of 840 hours were large and the corrosion resistance was poor, but the weather resistance was improved.
βヒドロキシアルキルアミドとトリグリシジルイソシアヌレートを併用した実施例３０を表４に示す。塗膜に亜鉛含有層と樹脂含有層とが形成され、評価結果が全て良好であった。 Table 4 shows Example 30 in which β-hydroxyalkylamide and triglycidyl isocyanurate were used in combination. A zinc-containing layer and a resin-containing layer were formed on the coating film, and all the evaluation results were good.
熱硬化性樹脂（Ａ）としてエポキシ樹脂系を使用した比較例１５を表６に示す。樹脂含有層の形成は見られなかった。外観、耐おもり落下性、耐食性は良好であったが、耐候性が非常に悪い結果であった。 Table 6 shows Comparative Example 15 using an epoxy resin as the thermosetting resin (A). No resin-containing layer was formed. The appearance, weight drop resistance and corrosion resistance were good, but the weather resistance was very poor.
これらの結果から、亜鉛粉末の含有量が粉体塗料組成物全体に対して３０〜８０質量％であれば、塗膜に亜鉛が多く含まれる層と樹脂成分が多く含まれる層とが形成され良好な結果が得られることがわかる。 From these results, when the content of the zinc powder is 30 to 80% by mass based on the entire powder coating composition, a layer containing a large amount of zinc and a layer containing a large amount of a resin component are formed in the coating film. It can be seen that good results are obtained.
上記の実施例、比較例に使用した原料は下記のとおりである。
＜水酸基含有ポリエステル樹脂＞
ＧＶ１２６：日本ユピカ(株)社製
ＧＶ５４５：日本ユピカ(株)社製
＜水酸基含有フッ素樹脂＞
ＬＦ７１０Ｆ：旭硝子（株）社製
ＥＸＬＰ−３６：旭硝子（株）社製
＜カルボキシ基含有ポリエステル樹脂＞
ＣＣ２６３０−２：ダイセル・オルネクス(株)社製
ＣＣ２４４１−２：ダイセル・オルネクス(株)社製
ＣＣ１６２３−０：ダイセル・オルネクス(株)社製
ＣＣ４４２０−０：ダイセル・オルネクス(株)社製
ＣＣ２４２５−０：ダイセル・オルネクス(株)社製
ＣＣ１６３１−０：ダイセル・オルネクス(株)社製
＜水酸基含有アクリル樹脂＞
Ａ−２５１：ＤＩＣ(株)社製
ＡＨ−６００ＳＦ：ＤＩＣ(株)社製
＜グリシジル基含有アクリル樹脂＞
Ａ−２６１：ＤＩＣ(株)社製
Ａ−２４９：ＤＩＣ(株)社製
Ａ−２６６：ＤＩＣ(株)社製
＜硬化剤＞
Ｂ−１５３０（ブロックイソシアネート）：エボニック(株)社製
ＸＬ−５５２（βヒドロキシアルキルアミド）：エムスケミー(株)社製
ＴＥＰＩＣ−Ｇ（トリグリシジルイソシアヌレート）：日産化学工業(株)社製
ＳＬ−１２（ジカルボン酸）：岡村製油(株)社製
ＤＩＣＹ７（ジシアンジアミド）：三菱化学(株)社製
＜添加剤＞
＃１００２（エポキシ樹脂）：三菱化学(株)社製
ＤＥＲ６６２Ｅ（エポキシ樹脂）：ダウケミカル(株)社製
Ｕ−８７０（ジブチルスズ化合物）：日東化成(株)社製
Ｃ１７Ｚ（２−ヘプタデシルイミダゾール）：四国化成(株)社製
ベンゾイン：美源スペシャリティケミカル(株)社製
ＰＬ５４０（アクリルポリマー）：楠本化成(株)社製
３６２０（ポリエチレン）：クラリアント(株)社製
＜顔料＞
ＭＡ１００（カーボンブラック）：三菱化学(株)社製
＜亜鉛末＞
Ｆ５００：本荘ケミカル(株)社製
＜防錆顔料＞
ＰＭ３００（モリブデン酸アルミ）：キクチカラー(株)社製
The raw materials used in the above Examples and Comparative Examples are as follows.
<Hydroxyl-containing polyester resin>
GV126: Nippon Yupika Co., Ltd. GV545: Nippon Yupika Co., Ltd. <hydroxyl-containing fluororesin>
LF710F: EXLP-36 manufactured by Asahi Glass Co., Ltd. <Carboxy group-containing polyester resin> manufactured by Asahi Glass Co., Ltd.
CC2630-2: Daicel-Ornex Co., Ltd. CC2441-2: Daicel-Ornex Co., Ltd. CC1623-0: Daicel-Ornex Co., Ltd. CC4420-0: Daicel-Ornex Co., Ltd. CC2425- 0: Daicel Ornex Co., Ltd. CC1631-0: Daicel Ornex Co., Ltd. <hydroxyl-containing acrylic resin>
A-251: AH-600SF manufactured by DIC Corporation: <Acrylic resin containing glycidyl group> manufactured by DIC Corporation
A-261: DIC Corporation A-249: DIC Corporation A-266: DIC Corporation <curing agent>
B-1530 (block isocyanate): XL-552 (β-hydroxyalkylamide) manufactured by Evonik Co., Ltd .: TEPIC-G (triglycidyl isocyanurate) manufactured by Ms. Chemie Co., Ltd .: SL- manufactured by Nissan Chemical Industry Co., Ltd. 12 (dicarboxylic acid): DICY7 (dicyandiamide) manufactured by Okamura Oil Co., Ltd .: <additive> manufactured by Mitsubishi Chemical Corporation
# 1002 (epoxy resin): DER662E (epoxy resin) manufactured by Mitsubishi Chemical Corporation: U-870 (dibutyltin compound) manufactured by Dow Chemical Company: C17Z (2-heptadecyl imidazole) manufactured by Nitto Kasei Corporation : Benzoin manufactured by Shikoku Kasei Co., Ltd .: PL540 (acrylic polymer) manufactured by Bigen Specialty Chemical Co., Ltd .: 3620 (polyethylene) manufactured by Kusumoto Kasei Co., Ltd .: <Pigment> manufactured by Clariant Co., Ltd.
MA100 (carbon black): manufactured by Mitsubishi Chemical Corporation <Zinc powder>
F500: manufactured by Honjo Chemical Co., Ltd. <Rust preventive pigment>
PM300 (aluminum molybdate): manufactured by Kikuchi Color Co., Ltd.
本発明の粉体塗料組成物は、一度の塗装で耐食性と耐候性に優れた塗膜を形成できる。屋外で使用される自動車部品、電気製品、建築資材等に好適である。 The powder coating composition of the present invention can form a coating film having excellent corrosion resistance and weather resistance in a single coating. It is suitable for automobile parts, electric appliances, building materials and the like used outdoors.
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