JPS6338072B2 - - Google Patents
Info
- Publication number
- JPS6338072B2 JPS6338072B2 JP60051523A JP5152385A JPS6338072B2 JP S6338072 B2 JPS6338072 B2 JP S6338072B2 JP 60051523 A JP60051523 A JP 60051523A JP 5152385 A JP5152385 A JP 5152385A JP S6338072 B2 JPS6338072 B2 JP S6338072B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- weight
- parts
- resin
- mountain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 148
- 239000003973 paint Substances 0.000 claims description 118
- 229920005989 resin Polymers 0.000 claims description 73
- 239000011347 resin Substances 0.000 claims description 73
- 238000000576 coating method Methods 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 53
- 239000000049 pigment Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 50
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 36
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 34
- 230000002265 prevention Effects 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 29
- 239000000835 fiber Substances 0.000 claims description 22
- 239000008199 coating composition Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000004576 sand Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- -1 potassium cadmium chromate Chemical compound 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- GLPMHULIKFGNIJ-UHFFFAOYSA-N cadmium(2+);dioxido(dioxo)chromium Chemical compound [Cd+2].[O-][Cr]([O-])(=O)=O GLPMHULIKFGNIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- QYTADNXBXAIJFH-UHFFFAOYSA-N potassium;zinc;dioxido(dioxo)chromium Chemical compound [K+].[Zn+2].[O-][Cr]([O-])(=O)=O QYTADNXBXAIJFH-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- ISHORFWZAQAGIA-UHFFFAOYSA-N sodium zinc dioxido(dioxo)chromium Chemical compound [Cr](=O)(=O)([O-])[O-].[Zn+2].[Na+] ISHORFWZAQAGIA-UHFFFAOYSA-N 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
〔産業上の利用分野〕
本発明は、自動車、電気・電子部品、土木・建
築物、家庭用品等およびそれらの金属製部品に用
いられる防錆塗料組成物に関し、更に詳しくは、
水性塗料に山皮およびクロム酸塩顔料を含有せし
めた水性塗料組成物およびその塗膜形成方法に関
するものである。
〔従来の技術および問題点〕
自動車輛、建築物、電気・電子部品、家庭用品
等、或いはそれらの部品の金属表面には、金属腐
食の防止や、美観を与えるために、塗装が施され
ている。この塗装用塗料の一種として水性塗料が
ある。水性塗料は、水溶き塗料の総称であり、水
溶性又は水分散性の塗膜形成要素を用いて作るも
のである（JIS塗料用語K5500―1068）。この水性
塗料は、塗料中に人体に有害な有機溶剤成分を含
む量が少ない上、塗料を扱う作業中においても火
気に対して引火性が無く安全衛生の面からも有用
な塗料である。しかしながら、この水性塗料組成
物は、その主成分の１つである樹脂が多くの親水
性の官能基を持つため、一般には塗膜が形成され
た後も水分が塗膜中へ浸入しやすく、結果として
耐水性、耐水密着性に劣り、更には、金属面に塗
布した際の防錆性に問題がある。
防錆性を向上させる手段として、防錆顔料を配
合する方法がある（特開昭57−141465号公報）。
しかし、一般に防錆顔料は重金属を主成分とする
顔料がほとんどで、これらの顔料は塗料中で沈降
しやすく、特に水性塗料組成物へ防錆顔料を加え
ても顔料の分散安定性が低下し、防錆性の向上も
あまり期待できない。
従つて水性塗料の従来の利点である乾燥性、光
択、硬度、耐酸性、耐アルカリ性などは可久的に
保持することはもちろん、これに加えて耐水性、
耐水密着性、防錆性が向上し、且つ顔料の分散安
定性の良好な水性塗料組成物および該組成物によ
る塗膜形成方法の開発がまたれていた。
そこで、本発明者等は、これら従来技術の問題
点を解決すべく鋭意・研究し、各種の系統的実験
を重ねた結果、本発明を成すに至つたものであ
る。
〔発明の目的〕
本発明の目的は、防錆性能に優れた水性塗料組
成物および該組成物による塗膜形成方法を提供す
るにある。
また、本発明の他の目的は、水性塗料の乾燥
性、光択、硬度、耐酸性、耐アルカリ性等を可久
的に保持し、かつこれに加えて耐水性および耐水
密着性に優れた水性塗料組成物および該組成物に
よる塗膜形成方法を提供するにある。
〔発明の構成〕
本発明の水性塗料組成物は、水性塗料用樹脂と
溶剤と山皮とクロム酸塩顔料とを主成分とする水
性塗料組成物であり、水性塗料用樹脂100重量部
に対して0.5ないし30重量部の山皮と0.05ないし
10重量部のクロム酸塩顔料とを含有し、しかも該
山皮は直径が0.002ないし0.1μｍに繊維状態化し
て不定形三次元方向に均一に分散して成り、防錆
性能に優れたことを特徴とするものである（以
下、本第一発明とする）。
次に、本発明の水性塗料組成物の塗膜形成方法
は、水性塗料用樹脂と、該水性塗料用樹脂100重
量部に対して0.5ないし30重量部の山皮と0.05な
いし10重量部のクロム酸塩顔料とを混合し、かつ
該混合物中の山皮を直径が0.02ないし0.1μｍとな
るまで繊維状態化するとともに、該繊維状態の山
皮とクロム酸塩顔料とが樹脂中に均一に分散した
混合物とする破砕混合工程と、該混合物に適宜量
の溶剤を混合して水性塗料組成物とする混合工程
と、該組成物を被塗物に塗布し、60ないし180℃
の温度で10ないし60分間焼付・乾燥して塗膜中の
水分含有率を硬化乾燥後の塗膜重量の５％以下に
する塗装工程とから成ることを特徴とするもので
ある（以下、本第二発明とする）。
以下、本発明の構成をより詳細に説明する。
本第一発明において用いる水性塗料用樹脂は、
アルキツド樹脂、アクリル樹脂、エポキシエステ
ル樹脂、オイルフリーアルキツド樹脂等の一種ま
たは二種以上、またはこれら樹脂とアミノ樹脂等
の硬化剤との混合樹脂である。
また、本第一発明において用いる山皮は、マグ
ネシウム含有粘土鉱物であり、その表面に反応性
に富む水酸基を有する鉱物で、具体的には、含水
マグネシウムシリケートを主成分とするセピオラ
イト（Sepiolite）、含水マグネシウムアルミニウ
ムシリケートを主成分とするアタパルジヤイト
（Attapulgite）であり、これらの一種または二種
以上を用いる。
本発明における山皮は通称、マウンテンコルク
（Mountain cork）、マウンテンレザー
（Mountain leather）、マウンテンウツド
（Mountain wood）等とも呼ばれている鉱物であ
り、日本における海泡石もこの一種である。該マ
グネシウム含有粘土性鉱物は、それ自身多量の水
を吸収する性質がある。
上記粘土性鉱物の結晶は、一辺が約0.1μｍの四
辺形断面を有する長繊維の集合体で、該集合体内
には、繊維の長さ方向に多数の孔を有している。
本第一発明でいう繊維状態化された山皮は、直
径が0.002〜0.1μｍ程度で、長さが0.1〜数μｍ程
度のものであり、水性塗料用樹脂中に不定形三次
元方向に、しかも均一に分散している。
山皮は、通常鉱山から採掘したものをクラツシ
ヤー等通常の方法によつて粉砕されるが、通常の
粉砕では、0.5〜200μｍの粒子である。すなわち、
本第一発明にいう繊維状態化された山皮は、従来
から一般に言われている山皮粒子とは異なり、さ
らに細く、細くほぐした細長比の大きな繊維形状
を有するものである。
ここで、繊維状態化された山皮と樹脂の混合量
は、水性塗料用樹脂100重量部に対して、山皮が
0.5〜30重量部であり、この範囲において、水性
塗料の長所を損なうことなく、得られる塗膜の耐
水性、金属板への耐水密着性が向上する。さらに
良好な効果を得るには、山皮の混合量は、３〜20
重量部であることが最も好ましい。
これは、山皮の混合量が0.5重量部未満の場合
には、塗膜に対しての耐水性、耐水密着性の効果
が得られず、また、30重量部を越えると、水性塗
料組成物の粘度が高くなりすぎ、塗装作業性が低
下するとともに、塗布後、焼付けて得られる塗膜
のつやがなくなり美観を損うからである。
また、本第一発明におけるクロム酸塩顔料は、
可溶性顔料として現在使用に供されているもの
で、これらの顔料は水分と接触するとクロム酸イ
オンを溶出し、その強い酸化作用によつて金属面
を不働態化し、防錆性を発揮すると言われてい
る。具体的には、ストロンチウムクロメート、バ
リウムクロメート、カドミウムクロメート、カド
ミウムモノオキシクロメート、ジンクテトラオキ
シクロメート、ジンクモノオキシクロメート、ナ
トリウムジンククロメート、ポタシウムカドミウ
ムクロメート、ポタシウムジンククロメート、ク
ロム酸第一鉛、クロム酸第二鉛、塩基性クロム酸
鉛等がある。
ここで、クロム酸塩顔料と樹脂の配合量は、水
性塗料用樹脂100重量部に対してクロム酸塩顔料
0.05〜10重量部であり、この範囲において水性塗
料の長所を損うことなく、得られる塗膜の金属板
への耐水密着性および防錆性が向上する。
これは、クロム酸塩顔料の配合量が0.05重量部
未満の場合には、塗膜に対しての耐水密着性およ
び防錆性の効果が得られず、また、10重量部を越
えると、それ以上添加しても耐水密着性および防
錆性の向上がそれ以上左程期待できず、また、ク
ロム酸イオンの溶出が増大して塗膜のふくれを誘
発し易くなり、更には、安全衛生上好ましくない
からである。
また、溶剤は、水の他、ブチルセロソルブ、エ
チルセロソルブ、イソプロピルアルコール、ブチ
ルカルビトール等を用いる。
本第一発明における水性塗料組成物には、顔料
添加剤が含まれていてもよい。顔料としては、カ
ーボンブラツク、ベンガラ、チタン白等の無機顔
料、フタ口シヤニン、キナクリドン等の有機顔料
及び炭酸カルシウム、タルク、クレイ、炭酸マグ
ネシウム、硫酸バリウム等の体質顔料等が使用で
きる。また、添加剤としては、ドライヤー、消泡
剤、レベリング剤、色分れ防止剤等が適宜使用で
きる。
本第一発明の水性塗料組成物は、水性塗料用樹
脂と溶剤と山皮とクロム酸塩顔料とを主成分と
し、必要に応じて顔料、添加剤等を含み、樹脂中
に繊維状態化した山皮が不定形三次元方向に均一
に分散しており、これらは上記溶剤により塗装作
業に適した粘度に調節されている。
本第１発明にかかる水性塗料組成物は、周知の
塗装方法によつて、例えば静電塗装、エアスプレ
ー塗装、浸漬塗装等によつて、被塗物表面に塗
布、乾燥して塗膜とする。第１図に、本発明によ
つて得られた塗料を試験板に塗布しその塗膜を透
過型電子顕微鏡により観察した結果を示す。同図
中から、繊維状態化した山皮１が不定形三次元方
向に均一に分散しているのが分る。
次に、本第二発明の水性塗料組成物の塗膜形成
方法は以下の様である。
この第二発明は、前述した第一発明にかかる水
性塗料組成物による塗膜形成方法である。
即ち、先ず、本第一発明で述べた水性塗料樹脂
と山皮とクロム酸塩顔料とを混合し、かつ該混合
物中の山皮を直径が0.002ないし0.1μｍとなるま
で繊維状態化するとともに、該繊維状態の山皮と
クロム酸塩顔料とが樹脂中に均一に分散した混合
物とする（破砕混合工程）。
これらの原料を混合する順番は、特に限定する
ものではないが、まず、水性塗料用樹脂を用意
し、該樹脂分100重量部に対して0.05〜10重量部
の割合でクロム酸塩顔料を該樹脂に加え均一に分
散する。このとき、必要に応じて、樹脂には適量
の溶剤を加え、また、樹脂分が樹脂溶液中で15〜
65％であるのが望ましい。水性塗料用樹脂に加え
るクロム酸塩顔料は、通常の市販品でよく、粒子
径は0.5〜200μｍ程度のものが好ましい。このク
ロム酸塩顔料の混合、分散に当つては、通常用い
る塗料用顔料の分散機を用い、具体的には、サン
ドグラインダー、ペイントシエーカー、ボールミ
ル等の分散機がある。
次に、クロム酸塩顔料を分散した樹脂に、該樹
脂分100重量部に対して0.5〜30重量部の割合で山
皮を該樹脂に加え、樹脂の存在下で山皮をほぐ
し、繊維状態化するとともに、これを樹脂中に分
散し、樹脂中に山皮とクロム酸塩顔料が均一に分
散した混合物を得る。この山皮は通常の方法で粉
砕したものでよく、その粒子径は、0.5〜200μｍ
程度であることが好ましい。これは、0.5μｍ以下
であつても、また200μｍ以上であつてもよいが、
粒子が大きいと山皮の破砕混合工程での作業性が
悪く、長時間を必要とするからである。
この山皮の破砕混合では、通常の方法で粉砕し
て得た山皮の繊維構造をさらに微細化し、繊維の
直径が0.002〜0.1μｍとなるまで破砕し、繊維状
態化することを特徴とする。
これは、繊維の直径が0.002〜0.1μｍより大き
い場合には、塗膜の耐水性、耐水密着性および防
錆性に効果が得られないばかりか場合によつては
逆効果をもたらすおそれがあるからである。
この破砕混合は、樹脂と山皮の混合物に大きな
せん断力を加えて行なうものである。このとき、
山皮は繊維状態化するとともに樹脂と強く接触し
て樹脂中に不定形三次元方向に均一に分散する。
この破砕混合は、サンドグライダー、ペイントシ
エーカー、ボールミル等の分散機を用いて行な
う。
以上、樹脂中に先ずクロム酸塩顔料を混合・分
散し、次に山皮を添加し破砕する方法を具体的に
述べたが、本破砕混合工程では、クロム酸塩顔料
と山皮とを同時に樹脂中に混合・分散してもよ
く、また、山皮を混合する際に、予め山皮の樹脂
分散液を作製し、該分散液を混合してもよい。
次に、破砕混合工程で得られた混合物に、溶剤
を混合し、更に、必要に応じて顔料、添加剤を混
合し、水性塗料組成物を得る（混合工程）。この
混合に際しては、上述の破砕混合工程で述べた分
散機を用いることができる。
次に、得られた水性塗料組成物を被塗物に塗布
し、60〜180℃の温度で10〜60分間焼付・乾燥し
て塗膜中の水分含有率を硬化乾燥後の塗膜重量の
５％以下にすることにより塗膜を形成する（塗装
工程）。
ここで、焼付・乾燥温度を60〜180℃としたの
は、該温度が60℃未満の場合、塗膜乾燥までに長
時間を要し生産性が悪い上に塗膜に必要な硬度が
得られにくく不都合であり、180℃を越えると温
度が高すぎて水分が急激に蒸発し塗膜表面が荒れ
るからである。また、焼付・乾燥時間を10〜60分
としたのは、10分未満の場合は温度を高くしなけ
ばならず、塗膜表面が荒れるからであり、また、
180分を越えると生産性が低下するので好ましく
ないからである。
また、水性塗料組成物の硬化乾燥後の塗膜内の
水分含有率が、硬化乾燥後の塗膜重量の５％以下
としたのは、５％以上の場合には塗膜硬度が低く
塗膜の機械的性質が低下すると同時に塗膜外部よ
り新たに浸入する水分に対する塗膜の耐久性が低
下するため、たとえクロム酸塩顔料が分散し、か
つ山皮が繊維状態化して、不定形三次元方向に均
一に分散させたものでも耐水性、耐水密着性およ
び防錆性の本発明の所期の効果は期待できないお
それがあるからである。
〔発明の作用および効果〕
本第一発明にかかる水性塗料組成物は、優れた
防錆性能を有する。
該組成物が、この様に優れた防錆性能を発揮す
るメカニズムについては、未だ必ずしも明らかで
はないが、次の様に考えられる。
即ち、該組成物により得られる乾燥塗膜中に
は、山皮が繊維状態化して不定形三次元方向に分
散しているので、塗膜外部からの水の浸入を防止
し、また、該乾燥塗膜中に分散せしめたクロム酸
塩顔料は、水分と接触した場合クロム酸イオンを
溶出し、その強い酸化作用によつて被塗装物であ
る金属表面を不動態化し、これら山皮による効果
とクロム酸塩顔料による効果が相補的に作用し、
相乗されて優れた防錆効果を発揮するものと思わ
れる。
また、本第一発明にかかる水性塗料組成物は、
繊維状態化された山皮が均一に分散しているので
適度の揺変性が得られる。このため、塗装作業性
がよくなる。例えば、スプレー塗装の場合、スプ
レー時には塗料にせん断力が加わり塗料の粘度が
下がるため、塗料の微粒化が良く、被塗装物に対
し塗装しやすく、塗膜の仕上りも向上する。ま
た、塗装直後にはせん断力がなくなるため、塗料
の粘度が高くなり、タレ等が防止できる。また、
塗料中では、山皮が繊維状態化して安定に均一分
散しているため、クロム酸塩顔料その他の添加剤
の沈降防止に効果がある。
さらに、該組成物により得られる乾燥塗膜中に
も山皮が繊維状態化して不定形三次元方向に分散
しているので、塗膜の補強効果と塗膜外部からの
水の浸入防止に効果がある。従つて、被塗装物を
長期間水中に浸漬しても、塗膜が被塗装物からは
がれることのなく、所 謂、耐水性、耐水密着性
が向上する。
また、本第一発明にかかる水性塗料組成物は、
山皮の効果とクロム酸塩顔料の効果が相補的に発
揮されるだけではなく、山皮とクロム酸塩顔料の
各々単独では達し得ない高レベルの耐水性、耐水
密着性が発揮される。
本第二発明にかかる水性塗料組成物の塗膜形成
方法によれば、山皮を樹脂の存在下で繊維状態化
したこと、およびクロム酸塩顔料を均一に分散し
たこと、さらには硬化乾燥後の塗膜内の水分含有
率を塗膜重量の５％以下としたことにより、塗膜
の強度向上および塗膜外部より浸入する水分が被
塗物と塗膜との界面にまで到達することを抑止
し、塗膜の密着力を持続させるとともに、被塗物
表面を不動態化することにより耐水性、耐水密着
性および防錆性に優れた効果を呈する。
〔実施例〕
以下、本発明の実施例を説明する。
まず、各実施例において行つた、塗膜の耐水
性、耐水密着性および防錆性を確めるための方法
は、次のようである。
被塗装板は、大きさ150ｍ／ｍ×70ｍ／ｍ、厚
さ0.8ｍ／ｍの軟鋼板（SPCC）で、塗装前にその
表面を有機溶剤で脱脂処理したものである。これ
らに塗装を行ない塗膜を形成したのち、40℃の純
水に浸漬し、ブリスターの発生するまでの時間を
測定し、これを耐水性判断の基準とした。
耐水密着性の判断は、先ず塗膜を40℃の純水に
一定時間浸漬した後、該塗膜に１ｍ／ｍ間隔の切
れ目をカツターナイフで縦と横の方向に入れ、１
ｍ／ｍ四方のマス目を100個作る。そしてマス目
の上にセロハンテープを直接貼着し、その後該セ
ロハンテープを剥離したときマス目の塗膜が剥離
したか否かを調べた。剥離しなかつた場合には、
さらに、純水に浸漬し、上記セロハンテープによ
る剥離試験をくり返す。そして、塗膜が剥離する
までに要した純水浸漬時間を求めることにより行
なつた。純水浸漬時間が長いぼど耐水密着性が優
れていることになる。
防錆性の判断は、塗装板表面の塗装膜にカツタ
ーナイフで基材に達する切り傷を付け、JIS・
K5400に準拠した塩水噴霧試験法（SS試験）に
よつて切り傷からの腐食の進行速度を調べた。こ
のSS試験では、切り傷からの腐食によるフクレ
が６mmに達するまでのSS試験時間を求めること
により行なつた。SS試験時間が長いほど防錆性
が優れていることになる。
本発明の実施例中に採用した水性塗料の製法に
ついて詳しく説明すれば、一般的に行なわれてい
る水性塗料の代表的な製法を取り入れて作製する
とともに、他の例では市販に供されている樹脂を
購入し、これに山皮およびクロム酸塩顔料を配し
て得た。
実施例 １〜８
撹拌機、還流冷却器、温度計、加熱設備を装備
するステンレス製反応容器にサフラワー油43.90
重量部を入れ、150℃に加熱し、トリメチロール
プロパン16.44重量部を加え、温度を220℃まで上
昇させた後、さらに、リサージ0.02重量部を加え
反応させた。次に、得られた生成物にメタノール
を添加し、該生成物１重量部がメタノール５重量
部に溶解するまでこの温度に保ち、反応を継続し
た。反応終了後、生成物を166℃まで冷却し、ブ
チルカルビトール12.54重量部を加え均一に分散
するまで撹拌した。その後、無水トリメリツト酸
23.60重量部を加えたのち、反応混合物を再び166
℃に加熱し、この温度に20分間保持した。その
後、さらに190℃で４時間加熱し反応させた。反
応生成物の酸価が35に達した時、温度を170℃に
下げ、これに無水フタル酸3.5重量部を加え、酸
価が45になるまで反応を続けた。得られた反応生
成物100重量部を、純水55重量部、イソプロピル
アルコール６重量部、28％アンモニア水５重量部
の混合物で希釈して水性塗料用樹脂溶液を得た。
この水性塗料用樹脂溶液の樹脂含有量は60％、粘
度（ガードナー）はZ4，PHは８であつた。
この得られた水性塗料用樹脂溶液を樹脂分換算
で92重量部および硬化剤としてメチル化メチロー
ルメラミン樹脂（スミマールＭ―40W、住友化学
工業株式会社製、不揮発分80％）10重量部に対し
てクロム酸ストロンチウム1.5重量部、顔料とし
てのカーボンブラツクを４重量部、炭酸カルシウ
ムを６重量部、消泡剤0.5重量部を加え、分散機
であるサンドグラインダーにて１時間混合した。
ひきつづいて、粒子径約0.1〜150μｍの山皮を10
重量部加え、該サンドグラインダーにて２時間山
皮を破砕混合することにより、クロム酸塩顔料お
よび山皮を分散した水性塗料用樹脂を得た。分散
後、すみやかに該水性塗料用樹脂分100重量部に
対しイソプロピルアルコール40重量部および純水
29重量部を順次配合混入させて本発明にかかる水
性塗料用組成物を得た。
この水性塗料用組成物中には、繊維状態化され
た直径0.002〜0.1μｍ、長さ0.1〜数μｍの山皮が
均一に不定形三次元方向に分散していた。
次に、該塗料組成物を、被塗装板にエアスプレ
ーにて塗装し、120℃にて20分間焼付・乾燥した
のち、耐水性、耐水密着性および防錆性を調査し
た。その結果を、第１表の実施例番号１の欄に塗
膜硬度（JIS K5400に準拠）、塗膜光沢（JIS
K5400に準拠）と合せて示す。また、塗膜を電子
顕微鏡で観察したところ、第１図に示すように、
山皮は、繊維状態化して、不定形三次元方向に分
散していた。
さらに、実施例１で得たものと同組成の水性塗
料用樹脂溶液に同様の硬化剤、顔料、添加剤を加
え、山皮とクロム酸ストロンチウムの量を種々変
化させた水性塗料組成物を本実施例１と同様の方
法で作製し、これを塗布後焼付けて得られた塗膜
の耐水性、耐水密着性および防錆性を調査した。
その結果を、第１表の実施例番号２〜８に示す。
また、比較のために、クロム酸ストロンチウム
を加えず山皮を10または40重量部加えたもの、山
皮を加えずクロム酸ストロンチウムを1.5または
15重量部を加えたもの、および山皮とクロム酸ス
トロンチウムを全く加えないものについても調査
した。その結果を比較例C1〜C5に併わせて示す。
また、前記のサンドグラインダーによる混合時
間を30分間に短縮して行い、その他は実施例１と
同様の方法で分散を行い、山皮を繊維状態化させ
ず、一部が粒状のまま残つている水性塗料組成物
を得、塗布後焼付けて得られた塗膜の耐水性、耐
水密着性および防錆性を調査した。その結果を、
第１表の比較例C6に併わせて示す。
[Industrial Application Field] The present invention relates to a rust-preventing paint composition used for automobiles, electric/electronic parts, civil engineering/buildings, household goods, etc. and their metal parts.
The present invention relates to an aqueous paint composition in which a water-based paint contains a pigment and a chromate pigment, and a method for forming a coating film thereof. [Prior art and problems] The metal surfaces of automobiles, buildings, electrical/electronic parts, household goods, etc., or their parts, are often painted to prevent metal corrosion and to give them a beautiful appearance. There is. Water-based paint is one type of paint for this purpose. Water-based paint is a general term for water-soluble paints, and is made using water-soluble or water-dispersible film-forming elements (JIS paint terminology K5500-1068). This water-based paint contains a small amount of organic solvent components that are harmful to the human body, and is also useful from the standpoint of safety and hygiene since it is not flammable to fire even during work with the paint. However, since the resin, which is one of the main components of this water-based paint composition, has many hydrophilic functional groups, it is generally easy for water to penetrate into the paint film even after the paint film is formed. As a result, it is inferior in water resistance and water-resistant adhesion, and furthermore, there is a problem in rust prevention when applied to a metal surface. As a means of improving rust prevention, there is a method of incorporating a rust prevention pigment (Japanese Patent Laid-Open No. 141465/1983).
However, in general, most anti-corrosion pigments are pigments whose main components are heavy metals, and these pigments tend to settle in paints.In particular, even when anti-rust pigments are added to water-based paint compositions, the dispersion stability of the pigments decreases. , we cannot expect much improvement in rust prevention. Therefore, the traditional advantages of water-based paints, such as drying properties, light selectivity, hardness, acid resistance, and alkali resistance, are not only permanently maintained, but also water resistance,
There has been a great deal of effort to develop a water-based coating composition with improved water-resistant adhesion and rust prevention properties and good pigment dispersion stability, as well as a method for forming a coating film using the composition. Therefore, the inventors of the present invention have diligently researched and conducted various systematic experiments in order to solve these problems of the prior art, and as a result, have accomplished the present invention. [Object of the Invention] An object of the present invention is to provide a water-based coating composition with excellent antirust performance and a method of forming a coating film using the composition. Another object of the present invention is to permanently maintain the drying properties, photoselectivity, hardness, acid resistance, alkali resistance, etc. of water-based paints, and in addition, to provide water-based paints with excellent water resistance and water-resistant adhesion. The present invention provides a coating composition and a method for forming a coating film using the composition. [Structure of the Invention] The water-based paint composition of the present invention is a water-based paint composition containing a water-based paint resin, a solvent, mountain bark, and a chromate pigment as main components, and contains a water-based paint composition based on 100 parts by weight of the water-based paint resin. 0.5 to 30 parts by weight of mountain bark and 0.05 to 30 parts by weight
Contains 10 parts by weight of chromate pigment, and the fibers have a diameter of 0.002 to 0.1 μm and are uniformly dispersed in an amorphous three-dimensional direction, and have excellent rust prevention performance. (hereinafter referred to as the first invention). Next, the method for forming a film of the water-based paint composition of the present invention comprises: a resin for water-based paint; 0.5 to 30 parts by weight of mountain bark and 0.05 to 10 parts by weight of chromium based on 100 parts by weight of the resin for water-based paint; The chromate pigment is mixed with the chromate pigment, and the mountain skin in the mixture is made into a fiber state until the diameter becomes 0.02 to 0.1 μm, and the fibrous mountain skin and the chromate pigment are uniformly dispersed in the resin. a crushing and mixing step for preparing a mixture, a mixing step for preparing a water-based coating composition by mixing an appropriate amount of a solvent with the mixture, and applying the composition to an object to be coated and heating the mixture at 60 to 180°C.
The coating process consists of baking and drying for 10 to 60 minutes at a temperature of (Second invention) Hereinafter, the configuration of the present invention will be explained in more detail. The water-based paint resin used in the first invention is:
One or more types of alkyd resins, acrylic resins, epoxy ester resins, oil-free alkyd resins, etc., or mixed resins of these resins and curing agents such as amino resins. In addition, the mountain bark used in the first invention is a magnesium-containing clay mineral, which has highly reactive hydroxyl groups on its surface, and specifically, sepiolite, which is mainly composed of hydrated magnesium silicate, Attapulgite is mainly composed of hydrated magnesium aluminum silicate, and one or more of these are used. Mountain bark in the present invention is a mineral commonly called mountain cork, mountain leather, mountain wood, etc., and meerschaum in Japan is also one of these minerals. The magnesium-containing clay mineral itself has the property of absorbing a large amount of water. The above-mentioned clay mineral crystal is an aggregate of long fibers having a rectangular cross section of about 0.1 μm on a side, and the aggregate has a large number of pores in the length direction of the fibers. The fibrous mountain skin referred to in the first invention has a diameter of about 0.002 to 0.1 μm and a length of about 0.1 to several μm, and is dispersed in an amorphous three-dimensional direction in a water-based paint resin. Moreover, it is evenly distributed. Mountain bark is usually mined from a mine and crushed using a conventional method such as a crusher, and the ordinary crushing produces particles of 0.5 to 200 μm. That is,
The fibrous mountain bark according to the first invention is different from the conventional mountain bark particles, and has a fiber shape that is thinner and loosened and has a large slenderness ratio. Here, the mixing amount of fibrous mountain bark and resin is as follows: 100 parts by weight of resin for water-based paint,
The amount is 0.5 to 30 parts by weight, and within this range, the water resistance of the resulting coating film and the water resistant adhesion to the metal plate are improved without impairing the advantages of water-based paints. To obtain even better effects, the amount of mountain bark mixed should be 3 to 20
Parts by weight are most preferred. This is because if the amount of mountain bark mixed is less than 0.5 parts by weight, the effect of water resistance and water resistant adhesion to the paint film cannot be obtained, and if it exceeds 30 parts by weight, the water-based paint composition This is because the viscosity of the paint becomes too high, reducing painting workability, and the paint film obtained by baking after application loses its luster, impairing its aesthetic appearance. Furthermore, the chromate pigment in the first invention is
These pigments are currently used as soluble pigments, and when they come into contact with moisture, they elute chromate ions, which passivate metal surfaces through their strong oxidizing action, and are said to exhibit rust prevention properties. ing. Specifically, strontium chromate, barium chromate, cadmium chromate, cadmium monooxychromate, zinc tetraoxychromate, zinc monooxychromate, sodium zinc chromate, potassium cadmium chromate, potassium zinc chromate, lead chromate, lead chromate, Dilead, basic lead chromate, etc. Here, the blending amount of chromate pigment and resin is 100 parts by weight of resin for water-based paint.
The amount is 0.05 to 10 parts by weight, and within this range, the water-resistant adhesion and rust prevention properties of the resulting coating film to the metal plate are improved without impairing the advantages of water-based paints. This is because if the amount of chromate pigment blended is less than 0.05 parts by weight, water-resistant adhesion and rust prevention effects cannot be obtained for the paint film, and if it exceeds 10 parts by weight, it will not be effective. Even if the above amount is added, it is not possible to expect any further improvement in water resistance adhesion and rust prevention, and the elution of chromate ions increases, which tends to cause blistering of the paint film, and furthermore, there are health and safety concerns. This is because it is not desirable. Further, as the solvent, in addition to water, butyl cellosolve, ethyl cellosolve, isopropyl alcohol, butyl carbitol, etc. are used. The aqueous coating composition in the first invention may contain a pigment additive. Examples of pigments that can be used include inorganic pigments such as carbon black, red iron oxide, and titanium white, organic pigments such as cyanocyanine and quinacridone, and extender pigments such as calcium carbonate, talc, clay, magnesium carbonate, and barium sulfate. Further, as additives, a dryer, an antifoaming agent, a leveling agent, a color separation preventing agent, etc. can be used as appropriate. The water-based paint composition of the first invention contains a resin for water-based paint, a solvent, mountain bark, and a chromate pigment as main components, and optionally contains pigments, additives, etc., and contains fibers in the resin. The mountain skin is uniformly dispersed in an amorphous three-dimensional direction, and the viscosity of these is adjusted by the above-mentioned solvent to be suitable for painting work. The aqueous coating composition according to the first invention is applied to the surface of the object to be coated by a well-known coating method, such as electrostatic coating, air spray coating, dip coating, etc., and is dried to form a coating film. . FIG. 1 shows the results of applying the paint obtained according to the present invention to a test plate and observing the coating film using a transmission electron microscope. It can be seen from the figure that the fibrous mountain skin 1 is uniformly dispersed in an amorphous three-dimensional direction. Next, the method for forming a coating film of the aqueous coating composition of the second invention is as follows. This second invention is a method for forming a coating film using the aqueous coating composition according to the first invention described above. That is, first, the water-based paint resin described in the first invention, the mountain skin, and the chromate pigment are mixed, and the mountain skin in the mixture is made into a fiber state until the diameter becomes 0.002 to 0.1 μm, A mixture is prepared in which the fibrous mountain skin and the chromate pigment are uniformly dispersed in the resin (pulverization and mixing step). The order in which these raw materials are mixed is not particularly limited, but first, a water-based paint resin is prepared, and a chromate pigment is added at a ratio of 0.05 to 10 parts by weight based on 100 parts by weight of the resin. Add to resin and disperse evenly. At this time, if necessary, add an appropriate amount of solvent to the resin, and make sure that the resin content is 15 to 15% in the resin solution.
Preferably it is 65%. The chromate pigment to be added to the water-based paint resin may be any ordinary commercially available product, and preferably has a particle size of about 0.5 to 200 μm. For mixing and dispersing the chromate pigment, a commonly used dispersing machine for paint pigments is used, and specific examples thereof include a sand grinder, a paint shaker, a ball mill, and the like. Next, mountain bark is added to the resin in which the chromate pigment is dispersed at a ratio of 0.5 to 30 parts by weight based on 100 parts by weight of the resin, and the mountain bark is loosened in the presence of the resin to form fibers. At the same time, this is dispersed in a resin to obtain a mixture in which mountain bark and chromate pigment are uniformly dispersed in the resin. This mountain bark may be crushed by a normal method, and its particle size is 0.5 to 200 μm.
It is preferable that the degree of This may be less than 0.5 μm or more than 200 μm,
This is because if the particles are large, the workability in the mountain bark crushing and mixing process is poor and requires a long time. This method of crushing and mixing mountain bark is characterized in that the fiber structure of the mountain bark obtained by crushing it by a normal method is further refined, and the fiber structure is crushed until the diameter of the fibers is 0.002 to 0.1 μm to form a fiber state. . This means that if the diameter of the fibers is larger than 0.002 to 0.1 μm, not only will the water resistance, water resistance adhesion, and rust prevention properties of the coating film be ineffective, but in some cases, it may even have the opposite effect. It is from. This crushing and mixing is performed by applying a large shearing force to the mixture of resin and mountain bark. At this time,
The mountain bark becomes fibrous, comes into strong contact with the resin, and is uniformly dispersed in the resin in an amorphous three-dimensional direction.
This crushing and mixing is performed using a dispersing machine such as a sand glider, paint shaker, or ball mill. Above, we specifically described the method of first mixing and dispersing the chromate pigment in the resin, then adding the mountain bark, and crushing it.In this crushing and mixing process, the chromate pigment and the mountain bark are simultaneously It may be mixed and dispersed in the resin, or when mixing the mountain bark, a resin dispersion of the mountain bark may be prepared in advance and the dispersion liquid may be mixed. Next, a solvent is mixed into the mixture obtained in the crushing and mixing step, and further, pigments and additives are mixed as necessary to obtain an aqueous coating composition (mixing step). For this mixing, the disperser described in the above-mentioned crushing and mixing step can be used. Next, the obtained aqueous paint composition is applied to the object to be coated, baked and dried at a temperature of 60 to 180°C for 10 to 60 minutes, and the water content in the coating is reduced to the weight of the coating after curing and drying. A coating film is formed by reducing the content to 5% or less (painting process). Here, the baking/drying temperature was set at 60 to 180°C.If the temperature is less than 60°C, it will take a long time to dry the coating, resulting in poor productivity and the hardness required for the coating will not be achieved. If the temperature exceeds 180°C, the water will evaporate rapidly and the surface of the coating will become rough. In addition, the reason why the baking and drying time was set at 10 to 60 minutes was because if it was less than 10 minutes, the temperature would have to be high, which would roughen the coating surface.
This is because if the time exceeds 180 minutes, productivity decreases, which is not preferable. In addition, the water content in the coating film after curing and drying of the aqueous coating composition was set to 5% or less of the coating weight after curing and drying, because if it was 5% or more, the coating film hardness would be low. At the same time, the mechanical properties of the paint film decrease, and at the same time, the durability of the paint film against moisture that newly enters from outside the paint film decreases. This is because even if the particles are uniformly dispersed in the direction, the desired effects of the present invention, such as water resistance, water resistant adhesion, and rust prevention, may not be expected. [Operations and Effects of the Invention] The water-based coating composition according to the first invention has excellent antirust performance. Although the mechanism by which this composition exhibits such excellent antirust performance is not yet clear, it is thought to be as follows. That is, in the dry coating film obtained from the composition, the mountain skin is in the form of fibers and dispersed in an amorphous three-dimensional direction, which prevents water from entering from the outside of the coating film, and also prevents water from entering from the outside of the coating film. When the chromate pigment dispersed in the paint film comes into contact with moisture, it elutes chromate ions, and its strong oxidizing action passesivates the metal surface to be coated, eliminating the effects of these flakes. The effects of chromate pigments work in a complementary manner,
It is thought that they work synergistically to exhibit an excellent antirust effect. Furthermore, the aqueous coating composition according to the first invention includes:
Appropriate thixotropy can be obtained because the fibrous mountain bark is uniformly dispersed. This improves painting workability. For example, in the case of spray painting, since shearing force is applied to the paint during spraying and the viscosity of the paint is reduced, the paint becomes finely atomized, making it easier to coat the object and improving the finish of the paint film. In addition, since there is no shearing force immediately after painting, the viscosity of the paint increases and sagging can be prevented. Also,
In paints, the mountain bark becomes fibrous and is stably and uniformly dispersed, which is effective in preventing the settling of chromate pigments and other additives. Furthermore, the dried paint film obtained from this composition also has mountain skin in the form of fibers and is dispersed in an amorphous three-dimensional direction, which is effective in reinforcing the paint film and preventing water from entering from outside the paint film. There is. Therefore, even if the object to be coated is immersed in water for a long period of time, the coating film will not peel off from the object to be coated, and the so-called water resistance and water-resistant adhesion will be improved. Furthermore, the aqueous coating composition according to the first invention includes:
Not only are the effects of mountain bark and chromate pigments complementary, but also a high level of water resistance and water-resistant adhesion that cannot be achieved by either mountain bark or chromate pigments alone is achieved. According to the method for forming a coating film of an aqueous coating composition according to the second invention, the mountain bark is made into a fiber state in the presence of a resin, the chromate pigment is uniformly dispersed, and furthermore, after curing and drying, By setting the water content in the paint film to 5% or less of the weight of the paint film, the strength of the paint film is improved and moisture that enters from outside the paint film can be prevented from reaching the interface between the coated object and the paint film. In addition to maintaining the adhesion of the coating film, it also provides excellent water resistance, water-resistant adhesion, and rust prevention by passivating the surface of the object being coated. [Examples] Examples of the present invention will be described below. First, the method used in each Example to confirm the water resistance, water resistant adhesion, and rust prevention properties of the coating film is as follows. The plate to be painted is a mild steel plate (SPCC) with a size of 150 m/m x 70 m/m and a thickness of 0.8 m/m, and its surface was degreased with an organic solvent before painting. After coating these to form a coating film, they were immersed in pure water at 40°C, and the time until blisters appeared was measured, and this was used as the standard for water resistance judgment. To judge water-resistant adhesion, first immerse the coating film in pure water at 40°C for a certain period of time, then make cuts in the coating film at 1 m/m intervals in the vertical and horizontal directions with a cutter knife.
Make 100 m/m square squares. Then, cellophane tape was applied directly onto the squares, and when the cellophane tape was then peeled off, it was examined whether the coating film on the squares was peeled off. If it does not peel off,
Furthermore, it is immersed in pure water and the above peeling test using cellophane tape is repeated. The test was then performed by determining the time required for immersion in pure water until the coating film peeled off. The longer the immersion time in pure water, the better the water resistant adhesion. To judge the rust prevention property, make a cut in the coating film on the surface of the painted board with a cutter knife that reaches the base material, and then
The rate of progression of corrosion from cuts was investigated using the salt spray test method (SS test) in accordance with K5400. This SS test was conducted by determining the SS test time until the swelling due to corrosion from the cut reached 6 mm. The longer the SS test time, the better the rust prevention. To explain in detail the manufacturing method of the water-based paint employed in the examples of the present invention, it was manufactured by incorporating a typical manufacturing method of commonly used water-based paints, and in other examples, A resin was purchased and coated with mountain bark and chromate pigments. Examples 1-8 Safflower oil 43.90 g in a stainless steel reaction vessel equipped with a stirrer, reflux condenser, thermometer and heating equipment
After adding 16.44 parts by weight of trimethylolpropane and raising the temperature to 220°C, 0.02 parts by weight of litharge was further added and reacted. Next, methanol was added to the obtained product, and the reaction was continued at this temperature until 1 part by weight of the product was dissolved in 5 parts by weight of methanol. After the reaction was completed, the product was cooled to 166°C, and 12.54 parts by weight of butyl carbitol was added and stirred until uniformly dispersed. Then trimellitic anhydride
After adding 23.60 parts by weight, the reaction mixture was again reduced to 166 parts by weight.
℃ and held at this temperature for 20 minutes. Thereafter, the reaction mixture was further heated at 190°C for 4 hours. When the acid value of the reaction product reached 35, the temperature was lowered to 170°C, 3.5 parts by weight of phthalic anhydride was added thereto, and the reaction was continued until the acid value reached 45. 100 parts by weight of the obtained reaction product was diluted with a mixture of 55 parts by weight of pure water, 6 parts by weight of isopropyl alcohol, and 5 parts by weight of 28% aqueous ammonia to obtain a resin solution for water-based paint.
The resin content of this aqueous paint resin solution was 60%, the viscosity (Gardner) was Z4 , and the pH was 8. This obtained resin solution for water-based paint is 92 parts by weight in terms of resin content and 10 parts by weight of methylated methylol melamine resin (Sumimar M-40W, manufactured by Sumitomo Chemical Co., Ltd., non-volatile content 80%) as a curing agent. 1.5 parts by weight of strontium chromate, 4 parts by weight of carbon black as a pigment, 6 parts by weight of calcium carbonate, and 0.5 parts by weight of an antifoaming agent were added and mixed for 1 hour using a sand grinder as a dispersing machine.
Subsequently, 10 pieces of mountain bark with a particle size of approximately 0.1 to 150 μm were collected.
By adding parts by weight and crushing and mixing the mountain bark for 2 hours using the sand grinder, a resin for water-based paint in which the chromate pigment and the mountain skin were dispersed was obtained. After dispersion, immediately add 40 parts by weight of isopropyl alcohol and pure water to 100 parts by weight of the resin for water-based paint.
A water-based paint composition according to the present invention was obtained by sequentially blending 29 parts by weight. In this aqueous paint composition, fibrous fibers having a diameter of 0.002 to 0.1 μm and a length of 0.1 to several μm were uniformly dispersed in an amorphous three-dimensional direction. Next, the coating composition was applied to a plate to be coated by air spray, baked and dried at 120° C. for 20 minutes, and then water resistance, water resistant adhesion, and rust prevention were investigated. The results are shown in the column of Example No. 1 in Table 1 for coating film hardness (according to JIS K5400) and coating film gloss (JIS K5400).
(Compliant with K5400). Furthermore, when the coating film was observed using an electron microscope, as shown in Figure 1,
The mountain bark had become fibrous and dispersed in an amorphous three-dimensional direction. Furthermore, water-based paint compositions were prepared by adding the same curing agent, pigment, and additives to the water-based paint resin solution having the same composition as that obtained in Example 1, and varying the amounts of mountain bark and strontium chromate. A coating film was prepared in the same manner as in Example 1, and the water resistance, water resistant adhesion, and rust prevention properties of the resulting coating film were investigated by baking it after coating.
The results are shown in Example numbers 2 to 8 in Table 1. For comparison, we also added 10 or 40 parts by weight of mountain bark without adding strontium chromate, and 1.5 or 1.5 parts by weight of strontium chromate without adding mountain bark.
A sample containing 15 parts by weight and a sample containing no mountain bark or strontium chromate were also investigated. The results are shown together with Comparative Examples C1 to C5. In addition, the mixing time using the sand grinder was shortened to 30 minutes, and otherwise the dispersion was carried out in the same manner as in Example 1, so that the mountain bark was not turned into a fibrous state, and some portions remained as granules. A water-based paint composition was obtained, and the water resistance, water-resistant adhesion, and rust prevention properties of the resulting paint film were investigated by baking after application. The result is
This is shown together with Comparative Example C6 in Table 1.
【表】【table】
【表】
第１表から明らかな如く、本発明にかかるもの
は、比較例C5に示す山皮、クロム酸ストロンチ
ウムを全く含まないものと比較してて、耐水性、
耐水密着性および防錆性（耐SS）が著しく向上
していることが分る。
また、比較例C1〜C4に示す山皮またはクロム
酸ストロンチウムのいずれか一方を含むものと比
較しても、耐水性、耐水密着性は言うまでもな
く、特に、防錆性が著しく向上していることが分
る。
水性塗料用樹脂100重量部に対し、山皮の量を
0.5重量部から30重量部まで添加して行つた実施
例の試験結果から、塗膜の硬さ、光沢をも勘案す
ると、山皮混合量の最も好ましい範囲は３〜20重
量部である。山皮に加えて添加するクロム酸スト
ロンチウムは、水性塗料用樹脂100重量部に対し、
0.1〜10重量部まで添加して行つた実施例の試験
結果から、0.1重量部の添加で防錆性に効果が認
められ、10重量部までの添加で著しい効果が認め
られる。しかしながら、10重量部以上の添加は、
安全衛生を考慮すると好ましくない。また、比較
例C6の結果は、効果が上がるとされる山皮とク
ロム酸ストロンチウムを配合しても、なお、工程
混合技術の相違によつては効果が上がらないこと
を示すもので、水性塗料組成物の組成物確認とし
て、山皮が不定形三次元方向に均一に分散されて
いなかつたために耐水性、耐水密着性および防錆
性の効果につながらなかつたことを示すもので、
その理由は水性塗料用樹脂溶液と山皮との混合工
程で、混合時間が短かかつたためである。
第２図に、該塗膜の透過電子顕微鏡観察結果を
示す。この結果から、粒子状山皮２がほぼそのま
ま分散していることがわかる。すなわち、水性塗
料用樹脂中の山皮が繊維状態化して均一に分散し
ている必要があることを示している。
実施例 ９〜11
撹拌機、還流冷却器、加熱設備を装備するガラ
スライニングの反応溶器にアクリル酸3.55重量
部、Ｎ―Ｘチロールアクリルアミド7.53重量部、
アクリル酸エチル16.6重量部、メタクリル酸メチ
ル16.6重量部、イソプロピルアルコール55.5重量
部、過酸化カプリリル0.22重量部を入れ、16時間
還流下に撹拌した。その後、純水230重量部と、
28％アンモニア水10重量部を加え、水性塗料用樹
脂溶液を得た。該樹脂溶液の不揮発分は30％、粘
度（ガードナー）はＶ―Ｗ，PHは8.8であつた。
この得られた樹脂溶液を樹脂分換算で92重量部お
よび硬化剤としてメチル化メチロールメラミン樹
脂（スミマールＭ―40W、住友化学工業株式会社
製、不揮発分80％）10重量部に対してクロム酸ス
トロンチウム1.5重量部、顔料としてのカーボン
ブラツクを４重量部、炭酸カルシウムを６重量
部、消泡剤0.5重量部を加え、分散機であるサン
ドグラインダーにて１時間混合した。ひきつづい
て、粒子径約0.1〜200μｍの山皮を10重量部加え、
該サンドグラインダーにて２時間山皮を破砕混合
することによりクロム酸塩顔料および山皮を分散
した水性塗料用樹脂を得た。分散後、すみやかに
該水性塗料用樹脂100重量部に対してイソプロピ
ルアルコール40重量部、および純水29重量部を順
次配合混入させて本発明にかかる水性塗料用組成
物を得た。
この水性塗料組成物中には、繊維状態化された
直径0.002〜0.1μｍ、長さ0.1〜数μｍの山皮が均
一に不定形三次元方向に分散していた。
次に、該塗料組成物を被塗装板にエアスプレー
にて塗装し、焼付・乾燥した後、耐水性、耐水密
着性および防錆性を調査した。その結果を、第２
表の実施例番号９の欄に焼付条件、塗膜硬度
（JIS K5400に準拠）、塗膜光沢（JIS K5400に準
拠）、硬化乾燥後の塗膜内の水分含有率を合わせ
て示す。また、焼付・乾燥条件を種々変化させた
塗膜の試験結果を、第２表の実施例番号10，11の
欄に示す。なお、塗膜内の水分含有率の測定に当
つては、水分気化装置（ADP―341、京都電子工
業株式会社製）にカールフイツシヤ水分計（京都
電子工業株式会社製）を付設した装置を用いて行
つた。
実施例 12
撹拌機と還流冷却器と加熱設備を装備するステ
ンレス製反応容器に、純水46.5重量部、亜硫酸水
素ナトリウム0.0425重量部、ラウリル硫酸ナトリ
ウム0.00425重量部を入れ180℃まで加熱し、スチ
レン23.4重量部、メタクリル酸2.12重量部、アク
リル酸エチル17.0重量部、過硫酸カリウム0.17重
量部、純水7.45重量部を順次滴下混合した。混合
物を30分間66℃に加熱した後、さらに2.5時間65
〜66℃で反応を続け、エマルジヨン塗料用樹脂溶
液を得た。得られたエマルジヨン塗料用樹脂溶液
の樹脂分100重量部に対して、カーボンブラツク
３重量部、炭酸カルシウム4.5重量部、消泡剤0.7
重量部、ブチルセロソルブ7.5重量部、純水13.5
重量部を順次配合してエマルジヨン塗料を得た。
このエマルジヨン塗料100重量部に実施例９で
得られた水性塗料組成物100重量部およびコバル
トドライヤー３重量部を加えて混合し、コロイド
エマルジヨン型の塗料組成物を得た。
このコロイドエマルジヨン型の塗料組成物を、
実施例９と同様の方法で塗装し、耐水性、耐水密
着性および防錆性を調査した。その結果を、第２
表の実施例番号12の欄に示す。すなわち、良好な
耐水性、耐水密着性および防錆性を示した。
〈比較例 ７〜９〉
実施例９と同様の製法を用い、相違する点はク
ロム酸ストロンチウムを配合しないで山皮を配合
したもの、山皮を配合しないでクロム酸ストロン
チウムを配合したもの、および山皮とクロム酸ス
トロンチウムを全く配合しないで水性塗料組成物
を得た。
これらの各水性塗料100重量部と実施例12で得
られたエマルジヨン塗料100重量部を加えて混合
し、コロイドエマルジヨン型の塗料を得た。
これらのコロイドエマルジヨン型の塗料を実施
例９と同様の方法で塗装し、耐水性、耐水密着性
および防錆性を調査した。その結果を、第２表の
比較例C7〜C9に併わせて示す。同表から明らか
のごとく、比較例C7〜C9のものは、耐水性、耐
水密着性および防錆性のいずれも低いものであつ
た。
第２表から明らかなごとく、水性塗料組成物の
硬化乾燥後の塗膜内の水分含有率が硬化乾燥後の
塗膜重量の５％以下の場合、塗膜の耐水性、耐水
密着性および防錆性は水分含有率が５％以上の塗
膜を比べて著しく優れていることが分かる。ま
た、水性塗料用樹脂100重量部に対して山皮10重
量部とクロム酸ストロンチウム1.5重量部を均一
に分散して得た水性塗料組成物とエマルジヨン塗
料を混合して得られたコロイドエマルジヨン型の
塗料を焼付けて得られた塗膜の耐水性、耐水密着
性および防錆性は、クロム酸ストロンチウムを配
合しないで山皮を配合したもの、山皮を配合しな
いでクロム酸ストロンチウムを配合したものおよ
び山皮とクロム酸ストロンチウムを全く配合しな
いものの各コロイドエマルジヨン型の塗料に比べ
で数段優れていた。
実施例 13
水性アルキツド樹脂（ウオーターゾールＳ―
123、大日本インキ化学工業株式会社製、不揮発
分50％）の樹脂100重量部および硬化剤と[Table] As is clear from Table 1, the product according to the present invention has better water resistance,
It can be seen that water resistant adhesion and rust prevention (SS resistance) are significantly improved. Furthermore, compared to Comparative Examples C1 to C4, which contain either mountain skin or strontium chromate, not only water resistance and water-resistant adhesion, but especially rust prevention are significantly improved. I understand. Add the amount of mountain bark to 100 parts by weight of resin for water-based paint.
Based on the test results of the Examples in which the amount of mountain bark was added from 0.5 parts by weight to 30 parts by weight, the most preferable range for the amount of mountain bark to be mixed is 3 to 20 parts by weight, taking into consideration the hardness and gloss of the coating film. Strontium chromate added in addition to mountain bark is added to 100 parts by weight of water-based paint resin.
From the test results of Examples in which 0.1 to 10 parts by weight were added, it was found that adding 0.1 part by weight was effective in rust prevention, and adding up to 10 parts by weight showed a significant effect. However, if more than 10 parts by weight is added,
Unfavorable from safety and health considerations. In addition, the results of Comparative Example C6 indicate that even if mountain bark and strontium chromate are mixed, which is said to be effective, the effect will not increase due to differences in process mixing technology. As confirmation of the composition of the composition, it is shown that the mountain skin was not uniformly dispersed in an irregular three-dimensional direction, so it did not lead to water resistance, water resistant adhesion, and rust prevention effects.
The reason for this is that the mixing time was short in the step of mixing the water-based paint resin solution and the mountain bark. FIG. 2 shows the results of transmission electron microscopic observation of the coating film. From this result, it can be seen that the particulate mountain skin 2 is dispersed almost as it is. In other words, it is shown that the mountain bark in the water-based paint resin needs to be in the form of fibers and uniformly dispersed. Examples 9-11 3.55 parts by weight of acrylic acid, 7.53 parts by weight of N-X tyroacrylamide,
16.6 parts by weight of ethyl acrylate, 16.6 parts by weight of methyl methacrylate, 55.5 parts by weight of isopropyl alcohol, and 0.22 parts by weight of caprylyl peroxide were added, and the mixture was stirred under reflux for 16 hours. Then, with 230 parts by weight of pure water,
10 parts by weight of 28% ammonia water was added to obtain a resin solution for water-based paint. The resin solution had a nonvolatile content of 30%, a viscosity (Gardner) of VW, and a pH of 8.8.
Strontium chromate was added to 92 parts by weight of the obtained resin solution in terms of resin content and 10 parts by weight of methylated methylolmelamine resin (Sumimar M-40W, manufactured by Sumitomo Chemical Co., Ltd., nonvolatile content 80%) as a curing agent. 1.5 parts by weight, 4 parts by weight of carbon black as a pigment, 6 parts by weight of calcium carbonate, and 0.5 parts by weight of an antifoaming agent were added, and mixed for 1 hour using a sand grinder as a dispersing machine. Subsequently, 10 parts by weight of mountain bark with a particle size of approximately 0.1 to 200 μm was added,
The mountain bark was crushed and mixed for 2 hours using the sand grinder to obtain a resin for water-based paint in which the chromate pigment and the mountain bark were dispersed. After dispersion, 40 parts by weight of isopropyl alcohol and 29 parts by weight of pure water were immediately mixed into 100 parts by weight of the water-based paint resin to obtain a water-based paint composition according to the present invention. In this aqueous coating composition, fibrous fibers having a diameter of 0.002 to 0.1 μm and a length of 0.1 to several μm were uniformly dispersed in an amorphous three-dimensional direction. Next, the coating composition was applied to a plate to be coated by air spray, baked and dried, and then water resistance, water resistant adhesion, and rust prevention were investigated. The results are shown in the second
In the column of Example No. 9 in the table, the baking conditions, coating film hardness (based on JIS K5400), coating film gloss (based on JIS K5400), and moisture content in the coating film after curing and drying are also shown. In addition, the test results of coating films with various baking and drying conditions are shown in the columns of Example Nos. 10 and 11 in Table 2. In addition, when measuring the moisture content in the paint film, we used a device equipped with a moisture vaporizer (ADP-341, manufactured by Kyoto Electronics Industry Co., Ltd.) and a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.). I went. Example 12 46.5 parts by weight of pure water, 0.0425 parts by weight of sodium hydrogen sulfite, and 0.00425 parts by weight of sodium lauryl sulfate were placed in a stainless steel reaction vessel equipped with a stirrer, reflux condenser, and heating equipment, and heated to 180°C, and 23.4 parts of styrene was added. parts by weight, 2.12 parts by weight of methacrylic acid, 17.0 parts by weight of ethyl acrylate, 0.17 parts by weight of potassium persulfate, and 7.45 parts by weight of pure water were sequentially added dropwise and mixed. The mixture was heated to 66 °C for 30 min, then 65 for an additional 2.5 h.
The reaction was continued at ~66°C to obtain a resin solution for emulsion paint. 3 parts by weight of carbon black, 4.5 parts by weight of calcium carbonate, and 0.7 parts by weight of antifoaming agent per 100 parts by weight of the resin content of the obtained resin solution for emulsion paint.
Parts by weight, 7.5 parts by weight of butyl cellosolve, 13.5 parts by weight of pure water
Parts by weight were sequentially blended to obtain an emulsion paint. To 100 parts by weight of this emulsion paint, 100 parts by weight of the aqueous paint composition obtained in Example 9 and 3 parts by weight of a cobalt dryer were added and mixed to obtain a colloidal emulsion type paint composition. This colloidal emulsion type coating composition is
It was painted in the same manner as in Example 9, and its water resistance, water resistant adhesion, and rust prevention properties were investigated. The results are shown in the second
It is shown in the column of Example number 12 in the table. That is, it exhibited good water resistance, water-resistant adhesion, and rust prevention. <Comparative Examples 7 to 9> The same manufacturing method as Example 9 was used, except that strontium chromate was not blended and mountain bark was blended, strontium chromate was blended without mountain bark, and A water-based paint composition was obtained without blending mountain bark and strontium chromate at all. 100 parts by weight of each of these water-based paints and 100 parts by weight of the emulsion paint obtained in Example 12 were added and mixed to obtain a colloidal emulsion type paint. These colloidal emulsion type paints were applied in the same manner as in Example 9, and their water resistance, water resistant adhesion, and rust prevention properties were investigated. The results are shown together with Comparative Examples C7 to C9 in Table 2. As is clear from the same table, Comparative Examples C7 to C9 had low water resistance, water-resistant adhesion, and rust prevention. As is clear from Table 2, when the water content in the coating film after curing and drying of the aqueous coating composition is 5% or less of the coating film weight after curing and drying, the water resistance, waterproof adhesion, and It can be seen that the rust resistance is significantly superior compared to coatings with a water content of 5% or more. In addition, a colloidal emulsion type obtained by mixing an emulsion paint with a water-based paint composition obtained by uniformly dispersing 10 parts by weight of mountain bark and 1.5 parts by weight of strontium chromate in 100 parts by weight of a water-based paint resin. The water resistance, water resistant adhesion, and rust prevention properties of the paint films obtained by baking the paints are as follows: those with strontium chromate mixed with mountain bark, and those with strontium chromate mixed without mountain bark. It was significantly superior to colloidal emulsion type paints, even though it did not contain mountain bark or strontium chromate at all. Example 13 Water-based alkyd resin (Watersol S-
123, manufactured by Dainippon Ink & Chemicals Co., Ltd., 100 parts by weight of resin (non-volatile content: 50%) and a curing agent.
【表】
してのメチル化メチロールメラミン樹脂（スミマ
ールＭ―40W、住友化学工業株式会社製、不揮発
分80％）の樹脂10重量部に対しカーボンブラツク
４重量部、炭酸カルシウム６重量部、消泡剤0.5
重量部クロム酸ストロンチウム1.5重量部を加え
サンドグラインダーにて１時間混合した。ひきつ
づいて粒子径約0.1〜150μｍの山皮を10重量部加
え該サンドグラインダーにて２時間山皮を破砕混
合することによりクロム酸塩顔料および山皮を分
散した水性塗料用樹脂を得た。分散後すみやかに
該水性塗料用樹脂分100重量部に対しブチルセロ
ソルブ40重量部および純水29重量部を順次配合さ
せて水性塗料組成物を得た。
該塗料組成物を実施例１と同様の方法で塗装
し、塗膜の耐水性、耐水密着性および防錆性を調
査し、その結果を第３表、実施例番号13の欄に示
した。また、比較例として、クロム酸ストロンチ
ウムを配合しないで山皮を配合したもの、山皮を
配合しないでクロム酸ストロンチウムを配合した
ものおよび山皮とクロム酸ストロンチウムを全く
配合しないものについても調査した。その結果を
第３表の比較例C10〜C12の欄に併わせて示す。
実施例13および比較例C10〜C12の試験結果よ
り、本願発明で使用する樹脂は、一般市販の樹脂
を用いてもほぼ同等の効果が得られることが確認
できた。[Table] 4 parts by weight of carbon black, 6 parts by weight of calcium carbonate, and antifoaming for 10 parts by weight of methylated methylolmelamine resin (Sumimar M-40W, manufactured by Sumitomo Chemical Co., Ltd., non-volatile content 80%). agent 0.5
1.5 parts by weight of strontium chromate was added and mixed for 1 hour using a sand grinder. Subsequently, 10 parts by weight of mountain bark having a particle size of approximately 0.1 to 150 μm were added, and the mountain bark was crushed and mixed for 2 hours using the sand grinder, thereby obtaining a resin for water-based paint in which the chromate pigment and mountain bark were dispersed. Immediately after dispersion, 40 parts by weight of butyl cellosolve and 29 parts by weight of pure water were sequentially added to 100 parts by weight of the resin for water-based paint to obtain a water-based paint composition. The coating composition was coated in the same manner as in Example 1, and the water resistance, water resistant adhesion and rust prevention properties of the coating film were investigated, and the results are shown in Table 3, in the column of Example No. 13. In addition, as comparative examples, we also investigated the following: one in which mountain bark was blended without strontium chromate, one in which strontium chromate was blended without mountain bark, and one in which mountain bark and strontium chromate were not blended at all. The results are also shown in the columns of Comparative Examples C10 to C12 in Table 3. From the test results of Example 13 and Comparative Examples C10 to C12, it was confirmed that almost the same effect can be obtained even when a commercially available resin is used as the resin used in the present invention.
【表】【table】
図は、本発明の実施例を示し、第１図は塗膜中
に繊維状化した山皮が均一に分散している様子を
示す図、第２図は塗膜中に粒子状山皮が分散して
いる様子を示す図である。
１……繊維状化した山皮、２……粒子状の山
皮。
The figures show examples of the present invention. Figure 1 shows fibrous mountain crusts uniformly dispersed in the paint film, and Figure 2 shows particulate mountain skin particles in the paint film. FIG. 3 is a diagram showing a state of being dispersed. 1...Fibrous mountain bark, 2...Particulate mountain bark.
Claims (1)
料とを主成分とする水性塗料組成物であり、水性
塗料用樹脂100重量部に対して0.5ないし30重量部
の山皮と0.05ないし10重量部のクロム酸塩顔料と
を含有し、しかも該山皮は直径が0.002ないし
0.1μｍに繊維状態化して不定形三次元方向に均一
に分散してなり、防錆性能に優れたことを特徴と
する水性塗料組成物。 ２ 水性塗料用樹脂と、該水性塗料用樹脂100重
量部に対して0.5ないし30重量部の山皮と0.05な
いし10重量部のクロム酸塩顔料とを混合し、かつ
該混合物中の山皮を直径が0.002ないし0.1μｍと
なるまで繊維状態化するとともに、該繊維状態の
山皮とクロム酸塩顔料とが樹脂中に均一に分散し
た混合物とする破砕混合工程と、該混合物に適宜
量の溶剤を混合して水性塗料組成物とする混合工
程と、該組成物を被塗物に塗布し、60ないし180
℃の温度で10ないし60分間焼付・乾燥して、塗膜
中の水分含有率を硬化乾燥後の塗膜重量の５％以
下にする塗装工程とから成ることを特徴とする水
性塗料組成物の塗膜形成方法。[Scope of Claims] 1. A water-based paint composition containing a water-based paint resin, a solvent, mountain bark, and a chromate pigment as main components, and in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the water-based paint resin. Contains mountain bark and 0.05 to 10 parts by weight of chromate pigment, and the mountain bark has a diameter of 0.002 to
A water-based paint composition characterized by being made into fibers of 0.1 μm and uniformly dispersed in an amorphous three-dimensional direction, and having excellent rust prevention performance. 2. Mix a water-based paint resin, 0.5 to 30 parts by weight of mountain bark and 0.05 to 10 parts by weight of chromate pigment per 100 parts by weight of the water-based paint resin, and add the mountain skin in the mixture. A crushing and mixing process in which the mountain skin in the fiber state and the chromate pigment are uniformly dispersed in the resin is made into a fiber state with a diameter of 0.002 to 0.1 μm, and an appropriate amount of solvent is added to the mixture. a mixing step of mixing to form an aqueous paint composition, and applying the composition to an object to be coated,
A water-based coating composition characterized by comprising a coating step of baking and drying at a temperature of 10 to 60 minutes at a temperature of 10 to 100°C to reduce the water content in the coating film to 5% or less of the weight of the coating film after curing and drying. Paint film formation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5152385A JPS61211373A (en) | 1985-03-14 | 1985-03-14 | Water paint composition and method for forming coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5152385A JPS61211373A (en) | 1985-03-14 | 1985-03-14 | Water paint composition and method for forming coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61211373A JPS61211373A (en) | 1986-09-19 |
| JPS6338072B2 true JPS6338072B2 (en) | 1988-07-28 |
Family
ID=12889369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5152385A Granted JPS61211373A (en) | 1985-03-14 | 1985-03-14 | Water paint composition and method for forming coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61211373A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214072U (en) * | 1988-07-14 | 1990-01-29 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63168474A (en) * | 1986-12-29 | 1988-07-12 | Nippon Parkerizing Co Ltd | Coating method to impart corrosion resistance |
| JPH0826282B2 (en) * | 1987-04-08 | 1996-03-13 | アイシン化工株式会社 | Aqueous coating composition for dip coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52111944A (en) * | 1976-03-17 | 1977-09-20 | Takeda Chem Ind Ltd | Water-based dispersion |
-
1985
- 1985-03-14 JP JP5152385A patent/JPS61211373A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52111944A (en) * | 1976-03-17 | 1977-09-20 | Takeda Chem Ind Ltd | Water-based dispersion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214072U (en) * | 1988-07-14 | 1990-01-29 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61211373A (en) | 1986-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5445754A (en) | Water-based, thermal paint | |
| US6638628B2 (en) | Silicate coating compositions | |
| EP0621890B1 (en) | Multipurpose, ecological water-paint | |
| DK166733B1 (en) | COMPOSITION WHICH ARE SUITABLE FOR CREATING A SURFACE PROTECTIVE BELAEGNINGSKOMPOSITION, BELAEGNINGSKOMPOSITION CONTAINING SUCH COMPOSITION, bipartite PACK, when constituted FORMING SUCH BELAEGNINGSKOMPOSITION, PAINT BY composition comprises, AND FERROUS METAL STRUCTURES COVERED WITH PAINT OR BELAEGNINGSKOMPOSITIONEN | |
| US5749946A (en) | Anticorrosive pigment preparation containing metal oxide-coated platelet adjuvant | |
| JPS63189475A (en) | Rust preventive coating agent | |
| DE3116736A1 (en) | DURABLE LATEXROST CONVERTER PRIMER | |
| KR20180061933A (en) | A chrome-free water-based corrosion inhibitor coating composition | |
| JPS6338072B2 (en) | ||
| JPS5815570A (en) | Paint composition for power transmission iron tower | |
| EP0412686A1 (en) | Corrosion inhibiting pigment | |
| WO2021193082A1 (en) | One-component aqueous coating composition | |
| JP2569178B2 (en) | Corrosion resistant pigment composition | |
| EP2128206A1 (en) | Composite oil paint | |
| JPS6328942B2 (en) | ||
| JPS63175078A (en) | Composition for metal surface treatment | |
| JPH0526833B2 (en) | ||
| JPS6176567A (en) | Coating composition | |
| JPS63157878A (en) | Metal surface treating composition and surface treatment with same | |
| JPS63451B2 (en) | ||
| WO2023067821A1 (en) | Method for producing iron rust-reducing rustproofing agent | |
| JPS5817176A (en) | Coating composition for powder transmission pylon | |
| EP2987835A1 (en) | Hybrid curing of aqueous silane systems | |
| JPS60235871A (en) | Primary rust-resisting paint composition | |
| JP2000015176A (en) | Organically coated galvanized steel sheet |