JPH03111468A - Corrosion-resistant coating composition - Google Patents
Corrosion-resistant coating compositionInfo
- Publication number
- JPH03111468A JPH03111468A JP25136489A JP25136489A JPH03111468A JP H03111468 A JPH03111468 A JP H03111468A JP 25136489 A JP25136489 A JP 25136489A JP 25136489 A JP25136489 A JP 25136489A JP H03111468 A JPH03111468 A JP H03111468A
- Authority
- JP
- Japan
- Prior art keywords
- bisphenol
- epoxy resin
- skeleton
- coating
- corrosion resistance
- 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.)
- Pending
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 239000008199 coating composition Substances 0.000 title description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 abstract description 39
- 238000000576 coating method Methods 0.000 abstract description 39
- 229910000831 Steel Inorganic materials 0.000 abstract description 30
- 239000010959 steel Substances 0.000 abstract description 30
- 125000002091 cationic group Chemical group 0.000 abstract description 21
- 238000004070 electrodeposition Methods 0.000 abstract description 21
- 229930185605 Bisphenol Natural products 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000002987 primer (paints) Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 VSNb Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- RFAXLXKIAKIUDT-UHFFFAOYSA-N IPA-3 Chemical compound C1=CC=C2C(SSC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 RFAXLXKIAKIUDT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- IOHIMQPBXKDRMQ-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Ba+2].[Sn+2]=O.S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Ba+2].[Sn+2]=O.S(=O)(=O)([O-])[O-] IOHIMQPBXKDRMQ-UHFFFAOYSA-J 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- JVQAJHYYWVAKPP-UHFFFAOYSA-N [O-2].[Ti+4].[Sn+2]=O.[O-2].[O-2] Chemical compound [O-2].[Ti+4].[Sn+2]=O.[O-2].[O-2] JVQAJHYYWVAKPP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009957 hemming Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は耐食性、カチオン電着塗装性、溶接性等に優れ
た塗膜を鋼板に形成することが可能な塗料組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a coating composition capable of forming a coating film having excellent corrosion resistance, cationic electrodeposition coating properties, weldability, etc. on a steel plate.
〈従来の技術及びその解決すべき課題〉近年、自動車車
体、家電製品等の各種用途に使用される鋼板として、耐
食性のよい表面処理鋼板が多く利用されるようになって
きた。<Prior art and problems to be solved> In recent years, surface-treated steel sheets with good corrosion resistance have come into widespread use as steel sheets used for various purposes such as automobile bodies and home appliances.
このような表面処理鋼板としては亜鉛メツキ鋼板を代表
的なものとして挙げることができるが、例えば自動車車
体内板や袋構造部及びヘミング部に適用される場合にお
いては、その要求性能に充分対応出来ず、そこでメツキ
鋼板の上に有機塗膜を施し、更にカチオン電着塗膜を施
すことで耐食性を向上させる方法が採用されるようにな
ってきた。そのため表面処理鋼板は、それ自体の高耐食
性とともに、カチオン電着塗装性のよいものが要求され
るようになっている。これら表面処理鋼板は、溶接等に
より成型加工するため溶接性のよいものも要求されてい
る。しかるにこれら耐食性、カチオン電着塗装性、溶接
性等の特性を満足する実用性のある表面処理鋼板は未だ
開発されていない。Galvanized steel sheets can be cited as a typical example of such surface-treated steel sheets, but for example, when applied to automobile body panels, bag structures, and hemming parts, they cannot sufficiently meet the required performance. Therefore, a method has been adopted in which the corrosion resistance is improved by applying an organic coating on the plated steel sheet and then applying a cationic electrodeposition coating. Therefore, surface-treated steel sheets are now required to have high corrosion resistance as well as good cationic electrodeposition coating properties. These surface-treated steel sheets are required to have good weldability because they are formed by welding or the like. However, a practical surface-treated steel sheet that satisfies these properties such as corrosion resistance, cationic electrodeposition coating properties, and weldability has not yet been developed.
例えば、特公昭４５−２４２３０号、特公昭４７−６８
８２号等の公報に記載の亜鉛粉末を多量に含有せしめた
皮膜を施した表面処理鋼板は、プレス加工により皮膜が
剥離しやすく、耐食性に問題点があった。For example, Special Publication No. 45-24230, Special Publication No. 47-68
The surface-treated steel sheets coated with a coating containing a large amount of zinc powder described in publications such as No. 82 had problems in corrosion resistance because the coating was easily peeled off during press working.
また、特開昭５７−１０８２９２号、特開昭６０−５０
１７９号、特開昭６０−５０１８０号、特公昭５４−３
４４０６号等の公報に記載の亜鉛合金メツキ鋼板に有機
−無機複合皮膜を施した表面処理鋼板は、カチオン電着
塗装性に必要な皮膜の通電性が不均一なため、カチオン
電着塗膜にガスピンホール、クレータ−等の塗膜欠陥が
生じやすくなる問題点があった。Also, JP-A-57-108292, JP-A-60-50
No. 179, JP-A-60-50180, JP-A-54-3
The surface-treated steel sheet described in publications such as No. 4406, in which an organic-inorganic composite film is applied to a zinc alloy plated steel sheet, has uneven conductivity of the film, which is necessary for cationic electrodeposition coating. There was a problem in that coating film defects such as gas pinholes and craters were likely to occur.
また、特開昭６１−６０７６６号、特開昭６３−８３１
７２号、特公昭６３−２３１０号等の公報に記載の亜鉛
、カーボンブラック、アルミニウム等の導電性物質を多
量に含有せしめた皮膜を施した表面処理鋼板は通電性が
よいためカチオン電着塗装性に優れているが薄膜塗装し
た時の平滑性が悪いため塗膜外観が悪く、更に加工によ
り皮膜が剥離しやすいため、耐食性に問題点があった。Also, JP-A-61-60766, JP-A-63-831
Surface-treated steel sheets coated with a film containing a large amount of conductive substances such as zinc, carbon black, and aluminum described in publications such as No. 72 and Japanese Patent Publication No. 63-2310 have good electrical conductivity and are therefore suitable for cationic electrodeposition coating. However, when a thin film is applied, the smoothness is poor, resulting in a poor appearance of the film, and the film is easily peeled off during processing, resulting in problems with corrosion resistance.
また、特開昭６３−３５７７９８号の公報に記載の、カ
チオン電着塗装性改良のため親水性ポリアミド樹脂を配
合した皮膜を亜鉛合金メツキ鋼板に施した表面処理鋼板
は、電着前処理におけるアルカリ処理で皮膜が剥離しや
すく、耐食性に問題点があった。In addition, a surface-treated steel sheet in which a zinc alloy-plated steel sheet is coated with a coating containing a hydrophilic polyamide resin to improve cationic electrodeposition coating properties is described in JP-A-63-357798. The coating was easily peeled off during treatment, and there were problems with corrosion resistance.
また、特開昭６２−１１７３３号等の公報に記載の、薄
膜皮膜を施した表面処理鋼板に、カチオン電着塗装性を
良くするため、ロールスキンバス等で皮膜にクラックを
形成させる方法は、処理工程が増加するだけでなく、ク
ラックを形成しているため耐食性に問題点があった。In addition, a method of forming cracks in a surface-treated steel sheet coated with a thin film using a roll skin bath or the like in order to improve the cationic electrodeposition coating properties is described in Japanese Patent Application Laid-open No. 62-11733. Not only does this increase the number of processing steps, but it also causes problems in corrosion resistance due to the formation of cracks.
〈発明の目的〉
本発明は、このような現状に鑑み、耐食性とともにカチ
オン電着塗装性、溶接性等に優れた表面処理鋼板を得る
ための塗料組成物を提供することを目的とする。<Object of the Invention> In view of the current situation, an object of the present invention is to provide a coating composition for obtaining a surface-treated steel sheet having excellent corrosion resistance, cationic electrodeposition coating properties, weldability, etc.
く課題を解決するための手段〉
本発明者らは、上記目的を達成するため鋭意検討した結
果、以下の成分：
（ｉ）ビスフェノールＡ骨格とビスフェノールＦ骨格と
の重量比率（９５： ５〜６０：４０）からなるビスフ
ェノール骨格と、エピクロルヒドリン骨格とより構成さ
れる、１分子中に２個以上のエポキシ基を有するビスフ
ェノール型エポキシ樹脂、
（ｉｉ）シリカ粒子、及び
（ｉｉｉ ）黒鉛粒子、
を含む耐食性塗料組成物により上記目的が達成されるこ
とを見出し、本発明に到達したものである。Means for Solving the Problems> In order to achieve the above object, the present inventors have made extensive studies and found that the following components: (i) Weight ratio of bisphenol A skeleton to bisphenol F skeleton (95:5 to 60 :40) A bisphenol-type epoxy resin having two or more epoxy groups in one molecule, consisting of a bisphenol skeleton and an epichlorohydrin skeleton, (ii) silica particles, and (iii) graphite particles. The inventors have discovered that the above object can be achieved by a coating composition, and have arrived at the present invention.
以下、本発明を詳述する。The present invention will be explained in detail below.
本発明の塗料組成物を構成するビスフェノール型エホキ
シ１１脂（ｉ）はビスフェノールＡとビスフェノールＦ
とからなるビスフェノール類と、エピクロルヒドリンと
を常法に従って縮合反応せしめたビスフェノール骨格と
、エピクロルヒドリン骨格とより構成される、１分子中
に２個以上のエポキシ基を有する樹脂であり、好ましく
は分子置駒５００〜ｉｏｏ、ｏｏｏの樹脂である。前記
ビスフェノール類とエピクロルヒドリンとの縮合反応は
、ビスフェノールＡとビスフェノールＦとを混合し、同
時にエピクロルヒドリンと反応させるのが適当であるが
、ビスフェノールＡとエピクロルヒドリンとを反応させ
、更にビスフェノールＦを加え反応させて得られるエポ
キシ樹脂あるいはビスフェノールＦとエピクロルヒドリ
ンとを反応させ、更にビスフェノールＡを加え反応させ
て得られるエポキシ樹脂も本発明に含まれるものである
。The bisphenol-type epoxy-11 fat (i) constituting the coating composition of the present invention is bisphenol A and bisphenol F.
It is a resin having two or more epoxy groups in one molecule, which is composed of a bisphenol skeleton obtained by condensation reaction of bisphenols consisting of and epichlorohydrin according to a conventional method, and an epichlorohydrin skeleton, and preferably has two or more epoxy groups in one molecule. 500 to ioo, ooo resin. For the condensation reaction between bisphenols and epichlorohydrin, it is appropriate to mix bisphenol A and bisphenol F and react with epichlorohydrin at the same time. The present invention also includes the obtained epoxy resin or the epoxy resin obtained by reacting bisphenol F and epichlorohydrin, and further adding bisphenol A and causing the reaction.
ところでビスフェノール類としてビスフェノールＡのみ
から得られる、ビスフェノールＡ型エポキシ樹脂は、得
られる塗膜が耐水性、耐薬品性等に優れ、かつ鋼板との
密着性、上塗塗膜との密着性に優れている一方、塗膜は
、硬くて可撓性に劣り、また電気絶縁性であるためカチ
オン電着塗装性がやや劣るものであった。そこで本発明
者等はビスフェノールＡ型エポキシ樹脂にビスフェノー
ルＦ型エポキシ樹脂をブレンドしたものを試みたが、耐
食性が低下し、またカチオン電着塗装性も向上しないこ
とが判明した。一方、ビスフェノールＡ骨格とビスフェ
ノールＦ骨格との特定比率からなるビスフェノール骨格
とエピクロルヒドリン骨格とより構成される１分子中に
２個以上のエポキシ基を有するビスフェノール型樹脂を
使用した場合、予想外にも耐食性とともにカチオン電着
塗装性も大巾に改良されることが分り、本発明に到った
ものである。By the way, bisphenol A type epoxy resin, which is obtained only from bisphenol A as a bisphenol, produces a coating film with excellent water resistance, chemical resistance, etc., and also has excellent adhesion to steel plates and top coats. On the other hand, the coating film was hard and had poor flexibility, and since it was electrically insulating, the cationic electrodeposition paintability was somewhat poor. Therefore, the present inventors tried a blend of bisphenol A type epoxy resin and bisphenol F type epoxy resin, but it was found that the corrosion resistance decreased and the cationic electrodeposition coating properties did not improve. On the other hand, when using a bisphenol resin having two or more epoxy groups in one molecule, which is composed of a bisphenol skeleton consisting of a specific ratio of bisphenol A skeleton and bisphenol F skeleton and an epichlorohydrin skeleton, it unexpectedly shows corrosion resistance. It was also found that the cationic electrodeposition coating properties were greatly improved, leading to the present invention.
すなわち、ビスフェノールＡ型エポキシ樹脂は、−最大
で示される樹脂であるが、式中のビスフェノールＡ骨格
の一部にビスフェノールＦ骨格を置換、導入することで
ビスフェノールＡ型エポキシ樹脂よりも親水性を示すよ
うになり、カチオン電着塗装時塗膜の通電抵抗が下がり
、膜全体が電気的に均一となるため、カチオン電着塗装
性がよくなるものと思われる。また、ビスフェノールＡ
型エポキシ樹脂は耐食性のよい樹脂として知られており
、薄膜塗装した場合、鋼板素地表面粗さを完全に被覆出
来ず、水分や酸素が侵入し、耐食性が悪くなるが、ビス
フェノールＡ骨格の一部にビスフェノールＦ骨格を置換
、導入することでガラス転移点が下り、得られる塗膜が
柔軟性をもつようになり、塗膜中に侵入した水分や酸素
が容易に系外へ出ていくため耐食性も向上するものと思
われる。That is, bisphenol A type epoxy resin is a resin represented by -maximum, but by replacing and introducing a bisphenol F skeleton into a part of the bisphenol A skeleton in the formula, it shows more hydrophilicity than bisphenol A type epoxy resin. As a result, the electrical conductivity resistance of the coating film during cationic electrodeposition is reduced, and the entire film becomes electrically uniform, which is thought to improve the cationic electrodeposition coating properties. Also, bisphenol A
Type epoxy resin is known as a resin with good corrosion resistance, but when a thin film is applied, it cannot completely cover the rough surface of the steel plate, allowing moisture and oxygen to enter, resulting in poor corrosion resistance. By substituting and introducing bisphenol F skeleton into , the glass transition point is lowered and the resulting coating film becomes flexible, and moisture and oxygen that have entered the coating film can easily escape from the system, resulting in improved corrosion resistance. It is also expected that this will improve.
このような効果が発揮されるためにはビスフェノールＡ
骨格とビスフェノールＦ骨格の重量比率は（９５： ５
〜６０：４０）のものが適当である。In order for this effect to be exhibited, bisphenol A
The weight ratio of the skeleton and bisphenol F skeleton is (95:5
~60:40) is suitable.
前記範−羽よりビスフェノールＡ骨格が多くなるとビス
フェノールＦ骨格で置換する前記効果が十分認められな
くなり、逆に前記範囲よりビスフェノールＡ骨格が少な
くなると塗膜がやわらかくなり過ぎて耐食性、耐水性等
が低下するので好ましくない。If the bisphenol A skeleton is more than the above range, the effect of substitution with the bisphenol F skeleton will not be sufficiently observed, and conversely, if the bisphenol A skeleton is less than the above range, the coating will become too soft and the corrosion resistance, water resistance, etc. will decrease. Therefore, it is not desirable.
本発明の塗料組成物を構成するシリカ粒子（ｉｉ ）は
、高耐食性を更に付与させるために配合するものであっ
て、具体的には粒径１ｍμ〜５００ｍμの有機溶剤分散
型コロイダルシリカ、粉末状フユームドシリ力が代表的
なものとして挙げられる。The silica particles (ii) constituting the coating composition of the present invention are blended to further impart high corrosion resistance, and specifically, organic solvent-dispersed colloidal silica with a particle size of 1 mμ to 500 mμ, powdered A typical example is the power of Fuyumdoshiri.
有機溶剤分散型コロイダルシリカはメチルアルコール、
エチルアルコール、プロピルアルコール、ブチルアルコ
ール、エチルセロソルブ、エチレングリコール、ジメチ
ルアセトアミド、ジメチルホルムアミド等の有機溶剤に
分散させたコロイダルシリカであり、市販品としては例
えば０３ＣＡＬ１１３２．１２３２．１３３２．１４３
２．１５３２．１６２２．１７２２．１７２４ （以上
、触媒化成工業社製商品名）；ＭＡ−３Ｔ、ＩＰＡ−３
ｒ、ＮＢＡ−３Ｔ、Ｉ ＢＡ−３Ｔ％ＥＧ−３Ｔ、ＥＴ
Ｃ−３ＴＳＤＭＡＣ−３ＴＳＤＭＦ−３Ｔ （以上、８
産化学工業社製商品名）等が挙げられる。Organic solvent-dispersed colloidal silica is methyl alcohol,
Colloidal silica dispersed in an organic solvent such as ethyl alcohol, propyl alcohol, butyl alcohol, ethyl cellosolve, ethylene glycol, dimethylacetamide, dimethylformamide, etc. Commercially available products include, for example, 03CAL1132.1232.1332.143
2.1532.1622.1722.1724 (all product names manufactured by Catalysts & Chemicals Co., Ltd.); MA-3T, IPA-3
r, NBA-3T, I BA-3T%EG-3T, ET
C-3TSDMAC-3TSDMF-3T (8
(product name manufactured by Sankagaku Kogyo Co., Ltd.).
粉末状フユームドシリ力の市販品としては例えばＲ９７
４、Ｒ８１１、Ｒ８１２、Ｒ９７２、Ｒ８０５、ＴａＯ
２、Ｒ２０２、ＲＸ２００、ＲＹ２００、ＲＹ３００、
ＲＹ３８０、ＲＹｌ ８０．０Ｘ５０（以上、日本エア
ロジル社製商品名）等が挙げられる。For example, R97 is a commercially available powdered fumed silicone product.
4, R811, R812, R972, R805, TaO
2, R202, RX200, RY200, RY300,
Examples include RY380 and RYl 80.0X50 (all trade names manufactured by Nippon Aerosil Co., Ltd.).
シリカ粒子を配合することにより塗膜を形成させた際シ
リカ粒子表面のシラノール基と鋼板表面及び上塗塗膜と
の間で水素結合が生じ、また塗膜を焼付けるとシラノー
ル基の脱水縮合反応が起こり、上塗塗膜−シリカ−鋼板
の一体化がなされ、著しく耐食性が向上する。When a coating film is formed by blending silica particles, hydrogen bonds occur between the silanol groups on the surface of the silica particles and the steel plate surface and the top coat, and when the coating film is baked, a dehydration condensation reaction of the silanol groups occurs. This causes the top coat, silica, and steel plate to become integrated, resulting in significantly improved corrosion resistance.
なお、シリカ粒子（ｉｉ）は前記ビスフェノール型エポ
キシ樹脂（ｉ）１００重量部に対し５〜４００重量部（
固形分換算）配合するのが適当であり、前記範囲より少
ないと耐食性が低下する傾向にあり、一方過剰に配合す
ると、加工性、耐アルカリ性、上塗塗膜との密着性が低
下する傾向にある。Incidentally, the silica particles (ii) are contained in an amount of 5 to 400 parts by weight (
If the amount is less than the above range, corrosion resistance tends to decrease, while if it is added in excess, processability, alkali resistance, and adhesion to the top coat tend to decrease. .
本発明の塗料組成物を構成する黒鉛粒子（ｉｉｉ ）は
、溶接性を改良するために配合するものであって、粒子
径１μｍ以下のものが望ましい。黒鉛粒子としては、市
販品としてヒタゾルＧｏ−１０２、ヒタゾルＧＰ−６０
、ヒタゾルＧＰ−８２（以上、日立粉末冶金社製商品名
）、スーパーコロハイド＃１５、スーパーコロハイド＃
１５Ｚ、スーパーコロハイ）＃１５Ｂ、 ７”ロハイ）
ＡＳ、’ｌ；’ロハイ）Ｗ−３００Ｄ、バニーハイトＴ
−６０２、バニーハイトＢＰ−４、バニーハイトＢＰ−
１１２、バニーハイトＣ−８１２、バニーハイトＣ−９
Ａ（以上、日本黒鉛商事社製商品名）が代表的なものと
して市販されている。The graphite particles (iii) constituting the coating composition of the present invention are blended to improve weldability, and preferably have a particle size of 1 μm or less. Commercially available graphite particles include Hitasol Go-102 and Hitasol GP-60.
, Hitazol GP-82 (trade names manufactured by Hitachi Powder Metallurgy Co., Ltd.), Super Corohide #15, Super Corohide #
15Z, super korohi) #15B, 7” rohai)
AS, 'l;' Rohai) W-300D, Bunny Height T
-602, Bunny Height BP-4, Bunny Height BP-
112, Bunny Height C-812, Bunny Height C-9
A (all trade names manufactured by Nippon Graphite Shoji Co., Ltd.) is commercially available as a typical product.
黒鉛粒子（ｉｉｉ ）は、前記ビスフェノール型エポキ
シ樹脂（ｉ）１００重量部に対し０．１〜３０重量部（
固形分換算）配合するのが適当であり、前記範囲より少
ないと溶接性改良効果が得られず、一方過剰に配合する
と、プレス加工時の加工性、耐食性が低下する傾向にあ
る。The graphite particles (iii) are contained in an amount of 0.1 to 30 parts by weight (
If the amount is less than the above range, no effect of improving weldability can be obtained, while if it is added in excess, workability during press working and corrosion resistance tend to deteriorate.
なお、本発明においてビスフェノールＦ骨格を一部含む
ビスフェノール型エポキシ樹脂を使用しているため前述
の如き、少量の黒鉛粒子でも効果を発揮するが、ビスフ
ェノールＦ骨格を含まないビスフェノールＡ骨格単独の
ビスフェノール型エポキシ樹脂を使用した場合、溶接性
をよくするためには、黒鉛粒子を多量に配合しなければ
ならないことが分かっている。In addition, since the present invention uses a bisphenol type epoxy resin that partially contains a bisphenol F skeleton, it is effective even with a small amount of graphite particles as described above, but a bisphenol type epoxy resin with only a bisphenol A skeleton that does not contain a bisphenol F skeleton is effective. It has been found that when using an epoxy resin, it is necessary to incorporate a large amount of graphite particles in order to improve weldability.
念のため説明を加えると、通常溶接性をよくするために
は通電性を良くすればよいことが知られており、通電性
を良くするために、従来から塗料中に配合される導電性
物質として、Ｚｎ５ＡＣＭｇ。Just to clarify, it is generally known that to improve weldability, it is necessary to improve electrical conductivity, and to improve electrical conductivity, conductive substances have traditionally been added to paints. As Zn5ACMg.
Ｆｅ５ＮｉＳＣｏＳＳｎＳＣｕＳＣｒ、 Ｍｎもしくは
これらの合金粉末； Ｔｉ、 Ｚｒ、 ＶＳＮｂ、 Ｗ
、 Ｍｏもしくはこれらの合金粉末、炭化物粉末；その
他リン化鉄粉末、アルミニウムドープ酸化亜鉛粉末、酸
化スズ−酸化チタン、酸化スズ−硫酸バリウム、酸化ニ
ッケルーアルミナなどの半導体酸化物粉末が知られてい
るが、これらは白錆が発生しやすく、耐食性の点で問題
があり、更に比重が高いため、沈澱、凝集等による塗料
安定性の点で問題があった。Fe5NiSCoSSnSCuSCr, Mn or alloy powder thereof; Ti, Zr, VSNb, W
, Mo or their alloy powder, carbide powder; other semiconductor oxide powders such as iron phosphide powder, aluminum-doped zinc oxide powder, tin oxide-titanium oxide, tin oxide-barium sulfate, and nickel oxide-alumina are known. However, these materials are prone to white rust and have problems in terms of corrosion resistance.Furthermore, since they have a high specific gravity, they have problems in terms of paint stability due to precipitation, aggregation, etc.
また、導電性カーボンブラックも広く利用されているが
、−次粒子は小さいものの凝集しやすく、それ故例えば
塗料を０．５〜４ ｇ ／ ｍ’の付着量で塗装した場
合、皮膜から頭を出し、加工性の点で問題があった。こ
れに対して、本発明は、導電性物質として、耐食性、塗
料安定性、加工性等に悪影響を及ぼさない黒鉛粒子を使
用した点に特徴がある。Conductive carbon black is also widely used, but although its secondary particles are small, they tend to aggregate, and therefore, for example, when a paint is applied at a coating weight of 0.5 to 4 g/m', the head from the film may be removed. There were problems in terms of production and processability. In contrast, the present invention is characterized by the use of graphite particles, which do not adversely affect corrosion resistance, paint stability, processability, etc., as the conductive material.
本発明の塗料組成物は以上説明したビスフェノール型エ
ポキシ樹脂（ｉ）とシリカ粒子（ｉｉ）と黒鉛粒子（ｉ
ｉｉ ）とを必須成分とする、好ましくは固形分１０〜
６０重量％の塗料である。The coating composition of the present invention comprises the above-described bisphenol-type epoxy resin (i), silica particles (ii), and graphite particles (i).
ii) as an essential component, preferably solid content 10~
It is a 60% by weight paint.
その他の成分としては必要に応じ適宜配合される従来か
ら公知の成分が配合される。具体的には各種炭化水素系
、エステル系、ケトン系、アルコール系、アミド系等の
有機溶剤；メラミン樹脂、ベンゾグアナミン樹脂、ポリ
ブロック化イソシアネート化合物等の架橋剤；有機また
は無機系顔料；分散剤、沈降防止剤、レベリング剤等の
添加剤あるいは各種改質樹脂等を配合することが可能で
ある。As other components, conventionally known components that are appropriately blended as necessary are blended. Specifically, organic solvents such as various hydrocarbons, esters, ketones, alcohols, and amide; crosslinking agents such as melamine resin, benzoguanamine resin, and polyblocked isocyanate compounds; organic or inorganic pigments; dispersants, Additives such as anti-settling agents and leveling agents or various modified resins can be added.
本発明の塗料組成物は自動車、家電製品、建材等に使用
されている溶融亜鉛メツキ鋼板、溶融亜鉛アルミ合金メ
ツキ鋼板、電気亜鉛メツキ鋼板、電気亜鉛ニッケル合金
メッキ鋼板、電気亜鉛鉄合金メツキ鋼板、電気亜鉛鉄二
層メツキ鋼板、冷延鋼板等の各種鋼板あるいはクロメー
ト化成処理、リン酸塩化成処理等の前処理した鋼板の下
塗り用塗料として好適に適用出来るが、これら被塗物に
限定されるものではない。The coating composition of the present invention is applicable to hot-dip galvanized steel sheets, hot-dip zinc-aluminum alloy-plated steel sheets, electrolytic galvanized steel sheets, electrolytic zinc-nickel alloy plated steel sheets, electrolytic zinc-iron alloy plated steel sheets, which are used in automobiles, home appliances, building materials, etc. It can be suitably applied as an undercoat paint for various steel plates such as electrolytic galvanized double-layered steel plates and cold-rolled steel plates, or pretreated steel plates such as chromate chemical conversion treatment and phosphate chemical conversion treatment, but it is limited to these objects to be coated. isn't it.
本発明の塗料組成物は、これら鋼板にスプレーロールコ
ート、シャワーコート等の手段により塗装し、１５〜３
００℃、好ましくは１００〜２５０℃の温度下で硬化さ
せることが出来る。なお、膜厚は数μｍ前後の薄膜でも
十分性能を発揮・するが、更に厚くすることを妨げるも
のではない。The coating composition of the present invention is applied to these steel plates by spray roll coating, shower coating, etc.
It can be cured at a temperature of 00°C, preferably 100 to 250°C. It should be noted that although a thin film of around several micrometers exhibits sufficient performance, this does not preclude making the film even thicker.
〈発明の効果〉
本発明の塗料組成物を塗布した表面処理鋼板は、得られ
る塗膜が高耐食性を付与し、また可撓性があるため加工
性もあり、更にカチオン電着塗装性、溶接性がよく、実
用的価値の高い塗料といえる。<Effects of the Invention> The surface-treated steel sheet coated with the coating composition of the present invention has high corrosion resistance, and is flexible and has good workability. It can be said to be a paint with good properties and high practical value.
以下、本発明を実施例により更に詳細に説明する。なお
、実施例中「部」、「％」は重量基準で示す。Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, "parts" and "%" are expressed on a weight basis.
還流冷却器、温度計、攪拌機を取付けた三つロフラスコ
中にビスフェノールＡ １０９．４Ｌビスフェノール
Ｆ６４．０部及び６０部の苛性ソーダを６００部の水に
溶解させた苛性ソーダ水溶液を加え、攪拌しながら５０
℃、１０分間加熱した。109.4 L of bisphenol A and 64.0 parts of bisphenol F and a caustic soda aqueous solution prepared by dissolving 60 parts of caustic soda in 600 parts of water were added to a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, and the mixture was heated to 50 liters with stirring.
℃ for 10 minutes.
次いでエピクロルヒドリン１１６部を加え徐々に昇温し
、２０分間で１００℃とし、この温度で攪拌しながら４
０分間保った。Next, 116 parts of epichlorohydrin was added and the temperature was gradually raised to 100°C for 20 minutes.
It was held for 0 minutes.
次いで冷却後傾斜法にて、上澄み水層を除き、更に６０
０部の水を加え、９０℃に加温し激しく攪拌した後、再
度の冷却後同様にして上澄み水層を除いた。このような
操作をアルカリ性を示さなくなるまで繰返し、最後に水
を充分分離した後、攪拌しながら１５０℃、３０分間加
熱脱水し、分子量約９００のエポキシ樹脂を製造した。After cooling, the supernatant water layer was removed using the decanting method, and the mixture was further heated for 60 min.
0 parts of water was added, heated to 90°C and stirred vigorously, and then cooled again and the supernatant water layer was removed in the same manner. These operations were repeated until the mixture no longer showed alkalinity, and finally, after sufficiently separating water, it was dehydrated by heating at 150° C. for 30 minutes with stirring to produce an epoxy resin with a molecular weight of about 900.
得られたエポキシ樹脂２００部を８０℃に加温したエチ
レングリコールモノエチルエーテル２００部中に溶解し
、固形分５０％のエポキシ樹脂溶液（１）を調製した。200 parts of the obtained epoxy resin was dissolved in 200 parts of ethylene glycol monoethyl ether heated to 80°C to prepare an epoxy resin solution (1) with a solid content of 50%.
攪拌機、温度計、滴下ロートを取付けたフラスコ中にビ
スフェノールＡ ７２９．６部、ビスフェノールＦ１６
０部及び１０％苛性ソーダ水溶液２５７２部を加え、攪
拌しながら５０℃、１０分間加熱した。次いでエピクロ
ルヒドリン４６３部を加え、攪拌しながら１００℃に加
温し、３０分間保った。729.6 parts of bisphenol A and bisphenol F16 were placed in a flask equipped with a stirrer, thermometer, and dropping funnel.
0 parts and 2572 parts of a 10% caustic soda aqueous solution were added, and the mixture was heated at 50°C for 10 minutes while stirring. Next, 463 parts of epichlorohydrin was added, and the mixture was heated to 100° C. while stirring and maintained for 30 minutes.
次いで傾斜法にて上澄み水層を除き、更に沸騰水で洗浄
を繰返し、アルカリ性を示さなくなった後、１５０℃に
加熱し、脱水し、分子量約１４００のエポキシ樹脂を製
造した。Next, the supernatant water layer was removed by a decanting method, and the mixture was washed repeatedly with boiling water until it no longer showed alkalinity, and then heated to 150°C and dehydrated to produce an epoxy resin with a molecular weight of about 1400.
得られたエポキシ樹脂３００部を８０℃に加温したエチ
レングリコールモノブチルエーテル３００部に溶解し、
固形分５０％のエポキシ樹脂溶液（Ｉ［）を調製した。300 parts of the obtained epoxy resin was dissolved in 300 parts of ethylene glycol monobutyl ether heated to 80°C,
An epoxy resin solution (I[) with a solid content of 50% was prepared.
〔エポキシ樹脂溶液（ＩＩＩ）の調製〕還流冷却器、温
度計、攪拌機を取付けた三つロフラスコ中にエチレング
リコールモノエチルエーテルアセテート６８０部を加え
、１００℃に加熱した後、ビスフェノールＡとエピクロ
ルヒドリンとを反応させて得られたエポキシ当量２８０
０〜３３００のエポキシ樹脂１０００部を少しずつ添加
し、溶解させた。次いでビスフェノールＦ２５部と塩化
リチウム１部を加え２００ｔ：、６０分間反応させ、分
子量約７０００、固形分６０％のエポキシ樹脂溶液（Ｉ
［Ｉ）を調製した。[Preparation of epoxy resin solution (III)] 680 parts of ethylene glycol monoethyl ether acetate was added to a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, and after heating to 100°C, bisphenol A and epichlorohydrin were added. Epoxy equivalent obtained by reaction: 280
0-3300 epoxy resin was added little by little and dissolved. Next, 25 parts of bisphenol F and 1 part of lithium chloride were added and reacted for 60 minutes to form an epoxy resin solution (I
[I) was prepared.
ビスフェノールＡを７２．９部、ビスフェノールＦを９
６部とする以外はエポキシ樹脂溶液（Ｉ）の調製法と同
様にして、分子量約９００のエポキシ樹脂を製造し、該
エポキシ樹脂２００部を１００℃に加温したエチレング
リコールモノエチルエーテル２００部中に溶解し、固形
分５０％のエポキシ樹脂溶液（ｒＶ）を調製した。72.9 parts of bisphenol A, 9 parts of bisphenol F
An epoxy resin having a molecular weight of about 900 was produced in the same manner as in the preparation method of epoxy resin solution (I) except that the amount was 6 parts, and 200 parts of the epoxy resin was heated to 100°C. to prepare an epoxy resin solution (rV) with a solid content of 50%.
ビスフェノールＡ型エポキシ樹脂〔［エビコー）１００
１Ｊ （シェル化学社製商品名）、エポキシ当量４５
０〜５００］３００部をエチレングリコールモノエチル
エーテル３００部に溶解し、固形分５０％のエポキシ樹
脂溶液（Ｖ）を調製した。Bisphenol A type epoxy resin [[Ebiko] 100
1J (trade name manufactured by Shell Chemical Co., Ltd.), epoxy equivalent weight 45
0 to 500] was dissolved in 300 parts of ethylene glycol monoethyl ether to prepare an epoxy resin solution (V) with a solid content of 50%.
ビスフェノールＦ型エポキシ樹脂〔［エヒクロン８３０
Ｊ（大日本インキ化学工業社製商品名）、エポキシ当量
約１７５］３００部をエチレングリコールモノエチルエ
ーテル３００部に溶解し、固形分５０％のエポキシ樹脂
溶液（Ｖｌ）を調製した。Bisphenol F type epoxy resin [[Ehikron 830]
J (trade name, manufactured by Dainippon Ink Chemical Industries, Ltd.), epoxy equivalent: approximately 175], was dissolved in 300 parts of ethylene glycol monoethyl ether to prepare an epoxy resin solution (Vl) with a solid content of 50%.
前記エポキシ樹脂溶液（Ｖ）とエポキシ樹脂溶液（ＶＩ
）との［：２ ： １］の混合物からなる、固形分５０
％のエポキシ樹脂溶液（■）を調製した。The epoxy resin solution (V) and the epoxy resin solution (VI
) with a solid content of 50 [:2:1]
% epoxy resin solution (■) was prepared.
実施例１
エポキシ樹脂溶液（１）２００部、コロイダルシリカＣ
ｒＥＴＣ−３ＴＪ （８産化学工業社製商品名）、エ
チレングリコールモノエチルエーテル分散タイプ、固形
分２０％〕４００部、黒鉛粉末〔「ヒタゾルＧＰ−６０
Ｊ（日立粉末冶金社製商品名）、平均粒子径０．５μｍ
〕３部及びエチレングリコールモノエチルエーテル４２
０部を混合溶解し、塗料を調製した。Example 1 200 parts of epoxy resin solution (1), colloidal silica C
rETC-3TJ (trade name manufactured by Yasan Kagaku Kogyo Co., Ltd.), ethylene glycol monoethyl ether dispersion type, solid content 20%] 400 parts, graphite powder ["Hitasol GP-60
J (trade name manufactured by Hitachi Powder Metallurgy Co., Ltd.), average particle size 0.5 μm
] 3 parts and ethylene glycol monoethyl ether 42
0 parts were mixed and dissolved to prepare a paint.
得られた塗料を第２表に示す各種鋼板に乾燥膜厚が３μ
ｍとなるようロールコート塗装し、最高到達板温が３０
秒で１５０℃になるよう焼付け、耐食性、カチオン電着
塗装性、上塗密着性、耐水二次密着性、溶接性の各試験
を行ない、その結果を第２表下欄に示した。The obtained paint was applied to various steel plates shown in Table 2 with a dry film thickness of 3 μm.
Roll coated so that the maximum board temperature is 30 m.
Baking to 150° C. in seconds, corrosion resistance, cationic electrodeposition coating properties, topcoat adhesion, water resistant secondary adhesion, and weldability tests were conducted, and the results are shown in the lower column of Table 2.
実施例２〜６及び比較例１〜５
エポキシ樹脂溶液、シリカ粒子、黒鉛粒子を第１表に示
す割合で配合した混合物を固形分が２０％になる量のエ
チレングリコールモノエチルエーテルにて溶解して塗料
を調製した。Examples 2 to 6 and Comparative Examples 1 to 5 A mixture of an epoxy resin solution, silica particles, and graphite particles in the proportions shown in Table 1 was dissolved in ethylene glycol monoethyl ether in an amount to give a solid content of 20%. A paint was prepared.
得られた塗料を実施例１と同様にして各試験を行ない、
その結果を第２表下欄に示した。The obtained paint was subjected to various tests in the same manner as in Example 1,
The results are shown in the lower column of Table 2.
第２表からも明らかの通り本発明の塗料組成物を使用し
た実施例１〜６はいずれも耐食性、カチオン電着塗装性
、密着性、溶接性とも優れていた。As is clear from Table 2, all Examples 1 to 6 using the coating compositions of the present invention were excellent in corrosion resistance, cationic electrodeposition coating properties, adhesion, and weldability.
一方、ビスフェノールＡ型エポキシ樹脂の塗料を使用し
た比較例１、ビスフェノール類としてビスフェノールＡ
の比率が低いエポキシ樹脂の塗料を使用した比較例２、
ビスフェノールＦ型エポキシ樹脂を使用し、かつシリカ
粒子、黒鉛粒子を含まない塗料を使用した比較例３及び
ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型
エポキシ樹脂の混合物の塗料を使用した比較例４は、い
ずれも耐食性、カチオン電着塗装性、密着性、溶接性と
も本発明のそれと比較し、劣っていた。On the other hand, in Comparative Example 1 using a bisphenol A type epoxy resin paint, bisphenol A was used as the bisphenol.
Comparative example 2 using an epoxy resin paint with a low ratio of
Comparative Example 3 used a paint containing bisphenol F type epoxy resin and did not contain silica particles or graphite particles, and Comparative Example 4 used a paint made of a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin. Also, the corrosion resistance, cationic electrodeposition coating properties, adhesion, and weldability were inferior to those of the present invention.
また、実施例１の塗料から黒鉛粒子を除いた比較例５は
溶接性が劣っていた。Furthermore, Comparative Example 5, in which graphite particles were removed from the paint of Example 1, had poor weldability.
注８）
注９）
試験板塗面にクロスカットを入れ、ＪＩＳ−Ｚ−２３７
１に基づく塩水噴霧試験を５００時間行ない、赤錆発生
状況を観察○：：錆発生せず △：赤赤錆５末
試験板塗面にアミン付加エポキシ樹脂−ブロックイソシ
アネート系カチオン電着塗料を浴温２８℃、１００ＶＸ
３分間の条件下でカチオン電着塗装し、１６５℃×２０
分間焼付け、塗膜（面積１００ｃｒｌ）外観を観察
注１０）
○ニガスピン及びクレータ−発生
０〜５点
△ニガスピン及びクレータ−発生
６〜２０点
Ｘニガスピン及びクレータ−発生
２０点以上
注９）で得られたカチオン電着塗装板を１ｍｍゴバン目
１００個をカッターナイフで切り込み、セロハンテープ
を用いて剥離試験注目）
注１２）
を行ない、電着塗膜の残存率を測定
○：９５〜１００％ △：９０〜９４％ｘ：８９％以下
注９）で得られたカチオン電着塗装板を４０℃の水中に
２４０時間浸漬し、乾燥させた後、注１０）と同様にし
て剥離試験を行ない、電着塗膜の残存率を測定
○：９５〜１００％ △：９０〜９４％×：８９％以下
電極Ｒ型（４０Ｒ）、加圧力１７０ｋｇ，溶接時間１０
０ｏの条件の下に各試験板を互い違いに２枚重ね連続溶
接打点数を調べた。Note 8) Note 9) Cross-cuts are made on the painted surface of the test plate, and JIS-Z-237
A salt spray test based on 1 was conducted for 500 hours, and the occurrence of red rust was observed. ○: No rust occurred. △: Amine-added epoxy resin-blocked isocyanate-based cationic electrodeposition paint was applied to the painted surface of the red rust 5-terminal test plate at a bath temperature of 28. °C, 100VX
Cationic electrodeposition coating for 3 minutes at 165℃ x 20
Baked for a minute and observed the appearance of the paint film (area 100 crl) Note 10) ○ Nigaspin and craters - 0 to 5 points △ Nigaspin and craters - 6 to 20 points X Nigaspins and craters - 20 points or more Note 9) Cut 100 1 mm squares on the cationic electrodeposition coated plate with a cutter knife, perform a peel test using cellophane tape (Note 12), and measure the residual rate of the electrodeposited film ○: 95-100% △: 90~94% Measure the residual rate of the deposited coating ○: 95-100% △: 90-94% ×: 89% or less Electrode R type (40R), pressing force 170 kg, welding time 10
Under the condition of 0o, two of each test plate was stacked alternately and the number of continuous welding points was examined.
○：９００：点以上 △：５００〜 ８９９：点 Ｘ：４９９打点以下○: 900: points or more △: 500~ 899: points X: 499 points or less
Claims (1)
の重量比率（９５：５〜６０：４０）からなるビスフェ
ノール骨格と、エピクロルヒドリン骨格とより構成され
る、１分子中に２個以上のエポキシ基を有するビスフェ
ノール型エポキシ樹脂、 （ｉｉ）シリカ粒子、及び （ｉｉｉ）黒鉛粒子、 を含む耐食性塗料組成物。[Scope of Claims] (i) Two or more in one molecule, consisting of a bisphenol skeleton consisting of a bisphenol A skeleton and a bisphenol F skeleton in a weight ratio (95:5 to 60:40) and an epichlorohydrin skeleton. A corrosion-resistant paint composition comprising: a bisphenol-type epoxy resin having an epoxy group; (ii) silica particles; and (iii) graphite particles.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25136489A JPH03111468A (en) | 1989-09-27 | 1989-09-27 | Corrosion-resistant coating composition |
| CA 2025865 CA2025865C (en) | 1989-09-27 | 1990-09-20 | Corrosion resistant coating composition |
| DE1990607393 DE69007393T2 (en) | 1989-09-27 | 1990-09-21 | Process for producing corrosion-resistant coating composition. |
| AT90118197T ATE102981T1 (en) | 1989-09-27 | 1990-09-21 | METHOD OF MAKING CORROSION RESISTANT COATING COMPOSITION. |
| EP19900118197 EP0420063B1 (en) | 1989-09-27 | 1990-09-21 | Method for forming corrosion resistant coating composition |
| AU63142/90A AU624533B2 (en) | 1989-09-27 | 1990-09-24 | Corrosion resistant coating composition |
| US07/781,668 US5213846A (en) | 1989-09-27 | 1991-10-24 | Corrison resistant coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25136489A JPH03111468A (en) | 1989-09-27 | 1989-09-27 | Corrosion-resistant coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03111468A true JPH03111468A (en) | 1991-05-13 |
Family
ID=17221731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25136489A Pending JPH03111468A (en) | 1989-09-27 | 1989-09-27 | Corrosion-resistant coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03111468A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011122326A1 (en) * | 2010-03-31 | 2011-10-06 | 株式会社神戸製鋼所 | Black metal sheet |
| JP2013199546A (en) * | 2012-03-23 | 2013-10-03 | Dainippon Toryo Co Ltd | Water-soluble anticorrosive paint composition and corrosion protection method |
-
1989
- 1989-09-27 JP JP25136489A patent/JPH03111468A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011122326A1 (en) * | 2010-03-31 | 2011-10-06 | 株式会社神戸製鋼所 | Black metal sheet |
| JP2011224972A (en) * | 2010-03-31 | 2011-11-10 | Kobe Steel Ltd | Black metal plate |
| JP2013199546A (en) * | 2012-03-23 | 2013-10-03 | Dainippon Toryo Co Ltd | Water-soluble anticorrosive paint composition and corrosion protection method |
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