JPH038673B2 - - Google Patents
Info
- Publication number
- JPH038673B2 JPH038673B2 JP58226528A JP22652883A JPH038673B2 JP H038673 B2 JPH038673 B2 JP H038673B2 JP 58226528 A JP58226528 A JP 58226528A JP 22652883 A JP22652883 A JP 22652883A JP H038673 B2 JPH038673 B2 JP H038673B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- bisphenol
- molecular weight
- reaction product
- epoxy equivalent
- 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 - Lifetime
Links
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 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 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RUZMUTWCUZLWQU-UHFFFAOYSA-N [ethoxy(hydroxy)phosphoryl] ethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OP(O)(=O)OCC RUZMUTWCUZLWQU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-L ethyl phosphate(2-) Chemical compound CCOP([O-])([O-])=O ZJXZSIYSNXKHEA-UHFFFAOYSA-L 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、新規な金属防蝕用被覆剤に関する。
更に詳しくは、特定のキレート反応性樹脂を有効
成分とする被覆用樹脂組成物に関するもので、そ
れだけで造膜性を持つラツカー型防蝕塗料に関す
るものである。特に錆の認められない鋼板や脱錆
鋼板は勿論のこと、発錆鋼板あるいは下地処理の
不備な鋼板及び亜鉛鋼板、アルミニウム、ステン
レス等に対してすぐれた密着性及び防蝕性を有す
る被覆用樹脂組成物に関するものである。
従来のラツカー型塗料は、発錆鋼板等に対して
単に浸透性を持たしたものであり、その密着性や
特に防蝕性が劣るため用途が限定されている。
本発明者らはかかる従来のラツカー型塗料の欠
点を改良すべく鋭意研究の結果、エポキシ樹脂を
ベースにして高分子量化し、かつ金属とキレート
形成能を持たせた樹脂を有効成分とする組成物が
従来のラツカー型塗料にくらべて金属に対してす
ぐれた密着性と特に著るしくすぐれた防蝕性を有
することを見い出し本発明に到達した。
即ち本発明の被覆用樹脂組成物は、必須の成分
として、一般式（）
（但し、R1；Ｈ又はCH3、
R2；−CH2−又は
The present invention relates to a novel coating for metal corrosion protection.
More specifically, the present invention relates to a coating resin composition containing a specific chelate-reactive resin as an active ingredient, and to a lacquer-type anticorrosive paint that has film-forming properties by itself. A coating resin composition that has excellent adhesion and corrosion resistance to not only rust-free steel plates and rust-free steel plates, but also rusted steel plates or poorly prepared steel plates, galvanized steel plates, aluminum, stainless steel, etc. It is about things. Conventional lacquer-type paints simply have permeability to rust-prone steel plates and the like, and their applications are limited because of their poor adhesion and particularly poor corrosion resistance. As a result of intensive research to improve the drawbacks of the conventional lacquer type paints, the present inventors have developed a composition whose active ingredient is a resin based on an epoxy resin, which has a high molecular weight and has the ability to form chelates with metals. The present inventors have discovered that the present invention has superior adhesion to metals and particularly excellent corrosion resistance compared to conventional lacquer-type paints. That is, the coating resin composition of the present invention has general formula () as an essential component. (However, R 1 ; H or CH 3 , R 2 ; -CH 2 - or
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝300）100部とオルトリン酸モノブチ
ル19部とメチルイソブチルケトン80部を混合し、
80℃で15時間反応を行つた。このようにして得ら
れた反応生成物〔〕の平均分子量は25000であ
つた。
〔製造例 ２〕
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝2300）100部とリン酸モノカリウム
3.2部とエチルセロソルブ70部を加えて、90℃で
10時間反応を続けた。このようにして得られた反
応生成物〔〕の平均分子量は18500であつた。
〔製造例 ３〕
ビスフエノールＡ・メチルエピクロルヒドリン
型エポキシ樹脂（エポキシ当量＝3500）100部と
ピロリン酸ジエチル3.5部とシクロヘキサノン100
部を混合して、撹拌しながら70℃℃で10時間反応
を行つた。このようにして得られた反応生成物
〔〕の平均分子量は13500であつた。
〔製造例 ４〕
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝300）100部とビスフエノールA74
部、メチルイソブチルケトン100部及び触媒とし
てトリエチルアミン0.1部を添加して撹拌しなが
ら100℃で18時間反応を続けた。このようにして
得られた反応生成物〔〕の平均分子量は31000
であつた。
〔製造例 ５〕
ビスフエノールＦ・ジグリシジルエーテル（エ
ポキシ当量＝2300）100部とビスフエノールF4.5
部とエチルセロソルブ70部及び触媒としてジメチ
ベンジルアミン0.15部を加えて、120℃で15時間
反応を続けた。このようにして得られた反応生成
物〔〕の平均分子量は21500であつた。
〔製造例 ６〕
ビスフエノールＡ・メチルエピクロルヒドリン
型エポキシ樹脂（エポキシ当量＝3500）100部と
ビスフエノールA6部とシクロヘキサノン80部及
び触媒としてトリエチルアミン0.15部を加えて
110℃で15時間反応を続けた。このようにして得
られた反応生成物〔〕の平均分子量は17000で
あつた。
実施例１〜６、比較例１〜３
製造例１〜６で得られた反応生成物〔〕〜
〔〕を錆面鋼板（１年間屋外バクロし、乳き錆
を落した鋼板）に膜厚70〜75μになるように塗布
し、室温で１週間乾燥後その塗膜の物性比較を行
つた。その結果を表１に示す。表１から明らかな
ように本発明実施例は、密着性、防蝕性とも著る
しく比較例よりすぐれていた。
Mix 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 300), 19 parts of monobutyl orthophosphate and 80 parts of methyl isobutyl ketone,
The reaction was carried out at 80°C for 15 hours. The average molecular weight of the reaction product [] thus obtained was 25,000. [Production Example 2] 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 2300) and monopotassium phosphate
Add 3.2 parts and 70 parts of ethyl cellosolve and heat at 90℃.
The reaction continued for 10 hours. The average molecular weight of the reaction product [] thus obtained was 18,500. [Production Example 3] 100 parts of bisphenol A/methyl epichlorohydrin type epoxy resin (epoxy equivalent = 3500), 3.5 parts of diethyl pyrophosphate, and 100 parts of cyclohexanone
The mixture was mixed and reacted at 70°C for 10 hours with stirring. The average molecular weight of the reaction product [] thus obtained was 13,500. [Production Example 4] 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 300) and bisphenol A74
100 parts of methyl isobutyl ketone and 0.1 part of triethylamine as a catalyst were added, and the reaction was continued at 100° C. for 18 hours with stirring. The average molecular weight of the reaction product [] obtained in this way is 31000
It was hot. [Production Example 5] 100 parts of bisphenol F diglycidyl ether (epoxy equivalent = 2300) and bisphenol F4.5
70 parts of ethyl cellosolve and 0.15 parts of dimethybenzylamine as a catalyst were added, and the reaction was continued at 120°C for 15 hours. The average molecular weight of the reaction product [] thus obtained was 21,500. [Production Example 6] Add 100 parts of bisphenol A/methyl epichlorohydrin type epoxy resin (epoxy equivalent = 3500), 6 parts of bisphenol A, 80 parts of cyclohexanone, and 0.15 parts of triethylamine as a catalyst.
The reaction was continued at 110°C for 15 hours. The average molecular weight of the reaction product [] thus obtained was 17,000. Examples 1 to 6, Comparative Examples 1 to 3 Reaction products obtained in Production Examples 1 to 6 [] to
[] was applied to a rusted steel plate (a steel plate that had been exposed outdoors for one year to remove any milky rust) to a film thickness of 70 to 75 μm, and after drying at room temperature for one week, the physical properties of the coating film were compared. The results are shown in Table 1. As is clear from Table 1, the Examples of the present invention were significantly superior to the Comparative Examples in both adhesion and corrosion resistance.
【表】【table】
【表】
比較例 ４
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝450）100部、リン酸モノエチル10
部、キシレン50部、メチルイソブチルケトン50部
を混合し、110℃で８時間撹拌反応し、分子量
4000（エポキシ当量＝2000）の縮合物を得た。
この縮合物を錆面鋼板に膜厚70μとなるように
塗布し、室温で１週間乾燥後、実施例１と同様の
物性試験を行つた。結果は以下の通りであつた。[Table] Comparative Example 4 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 450), 10 monoethyl phosphate
50 parts of xylene, and 50 parts of methyl isobutyl ketone were mixed and stirred at 110°C for 8 hours to determine the molecular weight.
A condensate of 4000 (epoxy equivalent = 2000) was obtained. This condensate was applied to a rusted steel plate to a film thickness of 70 μm, and after drying at room temperature for one week, the same physical property tests as in Example 1 were conducted. The results were as follows.
Claims (1)
なくとも１個有するリンの酸、そのエステル又は
塩とを溶剤中で反応せしめて得られる分子量１万
以上の反応生成物を有効成分として含有する被覆
用樹脂組成物。[Claims] 1. As an essential component, the following general formula () (However, R 1 ; H or CH 3 , R 2 ; -CH 2 - or [Formula] n = 0 to 35) and a phosphorus acid having at least one P-OH bond, an ester thereof, or A coating resin composition containing as an active ingredient a reaction product having a molecular weight of 10,000 or more obtained by reacting a salt with a solvent in a solvent.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22652883A JPS60118757A (en) | 1983-11-30 | 1983-11-30 | Resin composition for coating use |
| US06/667,250 US4560732A (en) | 1983-11-11 | 1984-11-01 | Coating composition |
| DK534284A DK171532B1 (en) | 1983-11-11 | 1984-11-09 | Anti-corrosive coating |
| DE19843441043 DE3441043A1 (en) | 1983-11-11 | 1984-11-09 | COATING COMPOSITION AND METHOD FOR PRODUCING AN ANTICORROSIVE COATING |
| GB8428506A GB2149409B (en) | 1983-11-11 | 1984-11-12 | Coating composition |
| US06/782,853 US4702962A (en) | 1983-11-11 | 1985-10-02 | Coating composition |
| GB8625215A GB2183239B (en) | 1983-11-11 | 1986-10-21 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22652883A JPS60118757A (en) | 1983-11-30 | 1983-11-30 | Resin composition for coating use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60118757A JPS60118757A (en) | 1985-06-26 |
| JPH038673B2 true JPH038673B2 (en) | 1991-02-06 |
Family
ID=16846541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22652883A Granted JPS60118757A (en) | 1983-11-11 | 1983-11-30 | Resin composition for coating use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60118757A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51143620A (en) * | 1975-06-06 | 1976-12-10 | Matsumoto Seiyaku Kogyo Kk | Process for preparation of epoxydiphosphonate |
| JPS56100824A (en) * | 1980-01-04 | 1981-08-13 | Ford Motor Co | Thermosetting composition |
| JPS58179273A (en) * | 1982-04-14 | 1983-10-20 | Asahi Denka Kogyo Kk | Coating composition |
-
1983
- 1983-11-30 JP JP22652883A patent/JPS60118757A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51143620A (en) * | 1975-06-06 | 1976-12-10 | Matsumoto Seiyaku Kogyo Kk | Process for preparation of epoxydiphosphonate |
| JPS56100824A (en) * | 1980-01-04 | 1981-08-13 | Ford Motor Co | Thermosetting composition |
| JPS58179273A (en) * | 1982-04-14 | 1983-10-20 | Asahi Denka Kogyo Kk | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60118757A (en) | 1985-06-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |