JPH0260697B2 - - Google Patents
Info
- Publication number
- JPH0260697B2 JPH0260697B2 JP56161538A JP16153881A JPH0260697B2 JP H0260697 B2 JPH0260697 B2 JP H0260697B2 JP 56161538 A JP56161538 A JP 56161538A JP 16153881 A JP16153881 A JP 16153881A JP H0260697 B2 JPH0260697 B2 JP H0260697B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- acid
- precondensate
- epoxy resin
- epoxy
- 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
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 description 26
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 150000001412 amines Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000576 coating method Methods 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 239000004848 polyfunctional curative Substances 0.000 description 11
- 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 9
- 239000004952 Polyamide Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- -1 phosphate ester Chemical class 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 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 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-L ethyl phosphate(2-) Chemical compound CCOP([O-])([O-])=O ZJXZSIYSNXKHEA-UHFFFAOYSA-L 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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もの
である。更に詳しくは、特定のキレート反応性エ
ポキシ樹脂と活性有機硬化剤を含む防蝕塗料に関
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、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
被覆用組成物に関するものである。
従来のエポキシ樹脂塗料はそのすぐれた防蝕性
の故に広範囲な分野で金属保護塗料として用いら
れている。しかしそのすぐれた防蝕性を保つには
鋼板面の錆を入念に除去し、下地処理を十分に施
す必要がある。この下地処理を不充分に行つた状
態で塗装した場合、密着不良を起こし、防蝕性能
も著しく低下する。
それ故、鋼板下地処理を簡略化したものあるい
は錆面鋼板に塗装しても密着性が良く、かつ防蝕
性の優れた塗膜が得られればそのメリツトは大き
い。
本発明の目的は、特に錆の認められない鋼板や
脱錆鋼板は勿論のこと、鋼板の下地処理の簡略化
したもの、あるいは錆面鋼板に直接塗装しても、
優れた密着性と耐蝕性を有する被覆用樹脂組成物
を提供することにある。
本発明の組成物は必須の成分として、
(A) Ｐ−OH結合を少なくとも１個有する、オル
トリン酸、メタリン酸、ピロリン酸、亜リン
酸、ポリリン酸、ホスホン酸、ホスフイン酸か
ら選ばれる１種以上のリンの酸、そのエステル
又は塩と、エポキシ樹脂とから、エポキシ基１
当量当たり水酸基が0.05〜0.9当量となる割合
で反応させて得られるエポキシ樹脂用硬化剤で
硬化し得る樹脂（以下予備縮合物と略記する）
及び
(B) エポキシ樹脂用活性有機硬化剤
を含有する。
本発明の組成物の必須成分である予備縮合物
は、エポキシ樹脂と、リン酸類、水酸基を含有す
るリン酸エステル類又はそれらの塩類等とを、エ
ポキシ基が残存する割合で溶剤の存在下又は不存
在下に加熱処理することにより得られる。
加熱温度としては、特に限定はないが、エポキ
シ樹脂の分解が起こらず、且つ適当な時間で反応
が終了するべく50〜130℃で行うのが良い。
ここで使用するエポキシ樹脂としては、
式
（ＺはＨ、CH3、C2H5基）
で示される置換又は非置換のグリシジルエーテル
基を分子内に１個より多く有するもの等種々のも
のを用いることができ、エポキシ当量には特に制
限はないが、好ましくはエポキシ当量200〜1000
程度のものが良い。
本発明に用いられる少なくとも１個のＰ−OH
結合を有するリンの酸とは、例えばオルトリン
酸、メタリン酸、ピロリン酸、亜リン酸、ポリリ
ン酸、ホスホン酸、ホスフイン酸等であり、特に
オルトリン酸が好ましい。
又、リンの酸のエステルとしては上記のリンの
酸のエステル、好ましくは炭素原子数８程度迄の
アルキルエステル（水酸基を１個以上有するも
の）及びヒドロキシアルキルエステル、例えば、
エチル、ｎ−ブチル、２−エチルヘキシル、ヒド
ロキシエチル、ヒドロキシブチル、ヒドロキシプ
ロピル、ヒドロキシペンチル等の基を持つものが
挙げられ、特にｎ−ブチル又は２−エチルヘキシ
ルのモノ又はジ−リン酸エステルが好ましい。
又、リンの酸の塩としては上記のリンの酸の
塩、例えばカリウム、ナトリウム、リチウム、カ
ルシウム、亜鉛、アルミニウム、スズ、バリウム
等の塩が挙げられ、特にカリウム、ナトリウム又
はカルシウムの第１又は第２リン酸塩が好まし
い。
エポキシ樹脂とリン酸類との反応はエポキシ樹
脂中のエポキシ基１当量当りリン酸類の水酸基が
0.05〜0.9当量、好ましくは0.05〜0.4当量の割合
で行い、生成した変性エポキシ樹脂（予備縮合
物）のエポキシ当量は3000以下とするのがよい。
本発明に用いられる活性有機硬化剤としては、
通常のエポキシ樹脂塗料用の硬化剤がすべて使用
可能であり、例えば脂肪族系ポリアミン、芳香族
系変性ポリアミン、脂肪族系変性ポリアミン、ポ
リアミド類、アミノ樹脂、カルボン酸類等が挙げ
られる。
更に本発明組成物には、必要とあれば他のエポ
キシ樹脂、稀釈剤、溶剤、着色顔料、防錆顔料、
充填剤、その他の添加剤を併用することができ
る。
本発明の被覆用組成物は、自然乾燥により塗膜
を得ることができるが、必要ならば加熱等による
強制乾燥によつても、目的とする塗膜が得られ
る。
以下、実施例により本発明を詳細に説明する。
尚、例中の部は重量基準である。
実施例 １
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝260）100部とアデカグリシロール
ED−501（エポキシ当量＝300）25部とオルトリン
酸６部を混合し80℃で５時間反応を行い得られた
予備縮合物を〔〕とする。
予備縮合物〔〕100部に対してエポキシ樹脂硬
化剤としてポリアミド（アミン価＝340）30部を
加え、本配合樹脂を錆面鋼板（１年間屋外バクロ
し、浮きサビを落した鋼板）に塗布、膜厚150μ
にし１週間室温硬化後表１にみるような塗膜性能
比較試験を行つた結果、密着性、防蝕性ともに著
しく比較例より優れていた。
実施例 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＝470）100部とリン酸モノエチル５部
とキシレン35部を混合して90℃で４時間撹拌反応
を行い得られた予備縮合物を〔〕とする。
予備縮合物〔〕100部に対してエポキシ樹脂硬
化剤として変性芳香族アミンのアデカハードナー
EH−551（アミン価＝280、旭電化工業(株)製商品
名）12部を加え、本配合樹脂を用い実施例１と同
様に塗り板を作成し比較した結果、表１に示すよ
うに比較例より密着性、防蝕性ともに著しく優れ
ていた。
実施例 ３
ビスフエノールＦ・ジグリシジルエーテル（エ
ポキシ当量＝280）100部とビスフエノールＡ・プ
ロピレンオキサイド付加物のジグリシジルエーテ
ル（エポキシ当量＝340）50部と第２リン酸カリ
ウム17部とを混合して110℃で５時間撹拌反応を
行い得られた予備縮合物を〔〕とする。
予備縮合物〔〕100部に対してエポキシ樹脂硬
化剤として変性脂肪族アミンのアデカハードナー
EH−220（アミン価＝375、旭電化工業(株)製商品
名）20部とキシレン50部を加え、本配合樹脂を用
い実施例１と同様に塗板を作成し比較した結果、
表１に示すように比較例より密着性、防蝕性とも
に著しく優れていた。
実施例 ４
ノボラツク・エポキシ樹脂（エポキシ当量＝
180）100部とビスフエノールＦ・エチレンオキサ
イド付加物のジグリシジルエーテル（エポキシ当
量＝310）50部とピロリン酸のジヒドロキシブチ
ルエステル15部とメチル・イソブチルケトン50部
を混合して70℃で６時間撹拌反応を行い得られた
予備縮合物を〔〕とする。
予備縮合物〔〕100部に対してエポキシ樹脂硬
化剤として変性ポリアミドアデカハードナーEH
−203（アミン価＝280、旭電化工業(株)製商品名）
30部を加え、本配合樹脂を用い実施例１と同様に
塗り板を作成し比較した結果、表１に示すように
比較例より密着性、防蝕性ともに著しく優れてい
た。
実施例 ５
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝470）100部とクレゾールノボラツ
ク・エポキシ樹脂（エポキシ当量＝185）30部と
亜リン酸モノエチル10部とアノン40部を混合して
85℃で３時間撹拌反応を行い得られた予備縮合物
を〔〕とする。
予備縮合物〔〕100部に対してエポキシ樹脂硬
化剤として変性脂肪族アミンのアデカハードナー
EH−218（アミン価＝375、旭電化工業(株)製商品
名）11部とキシレン30部を加え、本配合樹脂を用
い実施例１と同様に塗り板を作成し比較した結
果、表１に示すように比較例より密着性、防蝕性
ともに著しく優れていた。
比較例 １
未変性のビスフエノールＡ・ジグリシジルエー
テル（エポキシ当量＝190）100部に対して、ポリ
アミド（アミン価＝200）80部を混合した配合樹
脂をサビ面鋼板（１年間屋外バクロし浮きサビを
落した鋼板）に塗布、膜厚150〜200μにし、室温
で１週間硬化した。
比較例 ２
未変性のビスフエノールＡ・ジグリシジルエー
テル（エポキシ当量＝450）（固型分50％）100部
に対し、アデカハードナーEH−551 15部を混合
した配合樹脂を比較例１と同様にサビ面鋼板に塗
布し塗板を作成した。
比較例 ３
未変性のビスフエノールＡ・ジグリシジルエー
テル（エポキシ当量＝190）75部とビスフエノー
ルＡ・プロピレンオキサイド付加物のジグリシジ
ルエーテル（エポキシ当量＝340）25部とに対し、
アデカハードナーEH−220 30部を混合した配合
樹脂を比較例１と同様にサビ面鋼板に塗布し塗板
を作成した。
実施例 ６
ビスフエノールＡジグリシジルエーテル（エポ
キシ当量＝470）100部とホスホン酸2.5部、メチ
ルイソブチルケトン50部を混合し、80℃で３時間
撹拌し予備縮合物〔〕を得た。得られた予備縮合
物〔〕はエポキシ当量＝950、酸価＝0.1mgKOH／
ｇであつた。
縮合物〔〕100部に対し、硬化剤として変性ポ
リアミドアミンアデカハードナーEH−203（アミ
ン価＝280）12部とキシレン30部を加え、本配合
樹脂を用い実施例１と同様に塗り板を作成した。
実施例 ７
ビスフエノールＡジグリシジルエーテル（エポ
キシ当量＝470）100部にホスフイン酸６部、シク
ロヘキサノン50部を加え混合し、80℃で３時間撹
拌し予備縮合物〔〕を得た。得られた予備縮合物
〔〕はエポキシ当量1045、酸価0.05mgKOH／ｇで
あつた。
予備縮合物〔〕100部に対し、硬化剤として変
性脂肪族アミンアデカハードナーEH−218（アミ
ン価＝375）７部、トルエン20部を加え、本配合
樹脂を用い実施例１と同様に塗り板を作成した。
実施例 ８
ブチルグリシジルエーテル（エポキシ当量＝
140）56部にポリリン酸5.6部、メチルイソブチル
ケトン50部を加え、80℃で３時間撹拌した。更に
ビスフエノールＡジグリシジルエーテル（エポキ
シ当量＝190）190部、トルエン50部を加え、80℃
で３時間撹拌し予備縮合物〔〕を得た。予備縮合
物〔〕はエポキシ当量450、酸価0.5mgKOH／ｇで
あつた。
予備縮合物〔〕100部に硬化剤として変性ポリ
アミドアミンのアデカハードナーEH−203（アミ
ン価＝280）25部を加え、本配合樹脂を用い実施
例１と同様に塗り板を作成した。
比較例 ４
１−ヒドロキシエタン−１，１ジリン酸の60％
水溶液42部にグリセリンジグリシジルエーテル
（エポキシ当量＝102）100部、キシレン50部を加
え、80℃で３時間撹拌し予備縮合物〔〕を得た。
得られた予備縮合物〔〕はエポキシ当量415、酸
価0.15mgKOH／ｇであつた。
予備縮合物〔〕100部に硬化剤として変性ポリ
アミドアミンのアデカハードナーEH−203（アミ
ン価＝280）25部、キシレン20部を加え、本配合
樹脂を用い実施例１と同様に塗り板を作成した。
比較例 ５
ビスフエノールＡ・ジグリシジルエーテル（エ
ポキシ当量＝470）100部に水3.5部、ヒドロキシ
メタンホスホン酸8.9部、及びメチルエチルケト
ン65部を混合し、エポキシ基がなくなるまで反応
を続けた。
この縮合物は、酸価40mgKOH／ｇを有し、ト
リエチルアミンで酸基を中和して水に完全に溶解
した。
上記生成物100部に対し、硬化剤として変性ポ
リアミドアミンのアデカハードナーEH−203（ア
ミン価＝280）６部を混合したが、硬化すること
はできなかつた。
〔塗膜性能比較試験〕
実施例１〜５及び比較例１〜３で得られた塗板
について、塗膜性能比較試験を行つた。結果を表
１に示す。
The present invention relates to a novel metal corrosion-preventing coating. More particularly, the present invention relates to a corrosion-resistant coating containing a specific chelate-reactive epoxy resin and an active organic curing agent. A coating composition that has excellent adhesion and corrosion resistance for not only rust-free steel plates and rust-free steel plates, but also rusted steel plates, steel plates with insufficient surface treatment, galvanized steel plates, aluminum, stainless steel, etc. It is about things. Conventional epoxy resin paints are used as metal protective paints in a wide range of fields because of their excellent corrosion resistance. However, in order to maintain its excellent corrosion resistance, it is necessary to carefully remove rust from the surface of the steel plate and thoroughly prepare the surface. If the coating is applied with insufficient surface treatment, poor adhesion will occur and the anticorrosion performance will be significantly reduced. Therefore, it would be of great benefit if a coating film with good adhesion and excellent corrosion resistance could be obtained by simplifying the surface treatment of the steel plate or by coating it on a rusted steel plate. The purpose of the present invention is not only to produce rust-free steel plates and derusted steel plates, but also to simplify the surface treatment of steel plates, or even when directly painted on rusted steel plates.
An object of the present invention is to provide a coating resin composition having excellent adhesion and corrosion resistance. The composition of the present invention has as an essential component: (A) one type selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, and phosphinic acid having at least one P-OH bond; From the above phosphorus acid, its ester or salt, and an epoxy resin, epoxy group 1
A resin that can be cured with an epoxy resin curing agent obtained by reacting at a ratio of 0.05 to 0.9 equivalents of hydroxyl groups per equivalent (hereinafter abbreviated as precondensate)
and (B) an active organic curing agent for epoxy resins. The precondensate, which is an essential component of the composition of the present invention, is a mixture of an epoxy resin and a phosphoric acid, a hydroxyl group-containing phosphate ester, or a salt thereof in the presence of a solvent or in a proportion that leaves the epoxy group. Obtained by heat treatment in its absence. The heating temperature is not particularly limited, but it is preferably 50 to 130°C in order to prevent decomposition of the epoxy resin and to complete the reaction in an appropriate time. The epoxy resin used here has the formula (Z is H, CH 3 , C 2 H 5 group) Various types can be used, such as those having more than one substituted or unsubstituted glycidyl ether group in the molecule, and the epoxy equivalent is particularly There is no limit, but preferably epoxy equivalent is 200 to 1000
Something of a certain degree is good. At least one P-OH used in the present invention
Examples of the phosphorus acid having a bond include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, and phosphinic acid, with orthophosphoric acid being particularly preferred. Examples of phosphorus acid esters include the above-mentioned phosphorus acid esters, preferably alkyl esters having up to about 8 carbon atoms (those having one or more hydroxyl groups) and hydroxyalkyl esters, such as:
Examples include those having groups such as ethyl, n-butyl, 2-ethylhexyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, hydroxypentyl, etc. Mono- or di-phosphate esters of n-butyl or 2-ethylhexyl are particularly preferred. Examples of phosphorus acid salts include the above-mentioned phosphorus acid salts, such as potassium, sodium, lithium, calcium, zinc, aluminum, tin, barium, etc. salts, particularly potassium, sodium, or calcium salts. Secondary phosphates are preferred. The reaction between epoxy resin and phosphoric acids is that the hydroxyl group of phosphoric acid is
It is preferable that the epoxy equivalent of the modified epoxy resin (precondensate) produced is 3000 or less. The active organic curing agent used in the present invention includes:
All curing agents commonly used for epoxy resin coatings can be used, including aliphatic polyamines, aromatic modified polyamines, aliphatic modified polyamines, polyamides, amino resins, carboxylic acids, and the like. Furthermore, the composition of the present invention may contain other epoxy resins, diluents, solvents, color pigments, anti-corrosion pigments, if necessary.
Fillers and other additives can be used in combination. The coating composition of the present invention can be dried naturally to form a coating film, but if necessary, the desired coating film can also be obtained by forced drying by heating or the like. Hereinafter, the present invention will be explained in detail with reference to Examples.
Note that parts in the examples are based on weight. Example 1 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 260) and adeca glycilol
25 parts of ED-501 (epoxy equivalent = 300) and 6 parts of orthophosphoric acid were mixed and reacted at 80°C for 5 hours, and the resulting precondensate was designated as []. Add 30 parts of polyamide (amine value = 340) as an epoxy resin curing agent to 100 parts of the precondensate, and apply this blended resin to a rusted steel plate (a steel plate that has been exposed outdoors for one year to remove loose rust). , film thickness 150μ
After curing at room temperature for one week, a comparative test of coating film performance as shown in Table 1 was carried out, and the results showed that both adhesion and corrosion resistance were significantly superior to the comparative example. Example 2 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 470), 5 parts of monoethyl phosphate, and 35 parts of xylene were mixed and reacted with stirring at 90°C for 4 hours, and the resulting precondensate was [] shall be. Adeka hardener of modified aromatic amine as epoxy resin curing agent for 100 parts of precondensate []
Adding 12 parts of EH-551 (amine value = 280, trade name manufactured by Asahi Denka Kogyo Co., Ltd.) and using this blended resin, a coated board was prepared in the same manner as in Example 1 and compared, as shown in Table 1. Both adhesion and corrosion resistance were significantly superior to the comparative example. Example 3 100 parts of bisphenol F/diglycidyl ether (epoxy equivalent = 280), 50 parts of diglycidyl ether of bisphenol A/propylene oxide adduct (epoxy equivalent = 340), and 17 parts of dibasic potassium phosphate were mixed. The precondensate obtained by carrying out a stirring reaction at 110°C for 5 hours is referred to as []. Adeka hardener of modified aliphatic amine as epoxy resin curing agent for 100 parts of precondensate []
After adding 20 parts of EH-220 (amine value = 375, trade name manufactured by Asahi Denka Kogyo Co., Ltd.) and 50 parts of xylene, a coated plate was prepared using this blended resin in the same manner as in Example 1, and the results were compared.
As shown in Table 1, both adhesion and corrosion resistance were significantly superior to the comparative example. Example 4 Novolak epoxy resin (epoxy equivalent =
180) 100 parts of bisphenol F/ethylene oxide adduct diglycidyl ether (epoxy equivalent = 310), 50 parts, dihydroxybutyl ester of pyrophosphoric acid 15 parts, and 50 parts of methyl isobutyl ketone were mixed and heated at 70°C for 6 hours. The precondensate obtained by performing the stirring reaction is referred to as []. Modified polyamide deca hardener EH as epoxy resin curing agent for 100 parts of precondensate []
-203 (amine value = 280, product name manufactured by Asahi Denka Kogyo Co., Ltd.)
By adding 30 parts of this blended resin, a coated plate was prepared in the same manner as in Example 1 and compared. As shown in Table 1, both adhesion and corrosion resistance were significantly superior to the comparative example. Example 5 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 470), 30 parts of cresol novolak epoxy resin (epoxy equivalent = 185), 10 parts of monoethyl phosphite, and 40 parts of anone were mixed.
The precondensate obtained by carrying out the stirring reaction at 85°C for 3 hours is referred to as []. Adeka hardener of modified aliphatic amine as epoxy resin curing agent for 100 parts of precondensate []
A coated plate was prepared in the same manner as in Example 1 using this blended resin by adding 11 parts of EH-218 (amine value = 375, trade name manufactured by Asahi Denka Kogyo Co., Ltd.) and 30 parts of xylene, and the results were compared as shown in Table 1. As shown in Figure 3, both adhesion and corrosion resistance were significantly superior to the comparative example. Comparative Example 1 A blended resin prepared by mixing 80 parts of polyamide (amine value = 200) with 100 parts of unmodified bisphenol A diglycidyl ether (epoxy equivalent = 190) was mixed with a rusted steel plate (for one year in an outdoor vacuum cleaner). It was coated on a rust-free steel plate to a film thickness of 150 to 200 μm and cured at room temperature for one week. Comparative Example 2 A blended resin prepared by mixing 15 parts of Adeka Hardener EH-551 with 100 parts of unmodified bisphenol A diglycidyl ether (epoxy equivalent = 450) (solid content 50%) was prepared in the same manner as in Comparative Example 1. A coated plate was created by applying it to a rusted steel plate. Comparative Example 3 For 75 parts of unmodified bisphenol A/diglycidyl ether (epoxy equivalent = 190) and 25 parts of bisphenol A/propylene oxide adduct diglycidyl ether (epoxy equivalent = 340),
A blended resin mixed with 30 parts of Adeka Hardener EH-220 was applied to a rusted steel plate in the same manner as in Comparative Example 1 to prepare a coated plate. Example 6 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 470), 2.5 parts of phosphonic acid, and 50 parts of methyl isobutyl ketone were mixed and stirred at 80°C for 3 hours to obtain a precondensate. The obtained precondensate [] has an epoxy equivalent of 950 and an acid value of 0.1 mgKOH/
It was hot at g. To 100 parts of condensate [], 12 parts of modified polyamide amine Adeka Hardener EH-203 (amine value = 280) as a hardening agent and 30 parts of xylene were added, and a coated board was prepared in the same manner as in Example 1 using this blended resin. did. Example 7 6 parts of phosphinic acid and 50 parts of cyclohexanone were added to 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 470), mixed, and stirred at 80°C for 3 hours to obtain a precondensate []. The obtained precondensate [] had an epoxy equivalent of 1045 and an acid value of 0.05 mgKOH/g. To 100 parts of precondensate [], 7 parts of modified aliphatic amine Adeka hardener EH-218 (amine value = 375) as a hardening agent and 20 parts of toluene were added, and a plate was coated in the same manner as in Example 1 using this blended resin. It was created. Example 8 Butyl glycidyl ether (epoxy equivalent =
140) 5.6 parts of polyphosphoric acid and 50 parts of methyl isobutyl ketone were added to 56 parts, and the mixture was stirred at 80°C for 3 hours. Furthermore, 190 parts of bisphenol A diglycidyl ether (epoxy equivalent = 190) and 50 parts of toluene were added, and the mixture was heated at 80°C.
The mixture was stirred for 3 hours to obtain a precondensate [ ]. The precondensate [] had an epoxy equivalent of 450 and an acid value of 0.5 mgKOH/g. 25 parts of Adeka Hardener EH-203 (amine value = 280), which is a modified polyamide amine, was added as a hardening agent to 100 parts of the precondensate, and a coated board was prepared in the same manner as in Example 1 using this blended resin. Comparative Example 4 60% of 1-hydroxyethane-1,1 diphosphoric acid
100 parts of glycerin diglycidyl ether (epoxy equivalent = 102) and 50 parts of xylene were added to 42 parts of the aqueous solution, and the mixture was stirred at 80°C for 3 hours to obtain a precondensate.
The obtained precondensate [] had an epoxy equivalent of 415 and an acid value of 0.15 mgKOH/g. To 100 parts of precondensate [], 25 parts of modified polyamide amine Adeka Hardener EH-203 (amine value = 280) as a hardening agent and 20 parts of xylene were added, and a coated board was prepared in the same manner as in Example 1 using this blended resin. did. Comparative Example 5 100 parts of bisphenol A diglycidyl ether (epoxy equivalent = 470) were mixed with 3.5 parts of water, 8.9 parts of hydroxymethanephosphonic acid, and 65 parts of methyl ethyl ketone, and the reaction was continued until the epoxy group disappeared. This condensate had an acid value of 40 mgKOH/g and completely dissolved in water after neutralizing the acid groups with triethylamine. 6 parts of Adeka Hardener EH-203 (amine value = 280), a modified polyamide amine, was mixed as a curing agent with 100 parts of the above product, but the product could not be cured. [Coating film performance comparison test] A coating film performance comparison test was conducted on the coated plates obtained in Examples 1 to 5 and Comparative Examples 1 to 3. The results are shown in Table 1.
【表】【table】
Claims (1)
トリン酸、メタリン酸、ピロリン酸、亜リン
酸、ポリリン酸、ホスホン酸、ホスフイン酸か
ら選ばれる１種以上のリンの酸、そのエステル
又は塩と、エポキシ樹脂とから、エポキシ基１
当量当たり水酸基が0.05〜0.9当量となる割合
で反応させて得られるエポキシ樹脂用硬化剤で
硬化し得る樹脂、及び、 (B) エポキシ樹脂用活性有機硬化剤 を含有する被覆用組成物。[Claims] 1. As an essential component (A) one type selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, and phosphinic acid having at least one P-OH bond; From the above phosphorus acid, its ester or salt, and an epoxy resin, epoxy group 1
A coating composition containing a resin curable with a curing agent for epoxy resin obtained by reacting at a ratio of 0.05 to 0.9 equivalents of hydroxyl groups per equivalent, and (B) an active organic curing agent for epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16153881A JPS5863758A (en) | 1981-10-09 | 1981-10-09 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16153881A JPS5863758A (en) | 1981-10-09 | 1981-10-09 | Coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5863758A JPS5863758A (en) | 1983-04-15 |
| JPH0260697B2 true JPH0260697B2 (en) | 1990-12-18 |
Family
ID=15736997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16153881A Granted JPS5863758A (en) | 1981-10-09 | 1981-10-09 | Coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5863758A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191217A (en) * | 1984-10-12 | 1986-05-09 | Nitto Electric Ind Co Ltd | Protection of underwater structure |
| JPS61211327A (en) * | 1985-03-18 | 1986-09-19 | Nitto Electric Ind Co Ltd | Underwater-curable epoxy resin composition |
| JPS61211331A (en) * | 1985-03-18 | 1986-09-19 | Nitto Electric Ind Co Ltd | Underwater-curable epoxy resin composition |
| JPH0668008B2 (en) * | 1985-12-09 | 1994-08-31 | 日東電工株式会社 | Underwater curable epoxy resin composition |
| JP3630336B2 (en) | 1994-09-20 | 2005-03-16 | 旭電化工業株式会社 | Urethane modified epoxy resin |
| KR101482294B1 (en) | 2007-10-30 | 2015-01-13 | 헨켈 아게 운트 코 카게아아 | Epoxy paste adhesives resistant to wash-off |
| ES2662646T3 (en) | 2008-06-12 | 2018-04-09 | Henkel IP & Holding GmbH | Highly reinforced, new generation two-part structural epoxy adhesive compositions |
| JP5337526B2 (en) * | 2009-02-24 | 2013-11-06 | 国立大学法人 東京大学 | Method for bonding metal and resin, method for producing circuit forming component using the same, and circuit forming component |
| CA2806243C (en) | 2010-09-23 | 2020-10-27 | Henkel Corporation | Chemical vapor resistant epoxy composition |
| DE102014226826A1 (en) | 2014-12-22 | 2016-06-23 | Henkel Ag & Co. Kgaa | The epoxy resin composition |
| JP7295095B2 (en) | 2017-09-12 | 2023-06-20 | ディディピー スペシャルティ エレクトロニック マテリアルズ ユーエス，エルエルシー | One component reinforced epoxy adhesive |
| EP3798246B1 (en) | 2019-09-27 | 2024-01-31 | Henkel AG & Co. KGaA | One component (1k) composition based on modified epoxy resin |
Citations (2)
| 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 |
| JPS5560567A (en) * | 1978-10-31 | 1980-05-07 | Vianova Kunstharz Ag | Production of waterrsoluble paint bonding agent |
-
1981
- 1981-10-09 JP JP16153881A patent/JPS5863758A/en active Granted
Patent Citations (2)
| 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 |
| JPS5560567A (en) * | 1978-10-31 | 1980-05-07 | Vianova Kunstharz Ag | Production of waterrsoluble paint bonding agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5863758A (en) | 1983-04-15 |
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