JPH0556786B2 - - Google Patents
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- Publication number
- JPH0556786B2 JPH0556786B2 JP25788986A JP25788986A JPH0556786B2 JP H0556786 B2 JPH0556786 B2 JP H0556786B2 JP 25788986 A JP25788986 A JP 25788986A JP 25788986 A JP25788986 A JP 25788986A JP H0556786 B2 JPH0556786 B2 JP H0556786B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- resin
- parts
- hours
- bisphenol
- 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 - Fee Related
Links
- 229920005862 polyol Polymers 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 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 18
- -1 n-octyl Chemical group 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001118 alkylidene group Chemical group 0.000 description 6
- 239000003849 aromatic solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DXVYLFHTJZWTRF-UHFFFAOYSA-N Ethyl isobutyl ketone Chemical compound CCC(=O)CC(C)C DXVYLFHTJZWTRF-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- 125000005655 1,3-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([*:2])C1([H])[H] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 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
- 230000000694 effects Effects 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical group C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-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
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
〔産業上の利用分野〕
本発明は、被覆用樹脂組成物に関するものであ
る。
更に詳しくは、特定のキレート反応性ポリオー
ル樹脂とアミノ樹脂系硬化剤とを組み合わせて、
加熱硬化型塗膜形成用として機械特性、特に密着
性、折り曲げ加工性と防蝕性に優れた被覆用樹脂
組成物に関するものである。
特に本発明は、錆の認められない鋼板や脱錆鋼
板は勿論のこと下地処理不備の鋼板及びアルミニ
ウム、亜鉛鋼板、ステンレス鋼板等に対しても優
れた機械特性、特に密着性、折り曲げ加工性、防
蝕性を与える被覆用樹脂組成物に関するものであ
る。
〔従来の技術及び問題点〕
従来、被覆用樹脂組成物として二価フエノー
ル、特に2,2−ビス(4−ヒドロキシフエニ
ル)プロパン(以下ビスフエノールAという)と
エピクロルヒドリンから得られる低分子量エポキ
シ樹脂に更に二価フエノールを反応させることに
より高分子量エポキシ樹脂を得、これをアミノ樹
脂を主体とする硬化剤と加熱硬化せしめたものが
一般に使用されている。
しかしながら、上記のような高分子量エポキシ
樹脂をベースにしたものは、有機溶剤に対する溶
解性が不充分であり、又硬化物が可撓性に乏しい
欠点を持つため使用に大幅な制約があつた。又、
従来のポリオール樹脂は金属保護塗料として用い
るにはその密着性と防蝕性は充分でなく、満足す
る性能を発揮させるには下地処理を充分に行う必
要がある。
この下地処理を充分に行わなかつた状態で塗装
した場合、密着不良を起こし、防蝕性能も著しく
低下する。従つて、本発明の目的はキレート反応
性ポリオールを用いることによつて上記のような
欠点のない下地処理を簡略化した鋼板あるいは従
来密着性のよくなかつたアルミニウム、亜鉛鋼
板、ステンレス等に対しても優れた密着性と防蝕
性を有する被覆用樹脂組成物を提供することにあ
る。
〔問題点を解決するための手段〕
即ち、本発明は、二価フエノールのアルキレン
オキサイド付加物の置換又は非置換グリシジルエ
ーテル化物とP−OH結合を少なくとも1個有す
るリンの酸、そのエステル又は塩との反応から得
られる予備縮合物に二価フエノールを反応せしめ
高分子量のエポキシ樹脂を得、これを更にエポキ
シ基と反応性を有するアミノ基を含む化合物と反
応せしめて得られるポリオール樹脂(A)と、尿素、
メラミン、グアナミン樹脂等のアミノ樹脂(B)を主
体とする硬化剤とを含有することを特徴とする被
覆用樹脂組成物に関するものである。
本発明において使用される二価フエノールとし
ては、単核及び/又は多核の二価フエノールが挙
げられる。
かかる単核二価フエノールの例としては、例え
ばレゾルシノール、ハイドロキノン、パイロカテ
コール、フロログルシノール、1,5−ジヒドロ
キシルナフタレン、2,7−ジヒドロキシルナフ
タレン、2,6−ジヒドロキシナフタレンなどが
挙げられる。
また、多核二価フエノールの例としては、一般
式:
(式中Arはナフチレン基及びフエニレン基の様
な芳香族二価炭化水素で本発明の目的にはフエニ
レン基が好ましい。Y′及びY1は同一又は異なつ
ていてもよく、メチル基、n−プロピル基、n−
ブチル基、n−ヘキシル基、n−オクチル基のよ
うなアルキル基なるべくは最高4個の炭素原子を
持つアルキル基或いはハロゲン原子即ち塩素原
子、臭素原子、沃素原子又は弗素原子或いはメト
キシ基、メトキシメチル基、エトキシ基、エトキ
シエチル基、n−ブトキシ基、アミルオキシ基の
様なアルコキシ基なるべくは最高4個の炭素原子
を持つアルコキシ基である。前記の芳香族二価炭
化水素基の何れか又は両方に水素基以外に置換基
が存在する場合にはこれらの置換基は同一でも異
なるものでもよい。m及びzは置換基によつて置
換できる芳香環(Ar)の水素原子の数に対応す
る0(零)から最大値までの値を持つ整数で、同
一又は異なる値であることができる。R1は例え
ば
[Industrial Field of Application] The present invention relates to a coating resin composition. More specifically, by combining a specific chelate-reactive polyol resin and an amino resin curing agent,
The present invention relates to a coating resin composition that is used to form a heat-curable coating film and has excellent mechanical properties, particularly adhesion, bending processability, and corrosion resistance. In particular, the present invention has excellent mechanical properties, especially adhesion, bending workability, The present invention relates to a coating resin composition that provides corrosion resistance. [Prior Art and Problems] Conventionally, low molecular weight epoxy resins obtained from divalent phenols, particularly 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) and epichlorohydrin, have been used as coating resin compositions. A high molecular weight epoxy resin is obtained by further reacting the epoxy resin with dihydric phenol, and this is then heat-cured with a curing agent mainly composed of an amino resin, which is generally used. However, those based on high molecular weight epoxy resins as described above have insufficient solubility in organic solvents and have the drawback that the cured product has poor flexibility, which has greatly restricted their use. or,
Conventional polyol resins do not have sufficient adhesion and corrosion resistance to be used as metal protective coatings, and require sufficient surface treatment in order to exhibit satisfactory performance. If the coating is applied without sufficient surface treatment, poor adhesion will occur and the corrosion resistance will be significantly reduced. Therefore, the object of the present invention is to use a chelate-reactive polyol to provide a steel sheet that does not have the above-mentioned drawbacks and has a simplified surface treatment, or for aluminum, zinc steel sheets, stainless steel sheets, etc. that have conventionally had poor adhesion. Another object of the present invention is to provide a coating resin composition having excellent adhesion and corrosion resistance. [Means for Solving the Problems] That is, the present invention provides a substituted or unsubstituted glycidyl ether of an alkylene oxide adduct of a dihydric phenol, a phosphorus acid having at least one P-OH bond, an ester or salt thereof, Polyol resin (A) obtained by reacting the precondensate obtained from the reaction with dihydric phenol to obtain a high molecular weight epoxy resin, which is further reacted with a compound containing an amino group that is reactive with an epoxy group. and urea,
The present invention relates to a coating resin composition characterized by containing a curing agent mainly composed of an amino resin (B) such as melamine or guanamine resin. The divalent phenols used in the present invention include mononuclear and/or polynuclear divalent phenols. Examples of such mononuclear divalent phenols include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like. In addition, as an example of polynuclear divalent phenol, the general formula: (In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group and a phenylene group, and a phenylene group is preferable for the purpose of the present invention. Y′ and Y 1 may be the same or different, and a methyl group, n -propyl group, n-
Alkyl groups, preferably with up to 4 carbon atoms, such as butyl, n-hexyl, n-octyl, or halogen atoms, i.e. chlorine, bromine, iodine or fluorine, or methoxy, methoxymethyl Alkoxy groups, such as ethoxy, ethoxyethyl, n-butoxy, amyloxy, are preferably alkoxy groups having up to 4 carbon atoms. When a substituent other than a hydrogen group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and z are integers having values ranging from 0 (zero) to the maximum value corresponding to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted with a substituent, and can be the same or different values. R 1 is for example
【式】−O−、−S−、−SO−、−SO2−、
又はアルキンレン基例えばメチレン基、エチレン
基、トリメチレン基、テトラメチレン基、ペンタ
メチレン基、ヘキサメチレン基、2−エチルヘキ
サメチレン基、オクタメチレン基、ノナメチレン
基、デカメチレン基或いはアルキリデン基例えば
エチリデン基、プロピリデン基、イソプロピリデ
ン基、イソブチリデン基、アミリデン基、イソア
ミリデン基、1−フエニルエチリデン基或いは環
状脂肪族基例えば1,4−シクロヘキシレン基、
1,3−シクロヘキシレン基、シクロヘキシリデ
ン基或いはハロゲン化されたアルキレン基或いは
ハロゲン化されたアルキリデン基或いはハロゲン
化された環状脂肪族基或いはアルコキシ−及びア
リールオキシ−置換されたアルキリデン基或いは
アルコキシ−及びアリールオキシ−置換されたア
ルキレン基或いはアルコキシ−及びアリールオキ
シ−置換された環状脂肪族基例えばメトキシメチ
レン基、エトキシメチレン基、エトキシエチレン
基、2−エトキシトリメチレン基、3−エトキシ
ペンタメチレン基、1,4−(2−メトキシシク
ロヘキサン)基、フエノキシエチレン基、2−フ
エノキシトリメチレン基、1,3−(2−フエノ
キシシクロヘキサン)基或いはアルキレン基例え
ばフエニルエチレン基、2−フエニルトリメチレ
ン基、1−フエニルペンタメチレン基、2−フエ
ニルデカメチレン基或いは芳香族例えばフエニレ
ン基、ナフチレン基或いはハロゲン化された芳香
族基例えば1,4−(2−クロルフエニレン)基、
1,4−(2−ブロムフエニレン)基、1,4−
(2−フルオロフエニレン)基或いはアルコキシ
及びアリールオキシ置換された芳香族基例えば
1,4−(2−メトキシフエニレン)基、1,4
−(2−エトキシフエニレン)基、1,4−(2−
n−プロポキシフエニレン)基、1,4−(2−
フエノキシフエニレン)基或いはアルキル置換さ
れた芳香族基例えば1,4−(2−メチルフエニ
レン)基、1,4−(2−エチルフエニレン)基、
1,4−(2−n−プロピルフエニレン)基、1,
4−(2−n−ブチルフエニレン)基、1,4−
(2−n−ドデシルフエニレン)基の様な二価炭
化水素水素基などの二価の基であり、或いはR1
は例えば式
で表わされる化合物の場合の様に前記Ar基一つ
に融着している環であることもでき、或いはR1
はポリエトキシ基、ポリプロポキシ基、ポリチオ
エトキシ基、ポリブトキシ基、ポリフエニルエト
キシ基の様なポリアルコキシ基であることもで
き、或いはR1は例えばポリジメチルシロキシ基、
ポリジフエニルシロキシ基、ポリメチルフエニル
シロキシ基の様な珪素原子を含む基であることが
でき、或いはR1は芳香族環、第三−アミノ基エ
ーテル結合、カルボニル基又は硫黄又はスルホキ
シドの様な硫黄を含む結合によつて隔てられた2
個又はそれ以上のアルキレン基又はアルキリデン
基であることができる)で表わされる多核二価フ
エノールがある。
かかる多核二価フエノールであつて特に好まし
いのは一般式
(式中Y′及びY1前記と同じ意味であり、m及び
zは0〜4の値であり、R1はなるべくは1〜3
個の炭素原子を持つアルキレン基又はアルキリデ
ン基或いは式[Formula] -O-, -S-, -SO-, -SO 2 -, or an alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethylhexamethylene group octamethylene, nonamethylene, decamethylene or alkylidene groups such as ethylidene, propylidene, isopropylidene, isobutylidene, amylidene, isoamylidene, 1-phenylethylidene or cycloaliphatic groups such as 1,4- cyclohexylene group,
1,3-cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group, alkoxy- and aryloxy-substituted alkylidene group, or alkoxy-substituted alkylidene group and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene, 3-ethoxypentamethylene, 1,4-(2-methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2- phenyltrimethylene group, 1-phenylpentamethylene group, 2-phenyldecamethylene group or aromatic group such as phenylene group, naphthylene group or halogenated aromatic group such as 1,4-(2-chlorophenylene) group,
1,4-(2-bromphenylene) group, 1,4-
(2-fluorophenylene) group or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-(2-methoxyphenylene) group, 1,4
-(2-ethoxyphenylene) group, 1,4-(2-
n-propoxyphenylene) group, 1,4-(2-
phenoxyphenylene) group or an alkyl-substituted aromatic group such as 1,4-(2-methylphenylene) group, 1,4-(2-ethylphenylene) group,
1,4-(2-n-propylphenylene) group, 1,
4-(2-n-butylphenylene) group, 1,4-
It is a divalent group such as a divalent hydrocarbon group such as (2-n-dodecylphenylene) group, or R 1
For example, the expression It can also be a ring fused to one of the Ar groups, as in the case of the compound represented by R 1
can also be a polyalkoxy group, such as a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polyphenylethoxy group, or R 1 can be, for example, a polydimethylsiloxy group,
It can be a group containing a silicon atom, such as a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R 1 can be an aromatic ring, a tertiary-amino group, an ether bond, a carbonyl group, or a sulfur or sulfoxide group. 2 separated by a sulfur-containing bond
There are polynuclear dihydric phenols, which can be one or more alkylene or alkylidene groups. Particularly preferred among such polynuclear divalent phenols is the general formula (In the formula, Y' and Y 1 have the same meanings as above, m and z have values of 0 to 4, and R 1 preferably has a value of 1 to 3.
alkylene or alkylidene group or formula with 5 carbon atoms
【式】 又は【formula】 or
以下、本発明を実施例により更に詳述する。
尚、例中の部は重量基準である。
製造例 1
ビスフエノールAにエチレンオキサイドを付加
し、グリシジルエーテル化した液状エポキシ樹脂
(エポキシ当量=410)150部とリン酸モノエチル
10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
〔〕200部に対してビスフエノールA20部に触媒
として水酸化ナトリウムを加え、200℃で6時間
加熱撹拌を続けた。得られた高分子量のエポキシ
樹脂は、エポキシ当量2700であつた。更にジエタ
ノールアミン9部を加え、100℃で3時間撹拌し
てポリオール樹脂()を得た。該ポリオール樹
脂の水酸基当量は360であり、キシレン、トルエ
ンなど芳香族溶剤に容易に溶解するものであつ
た。
製造例 2
ビスフエノールFにプロピレンオキサイドを付
加し、グリシジルエーテル化した液状エポキシ樹
脂(エポキシ当量=300)150部と第2リン酸カリ
ウム15部とを混合して、100℃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〔〕300部に対してビスフエノー
ルF50部に触媒としてジメチルアミンを加えて、
150℃で8時間加熱撹拌を続けた。得られた高分
子量のエポキシ樹脂は、エポキシ当量1300であつ
た。更にジブチルアミン35部を加えて、100℃で
3時間撹拌してポリオール樹脂()を得た。
該ポリオール樹脂の水酸基当量は、490であり、
キシレン、トルエンなど芳香族溶剤に容易に溶解
するものであつた。
製造例 3
ビスフエノールAにプロピレンオキサイドを付
加し、グリシジルエーテル化した液状エポキシ樹
脂(エポキシ当量=520)200部とオルトリン酸6
部を混合して80℃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〔〕
200部に対してビスフエノールF14部に触媒とし
て水酸化カリウムを加えて、180℃で6時間加熱
撹拌を続けた。得られた高分子量のエポキシ樹脂
は、エポキシ当量3800であつた。更にジイソプロ
パノールアミン8部を加えて100℃で3時間撹拌
してポリオール樹脂()を得た。該ポリオール
樹脂の水酸基当量は450であり、キシレン、トル
エンなど芳香族溶剤に容易に溶解するものであつ
た。
製造例 4
ビスフエノールA・ジギルシジルエーテル(エ
ポキシ当量=480)150部とビスフエノールA27部
に触媒として水酸化ナトリウムを加えて180℃で
5時間加熱撹拌を続けた。
得られた高分子量のエポキシ樹脂は、エポキシ
当量2700であつた。更にキシレン25部、メチルイ
ソブチルケトン25部及びジエタノールアミン8部
を加えて90℃で3時間撹拌してポリオール樹脂
()を得た。該ポリオール樹脂()の水酸基
当量は300であり、キシレン、トルエンなどの芳
香族溶剤単独では溶解せずケトン系溶剤、アルコ
ール溶剤を加える必要がある。
製造例 5
ビスフエノールFとエピクロルヒリドンから得
られるビスフエノールF・ジグリシシルエーテル
(エポキシ当量=190)150部とビスフエノール
F70部に触媒としてジメチルアミンを加えて150
℃で15時間加熱撹拌を続けた。
得られた高分子量のエポキシ樹脂は、エポキシ
当量2300であつた。更にキシレン20部、エチルイ
ソブチルケトン20部及びジブチルアミン12部を加
えて100℃で3時間加熱撹拌してポリオール樹脂
()を得た。該ポリオール樹脂の水酸基当量は
290であり、キシレン、トルエンなどの芳香族溶
剤単独では溶解せず、ケトン系溶剤、アルコール
溶剤を加える必要がある。
製造例 6
ビスフエノールAにプロピレンオキサイドを付
加し、グリシジルエーテル化した液状エポキシ樹
脂(エポキシ当量=520)200部とビスフエノール
F32部に触媒として水酸化カリウムを加えて180
℃で6時間加熱撹拌を続けた。
得られた高分子量のエポキシ樹脂は、エポキシ
当量3700であつた。更にジイソプロパノールアミ
ン7部を加えて100℃で3時間撹拌してポリオー
ル樹脂()を得た。該ポリオール樹脂の水酸基
当量は450であり、キシレン、トルエンなど芳香
族溶剤に容易に溶解するものであつた。
実施例1〜3、比較例1〜3
前記の製造例で得られたポリオール樹脂()
〜()を使用し、表1に示される組成の被覆用
樹脂組成物を調製し、所定の焼付け条件で硬化さ
せた。その後、塗膜の物性試験を行つた。その結
果を表−1に示す。
Hereinafter, the present invention will be explained in more detail with reference to Examples.
Note that parts in the examples are based on weight. Production example 1 150 parts of liquid epoxy resin (epoxy equivalent = 410) obtained by adding ethylene oxide to bisphenol A and converting it into glycidyl ether and monoethyl phosphate
The precondensate obtained by mixing 10 parts and stirring at 90°C for 4 hours is referred to as []. Sodium hydroxide was added as a catalyst to 20 parts of bisphenol A to 200 parts of the precondensate, and the mixture was heated and stirred at 200°C for 6 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 2,700. Furthermore, 9 parts of diethanolamine was added, and the mixture was stirred at 100°C for 3 hours to obtain a polyol resin (2). The polyol resin had a hydroxyl equivalent of 360 and was easily soluble in aromatic solvents such as xylene and toluene. Production Example 2 150 parts of a liquid epoxy resin (epoxy equivalent = 300) obtained by adding propylene oxide to bisphenol F and converting it into glycidyl ether were mixed with 15 parts of dibasic potassium phosphate, and the reaction was stirred at 100°C for 6 hours. The precondensate obtained is referred to as []. Add dimethylamine as a catalyst to 50 parts of bisphenol F to 300 parts of precondensate,
Heating and stirring was continued at 150°C for 8 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1300. Further, 35 parts of dibutylamine was added and stirred at 100°C for 3 hours to obtain a polyol resin (2). The hydroxyl equivalent of the polyol resin is 490,
It was easily soluble in aromatic solvents such as xylene and toluene. Production example 3 200 parts of liquid epoxy resin (epoxy equivalent = 520) obtained by adding propylene oxide to bisphenol A and converting it into glycidyl ether and orthophosphoric acid 6
The precondensate obtained was mixed and reacted with stirring at 80°C for 5 hours. Precondensation []
Potassium hydroxide was added as a catalyst to 14 parts of bisphenol F per 200 parts, and the mixture was heated and stirred at 180°C for 6 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 3,800. Furthermore, 8 parts of diisopropanolamine was added and stirred at 100°C for 3 hours to obtain a polyol resin (2). The polyol resin had a hydroxyl equivalent of 450 and was easily soluble in aromatic solvents such as xylene and toluene. Production Example 4 Sodium hydroxide was added as a catalyst to 150 parts of bisphenol A digyl cidyl ether (epoxy equivalent = 480) and 27 parts of bisphenol A, and the mixture was heated and stirred at 180°C for 5 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 2,700. Further, 25 parts of xylene, 25 parts of methyl isobutyl ketone and 8 parts of diethanolamine were added and stirred at 90°C for 3 hours to obtain a polyol resin (2). The hydroxyl equivalent of the polyol resin () is 300, and cannot be dissolved in an aromatic solvent such as xylene or toluene alone, so it is necessary to add a ketone solvent or an alcohol solvent. Production Example 5 150 parts of bisphenol F diglycyl ether (epoxy equivalent = 190) obtained from bisphenol F and epichlorohyridone and bisphenol
Add dimethylamine as a catalyst to 70 parts of F to 150
The mixture was heated and stirred at ℃ for 15 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 2,300. Furthermore, 20 parts of xylene, 20 parts of ethyl isobutyl ketone, and 12 parts of dibutylamine were added, and the mixture was heated and stirred at 100°C for 3 hours to obtain a polyol resin (2). The hydroxyl equivalent of the polyol resin is
290, and cannot be dissolved in aromatic solvents such as xylene or toluene alone, so it is necessary to add a ketone solvent or alcohol solvent. Production Example 6 200 parts of liquid epoxy resin (epoxy equivalent = 520) obtained by adding propylene oxide to bisphenol A and converting it into glycidyl ether and bisphenol
Add potassium hydroxide as a catalyst to 2 parts of F3 to 180
The mixture was heated and stirred at ℃ for 6 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 3,700. Furthermore, 7 parts of diisopropanolamine was added and stirred at 100°C for 3 hours to obtain a polyol resin (2). The polyol resin had a hydroxyl equivalent of 450 and was easily soluble in aromatic solvents such as xylene and toluene. Examples 1 to 3, Comparative Examples 1 to 3 Polyol resin () obtained in the above production example
A coating resin composition having the composition shown in Table 1 was prepared using ~() and cured under predetermined baking conditions. Thereafter, the physical properties of the coating film were tested. The results are shown in Table-1.
【表】
**;商品名;日立化成製 尿素樹脂
焼付条件;無処理冷延鋼板、膜厚10〜12μ、20
0℃×5分
〔効果〕
本発明により、下地処理を行わなくても、鋼板
等に対して優れた機械特性、特に、密着性、折り
曲げ加工性、防蝕性を与え、しかも、有機溶剤に
対する溶解性の良好な被覆用樹脂組成物を得るこ
とができる。[Table] **Product name: Hitachi Chemical urea resin Baking conditions: Untreated cold-rolled steel sheet, film thickness 10-12μ, 20
0°C x 5 minutes [Effects] The present invention provides excellent mechanical properties, especially adhesion, bending workability, and corrosion resistance to steel plates, etc., without any surface treatment, and is soluble in organic solvents. A coating resin composition with good properties can be obtained.
Claims (1)
物の置換又は非置換グリシジルエーテル化物とP
−OH結合を少なくとも1個有するリンの酸、そ
のエステル又は塩との反応から得られる予備縮合
物に二価フエノールを反応せしめ、高分子量のエ
ポキシ樹脂を得、これを更にエポキシ基と反応性
を有するアミノ基を含む化合物と反応せしめて得
られるポリオール樹脂(A)とアミノ樹脂(B)を主体と
する硬化剤とを含有することを特徴とする被覆用
樹脂組成物。1 Substituted or unsubstituted glycidyl etherified product of alkylene oxide adduct of dihydric phenol and P
A precondensate obtained from the reaction of phosphorus having at least one -OH bond with an acid, its ester or salt is reacted with dihydric phenol to obtain a high molecular weight epoxy resin, which is further made reactive with epoxy groups. 1. A resin composition for coating, comprising a polyol resin (A) obtained by reacting with a compound containing an amino group, and a curing agent mainly composed of an amino resin (B).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25788986A JPS63112668A (en) | 1986-10-29 | 1986-10-29 | Coating resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25788986A JPS63112668A (en) | 1986-10-29 | 1986-10-29 | Coating resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63112668A JPS63112668A (en) | 1988-05-17 |
JPH0556786B2 true JPH0556786B2 (en) | 1993-08-20 |
Family
ID=17312591
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25788986A Granted JPS63112668A (en) | 1986-10-29 | 1986-10-29 | Coating resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63112668A (en) |
-
1986
- 1986-10-29 JP JP25788986A patent/JPS63112668A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS63112668A (en) | 1988-05-17 |
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