JPS6121575B2 - - Google Patents
Info
- Publication number
- JPS6121575B2 JPS6121575B2 JP12423682A JP12423682A JPS6121575B2 JP S6121575 B2 JPS6121575 B2 JP S6121575B2 JP 12423682 A JP12423682 A JP 12423682A JP 12423682 A JP12423682 A JP 12423682A JP S6121575 B2 JPS6121575 B2 JP S6121575B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- epoxy
- resin
- rust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- -1 2-imidazolyl group Chemical group 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
- 239000003973 paint Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 7
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical group CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 7
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 241000208227 Toxicodendron vernicifluum Species 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 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
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002929 natural lacquer Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 本発明は防錆用塗料組成物に関する。[Detailed description of the invention] The present invention relates to a rust-preventing coating composition.
ウオツシユプライマーを含み現在使用されてい
る防錆用塗料は防錆顔料として酸化鉛、硫酸鉛、
クロム酸塩等の重金属を塗料中に含有し、その排
気及び排水は公害汚染の1つの原因とされてい
る。最近、特に注目を浴びている自己研磨型の船
底塗料も例外にもれず防錆顔料として重金属を含
有し海洋汚染の原因となる。 Rust-preventing paints currently in use, including wash primers, contain lead oxide, lead sulfate, and lead sulfate as rust-preventing pigments.
Paints contain heavy metals such as chromates, and their exhaust and wastewater are considered to be one of the causes of pollution. Self-polishing ship bottom paints, which have recently attracted particular attention, contain heavy metals as anti-corrosion pigments and cause marine pollution.
上記塗料以外に、重金属ではない金属亜鉛、ア
ルミ、ステンレス粉末あるいは鱗片状酸化鉄のよ
うなより毒性の少ない金属を防錆顔料として含む
塗料もあるが、この場合には斯かる金属を多量に
含有しているために塗装が困難であつたり、ある
いは薄膜に塗装することができず使用量が多くな
るという欠陥を有している。 In addition to the above-mentioned paints, there are also paints that contain less toxic metals such as non-heavy metals such as zinc, aluminum, stainless steel powder, or scaly iron oxide as anti-rust pigments, but in these cases, they contain large amounts of such metals. It has the disadvantage that it is difficult to coat because of the coating, or it cannot be coated in a thin film, resulting in a large amount of paint being used.
本発明の目的は毒性の高い重金属は勿論のこと
毒性の低い金属を使用することなく極めて優れた
防錆力を有する塗料を提供することにある。 An object of the present invention is to provide a coating material that has extremely excellent antirust properties without using not only highly toxic heavy metals but also lowly toxic metals.
また本発明の目的は5〜10ミクロン程度の薄膜
にも塗装可能で且つ極めて優れた防錆力を有する
塗料を提供することにある。 Another object of the present invention is to provide a paint that can be applied to a thin film of about 5 to 10 microns and has extremely excellent antirust properties.
本発明はエポキシ当量900〜3000のエポキシ樹
脂100重量部、1価もしくは2価のフエノール樹
脂5〜40重量部及び2位に置換基として水素又は
炭素数1〜4のアルキル基を有する2−イミダゾ
リル基含有化合物0.5〜6重量部からなる共縮合
物に、金属イオンと結合してキレート化合物を形
成するアミノフエノール及び8−オキシキノリン
から選ばれた少なくとも1種のキレート試薬0.3
〜5重量部を配合したことを特徴とする防錆用塗
料組成物に係る。 The present invention comprises 100 parts by weight of an epoxy resin having an epoxy equivalent of 900 to 3000, 5 to 40 parts by weight of a monovalent or divalent phenol resin, and 2-imidazolyl having hydrogen or an alkyl group having 1 to 4 carbon atoms as a substituent at the 2-position. A cocondensate consisting of 0.5 to 6 parts by weight of a group-containing compound is mixed with 0.3 parts of at least one chelating reagent selected from aminophenol and 8-oxyquinoline that binds with metal ions to form a chelate compound.
It relates to a rust-preventing coating composition characterized in that it contains ~5 parts by weight.
以下本発明について説明する。エポキシ樹脂は
それ自身で良好な金属面への密着性を有し、酸、
アルカリ等への耐薬品性も良く、防錆力が優れて
いる。本発明では斯かるエポキシ樹脂のうち、特
にエポキシ当量が900〜3000のものが好適に使用
される。具体的にはエピコート1004、1007、1009
(シエル化学社製)等が例示できる。 The present invention will be explained below. Epoxy resin itself has good adhesion to metal surfaces, and
It also has good chemical resistance to alkalis and other substances, and has excellent rust prevention properties. In the present invention, among such epoxy resins, those having an epoxy equivalent of 900 to 3000 are particularly preferably used. Specifically Epicote 1004, 1007, 1009
(manufactured by Ciel Kagaku Co., Ltd.), etc. can be exemplified.
本発明においてフエノール樹脂としては1価も
しくは2価のフエノール類、例えばフエノール、
クレゾール、キシレノール、カテコール、レゾル
シン等と、アルデヒド類、例えばホルムアルデヒ
ド、アセトアルデヒド、フルフラール等から得ら
れる樹脂およびそれらの変性樹脂が使用され、特
に2価フエノールは天然の漆をはじめとし、2価
フエノールに側鎖を結合させた例えばアルキルカ
テコール等は、特に金属と結合してキレート化合
物を形成して金属面を保護する作用が大きい。こ
のようなフエノール樹脂はエポキシ樹脂100部
(重量部、以下同様)に対して5〜40部使用する
のが好ましい。 In the present invention, the phenolic resin includes monovalent or divalent phenols, such as phenol,
Resins obtained from cresol, xylenol, catechol, resorcinol, etc. and aldehydes such as formaldehyde, acetaldehyde, furfural, etc., and their modified resins are used. In particular, divalent phenols are used in natural lacquer, etc. For example, alkylcatechols with linked chains bond with metals to form chelate compounds and have a strong effect of protecting metal surfaces. It is preferable to use 5 to 40 parts of such phenolic resin based on 100 parts (by weight, the same applies hereinafter) of the epoxy resin.
次に2−イミダゾリル基含有化合物としてはイ
ミダゾールの2位に置換基として水素、炭素数1
〜12のアルキル基、アリール基を有する化合物を
使用することができる。好ましい具体例としては
イミダゾール、2−メチルイミダゾール、2−ブ
チルイミダゾール、2−ウンデシルイミダゾー
ル、2−フエニルイミダゾール等を例示できる。
斯かる2−イミダゾリル基含有化合物はそれ自身
で金属キレートを形成すると共にエポキシ樹脂の
硬化剤として作用し、通常エポキシ樹脂100部に
対して0.5〜6重量部用いられる。 Next, as a compound containing a 2-imidazolyl group, hydrogen is added as a substituent at the 2-position of imidazole, and the number of carbon atoms is 1.
Compounds having ~12 alkyl, aryl groups can be used. Preferred specific examples include imidazole, 2-methylimidazole, 2-butylimidazole, 2-undecylimidazole, and 2-phenylimidazole.
Such a 2-imidazolyl group-containing compound forms a metal chelate by itself and acts as a curing agent for the epoxy resin, and is usually used in an amount of 0.5 to 6 parts by weight per 100 parts of the epoxy resin.
本発明においてはエポキシ樹脂本来の優れた性
質を利用し、更に硬化剤としてフエノール樹脂及
びそれ自体でも金属キレートを形成して金属面を
保護する2−イミダゾリル基を含有する化合物を
エポキシ硬化剤として使用しエポキシ樹脂の性能
を向上させる。エポキシ樹脂の硬化剤としてはア
ミン類、ポリアミド樹脂、酸あるいは酸無水物な
どがあり、アミン類にはジエチレントリアミンの
如く金属キレートを形成し易いものがあるが、エ
ポキシ樹脂との反応が激しく、保存中に硬化が進
んでゲル化を起こし塗料を安定性良く保存するこ
とができない。またポリアミド樹脂、酸あるいは
酸無水物をエポキシ硬化剤として使用すると硬化
剤中の酸成分のためか防錆効果が劣る。 In the present invention, the inherent excellent properties of epoxy resin are utilized, and a phenol resin and a compound containing a 2-imidazolyl group, which itself forms a metal chelate and protects the metal surface, are used as the epoxy curing agent. and improve the performance of epoxy resins. Curing agents for epoxy resins include amines, polyamide resins, acids, and acid anhydrides. Some amines, such as diethylenetriamine, easily form metal chelates, but they react violently with epoxy resins, and during storage. As the curing progresses, gelation occurs, making it impossible to store the paint with good stability. Furthermore, when a polyamide resin, acid, or acid anhydride is used as an epoxy curing agent, the rust prevention effect is poor, probably due to the acid component in the curing agent.
本発明では上記エポキシ樹脂、フエノール樹脂
及び2−イミダゾリル基含有化合物を共縮合さ
せ、エポキシ樹脂の特性を向上させた共縮合物を
得、次に金属とキレート化合物を形成するキレー
ト試薬を配合することにより共縮合物の特性を更
に向上させて、何ら重金属等を用いることなく防
錆力の高い防錆塗料を得ることができる。 In the present invention, the above-mentioned epoxy resin, phenol resin, and 2-imidazolyl group-containing compound are co-condensed to obtain a co-condensate with improved properties of the epoxy resin, and then a chelating reagent that forms a chelate compound with a metal is added. By further improving the properties of the co-condensate, it is possible to obtain a rust-preventing paint with high rust-preventing power without using any heavy metals or the like.
本発明で用いられる上記キレート試薬としては
各種の試薬のうち、特にアミノフエノール、8−
オキシキノリン等の水酸基及びアミノ基を同一分
子内に有するキレート試薬を用いることが必要で
ある。ここでアミノ基は第1級アミノ基、第2級
アミノ基又は第3級アミノ基のいずれであつても
良い。斯かるキレート試薬を使用することにより
塗料の安定性及び防錆効果を著しく向上せしめる
ことができる。他のキレート試薬として例えばサ
リチル酸、マレイン酸等の酸基を含むものがある
が、これらはその防錆効果は低い。またアミノ基
を2個以上有するキレート試薬はエポキシの硬化
剤として作用し塗料の安定性を悪くする欠点があ
る。更にキレート試薬として2価及び3価のフエ
ノール類を使用した場合、斯かるフエノール類は
樹脂化していないために着色化現象が甚しく、ま
た溶剤に溶解し易く、特に上塗り塗料を塗布した
場合にブリード現象を起こし上塗り塗料が変色す
る欠点を有している。 Among various reagents, aminophenol, 8-
It is necessary to use a chelating reagent having a hydroxyl group and an amino group in the same molecule, such as oxyquinoline. The amino group here may be any of a primary amino group, a secondary amino group, or a tertiary amino group. By using such a chelating reagent, the stability and antirust effect of the paint can be significantly improved. Other chelating reagents include those containing acid groups, such as salicylic acid and maleic acid, but these have low antirust effects. In addition, chelating reagents having two or more amino groups have the disadvantage of acting as curing agents for epoxy and impairing the stability of paints. Furthermore, when divalent and trivalent phenols are used as chelating reagents, the phenols are not converted into resins, so the coloring phenomenon is severe, and they are easily dissolved in solvents, especially when a top coat is applied. It has the disadvantage of causing a bleed phenomenon and discoloring the top coat.
本発明では上記キレート試薬をエポキシ樹脂
100部に対して0.3〜5部配合するのが好ましい。
本発明の塗料組成物の製造の1例を示せば、先ず
上記したエポキシ樹脂、フエノール樹脂を有機溶
剤中に加えて加熱撹拌し溶解させ、次に2−イミ
ダゾリル基含有化合物を加えて加熱、撹拌して反
応させ共縮合物を得る。この共縮合物の溶液に本
発明で使用するキレート試薬を添加し溶解させる
と目的とする塗料組成物が得られる。有機溶剤と
しては種々のものを使用できるが、メチルセロソ
ルブ、エチルセロソルブ、ブチルセロソルブ等の
セロソルブ系溶剤、アセトン、メチルエチルケト
ン等のケトン系溶剤、トルエン、キシレン等の芳
香族炭化水素系溶剤等が好ましい。またその他の
公知の塗料用添加剤を加えることもできる。 In the present invention, the above chelating reagent is used as an epoxy resin.
It is preferable to mix 0.3 to 5 parts per 100 parts.
To give an example of manufacturing the coating composition of the present invention, first, the above-mentioned epoxy resin and phenol resin are added to an organic solvent and dissolved by heating and stirring, and then a 2-imidazolyl group-containing compound is added and heated and stirred. and react to obtain a co-condensate. When the chelating reagent used in the present invention is added and dissolved in the solution of this cocondensate, the desired coating composition is obtained. Various organic solvents can be used, but preferred are cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene and xylene. Other known paint additives may also be added.
以下に実施例を挙げて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 1
エピコート1007(エポキシ当量1750〜2100、シ
エル化学)500g、フエノール樹脂(レジトツプ
PS−2780、淡黄色塊状、郡栄化学)50g、トル
オール775g、エチルセロソルブ775gを3の3
口フラスコに入れ、湯煎上で70〜80℃に保持し静
かに撹拌して溶解する。Example 1 500 g of Epicote 1007 (epoxy equivalent 1750-2100, Ciel Chemical), phenol resin (Resistop)
PS-2780, light yellow lumps, Gunei Chemical) 50g, toluol 775g, ethyl cellosolve 775g 3/3
Pour into a neck flask, keep at 70-80℃ over a water bath, and stir gently to dissolve.
エピコート1007及びフエノール樹脂が完全に溶
解したら、イミダゾール4gを添加し95〜98℃に
加熱し、その温度で約3時間撹拌しながら反応さ
せる。その間にイミダゾールとエポキシ樹脂は殆
んど反応し、フエノール樹脂とエピコート1007の
相溶性が悪く幾分混濁しているが反応が進むにつ
れ透明性が増加し、2〜3時間の反応後は完全に
透明になる。これにパラアミノフエノール5gを
添加溶解し冷却すると2100gの塗料組成物を得
る。 When Epicote 1007 and the phenolic resin are completely dissolved, 4 g of imidazole is added, heated to 95-98°C, and reacted at that temperature with stirring for about 3 hours. During that time, most of the imidazole and epoxy resin have reacted, and the compatibility between the phenolic resin and Epicote 1007 is poor, making it somewhat cloudy, but as the reaction progresses, the transparency increases, and after 2 to 3 hours of reaction, it becomes completely cloudy. Becomes transparent. Add and dissolve 5 g of para-aminophenol and cool to obtain 2100 g of a coating composition.
この組成物100gをとりトルオール25g、エチ
ルセロソルブ25gを加え、溶剤脱脂した軟鋼板に
塗装すると乾燥塗膜は5〜10ミクロンであつた。
更に室温にて4日間乾燥又は60℃×30分又は120
℃×20分の乾燥をした試験片に就いて塩水噴霧試
験(5%食塩水、35℃)144時間の結果、ナイフ
にて切目を入れた部分よりのセロハンテープ剥離
巾は何れも1mm以内で防錆顔料に重金属を使用し
た2液性ウオツシユプライマーと同等であつた。 When 100 g of this composition was added with 25 g of toluene and 25 g of ethyl cellosolve and applied to a mild steel plate that had been degreased with a solvent, the dry coating film was 5 to 10 microns thick.
Further dry at room temperature for 4 days or 60℃ x 30 minutes or 120℃
As a result of a salt spray test (5% saline solution, 35°C) for 144 hours on a test piece that had been dried for 20 minutes at ℃, the peeling width of the cellophane tape from the part cut with a knife was within 1 mm. It was equivalent to a two-component wash primer that uses heavy metals as antirust pigments.
金属素地として軟鋼板、アルミ板、銅板、ステ
ンレス板、亜鉛引き鋼板等を使用して塗料組成物
を塗装し室温にて20分乾燥後、更にメラミンアル
キド塗料をかけ、120℃×20分焼付乾燥した試験
片を沸謄水中1時間浸漬した後に調べたが、発泡
等の外観異状はなく、密着性にも異状は認められ
ない。 Apply the paint composition to a mild steel plate, aluminum plate, copper plate, stainless steel plate, galvanized steel plate, etc. as a metal base, dry at room temperature for 20 minutes, then apply melamine alkyd paint and bake dry for 20 minutes at 120℃. The test pieces were immersed in boiling water for 1 hour and then examined, but there were no abnormalities in appearance such as foaming, and no abnormalities in adhesion were observed.
実施例 2
中国産生漆の主成分はウルシオールでこれは2
価フエノールに側鎖のついた典型的な天然のアル
キル化2価フエノールである。この中国産生漆に
トルオールを加え撹拌静置すると上部に褐色のト
ルオール相と下部に水を含んだ水相に分離され
る。上部のトルオール相は生漆の主成分ウルシオ
ールを含んだトルオールでこの溶液を減圧蒸留す
るとウルシオールの粘稠液を得る。ウルシオール
200gにウロトロピン10gを加え加熱すると約90
℃で発泡し反応が始まる。120〜125℃で30分間撹
拌すると発泡は完全になくなり、高温時粘稠、室
温時固体のウルシオール樹脂液を得る。この樹脂
液はウルシオールとホルマリンがアンモニア触媒
下に反応したもので、加熱、アンモニアのために
生漆独特の漆カブレが少なくなりその後の操作が
容易になる。Example 2 The main component of Chinese lacquer is urushiol, which is 2
It is a typical natural alkylated divalent phenol with a side chain attached to the monovalent phenol. When toluene is added to this Chinese lacquer and left to stand while stirring, it separates into a brown toluol phase at the top and an aqueous phase containing water at the bottom. The upper toluol phase contains toluol, the main component of raw lacquer, and when this solution is distilled under reduced pressure, a viscous liquid of urushiol is obtained. Urushiol
When you add 10g of urotropin to 200g and heat it, it becomes about 90%
The reaction begins with foaming at ℃. After stirring at 120 to 125°C for 30 minutes, foaming completely disappears, and a urushiol resin liquid that is viscous at high temperatures and solid at room temperature is obtained. This resin liquid is made by reacting urushiol and formalin in the presence of an ammonia catalyst, and due to the heating and ammonia, the lacquer flaking characteristic of raw lacquer is reduced, making subsequent operations easier.
エピコート1009、(エポキシ当量2400〜3000)
500g、上記のウルシオール樹脂液75g、トルオ
ール800g、エチルセロソルブ800gを3の3口
フラスコに入れ湯煎上で70〜80℃に保持し撹拌溶
解する。エピコート1009及びウルシオール樹脂液
が完全に溶解したら2−メチルイミダゾール4g
を添加し、95〜98℃に加熱しその温度で約3時間
撹拌反応させる。反応後8−オキシキノリン5g
を加え溶解すると2150gの塗料組成物を得る。こ
の塗料組成物を軟鋼板に塗装して塩水噴霧試験を
行つた結果、実施例1と同じ結果が得られた。 Epicote 1009, (epoxy equivalent 2400-3000)
Put 500 g of the above urushiol resin solution, 800 g of toluol, and 800 g of ethyl cellosolve into a 3-necked flask from step 3, maintain the temperature at 70 to 80°C over a hot water bath, and stir to dissolve. When Epicote 1009 and urushiol resin liquid are completely dissolved, add 4 g of 2-methylimidazole.
is added, heated to 95-98°C, and stirred and reacted at that temperature for about 3 hours. 5g of 8-oxyquinoline after reaction
Add and dissolve to obtain 2150g of paint composition. When this coating composition was applied to a mild steel plate and a salt spray test was conducted, the same results as in Example 1 were obtained.
比較例 1
アミノフエノールを添加しない他は実施例1と
同様にして塗料組成物を得た。Comparative Example 1 A coating composition was obtained in the same manner as in Example 1 except that aminophenol was not added.
この塗料組成物を実施例1と同様にして軟鋼板
に乾燥膜厚5〜10ミクロンに塗布乾燥した試験片
に就いて、同様に塩水噴霧試験144時間を行つた
ところ、ナイフカツト部のセロハンテープによる
剥離巾は6mmであつた。 This coating composition was applied to a mild steel plate in the same manner as in Example 1 to a dry film thickness of 5 to 10 microns, and a test piece was subjected to a salt spray test for 144 hours. The peeling width was 6 mm.
また実施例1と同様に上記塗料組成物を塗装、
乾燥後、メラミンアルキド塗料をかけ、120℃×
20分焼付乾燥した試験片を沸謄水中1時間浸漬し
た試験片について、ナイフで1mm間隔で縦、横に
カツトを入れ100ケのゴバン目を作り、セロハン
テープで剥離し残存するゴバン目の数を数えると
0/100であつた。一方キレート剤を添加した実
施例1のものは100/100で全く異状がなかつた。 Further, in the same manner as in Example 1, the above coating composition was applied,
After drying, apply melamine alkyd paint and heat at 120℃
The test piece was baked and dried for 20 minutes and immersed in boiling water for 1 hour. Using a knife, make cuts vertically and horizontally at 1 mm intervals to make 100 goblets. Peel off with cellophane tape to determine the number of remaining goblets. When I counted it, it was 0/100. On the other hand, the sample of Example 1 in which a chelating agent was added had a score of 100/100 and had no abnormalities at all.
Claims (1)
量部、1価もしくは2価のフエノール樹脂5〜40
重量部及び2位に置換基として水素又は炭素数1
〜4のアルキル基を有する2−イミダゾリル基含
有化合物0.5〜6重量部からなる共縮合物に、金
属イオンと結合してキレート化合物を形成するア
ミノフエノール及び8−オキシキノリンから選ば
れた少なくとも1種のキレート試薬0.3〜5重量
部を配合したことを特徴とする防錆用塗料組成
物。1 100 parts by weight of epoxy resin with an epoxy equivalent of 900 to 3000, 5 to 40 parts of monovalent or divalent phenolic resin
Hydrogen or carbon number 1 as a substituent in weight part and 2-position
A co-condensate consisting of 0.5 to 6 parts by weight of a 2-imidazolyl group-containing compound having ~4 alkyl groups, at least one selected from aminophenol and 8-oxyquinoline that binds with metal ions to form a chelate compound. 1. A rust-preventing coating composition comprising 0.3 to 5 parts by weight of a chelating reagent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12423682A JPS5936165A (en) | 1982-07-15 | 1982-07-15 | Coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12423682A JPS5936165A (en) | 1982-07-15 | 1982-07-15 | Coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5936165A JPS5936165A (en) | 1984-02-28 |
JPS6121575B2 true JPS6121575B2 (en) | 1986-05-28 |
Family
ID=14880335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12423682A Granted JPS5936165A (en) | 1982-07-15 | 1982-07-15 | Coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5936165A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992013902A1 (en) * | 1991-02-05 | 1992-08-20 | Kansai Paint Company, Limited | Film-forming chelating resin, production thereof, use thereof, and formation of electrodeposition coating |
-
1982
- 1982-07-15 JP JP12423682A patent/JPS5936165A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992013902A1 (en) * | 1991-02-05 | 1992-08-20 | Kansai Paint Company, Limited | Film-forming chelating resin, production thereof, use thereof, and formation of electrodeposition coating |
Also Published As
Publication number | Publication date |
---|---|
JPS5936165A (en) | 1984-02-28 |
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