JPH0553874B2 - - Google Patents
Info
- Publication number
- JPH0553874B2 JPH0553874B2 JP62262837A JP26283787A JPH0553874B2 JP H0553874 B2 JPH0553874 B2 JP H0553874B2 JP 62262837 A JP62262837 A JP 62262837A JP 26283787 A JP26283787 A JP 26283787A JP H0553874 B2 JPH0553874 B2 JP H0553874B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- less
- composition
- phosphoric acid
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 Nitrogen-containing organic compound Chemical class 0.000 claims description 9
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 9
- 235000013824 polyphenols Nutrition 0.000 claims description 9
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 230000003381 solubilizing effect Effects 0.000 claims description 6
- 229940126639 Compound 33 Drugs 0.000 claims 1
- 229940126208 compound 22 Drugs 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000000576 coating method Methods 0.000 description 14
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 229910000398 iron phosphate Inorganic materials 0.000 description 11
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- GIXFALHDORQSOQ-UHFFFAOYSA-N 2,4,6,8-tetrahydroxy-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- AZSFNUJOCKMOGB-UHFFFAOYSA-N cyclotriphosphoric acid Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 229910052742 iron 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
- 229940073584 methylene chloride Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
- C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
Description
〈技術分野〉
この発明はハロゲン化炭化水素溶媒を媒質とす
るリン酸塩化処理組成物に関する。
〈発明の背景〉
従来の塩素化炭化水素溶媒を媒質となるリン酸
塩化処理組成物としては、特公昭39−18219、特
公昭40−5288、特許296451号、特許427732号、特
公昭57−49111あるいは特公昭56−31871等に開示
されている。例えば、特公昭57−49111は金属表
面をリン酸塩化して実質的に水不溶性の被膜を形
成するのに適し、塩化メチレン46重量％以上と、
リン酸を塩化メチレン中に可溶化できる可溶化溶
媒50重量％以下と、リン酸塩化比率のリン酸0.1
〜３重量％と、非プロトン極性有機化合物15重量
％以下と、有機促進化合物１重量％未満と、リン
酸塩化比率のリン酸より量が多く同時に実質的に
水不溶性のリン酸塩化被膜を形成するに十分な量
であり、同時に液相の均質性を保持する量の水と
からなる塩化メチレン含有リン酸塩化組成物であ
り、「クールフオス（Cool−Phos）
」と呼ばれ
ているものである。
この組成物に金属基体を接触させることによつ
てリン酸塩被膜ができる。例えば、この組成物に
鉄からなる被処理物を接触させると、リン酸鉄化
成被膜が形成され、これは塗装のための前処理と
して、塗膜の密着性と耐湿性を大幅に向上させ
る。この塩化メチレン含有リン酸塩化組成物から
形成されるリン酸鉄被膜はそれ以前から市販され
ている水を媒質とするリン酸塩化組成物から形成
されるリン酸鉄被膜と同等の性能を示す。
このリン酸鉄被膜は、ある分野における塗装下
地処理としては十分な性能を示すが、自動車工業
界、家電工業界等で広く使用されている水を媒体
とする組成物から形成されるもう一つの塗装下地
処理被膜であるリン酸亜鉛被膜と比較すると耐食
性の点でリン酸鉄被膜は劣る。リン酸鉄被膜が加
工性に優れているにもかかわらず、これは大きな
欠点である。
このような状況のもとに、本発明者らは鋭意研
究の結果、ハロゲン化炭化水素を媒質とするリン
酸塩化処理の特性を損ねることなく、リン酸亜鉛
被膜の耐食性能と同等の耐食性を示す組成物を発
明した。
〔発明の構成〕
本発明は
ハロゲン化炭化水素溶媒100重量部と、
リン酸 0.1〜７重量部
水 0.2重量部以上、均一相形成限界まで
可溶化溶媒 110重量部以下
窒素含有有機化合物 ０〜22重量部以下
非プロトン極性有機化合物 ０〜33重量部以下
ポリフエノール樹脂
0.1重量部以上作業可能粘度限界まで
からなるリン酸塩化処理組成物を提供する。
ハロゲン化炭化水素溶媒は当技術分野ではよく
知られ、塩化メチレン、トリクロロエテン、テト
ラクロロエテン、トリクロロトリフルオロエタ
ン、等である。
リン酸はリン酸塩化物質であつて、リンの酸素
酸、即ちオルトリン酸、ポリリン酸、トリメタリ
ン酸、テトラメタリン酸等であり、好ましくは、
オルトリン酸、ポリリン酸であり、より好ましく
は、経済的見地からオルトリン酸である。
水は反応促進剤である。
本発明において可溶化剤とは、リン酸化合物を
塩素化炭化水素に溶解させる化合物で、当技術分
野ではよく知られている。具体的には、炭素原子
数６以下のアルコールであり、好ましいものは、
メタノール、エタノール、イソプロパノール、ｎ
−ペンタノール、２−ブトキシエタノール、ｎ−
プロパノール、ｎ−ブタノール、アリルアルコー
ル、sec−ブタノール、ｔ−ブタノール等であり、
好ましいものは、メタノール、エタノール、イソ
プパロノール、ｔ−ブタノールであり、より好ま
しいものは、メタノール、エタノールである。
窒素含有有機化合物は、これも当技術分野では
よく知られており、リン酸塩化処理操作中に被膜
の形成速度を増加する成分であり、有機溶媒より
高い沸点を示す尿素、ピリジン、チオ尿素、ジメ
チルスルホキシド、アミン類、ニトロ基を含む硝
酸化芳香族化合物、エチレンジアミンテトラ酢酸
であり、好ましいものは尿素、ピリジン、チオ尿
素、ジメチルスルホキシド、ジニトロトルエンで
あり、より好ましいものはジメチルスルホキシ
ド、ジニトロトルエンである。窒素含有有機化合
物は必須成分ではない。
非プロトン極性有機化合物も当技術分野ではよ
く知られており、望ましくない粒状被膜の形成を
抑制する表面調整剤であり、有機溶媒より高い沸
点を示す、Ｎ，Ｎ−ジメチルホルムアミド、ジメ
チルスルホキシド、アセトニトリル、アセトン、
ニトロメタン、ニトロベンゼン、テトラメチレン
スルホン等であり、好ましいものは、Ｎ，Ｎ−ジ
メチルホルムアミド、ジメチルスルホキシドであ
り、もつとも好ましいものは、Ｎ，Ｎ−ジメチル
ホルムアミドである。非プロトン極性有機化合物
は必須成分ではない。
以上の成分からなる組成物は基地であつて確立
された技術である。
本発明の特徴は、ポリフエノール樹脂を含むこ
とである。
ポリフエノール樹脂は、
構造式
で表わされる分子量（Mw）2000〜30000のパラ
ビニルフエノールおよびその誘導体、ならびに
構造式
で表わされ、式中Ｒが
で表わされる基であるポリタンニン酸等である。
具体的には、マルカリンカーＭ、マルカリンカー
ＭとMMA、スチレン、またはHEMA等との共
重合体（丸善石油化学(株)）、Ｋ−ポリマーＬ−、
Ｋ−ポリマーＬ−、Ｋ−ポリマーＬ−および
Ｋ−ポリマーＮ−50（帝国化工(株)）等であり、好
ましいものは、マルカリンカーＭ，Ｋ−ポリマー
Ｌ−、Ｋ−ポリマーＬ−、およびＫ−ポリマ
ーＬ−であり、より好ましいものは、マルカリ
ンカーＭ，Ｋ−ポリマーＬ−である。ポリフエ
ノール樹脂は作業が困難になる粘度に達するまで
添加できるが、その限界は大体においてハロゲン
化炭化水素溶媒100重量部につき30重量部である。
本発明の組成物はハロゲン化炭化水素に100重
量部に対して、リン酸好ましくは0.1〜２重量部、
より好ましくは0.1〜0.5重量部；水（好ましくは
イオン交換水）好ましくは0.2重量部〜均一相形
成限界、より好ましくは２重量部〜均一相形成限
界；可溶化溶媒好ましくは５〜50重量部、より好
ましくは10〜40重量部；窒素含有有機化合物好ま
しくは0.001〜10重量部、より好ましくは0.05〜
２重量部、非プロトン極性有機化合物好ましくは
０〜20重量部、より好ましくは0.5〜５重量部；
ポリフエノール樹脂0.1〜10重量部、より好まし
くは0.5〜５重量部を含む。
本発明の組成物は乾燥膜厚が0.01〜5μとなるよ
うに、形成されるリン酸鉄被膜が200〜1000mg／
m2となるように塗布される。浸漬塗布の場合、膜
厚は樹脂濃度と引上げ速度によつて決まり、リン
酸鉄被膜厚さはリン酸濃度と浸漬時間によつて決
まる。
本発明によれば、リン酸鉄付着重量が200〜
1000mg／m2であり、乾燥膜厚が、0.1μであると
き、リン酸亜鉛被膜と同等の耐食性が得られる。
他の樹脂、例えばポリエステル樹脂、エポキシ
樹脂、メラミンアルキド樹脂で乾燥膜厚が0.1μと
なるように処理しても耐食性の向上は見られなか
つた。このことはポリフエノール樹脂が高分子量
である上にその構造中に多量の−OH基が存在す
ることによつて、リン酸塩処理被膜の欠陥部分を
も均一に覆い、さらにそのキレート化作用によつ
て耐食性が向上するものと思われる。
〈発明の具体的開示〉
以下本発明を実施例によつて具体的に説明す
る。
実施例
攪拌機を備えた容器に塩化メチレン100％重量
部、イオン交換水５重量部、可溶化溶媒としてメ
タノール20重量部、ジニトロトルエンを0.1重量
部、非プロトン極性有機化合物としてＮ，Ｎ−ジ
メチルホルムアルデヒド1.5重量部、オルトリン
酸0.2重量部および表に記載するポリフエノール
樹脂をそれぞれ表に記載する量を入れてリン酸塩
化処理組成物（溶液）を調製した。
予め脱脂した鋼板を本処理液にリン酸鉄被膜重
量が200mg／m2〜1000mg／m2となるように15秒〜
10分間浸漬し、該時間後に乾燥膜厚が0.01μ〜5μ
になるようにゆつくりと引き上げた。このように
調製した試料を耐食性試験に供した。
結果は次の表にまとめて示した。表中耐食性試
験はJIS−Ｚ−2371による塩水噴霧試験を示し、
裸耐食性とは塗料を塗装する直前のリン酸塩処理
された鋼板の耐食性を、塗装後耐食性とは塗料が
塗装された鋼板の耐食性を示す。
比較例としてポリフエノール樹脂を所定量含ま
ない組成物、ポリフエノール樹脂以外の樹脂を含
む組成物、市販の水を媒質としたリン酸鉄、リン
酸亜鉛防食組成物の耐食性能を示す。
<Technical Field> The present invention relates to a phosphating composition using a halogenated hydrocarbon solvent as a medium. <Background of the Invention> Conventional phosphatizing compositions using chlorinated hydrocarbon solvents as a medium include Japanese Patent Publications No. 39-18219, Japanese Patent Publication No. 5288-1988, Japanese Patent Publication No. 296451, Japanese Patent No. 427732, and Japanese Patent Publication No. 57-49111. Alternatively, it is disclosed in Japanese Patent Publication No. 56-31871. For example, Japanese Patent Publication No. 57-49111 is suitable for phosphating metal surfaces to form a substantially water-insoluble film, and contains 46% by weight or more of methylene chloride,
50% by weight or less of a solubilizing solvent that can solubilize phosphoric acid in methylene chloride and phosphoric acid with a phosphate conversion ratio of 0.1
~3% by weight, less than 15% by weight of aprotic polar organic compounds, and less than 1% by weight of organic promoting compounds, which are greater in amount than phosphoric acid in the phosphorylation ratio and simultaneously form a substantially water-insoluble phosphatization film. ``Cool-Phos'' is a methylene chloride-containing phosphate composition consisting of a sufficient amount of water to maintain the homogeneity of the liquid phase while at the same time maintaining the homogeneity of the liquid phase. . A phosphate coating is formed by contacting a metal substrate with this composition. For example, when a workpiece made of iron is brought into contact with this composition, an iron phosphate conversion film is formed, which, as a pretreatment for painting, greatly improves the adhesion and moisture resistance of the paint film. Iron phosphate coatings formed from this methylene chloride-containing phosphate composition exhibit performance comparable to iron phosphate coatings formed from previously commercially available water-based phosphate compositions. Although this iron phosphate coating shows sufficient performance as a paint base treatment in certain fields, it is also a coating formed from a water-based composition that is widely used in the automobile industry, home appliance industry, etc. Iron phosphate coatings are inferior in terms of corrosion resistance when compared to zinc phosphate coatings, which are used as prepainting coatings. Despite the excellent processability of iron phosphate coatings, this is a major drawback. Under these circumstances, the inventors of the present invention have conducted intensive research and have found that corrosion resistance equivalent to that of zinc phosphate coatings can be achieved without impairing the characteristics of phosphating treatment using halogenated hydrocarbons as a medium. The following composition was invented. [Structure of the Invention] The present invention consists of 100 parts by weight of a halogenated hydrocarbon solvent, 0.1 to 7 parts by weight of phosphoric acid, 0.2 parts by weight or more of water, up to the limit of homogeneous phase formation, 110 parts by weight or less of a solubilizing solvent, and 0 to 22 parts by weight of a nitrogen-containing organic compound. Parts by weight or less Aprotic polar organic compound 0 to 33 parts by weight or less Polyphenol resin
Provided is a phosphating composition comprising 0.1 part by weight or more up to the workable viscosity limit. Halogenated hydrocarbon solvents are well known in the art and include methylene chloride, trichloroethene, tetrachloroethene, trichlorotrifluoroethane, and the like. The phosphoric acid is a phosphoric acid, and is an oxygen acid of phosphorus, such as orthophosphoric acid, polyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, etc., and is preferably
These include orthophosphoric acid and polyphosphoric acid, and more preferably orthophosphoric acid from an economic standpoint. Water is a reaction accelerator. In the present invention, a solubilizer is a compound that dissolves a phosphoric acid compound in a chlorinated hydrocarbon, and is well known in the art. Specifically, alcohols having 6 or less carbon atoms are preferred;
methanol, ethanol, isopropanol, n
-pentanol, 2-butoxyethanol, n-
Propanol, n-butanol, allyl alcohol, sec-butanol, t-butanol, etc.
Preferred are methanol, ethanol, isoproparonol, and t-butanol, and more preferred are methanol and ethanol. Nitrogen-containing organic compounds, also well known in the art, are components that increase the rate of film formation during phosphating operations, and include urea, pyridine, thiourea, which have higher boiling points than organic solvents. Dimethyl sulfoxide, amines, nitro aromatic compounds containing nitro groups, ethylenediaminetetraacetic acid, preferred are urea, pyridine, thiourea, dimethyl sulfoxide, dinitrotoluene, and more preferred are dimethyl sulfoxide and dinitrotoluene. be. Nitrogen-containing organic compounds are not essential components. Aprotic polar organic compounds are also well known in the art and are surface modifiers that inhibit the formation of undesirable particulate films, such as N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile, which have higher boiling points than organic solvents. ,acetone,
Nitromethane, nitrobenzene, tetramethylene sulfone, etc. are preferred, and N,N-dimethylformamide and dimethylsulfoxide are preferred, with N,N-dimethylformamide being particularly preferred. Aprotic polar organic compounds are not essential components. The composition consisting of the above components is the basis and is an established technology. A feature of the present invention is that it includes a polyphenol resin. Polyphenol resin has the structural formula Paravinylphenol and its derivatives with a molecular weight (Mw) of 2000 to 30000, and the structural formula In the formula, R is Polytannic acid, which is a group represented by:
Specifically, Maruka Linker M, a copolymer of Maruka Linker M and MMA, styrene, HEMA, etc. (Maruzen Petrochemical Co., Ltd.), K-polymer L-,
K-Polymer L-, K-Polymer L-, K-Polymer N-50 (Teikoku Kako Co., Ltd.), etc., and preferred ones are Maruka Linker M, K-Polymer L-, K-Polymer L-, and K-polymer L-, and more preferred is Maruka Linker M, K-polymer L-. Polyphenolic resins can be added up to a viscosity that becomes difficult to work with, but the limit is generally 30 parts by weight per 100 parts by weight of halogenated hydrocarbon solvent. The composition of the present invention preferably contains phosphoric acid, preferably 0.1 to 2 parts by weight, per 100 parts by weight of halogenated hydrocarbon.
More preferably 0.1 to 0.5 parts by weight; water (preferably ion-exchanged water) preferably 0.2 parts by weight to the limit of homogeneous phase formation, more preferably 2 parts by weight to the limit of homogeneous phase formation; solubilizing solvent preferably 5 to 50 parts by weight , more preferably 10 to 40 parts by weight; nitrogen-containing organic compound preferably 0.001 to 10 parts by weight, more preferably 0.05 to 40 parts by weight
2 parts by weight, preferably 0 to 20 parts by weight, more preferably 0.5 to 5 parts by weight of an aprotic polar organic compound;
It contains 0.1 to 10 parts by weight of polyphenolic resin, more preferably 0.5 to 5 parts by weight. The composition of the present invention has an iron phosphate coating of 200 to 1000 mg/min so that the dry film thickness is 0.01 to 5μ.
It is applied so that it is m 2 . In the case of dip coating, the film thickness is determined by the resin concentration and the pull rate, and the iron phosphate coating thickness is determined by the phosphoric acid concentration and soak time. According to the present invention, the iron phosphate deposited weight is 200~
When it is 1000 mg/m 2 and the dry film thickness is 0.1 μ, corrosion resistance equivalent to that of a zinc phosphate film can be obtained. Even when treated with other resins such as polyester resin, epoxy resin, and melamine alkyd resin so that the dry film thickness was 0.1μ, no improvement in corrosion resistance was observed. This is because the polyphenol resin has a high molecular weight and a large amount of -OH groups in its structure, which allows it to uniformly cover the defective areas of the phosphate treatment film and further enhances its chelating effect. It is thought that this improves corrosion resistance. <Specific Disclosure of the Invention> The present invention will be specifically described below with reference to Examples. Example In a container equipped with a stirrer, 100% by weight methylene chloride, 5 parts by weight of ion-exchanged water, 20 parts by weight of methanol as a solubilizing solvent, 0.1 part by weight of dinitrotoluene, and N,N-dimethylformaldehyde as an aprotic polar organic compound. A phosphating treatment composition (solution) was prepared by adding 1.5 parts by weight of orthophosphoric acid, 0.2 parts by weight of orthophosphoric acid, and the amounts of polyphenol resins shown in the table. Apply the pre-degreased steel plate to this treatment solution for 15 seconds or more so that the weight of the iron phosphate coating is 200mg/ m2 to 1000mg/ m2 .
Immerse for 10 minutes, and after that time the dry film thickness is 0.01μ~5μ
I slowly pulled it up so that it was. The samples prepared in this manner were subjected to a corrosion resistance test. The results are summarized in the table below. The corrosion resistance test in the table indicates the salt spray test according to JIS-Z-2371.
Bare corrosion resistance refers to the corrosion resistance of a phosphate-treated steel plate immediately before coating with paint, and post-painting corrosion resistance refers to the corrosion resistance of a steel plate coated with paint. As comparative examples, the corrosion resistance performance of a composition that does not contain a predetermined amount of polyphenol resin, a composition that contains a resin other than polyphenol resin, and a commercially available water-based iron phosphate and zinc phosphate anticorrosion composition is shown.
【表】【table】
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62262837A JPH01108385A (en) | 1987-10-20 | 1987-10-20 | Phosphating composition containing halogenated hydrocarbon as medium |
| KR1019880013589A KR930001014B1 (en) | 1987-10-20 | 1988-10-19 | Phosphating composition containing halogenated hydrocarbon as medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62262837A JPH01108385A (en) | 1987-10-20 | 1987-10-20 | Phosphating composition containing halogenated hydrocarbon as medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01108385A JPH01108385A (en) | 1989-04-25 |
| JPH0553874B2 true JPH0553874B2 (en) | 1993-08-11 |
Family
ID=17381306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62262837A Granted JPH01108385A (en) | 1987-10-20 | 1987-10-20 | Phosphating composition containing halogenated hydrocarbon as medium |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH01108385A (en) |
| KR (1) | KR930001014B1 (en) |
-
1987
- 1987-10-20 JP JP62262837A patent/JPH01108385A/en active Granted
-
1988
- 1988-10-19 KR KR1019880013589A patent/KR930001014B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR890006852A (en) | 1989-06-16 |
| KR930001014B1 (en) | 1993-02-12 |
| JPH01108385A (en) | 1989-04-25 |
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