JPH0454747B2 - - Google Patents
Info
- Publication number
- JPH0454747B2 JPH0454747B2 JP22186884A JP22186884A JPH0454747B2 JP H0454747 B2 JPH0454747 B2 JP H0454747B2 JP 22186884 A JP22186884 A JP 22186884A JP 22186884 A JP22186884 A JP 22186884A JP H0454747 B2 JPH0454747 B2 JP H0454747B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- chromate
- copper
- coupling agent
- film
- 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
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 229910000831 Steel Inorganic materials 0.000 claims description 26
- 239000010959 steel Substances 0.000 claims description 26
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229920006026 co-polymeric resin Polymers 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000004649 discoloration prevention Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- -1 2-ethylhexyl Chemical group 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- XTUHPOUJWWTMNC-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)chromium Chemical compound [Co+2].[O-][Cr]([O-])(=O)=O XTUHPOUJWWTMNC-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- YFDWDAIVRZETEB-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium manganese Chemical compound [Mn].[Cr](=O)(=O)(O)O[Cr](=O)(=O)O YFDWDAIVRZETEB-UHFFFAOYSA-L 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 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
- 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004243 sweat Anatomy 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 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
- 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
- C23C22/05—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 aqueous solutions
- C23C22/06—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 aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—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 aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/26—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 aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
- C23C22/28—Macromolecular 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
（産業上の利用分野）
本発明は銅めつき鋼板表面に直接もしくはクロ
メート皮膜を介して耐食性に優れた樹脂皮膜を形
成して、銅めつきの欠点である耐変色性、耐指紋
性などを改善した銅めつき鋼板に関する。
（従来技術）
銅めつき鋼板は優れた外観を有しているが、大
気中で表面が酸化されて褐色に変色しやすく、ま
た取り扱い時に傷や指紋が付くと目立ちやすいと
いう欠点がある。このため従来銅めつき鋼板製造
の際には変色防止処理としてクロメート処理、ベ
ンゾトリアゾール処理、ベンゾトリアゾール誘導
体処理などを、また傷や指紋防止処理として保護
フイルム張り付けやストリツパブルペイント塗布
などを行つていた。
（発明が解決しようとする問題点）
しかしながらクロメート処理やベンゾトリアゾ
ール処理などを行つても短時間しか変色を防止す
ることが出来ないものであつた。一方保護フイル
ム張り付けやストリツパブルペイント塗布などを
行えば取り扱い時の傷や指紋付着は防止すること
ができたが、処理費用が高く、加工後それらを剥
がすのに多くの労力と時間を必要としていた。ま
た保護フイルムやストリツパブルペイントには変
色防止作用がないため下にクロメート処理やベン
ゾトリアゾール処理などの変色防止処理を施す必
要があつた。このため傷や指紋付着を防止するに
は二重処理が必要であつた。
一方二重処理にはなるが、保護フイルム張り付
けやストリツパブルペイント塗布などより安価な
方法として変色防止処理後に水に可溶な樹脂の水
溶液で樹脂皮膜を形成する方法が考えられる。し
かしこの方法で耐変色性をさらに向上させるには
変色処理を強化するしか方法がないため、耐変色
性を向上させるには限界があつた。このため耐変
色性をさらに向上させるには樹脂皮膜の耐食性を
向上させ、耐変色性を向上させる必要があつた。
樹脂皮膜の耐食性を向上させる工業的安価な方
法としては樹脂皮膜中に６価クロムを含有させる
方法が考えられるが、この方法により６価クロム
を含有させるには６価クロムを含有する樹脂皮膜
処理液で処理する必要がある。しかし従来このよ
うな樹脂皮膜処理後に使用されていた樹脂は水酸
基により親水性を持たせたものであつたため、処
理液に６価クロムを含有させるのに無水クロム酸
やクロム酸塩を添加すると樹脂分子の水酸基が酸
化されて、処理液はゲル化し、鋼板に塗布できな
くなり、また６価クロムも３価クロムに還元され
て耐変色性を発揮しなくなつてしまうものであつ
た。このため従来樹脂皮膜中に６価クロムを含有
させることは困難であつた。
（問題点を解決するための手段）
本発明は従来このように困難であつた樹脂皮膜
中への６価クロムの含有を可能にした有機被覆銅
めつき鋼板を提供するものである。
本発明の銅めつき鋼板は被覆する樹脂皮膜の樹
脂を水酸基を有しない水分散性共重合体にするこ
とにより処理液段階で樹脂がクロム酸により酸化
されないようにするとともに、その共重合体の酸
価調整、シランカツプリング剤または／およびチ
タネートカツプリング剤の配合により樹脂皮膜の
耐水性、密着性および物性などを向上させたもの
である。すなわち本発明は樹脂皮膜の樹脂として
(A)一般式CH2＝CR1−COOR2（式中R1はＨ、
CH3，R2はＣが１〜８のアルキル基）で示され
る単量体の１種または２種以上１〜95重量％と、
(B)α、β不飽和カルボン酸単量体３〜20重量％
と、(C)これらの単量体と共重合可能な単量体0.1
〜50重量％とを［但し(A)、(B)および(C)の合計は
100重量％］乳化重合して得られる固形分当たり
の酸価10〜200の共重合体樹脂にシランカツプリ
ング剤または／およびチタネートカツプリング剤
を配合したものを用いるのである。
ここで共重合体樹脂を構成する一般式CH2＝
CR1−COOR2単量体の例としては（メタ）アク
リル酸メチル、（メタ）アクリル酸エチル、（メ
タ）アクリル酸プロピル、（メタ）アクリル酸ブ
チル、（メタ）アクリル酸２−エチルヘキシルな
どを、またα、β不飽和カルボン酸単量体の例と
してはアクリル酸、メタアクリル酸、イタコン
酸、マレイン酸などを、さらにこれらの単量体と
共重合可能な単量体の例としてはスチレン、α−
メチルスチレン、酢酸ビニル、塩化ビニル、塩化
ビニリデンなどを挙げることができる。
本発明で上記のような共重合体樹脂を用いるの
は目的とする物性の皮膜が得られ、共重合体樹脂
の工業的製造も容易であるからである。また共重
合体樹脂の酸価を固形分当たり10〜200にした理
由は、10未満であると耐水性はよいが鋼板に対す
る密着性が劣るからであり、また200を越えると
耐水性が劣つて耐食性が低下してくるからであ
る。この酸価についてはとくに15〜100にすると
皮膜は耐水性、密着性が良好になるので、その範
囲にするのが好ましい。
シランカツプリング剤、チタネートカツプリン
グ剤は一方または両方を配合するにしても共重合
体樹脂100重量部に対して0.05〜10重量部配合す
るのが好ましい。シランカツプリング剤としては
種々のタイプのものがあるが、水分散性もしくは
水溶性のものであれば、モノマータイプ［例えば
ビニルトリ（β−メトキシエトキシ）シラン、γ
−グリシドキシプロピルトリメトキシシラン］、
オリゴマータイプ（例えばグリシド系のもの）、
樹脂変性タイプ（例えばアクリル変性、エポキシ
変性のもの）、カチオン系タイプのものなどいず
れでも使用できる。またチタネートカツプリング
剤も水分散性もしくは水溶性のものであれば用い
ることができ、好ましいものを挙げればテトラ
（２，２−ジアリルオキシメチル−１−ブチル）
ビス（ジ−トリデシル）ホスフアイトチタネー
ト、ビス（ジオクチルパイロホスフエート）オキ
シアセテートチタネート、ビス（ジオクチルパイ
ロホスフエート）エチレンチタネートなどがあ
る。
本発明は樹脂皮膜を上述のようにして、その皮
膜中に６価クロム源としてクロム酸塩を含有さ
せ、さらに皮膜の物性や耐食性を向上させるため
にシリカゾルを含有させる。ここで含有させるク
ロム酸塩としては水溶性で、安価なものが好まし
く、例えばクロム酸アンモニウム、クロム酸マグ
ネシウムなどであり、重クロム酸カリウム、クロ
ム酸カルシウム、クロム酸亜鉛、クロム酸マンガ
ン、クロム酸ニツケル、クロム酸コバルト、クロ
ム酸ストロンチウムなども使用できる。
樹脂皮膜中に含有させるこれらのクロム酸塩お
よびシリカゾルの量としては共重合体樹脂100重
量部当たりクロム酸塩の場合0.1〜50重量部、シ
リカゾルの場合0.5〜100重量部にするのが好まし
い。また樹脂皮膜の皮膜厚としては0.2〜10μｍに
するのが好ましい。これは0.2μｍ未満では均一な
皮膜の形成が難しく、スポツト的な皮膜となり、
耐変色性に乏しく、かつ傷防止効果も小さいから
である。一方10μｍより厚くしても効果は変わら
ず、コスト高になる。このような含有量および皮
膜厚の樹脂皮膜は例えば共重合体樹脂200〜400
ｇ／、シランカツプリング剤または／およびチ
タネートカツプリング剤0.1〜40ｇ／、クロム
酸塩0.2〜200ｇ／、シリカゾル１〜400ｇ／
を含有する処理液により形成することができる。
樹脂皮膜はクロム酸塩を含有しているので銅めつ
き鋼板の上に直接形成しても耐変色性を発揮する
が、さらに耐変色性を発揮させるには銅めつき鋼
板にクロメート皮膜を形成して、その上に形成す
る。この場合クロメート皮膜は反応型、塗布型な
ど一般に種類を問わないが、皮膜量は全クロム量
で１〜50mg／m2にするのが好ましい。
なお本発明の銅めつき鋼板は鋼板に純銅をめつ
きしたものばかりでなく、添加金属を含む合金を
めつきしたものも含む。素材鋼板としても冷延鋼
板だけでなく、ステンレス鋼板など他の鋼板をも
含む。
次ぎに本発明を実施例により説明する。
（実施例）
メチルメタアクリレート50重量％と、ブチルア
クリレート40重量％と、アクリル酸9.8重量％と、
スチレン0.2重量％とを乳化重合して得られたア
クリルエマルジヨン［樹脂分40重量％、PH2.3、
粘度25cps（25℃、Ｂ型粘度計）、固形分当たりの
酸価約78、以下このエマルジヨン中の共重合体樹
脂をＸとする］およびメチルアクリレート55重量
％と、ブチルアクリレート40重量％と、アクリル
酸4.7重量％と、酢酸ビニル0.3重量％とを乳化重
合して得られたアクリルエマルジヨン［樹脂分40
重量％、PH2.6、粘度150cps（同上）、固形分当た
りの酸価約40、以下このエマルジヨン中の共重合
体樹脂をＹとする］にシランカツプリング剤また
は／およびチタネートカツプリング剤、クロム酸
塩、シリカゾル（スノーテツクス−Ｏ、日産化学
製）を種々添加して樹脂皮膜処理液を調整した
後、この処理液を下記工程で製造した板厚0.6mm
銅めつき鋼板（銅めつき厚15μｍ）の表面に直接
またはクロメート皮膜を形成した後塗布した。
銅めつき鋼板の製造工程
冷延鋼板→アルカリ電解脱脂（注１）→水洗→
酸洗（注２）水洗→→Niフラツシユめつき（注
３）→水洗→銅めつき（注４）→［クロメート処
理（注５）］→樹脂皮膜処理液塗布→乾燥（150
℃、10秒）。
（注１） NaSiO450ｇ／の70℃溶液にて、電
流密度5A／Ｄm2で５分電解。
（注２） HCl2％の溶液にて、常温で１分酸洗。
（注３） NiSO4・6H2O300ｇ／、NiCl2・
6H2O45ｇ／、H3PO434ｇ／、55℃の浴に
て電流密度4A／Ｄm2で30秒めつき。
（注４） CuSO420ｇ／、H2SO440ｇ／常
温の浴にて電流密度15A／Ｄm2でめつき。
（注５） CrO35ｇ／、30℃の溶液にて20秒処
理。
一方比較例として、上記のようにして製造した
銅めつき鋼板にエマルジヨン中にシランカツプリ
ング剤、チタネートカツプリング剤、クロム酸塩
およびシリカゾルのいずれをも含有しない処理液
を塗布したものや従来の変色防止処理を施したも
のなどを調整した。なおこの比較例のクロメート
処理は前記（注５）の処理液で行い、ベンゾトリ
アゾール処理はベンゾトリアゾール５ｇ／、40
℃の溶液に20秒浸漬した後ロールスクイズした。
その後これらの鋼板に次ぎの要領で湿潤試験と
耐指紋性試験を施した。
(1) 湿潤試験
JISZ0228に準拠して温度50℃、湿度98％RH
の雰囲気中に300時間放置した後銅めつき表面
の変色程度を次ぎの基準に従つて目視で評価し
た。
◎ 全く変色しないもの
○ 若干褐色化したもの
△ 褐色化したもの
△- 茶褐色〜黒色化したもの
× 黒色化したもの
(2) 耐指紋性試験
人工汗を塗つた人工指を一定の荷重（１Kg／
cm2）で資料に押し付け、付着した指紋の量を次
の基準に従つて目視で評価した。
◎ 指紋が全く検出できないもの
○ 指紋が付いているか、付いていないか殆ど
わからないもの
△ 指紋の付いているのがわかるもの
△- 指紋のかなり付いているのがわかるもの
× 指紋の付いているのが非常に目立つもの
第１表は樹脂皮膜形成条件とこれらの試験結果
を示したものであるが、本発明の銅めつき鋼板は
鋼板に直接樹脂皮膜を形成したものでも従来の変
色処理を施したものやクロメート皮膜の上に樹脂
単独の皮膜を形成したものより優れている。
(Industrial Application Field) The present invention forms a resin film with excellent corrosion resistance on the surface of a copper-plated steel sheet directly or through a chromate film, thereby improving discoloration resistance, fingerprint resistance, etc., which are disadvantages of copper plating. related to copper-plated steel sheets. (Prior Art) Copper-plated steel sheets have an excellent appearance, but have the disadvantage that the surface is easily oxidized and discolored to brown in the atmosphere, and scratches and fingerprints are easily noticeable when handled. For this reason, conventionally, when manufacturing copper-plated steel sheets, chromate treatment, benzotriazole treatment, benzotriazole derivative treatment, etc. are used to prevent discoloration, and treatments such as applying a protective film and applying strippable paint are used to prevent scratches and fingerprints. was. (Problems to be Solved by the Invention) However, even when chromate treatment or benzotriazole treatment is performed, discoloration can only be prevented for a short period of time. On the other hand, it was possible to prevent scratches and fingerprints during handling by attaching a protective film or applying strippable paint, but the processing cost was high and it required a lot of effort and time to remove them after processing. there was. Furthermore, since the protective film and strippable paint do not have any discoloration prevention effect, it is necessary to apply discoloration prevention treatment such as chromate treatment or benzotriazole treatment underneath. Therefore, double processing was required to prevent scratches and fingerprints. On the other hand, although it requires double treatment, a cheaper method such as attaching a protective film or applying strippable paint is to form a resin film with an aqueous solution of a water-soluble resin after discoloration prevention treatment. However, the only way to further improve color fastness with this method is to strengthen the color change treatment, so there was a limit to how much color fastness could be improved. Therefore, in order to further improve the color fastness, it was necessary to improve the corrosion resistance of the resin film and improve the color fastness. An industrially inexpensive method to improve the corrosion resistance of a resin film is to include hexavalent chromium in the resin film, but in order to incorporate hexavalent chromium using this method, it is necessary to treat the resin film containing hexavalent chromium. Must be treated with liquid. However, since the resins conventionally used after such resin film treatment were made hydrophilic by hydroxyl groups, adding chromic anhydride or chromate to contain hexavalent chromium in the treatment solution caused the resin to become hydrophilic. The hydroxyl groups in the molecules were oxidized, and the treatment solution turned into a gel, making it impossible to apply it to the steel plate, and the hexavalent chromium was also reduced to trivalent chromium, making it no longer possible to exhibit discoloration resistance. For this reason, it has conventionally been difficult to incorporate hexavalent chromium into a resin film. (Means for Solving the Problems) The present invention provides an organic-coated copper-plated steel sheet that makes it possible to incorporate hexavalent chromium into the resin film, which has been difficult in the past. The copper-plated steel sheet of the present invention uses a water-dispersible copolymer that does not have hydroxyl groups as the resin for the resin coating, which prevents the resin from being oxidized by chromic acid in the treatment solution stage. The water resistance, adhesion, and physical properties of the resin film are improved by adjusting the acid value and incorporating a silane coupling agent and/or a titanate coupling agent. That is, the present invention can be used as a resin for a resin film.
(A) General formula CH 2 = CR 1 −COOR 2 (in the formula, R 1 is H,
CH 3 , R 2 is an alkyl group having 1 to 8 carbon atoms), and 1 to 95% by weight of one or more monomers;
(B) α, β unsaturated carboxylic acid monomer 3 to 20% by weight
and (C) 0.1 of a monomer copolymerizable with these monomers.
~50% by weight [however, the total of (A), (B) and (C) is
A copolymer resin obtained by emulsion polymerization and having an acid value of 10 to 200 per solid content is blended with a silane coupling agent and/or a titanate coupling agent. Here, the general formula that constitutes the copolymer resin is CH 2 =
Examples of CR 1 -COOR 2 monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples of α, β unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and examples of monomers that can be copolymerized with these monomers include styrene. , α−
Examples include methylstyrene, vinyl acetate, vinyl chloride, and vinylidene chloride. The reason for using the above-mentioned copolymer resin in the present invention is that a film having the desired physical properties can be obtained and the industrial production of the copolymer resin is easy. The reason why the acid value of the copolymer resin is set to 10 to 200 per solid content is that if it is less than 10, the water resistance is good but the adhesion to the steel plate is poor, and if it exceeds 200, the water resistance is poor. This is because corrosion resistance decreases. When the acid value is set to 15 to 100, the film will have good water resistance and adhesion, so it is preferable to set it within that range. Even if one or both of the silane coupling agent and the titanate coupling agent are blended, it is preferable to blend them in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the copolymer resin. There are various types of silane coupling agents, but as long as they are water-dispersible or water-soluble, monomer types [e.g. vinyltri(β-methoxyethoxy)silane, γ
-glycidoxypropyltrimethoxysilane],
Oligomer type (e.g. glycide type),
Either a resin-modified type (for example, an acrylic-modified or epoxy-modified type) or a cationic type can be used. Titanate coupling agents can also be used as long as they are water-dispersible or water-soluble. Preferred examples include tetra(2,2-diallyloxymethyl-1-butyl).
Examples include bis(di-tridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, and bis(dioctyl pyrophosphate) ethylene titanate. In the present invention, the resin film is formed as described above, and the film contains chromate as a source of hexavalent chromium, and further contains silica sol to improve the physical properties and corrosion resistance of the film. The chromate to be contained here is preferably water-soluble and inexpensive, such as ammonium chromate, magnesium chromate, potassium dichromate, calcium chromate, zinc chromate, manganese chromate, chromate, etc. Nickel, cobalt chromate, strontium chromate, etc. can also be used. The amount of chromate and silica sol contained in the resin film is preferably 0.1 to 50 parts by weight in the case of chromate and 0.5 to 100 parts by weight in the case of silica sol per 100 parts by weight of the copolymer resin. The thickness of the resin film is preferably 0.2 to 10 μm. If it is less than 0.2 μm, it is difficult to form a uniform film, and the film becomes spotty.
This is because the color fastness is poor and the scratch prevention effect is also low. On the other hand, even if it is thicker than 10 μm, the effect remains the same and the cost increases. A resin film with such content and film thickness is, for example, copolymer resin 200 to 400
g/, silane coupling agent or/and titanate coupling agent 0.1-40g/, chromate 0.2-200g/, silica sol 1-400g/
It can be formed using a processing liquid containing.
Since the resin film contains chromate, it exhibits discoloration resistance even when formed directly on copper-plated steel sheets, but in order to exhibit even more discoloration resistance, a chromate film is formed on copper-plated steel sheets. and form on top of it. In this case, the chromate film may be of any type, such as a reactive type or a coating type, but the amount of the chromate film is preferably 1 to 50 mg/m 2 in terms of total chromium content. Note that the copper-plated steel sheet of the present invention includes not only a steel sheet plated with pure copper but also a steel plate plated with an alloy containing an additive metal. The material steel sheet includes not only cold-rolled steel sheet but also other steel sheets such as stainless steel sheet. Next, the present invention will be explained by examples. (Example) 50% by weight of methyl methacrylate, 40% by weight of butyl acrylate, 9.8% by weight of acrylic acid,
Acrylic emulsion obtained by emulsion polymerization with 0.2% by weight of styrene [resin content: 40% by weight, PH2.3,
viscosity 25 cps (25°C, Type B viscometer), acid value per solid content of about 78, hereinafter the copolymer resin in this emulsion will be referred to as X], 55% by weight of methyl acrylate, 40% by weight of butyl acrylate, Acrylic emulsion obtained by emulsion polymerization of 4.7% by weight of acrylic acid and 0.3% by weight of vinyl acetate [resin content: 40% by weight]
% by weight, PH2.6, viscosity 150 cps (same as above), acid value per solid content of about 40, hereinafter the copolymer resin in this emulsion will be referred to as Y], a silane coupling agent or/and a titanate coupling agent, and chromium. After adjusting the resin film treatment solution by adding various acid salts and silica sol (Snowtex-O, manufactured by Nissan Chemical), this treatment solution was used to produce a plate with a thickness of 0.6 mm using the following process.
It was applied directly to the surface of a copper-plated steel plate (copper plating thickness: 15 μm) or after forming a chromate film. Manufacturing process of copper-plated steel sheet Cold rolled steel sheet → Alkaline electrolytic degreasing (Note 1) → Water washing →
Pickling (Note 2) Water washing → → Ni flash plating (Note 3) → Water washing → Copper plating (Note 4) → [Chromate treatment (Note 5)] → Resin film treatment solution application → Drying (150
°C, 10 seconds). (Note 1) Electrolyzed in a 70°C solution of 50 g of NaSiO 4 at a current density of 5 A/Dm 2 for 5 minutes. (Note 2) Pickle with a 2% HCl solution for 1 minute at room temperature. (Note 3) NiSO 4・6H 2 O300g/, NiCl 2・
6H 2 O 45g/, H 3 PO 4 34g/, plating for 30 seconds at a current density of 4A/Dm 2 in a 55°C bath. (Note 4) CuSO 4 20g/H 2 SO 4 40g/Plated at a current density of 15A/Dm 2 in a bath at room temperature. (Note 5) Treated with CrO 3 5g/30℃ solution for 20 seconds. On the other hand, as a comparative example, a copper-plated steel sheet produced as described above was coated with a treatment solution containing neither a silane coupling agent, a titanate coupling agent, a chromate, nor a silica sol in the emulsion, and a conventional Adjustments have been made to those that have been treated to prevent discoloration. The chromate treatment in this comparative example was carried out using the treatment solution described above (Note 5), and the benzotriazole treatment was carried out using benzotriazole 5 g/40
It was immersed in the solution at ℃ for 20 seconds and then rolled squeezed. Thereafter, these steel plates were subjected to a wet test and a fingerprint resistance test in the following manner. (1) Humidity test Temperature 50℃, humidity 98%RH according to JISZ0228
After being left in an atmosphere for 300 hours, the degree of discoloration of the copper-plated surface was visually evaluated according to the following criteria. ◎ No discoloration at all ○ Slightly browned △ Browned △ - Brown to black × Blackened (2) Fingerprint resistance test An artificial finger coated with artificial sweat was subjected to a certain load (1 kg/
cm 2 ) onto the material, and the amount of attached fingerprints was visually evaluated according to the following criteria. ◎ Items where no fingerprints can be detected ○ Items where it is almost impossible to tell whether there are fingerprints or not △ Items where you can see that there are fingerprints △ - Items where you can see a lot of fingerprints × Items with fingerprints Table 1 shows the conditions for resin film formation and the test results.The copper-plated steel sheets of the present invention, even those in which the resin film is directly formed on the steel sheet, cannot be treated with conventional discoloration treatment. It is superior to those with a resin film formed on top of a chromate film.
【表】
（効果）
以上説明したごとく、本発明の銅めつき鋼板は
被覆する樹脂皮膜の樹脂が水酸基を有しないの
で、製造の際処理液中にクロム酸塩を含有してい
ても、樹脂は酸化されず、ゲル化はしない。また
樹脂皮膜中にクロム酸塩を含有しているので、一
回処理でも従来の変色防止処理より変色防止効果
を発揮し、しかも傷や指紋付着を防止する。さら
にシリカゾルとシランカツプリング剤または／お
よびチタネートカツプリング剤をも含有している
ので、樹脂皮膜は耐水性、密着性および物性に優
れている。[Table] (Effects) As explained above, the copper-plated steel sheet of the present invention has no hydroxyl group in the resin coating, so even if the treatment solution contains chromate during manufacturing, the resin is not oxidized and does not gel. Furthermore, since the resin film contains chromate, even a single treatment provides a more effective discoloration prevention effect than conventional discoloration prevention treatments, and also prevents scratches and fingerprints. Furthermore, since it also contains silica sol and a silane coupling agent or/and a titanate coupling agent, the resin film has excellent water resistance, adhesion, and physical properties.
Claims (1)
COOR2（式中R1はＨ、CH3，R2はＣが１〜８の
アルキル基）で示される単量体の１種または２種
以上１〜95重量％と、(B)α、β不飽和カルボン酸
単量体３〜20重量％と、(C)これらの単量体と共重
合可能な単量体0.1〜50重量％とを［但し(A)、(B)
および(C)の合計は100重量％］乳化重合して得ら
れる固形分当たりの酸価10〜200の共重合体樹脂
にシランカツプリング剤または／およびチタネー
トカツプリング剤を配合した樹脂皮膜で、その皮
膜中にクロム酸塩とシリカゾルとを含有するもの
が形成され、被覆されていることを特徴とする有
機被覆銅めつき鋼板。 ２ 銅めつき鋼板の表面にクロメート皮膜が形成
され、さらにそのクロメート皮膜の上に(A)一般式
CH2＝CR1−COOR2（式中R1はＨ、CH3，R2はＣ
が１〜８のアルキル基）で示される単量体の１種
または２種以上１〜95重量％と、(B)α、β不飽和
カルボン酸単量体３〜20重量％と、(C)これらの単
量体と共重合可能な単量体0.1〜50重量％とを
［但し(A)、(B)および(C)の合計は100重量％］乳化重
合して得られる固形分当たりの酸価10〜200の共
重合体樹脂にシランカツプリング剤または／およ
びチタネートカツプリング剤を配合した樹脂皮膜
で、その皮膜中にクロム酸塩とシリカゾルとを含
有するものが形成され、被覆されていることを特
徴とする有機被覆銅めつき鋼板。[Claims] 1. On the surface of a copper-plated steel plate (A) General formula CH 2 = CR 1 −
1 to 95% by weight of one or more monomers represented by COOR 2 (in the formula, R 1 is H, CH 3 , R 2 is an alkyl group having 1 to 8 carbons), (B) α, 3 to 20% by weight of a β-unsaturated carboxylic acid monomer and (C) 0.1 to 50% by weight of a monomer copolymerizable with these monomers [However, (A), (B)
and (C) total is 100% by weight] A resin film obtained by blending a silane coupling agent or/and a titanate coupling agent with a copolymer resin having an acid value of 10 to 200 per solid content obtained by emulsion polymerization, An organic coated copper-plated steel sheet characterized in that the film is coated with a film containing chromate and silica sol. 2 A chromate film is formed on the surface of the copper-plated steel sheet, and (A) general formula
CH 2 = CR 1 −COOR 2 (in the formula, R 1 is H, CH 3 , R 2 is C
1 to 95% by weight of one or more monomers represented by 1 to 8 alkyl groups), 3 to 20% by weight of (B) α, β unsaturated carboxylic acid monomer, and (C ) Based on the solid content obtained by emulsion polymerization of these monomers and 0.1 to 50% by weight of a copolymerizable monomer [however, the total of (A), (B) and (C) is 100% by weight] A resin film containing a chromate and silica sol is formed by blending a silane coupling agent and/or a titanate coupling agent with a copolymer resin with an acid value of 10 to 200. Organic-coated copper-plated steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22186884A JPS6199680A (en) | 1984-10-22 | 1984-10-22 | Organic substance coated copper plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22186884A JPS6199680A (en) | 1984-10-22 | 1984-10-22 | Organic substance coated copper plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6199680A JPS6199680A (en) | 1986-05-17 |
| JPH0454747B2 true JPH0454747B2 (en) | 1992-09-01 |
Family
ID=16773437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22186884A Granted JPS6199680A (en) | 1984-10-22 | 1984-10-22 | Organic substance coated copper plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6199680A (en) |
-
1984
- 1984-10-22 JP JP22186884A patent/JPS6199680A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6199680A (en) | 1986-05-17 |
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