JPS621476B2 - - Google Patents
Info
- Publication number
- JPS621476B2 JPS621476B2 JP57071577A JP7157782A JPS621476B2 JP S621476 B2 JPS621476 B2 JP S621476B2 JP 57071577 A JP57071577 A JP 57071577A JP 7157782 A JP7157782 A JP 7157782A JP S621476 B2 JPS621476 B2 JP S621476B2
- Authority
- JP
- Japan
- Prior art keywords
- surface treatment
- treatment agent
- chromium
- film
- water
- 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
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 21
- 229910001430 chromium ion Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- -1 fluorine ions Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229940085991 phosphate ion Drugs 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000011651 chromium Substances 0.000 description 53
- 239000012756 surface treatment agent Substances 0.000 description 38
- 238000011282 treatment Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229960002050 hydrofluoric acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NCNKLTFZTZEYLK-AHUNZLEGSA-H [Cr+3].[Cr+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Cr+3].[Cr+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O NCNKLTFZTZEYLK-AHUNZLEGSA-H 0.000 description 1
- PKAQRKWFFOIEPX-UHFFFAOYSA-K [O-]P([O-])([O-])=O.O.O.O.[Cr+3] Chemical compound [O-]P([O-])([O-])=O.O.O.O.[Cr+3] PKAQRKWFFOIEPX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/37—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 fluorides or complex fluorides containing also hexavalent chromium compounds
- C23C22/38—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 fluorides or complex fluorides containing also hexavalent chromium compounds containing also phosphates
-
- 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
- C23C22/33—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 phosphates
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)
Description
【発明の詳細な説明】
本発明は、アルミニウム及びその合金の表面の
防食処理あるいは塗装の下地処理に用いられる表
面処理剤に関するものである。
従来から、アルミニウム及びその合金材（以
下、アルミニウム材という）の表面の防食処理あ
るいは塗装の下地処理用として各種の表面処理剤
が知られている。これらのうち、クロム系の表面
処理剤は、皮膜形成の機構上から、いわゆるリン
ス型と呼ばれる変換皮膜形成型と、ノンリンス型
と呼ばれる塗布型とに分類できる。
しかして、リンス型の表面処理剤は、アルミニ
ウム表面に広範な用途に対応できる良好な性能を
有する皮膜を形成するので長く使用されている。
しかしながら、この型の表面処理剤は、表面処理
剤を使用して行なうアルミニウム表面の化成処理
の後に水洗をする必要がある。このために、多量
に排出される洗浄水中に表面処理剤に含有される
６価クロムやフツ化物などの有害物質が含有され
ることになり、洗浄水を排棄するためには、これ
らの有害物質を除かねばならず、莫大な除去設備
投資、除去費などを必要とするといつた欠点があ
る。
また、ノンリンス型と呼ばれる塗布型の表面処
理剤は、表面処理剤を塗布した後に水洗が不要で
あるためにリンス型の表面処理剤のような排水処
理を必要とせず、表面処理剤を塗布したアルミニ
ウム材は、乾燥後、そのまま防食皮膜処理剤とし
て、あるいは、さらに塗装を行なつた後に使用し
得るという利点がある。
しかして、この型の表面処理剤にも含有する主
要成分であるクロムの原子価によつて、Cr
（）型、Cr（）型、Cr（）＋Cr（）型の
三つに分類される。すなわち、Cr（）は、
Cr3+、PO３＋ ４を主要成分とし、これに有機物とか
コロイダルシリカ、F-、NO− ３などを添加した組
成を有している。（たとえば、特開昭53−37350、
特開昭53−115625など）この型の表面処理剤で処
理して生成される皮膜は無色であり、さらに皮膜
中に６価のクロムが存在しない利点があるので広
範な分野への応用が考えられる。ことに、わが国
においてはアルミニウム素地の有する美しい金属
感を表面処理においても積極的に生かしたものが
好まれるので、生成する皮膜が無色であることの
実際面でのメリツトは大きなものがある。しかし
ながら、Cr（）型の皮膜は、とくに塗装の下
地処理皮膜としての性能は上塗り塗料の硬化温度
によつて大きく変化する。すなわち、硬化を通常
140〜190℃（被塗物の温度、以下同様）で行なわ
れるが、このものを高温度雰囲気下に放置すると
ブリスターあるいは塗膜下腐食という形の欠陥を
呈するように防食性の点で満足し得ない。そし
て、この欠陥は、雰囲気の腐食性が増すにつれ一
層顕著になつてくる。このためにCr（）型の
表面処理剤は、その用塗をコイル塗装ラインのよ
うな塗膜硬化時の温度が200℃を超える条件で処
理される場合に限定せざるを得ない欠点がある。
次に、Cr（）型の表面処理剤は、Cr6+、
PO３＋ ４を主要成分とし、各種成分が添加された組
成を有する。（たとえば、特開昭54−31043など）
しかして、この型の表面処理剤によつて形成され
る皮膜の防食性あるいは塗装の下地としての性能
は、広い各処理条件に亘つて良好ではあるが、得
られる皮膜が淡褐色の見苦しい色に着色してい
る。このために、クリアー塗料は勿論、隠蔽力の
低い塗料の下地処理としても使えないし、さら
に、生成皮膜中に６価クロムが残留しているなど
の欠点がある。
さらに、Cr（）＋Cr（）型の表面処理剤
は、Cr3+、及びCr6+を主要成分とし、これに
PO３＋ ４、SiO2あるいはポリアクリル酸などが添加
された組成を有する。（たとえば、特開昭54−
110149、米国特許第3185596号、米国特許370603
号など）この型の表面処理剤の６価クロムは、３
価クロムと６価クロムの合計した総クロムに対
し、0.4〜0.8が好ましいとされ、特開昭54−
11049明細書の記載によれば、この比が0.5以下の
場合には溶液の安定性が損なわれるとされている
し、Cr（）型と同様に皮膜が淡褐色に着色さ
れ、また皮膜中に６価クロムが残存しているなど
の欠点が認められる。
本発明者らは、これらの欠点のない表面処理剤
を得べく多くの研究を重ねた結果、Cr（）型
の表面処理剤に６価のクロムを少量添加した表面
処理剤にすることによつて、着色もなく、６価ク
ロムが残留していない皮膜が得られることを見出
して本発明をなしたものである。すなわち、本発
明は、水１中に、３価クロムイオン0.8〜1.5
ｇ、６価クロムと総クロムイオンの比が0.1−0.3
の範囲の６価クロムイオン、リン酸イオン1.5〜
15ｇフツ素イオン0.1〜２ｇ及び水溶性アクリル
ポリマー0.5〜15ｇを配合してなるアルミニウム
及びその合金の表面処理剤である。
本発明における３価クロムイオン（Cr3+）は、
クロムの水酸化物、無機酸塩、有機酸塩たとえば
水酸化クロム、硝酸クロム、リン酸クロム、酢酸
クロムあるいはマレイン酸クロムその他適宜のク
ロム塩の形で供給でき、Cr3+の濃度は、0.8〜1.5
ｇ/の範囲が好ましい。
６価クロムイオン（Cr6+）は、たとえば三酸化
クロムあるいは重クロム酸塩、クロム酸塩などの
水溶性６価クロム化合物の形で供給される。
Cr6+の濃度は、６価クロムイオンと総クロムイ
オンとの比、すなわち、Cr6+／Cr3+＋Cr6+の比
が0.05〜0.35、より好ましくは、0.1〜0.3の範囲
に保たれる範囲であり、かつ、Cr6+の濃度が0.1
〜0.6ｇ/の範囲であり、0.4〜0.5ｇ/の範囲が
好ましい。しかして、６価クロムイオンの配合割
合が、Cr6+／Cr3+＋Cr6+＝0.1〜0.3における下限
値以下では、６価クロム添加の効果が激減し、上
限値を超えると得られる皮膜が着色し、クリヤー
塗装は勿論、淡色の塗料の塗装下地として使用し
得ないので用途が大巾に限定されるものである。
リン酸イオン（PO３＋ ４）は、通常、リン酸、リ
ン酸塩として供給され、PO３＋ ４の濃度は、0.1〜0.6
ｇの範囲で配合され、0.4〜0.5ｇ/の範囲が好
ましい。
水溶性アクリルポリマーは、たとえば、アクリ
ゾールＡ−１（商品名、ロームアンドハース社、
アクリル酸固型分25重量％を含む水溶液）のよう
なポリアクリル酸またはそのエステルが用いら
れ、0.5〜15ｇ/、好ましくは、３〜８ｇ/の
範囲で用いる。
フツ素イオンは、フツ酸またはその水溶性化合
物の形態でF-として0.1〜２ｇ/の範囲で添加
する。
なお、この他、0.1〜15ｇ/程度の不溶性コロ
イダルシリカの添加は支障がない。
本発明の表面処理剤は、このような各原料の所
定量をとり水に溶解混合することによつて調製す
ることができる。なお、使用する水は、脱イオン
水であることが好ましい。
また、従来のCr（）型の表面処理剤に、６
価クロムイオンを前記の条件を満足するように添
加することによつて調製することもできる。
しかして、このようにして得られた表面処理剤
のPHは１〜2.5の範囲にある。また、表面処理剤
の蒸発残分は、２〜35ｇ/である。なお、表面
処理剤の安定性がよく、Cr6+の濃度は、調製後
約３週間変化が認められなかつた。
このようにして得た本発明の金属処理剤は、通
常のように、ロール塗り、リバースロール塗り、
浸漬、流し塗り、吹き付け、またはミスト塗装な
どによつて塗布することができ、金属表面に液膜
の膜厚が５〜20μｍ、好ましくは15μｍ前後の厚
さになるように塗布する。表面処理剤を塗布後、
加熱乾燥するが、被処理板の温度が170℃以下で
乾燥することが好ましい。しかして、乾燥後の水
洗は不要であり、そのままの状態で、あるいは、
さらに塗料を塗装して使用する。
このようにして、本発明の表面処理剤を使用し
て得られた金属表面の皮膜は、無色であつて、湿
式法によつて分析した結果は、Cr6+は検出され
なかつた。さらに、皮膜を施行した皮膜材を、温
度35℃に保持した脱イオン水中に１週間浸漬（比
液量95ml/dm2）し、Cr6+の抽出を試みたが、理
由は明確ではないが、Cr6+は検出されなかつ
た。
本発明は、３価クロムイオン、及び６価クロム
イオンと総クロムイオンとの比を0.1〜0.3となる
ような６価クロムイオンを主要成分として配合し
たので、表面処理剤の安定性がよく、アルミニウ
ム及びその合金の表面処理剤に使用した場合、通
常通りの塗布操作が行ない得、水洗をする必要が
ないので排水処理の必要がなく、皮膜自身の防食
性は勿論、塗装の下地皮膜としての性質も向上し
得、無色の皮膜で皮膜中に６価クロムが残留して
いない皮膜が得られ、広範囲の用途に用い得るな
どすぐれた効果が認められる。
次に、実施例を述べる。
実施例 １
１ 表面処理剤の調製
リン酸クロム三水和物を3.9ｇ/、三酸化ク
ロムを0.8ｇ/、リン酸を8.3ｇ/、フツ化水
素酸を1.2ｇ/、水溶性アクリル酸ポリマー
（商品名アクリルゾールＡ−１）を９ｇ/の割
合でとり、脱イオン水を用いて表面処理剤を調
製した。
このようにして、Cr3+1.0ｇ/、Cr6+0.4ｇ/
、Cr6+／Cr3+＋Cr6+＝0.29、PO３＋ ４8.0ｇ/
、F-1.1ｇ/、水溶性アクリルポリマー9.0
ｇ/、PH1.7のような組成を有する表面処理剤
が得られた。
２ 表面処理結果
アルミニウム板（1100−H24、１mm厚）を通
常の非エツチング性クリーナーを使用して脱脂
洗浄し、１）により調製した表面処理剤を約15
μｍの液膜として塗り上げた。その後、130℃
（板温90℃）の熱風で１分間加熱乾燥した。処
理後の無色の皮膜を有する板を室温まで放冷し
た後、熱硬化型の塗料を用いて塗装し、塗料の
焼付けを150℃で30分間行なつた。得られた乾
燥塗膜厚は20μｍであつた。
被塗物は、碁板目テープ剥離試験による塗膜
の付着性試験、塗面に十字の傷を入れた後キヤ
ス試験を72時間、及び、JIS−Ｚ−2371の方法
に基づく、塩水噴霧試験を500時間行なう耐食
試験などを行なつた。結果を第１表に示す。
なお、皮膜を湿式法によつて分析した結果、
６価クロムは認められなかつた。
実施例 ２
（実施例１−１）で調製した表面処理液を用
い、アルミニウム板（1100−H24、１mm厚）に対
し約15μｍの厚さに塗り広げた後、170℃で５分
間皮膜不溶化処理を行なつた。生成された無色の
皮膜の耐食性を塩水噴霧試験を100時間行なつて
調べた。結果を第１表に示す。
なお、皮膜材を35℃に保持した脱イオン水中に
１週間浸漬（比液量95ml/dm2）し、Cr6+の抽出
を試みたが検出されなかつた。また、皮膜の湿式
分析でもCr6+は検出されなかつた。
比較例 １
（実施例１−１）で調製した表面処理剤から
Cr6+を除いた組成のいわゆるCr（）型の表面
処理剤を使用して、実施例１と同様な条件下で処
理した後、同様な試験を行なつた。結果を第１表
に示す。
比較例 ２
比較例１と同様な組成のCr（）型の表面処
理剤を使用して、実施例２と同様な条件下で処理
した後、同様な試験を行なつた。結果を第１表に
示す。
比較例 ３
（実施例１−１）と同様にしてCr6+／Cr3+＋
Cr6+＝0.6のいわゆるCr（）＋Cr（）型の表
面処理剤を調製し、実施例２と同様に条件下に処
理した後、同様な試験を行なつた。結果を第１表
に示す。
なお、実施例２と同様に皮膜のCr6+抽出試験
と湿式分析を行なつた結果は、いずれもCr6+が
検出された。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface treatment agent used for anticorrosion treatment of the surface of aluminum and its alloys or for surface treatment for painting. BACKGROUND ART Various surface treatment agents have been known for anticorrosive treatment of the surface of aluminum and its alloy materials (hereinafter referred to as aluminum materials) or for surface treatment for painting. Among these, chromium-based surface treatment agents can be classified into conversion film-forming types called so-called rinse types and coating types called non-rinsing types based on the mechanism of film formation. Rinse-type surface treatment agents have been used for a long time because they form a film on aluminum surfaces that has good performance and can be used in a wide range of applications.
However, this type of surface treatment agent requires washing with water after the chemical conversion treatment of the aluminum surface using the surface treatment agent. For this reason, the large amount of cleaning water that is discharged contains harmful substances such as hexavalent chromium and fluoride contained in surface treatment agents. The disadvantage is that the substance must be removed, requiring a huge investment in removal equipment and removal costs. In addition, the non-rinse type surface treatment agent does not require washing with water after applying the surface treatment agent, so it does not require drainage treatment like the rinse type surface treatment agent. An advantage of aluminum material is that after drying, it can be used as an anticorrosion coating treatment agent, or after being further coated. However, due to the valence of chromium, which is the main component contained in this type of surface treatment agent, Cr
It is classified into three types: () type, Cr() type, and Cr() + Cr() type. That is, Cr() is
It has a composition in which Cr 3+ and PO 3+ 4 are the main components, to which organic substances, colloidal silica, F - , NO - 3 , etc. are added. (For example, JP-A-53-37350,
The film produced by treatment with this type of surface treatment agent (Japanese Patent Application Laid-open No. 53-115625, etc.) is colorless and has the advantage that hexavalent chromium is not present in the film, so it can be applied to a wide range of fields. It will be done. In particular, in Japan, people prefer surface treatments that take advantage of the beautiful metallic appearance of aluminum substrates, so the fact that the resulting film is colorless has great practical merits. However, the performance of the Cr() type film, especially as a base treatment film for painting, varies greatly depending on the curing temperature of the top coat. That is, hardening normally
The coating is carried out at a temperature of 140 to 190℃ (temperature of the object to be coated, the same applies hereafter), but it is not satisfactory in terms of corrosion resistance, as if it is left in a high-temperature atmosphere, defects in the form of blisters or corrosion under the coating will appear. I don't get it. This defect becomes more noticeable as the atmosphere becomes more corrosive. For this reason, the Cr() type surface treatment agent has the disadvantage that its application must be limited to cases where the coating is cured at a temperature exceeding 200℃, such as on a coil coating line. . Next, the Cr() type surface treatment agent is Cr 6+ ,
It has a composition in which PO 3+ 4 is the main component and various other components are added. (For example, JP-A-54-31043, etc.)
However, although the anti-corrosion properties of the film formed by this type of surface treatment agent or its performance as a base for painting are good over a wide range of treatment conditions, the resulting film has an unsightly light brown color. It's colored. For this reason, it cannot be used as a base treatment for paints with low hiding power, let alone clear paints, and furthermore, it has drawbacks such as residual hexavalent chromium in the resulting film. Furthermore, the Cr()+Cr() type surface treatment agent has Cr 3+ and Cr 6+ as its main components.
It has a composition in which PO 3+ 4 , SiO 2 or polyacrylic acid is added. (For example, JP-A-54-
110149, U.S. Patent No. 3185596, U.S. Patent No. 370603
The hexavalent chromium in this type of surface treatment agent is 3
It is said that 0.4 to 0.8 is preferable for the total chromium, which is the sum of valent chromium and hexavalent chromium.
According to the specification of 11049, if this ratio is less than 0.5, the stability of the solution will be impaired, and like the Cr() type, the film will be colored light brown, and the film will contain Defects such as residual hexavalent chromium are recognized. As a result of extensive research in order to obtain a surface treatment agent that does not have these drawbacks, the inventors of the present invention have developed a surface treatment agent by adding a small amount of hexavalent chromium to a Cr() type surface treatment agent. The present invention was made based on the discovery that a film without coloration and no residual hexavalent chromium can be obtained. That is, the present invention contains 0.8 to 1.5 trivalent chromium ions in 1 water.
g, the ratio of hexavalent chromium to total chromium ions is 0.1−0.3
Hexavalent chromium ion in the range of 1.5 to phosphate ion
This is a surface treatment agent for aluminum and its alloys, which contains 0.1 to 2 g of fluorine ion and 0.5 to 15 g of water-soluble acrylic polymer. The trivalent chromium ion (Cr 3+ ) in the present invention is
Chromium hydroxide, inorganic acid salts, organic acid salts can be supplied in the form of chromium hydroxide, chromium nitrate, chromium phosphate, chromium acetate or chromium maleate and other suitable chromium salts, with a concentration of Cr 3+ of 0.8 ~1.5
A range of g/ is preferred. The hexavalent chromium ion (Cr 6+ ) is supplied in the form of a water-soluble hexavalent chromium compound such as chromium trioxide or dichromate or chromate.
The concentration of Cr 6+ is such that the ratio of hexavalent chromium ions to total chromium ions, that is, the ratio of Cr 6+ /Cr 3+ + Cr 6+ is maintained in the range of 0.05 to 0.35, more preferably 0.1 to 0.3. and the concentration of Cr 6+ is 0.1
-0.6g/, preferably 0.4-0.5g/. However, if the blending ratio of hexavalent chromium ions is below the lower limit of Cr 6+ /Cr 3+ +Cr 6+ = 0.1 to 0.3, the effect of adding hexavalent chromium will be drastically reduced, and if it exceeds the upper limit, the resulting film will be It is colored and cannot be used as a base for light-colored paints, let alone clear paints, so its uses are largely limited. Phosphate ion (PO 3+ 4 ) is usually supplied as phosphoric acid or phosphate, and the concentration of PO 3+ 4 is 0.1 to 0.6.
The amount is preferably in the range of 0.4 to 0.5 g/g. The water-soluble acrylic polymer is, for example, Acrisol A-1 (trade name, Rohm and Haas Co., Ltd.,
Polyacrylic acid or its ester, such as an aqueous solution containing 25% by weight of acrylic acid solids, is used in an amount ranging from 0.5 to 15 g/, preferably from 3 to 8 g/. The fluorine ion is added in the form of fluoric acid or its water-soluble compound in an amount of 0.1 to 2 g/F - . In addition, there is no problem in adding about 0.1 to 15 g/insoluble colloidal silica. The surface treatment agent of the present invention can be prepared by taking a predetermined amount of each of these raw materials and dissolving and mixing them in water. Note that the water used is preferably deionized water. In addition, in addition to the conventional Cr() type surface treatment agent, 6
It can also be prepared by adding valent chromium ions so as to satisfy the above conditions. Therefore, the pH of the surface treatment agent thus obtained is in the range of 1 to 2.5. Moreover, the evaporation residue of the surface treatment agent is 2 to 35 g/. The stability of the surface treatment agent was good, and no change in the concentration of Cr 6+ was observed for about 3 weeks after preparation. The metal treating agent of the present invention obtained in this way can be applied by roll coating, reverse roll coating,
It can be applied by dipping, flow coating, spraying, or mist coating, and is applied to the metal surface so that the liquid film has a thickness of 5 to 20 μm, preferably around 15 μm. After applying the surface treatment agent,
Although drying is performed by heating, it is preferable to dry the plate at a temperature of 170° C. or lower. Therefore, washing with water after drying is not necessary, and it can be left as is or
Furthermore, paint is applied and used. The film on the metal surface thus obtained using the surface treatment agent of the present invention was colorless, and as a result of wet analysis, no Cr 6+ was detected. Furthermore, an attempt was made to extract Cr 6+ by immersing the coated material in deionized water maintained at a temperature of 35°C for one week (specific liquid volume 95ml/dm 2 ), but the reason was not clear. , Cr 6+ was not detected. The present invention contains trivalent chromium ions and hexavalent chromium ions such that the ratio of hexavalent chromium ions to total chromium ions is 0.1 to 0.3 as main components, so the surface treatment agent has good stability. When used as a surface treatment agent for aluminum and its alloys, the application process can be carried out as usual, and there is no need to wash with water, so there is no need for drainage treatment. The properties can be improved, a colorless film with no hexavalent chromium remaining in the film can be obtained, and it can be used in a wide range of applications, and is recognized to have excellent effects. Next, an example will be described. Example 1 1 Preparation of surface treatment agent Chromium phosphate trihydrate 3.9g/, chromium trioxide 0.8g/, phosphoric acid 8.3g/, hydrofluoric acid 1.2g/, water-soluble acrylic acid polymer (Trade name: Acrylsole A-1) was taken at a ratio of 9 g/day, and a surface treatment agent was prepared using deionized water. In this way, Cr 3+ 1.0g/, Cr 6+ 0.4g/
, Cr 6+ /Cr 3+ +Cr 6+ =0.29, PO 3+ 4 8.0g/
, F - 1.1g/, water-soluble acrylic polymer 9.0
A surface treatment agent having a composition of 1.5 g/g/, pH 1.7 was obtained. 2 Surface treatment results An aluminum plate (1100-H24, 1 mm thick) was degreased and cleaned using a normal non-etching cleaner, and the surface treatment agent prepared in 1) was applied to the
It was painted as a μm liquid film. Then 130℃
The plate was dried by heating with hot air (plate temperature: 90°C) for 1 minute. After the treated board with the colorless film was allowed to cool to room temperature, it was painted with a thermosetting paint, and the paint was baked at 150°C for 30 minutes. The dry coating thickness obtained was 20 μm. The object to be coated was tested for adhesion of the paint film using a grid tape peel test, a cross-shaped scratch was made on the painted surface and then a 72-hour cast test, and a salt spray test based on the method of JIS-Z-2371. Corrosion resistance tests were conducted for 500 hours. The results are shown in Table 1. In addition, as a result of analyzing the film by wet method,
No hexavalent chromium was detected. Example 2 Using the surface treatment solution prepared in (Example 1-1), spread it on an aluminum plate (1100-H24, 1 mm thickness) to a thickness of about 15 μm, and then insolubilize the film at 170°C for 5 minutes. I did this. The corrosion resistance of the produced colorless film was investigated by conducting a salt spray test for 100 hours. The results are shown in Table 1. In addition, an attempt was made to extract Cr 6+ by immersing the coating material in deionized water maintained at 35° C. for one week (specific liquid volume: 95 ml/dm 2 ), but no Cr 6+ was detected. Furthermore, no Cr 6+ was detected in the wet analysis of the film. From the surface treatment agent prepared in Comparative Example 1 (Example 1-1)
A so-called Cr() type surface treatment agent having a composition excluding Cr 6+ was used, and after treatment was carried out under the same conditions as in Example 1, a similar test was conducted. The results are shown in Table 1. Comparative Example 2 A Cr( ) type surface treatment agent having the same composition as in Comparative Example 1 was used, and after treatment was carried out under the same conditions as in Example 2, the same test was conducted. The results are shown in Table 1. Comparative Example 3 Cr 6+ /Cr 3+ + in the same manner as (Example 1-1)
A so-called Cr()+Cr() type surface treatment agent with Cr 6+ =0.6 was prepared, treated under the same conditions as in Example 2, and then subjected to the same test. The results are shown in Table 1. In addition, as in Example 2, Cr 6+ extraction test and wet analysis of the film were performed, and Cr 6+ was detected in both cases. 【table】
Claims (1)
６価クロムイオンと総クロムイオンの比が0.1〜
0.3の範囲の６価クロムイオン、リン酸イオン1.5
〜15ｇ、フツ素イオン0.1〜２ｇ及び水溶性アク
リルポリマー0.5〜15ｇを配合してなることを特
徴とするアルミニウム及びその合金の表面処理
剤。1 In 1 water, 0.8 to 1.5 g of trivalent chromium ion,
The ratio of hexavalent chromium ions to total chromium ions is 0.1~
Hexavalent chromium ion in the range of 0.3, phosphate ion 1.5
15 g of aluminum, 0.1 to 2 g of fluorine ions, and 0.5 to 15 g of a water-soluble acrylic polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7157782A JPS58189377A (en) | 1982-04-30 | 1982-04-30 | Surface treating agent for aluminum and its alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7157782A JPS58189377A (en) | 1982-04-30 | 1982-04-30 | Surface treating agent for aluminum and its alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58189377A JPS58189377A (en) | 1983-11-05 |
| JPS621476B2 true JPS621476B2 (en) | 1987-01-13 |
Family
ID=13464688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7157782A Granted JPS58189377A (en) | 1982-04-30 | 1982-04-30 | Surface treating agent for aluminum and its alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58189377A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039169A (en) * | 1983-08-12 | 1985-02-28 | Nippon Light Metal Co Ltd | Hydrophilic surface treating agent for metal |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50158535A (en) * | 1974-06-12 | 1975-12-22 | ||
| JPS5230235A (en) * | 1975-09-02 | 1977-03-07 | Nippon Paint Co Ltd | Chromating process |
| JPS5230230A (en) * | 1975-09-03 | 1977-03-07 | Toyota Motor Co Ltd | Method of cutting off gate and runner during material melting |
| JPS542231A (en) * | 1977-06-07 | 1979-01-09 | Nippon Paint Co Ltd | Metal surface treating method |
| JPS54110145A (en) * | 1978-01-30 | 1979-08-29 | Amchem Prod | Metal surface coating composition* preparation thereof* and application using same |
| JPS54133440A (en) * | 1978-03-31 | 1979-10-17 | Amchem Prod | Aluminum coating composition and method for coating |
| JPS5631877A (en) * | 1979-08-10 | 1981-03-31 | Isao Minagawa | Loading bed connected to tractor |
-
1982
- 1982-04-30 JP JP7157782A patent/JPS58189377A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50158535A (en) * | 1974-06-12 | 1975-12-22 | ||
| JPS5230235A (en) * | 1975-09-02 | 1977-03-07 | Nippon Paint Co Ltd | Chromating process |
| JPS5230230A (en) * | 1975-09-03 | 1977-03-07 | Toyota Motor Co Ltd | Method of cutting off gate and runner during material melting |
| JPS542231A (en) * | 1977-06-07 | 1979-01-09 | Nippon Paint Co Ltd | Metal surface treating method |
| JPS54110145A (en) * | 1978-01-30 | 1979-08-29 | Amchem Prod | Metal surface coating composition* preparation thereof* and application using same |
| JPS54133440A (en) * | 1978-03-31 | 1979-10-17 | Amchem Prod | Aluminum coating composition and method for coating |
| JPS5631877A (en) * | 1979-08-10 | 1981-03-31 | Isao Minagawa | Loading bed connected to tractor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58189377A (en) | 1983-11-05 |
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