JPS60258476A - Electroless chromate coating, plastic coating process and bath therefor - Google Patents
Electroless chromate coating, plastic coating process and bath thereforInfo
- Publication number
- JPS60258476A JPS60258476A JP3669785A JP3669785A JPS60258476A JP S60258476 A JPS60258476 A JP S60258476A JP 3669785 A JP3669785 A JP 3669785A JP 3669785 A JP3669785 A JP 3669785A JP S60258476 A JPS60258476 A JP S60258476A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- ester
- acid
- chromate
- bath
- 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.)
- Pending
Links
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
- 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
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔発明の要約〕
亜鉛とカドミウム表面は、この表面を普通の無電解クロ
メート被覆方法で使用される第２クロム塩類と他の塩類
と酸類とだけでなく、更に少なくとも１つのアクリル酸
エステル又はメタクリル酸エステルの重合体又はアクリ
ル酸エステル又はメタクリル酸エステル−スチレン−共
重合体にクロム酸アルカリ及び塩酸を含むｐＨ１〜２の
水性分散体を含む浴に浸漬することによりアルカリ酸エ
ステル又はメタクリル酸エステル基礎重合体又はスチレ
ンとの共重合体による保護層のみならず同時にクロメー
ト被覆される。DETAILED DESCRIPTION OF THE INVENTION [Summary of the Invention] Zinc and cadmium surfaces are coated with not only the ferric chromium salts and other salts and acids used in conventional electroless chromate coating processes, but also with at least one By immersing a polymer of acrylic ester or methacrylic ester or an acrylic ester or methacrylic ester-styrene-copolymer in a bath containing an aqueous dispersion of pH 1 to 2 containing alkali chromate and hydrochloric acid, alkaline acid is added. As well as a protective layer of ester or methacrylic acid ester base polymers or copolymers with styrene, there is a chromate coating at the same time.
本発明は、クロメート被覆可能の表面を一定のプラスチ
ック材料のみならずクロメートにて無電解被覆する方法
に関するものである。The present invention relates to a method for electrolessly coating chromate-coatable surfaces with chromate as well as certain plastic materials.
従来、耐食性を増大しラッカー又はフェス塗膜のような
被覆並びに装飾的色彩効果を得る基礎を生成する為に、
金属物品の表面、特に亜鉛及びカドミウムの表面又は亜
鉛又はカドミウムで被覆した表面を先ずクロメート処理
し、その後でプラスチック被覆を施すことば知られてい
る。Traditionally, in order to increase corrosion resistance and to produce coatings such as lacquers or face coatings as well as the basis for decorative color effects,
It is known to first chromate the surfaces of metal articles, in particular zinc and cadmium surfaces or surfaces coated with zinc or cadmium, and then apply a plastic coating.
亜鉛及びカドミウムの金属表面又は亜鉛及びカドミウム
で鋼及び鉄のような他の金属を夫々めっきした金属表面
が好適で、これらは米国特許第３，９６３，５２７号明
細書に開示されるようにフン化水素アンモニウム、塩化
アルカリ及び／又は硫酸アルカリのような塩類の存在下
に第２クロム塩類と強鉱酸類とにて容易にクロメート被
覆される。Zinc and cadmium metal surfaces or metal surfaces plated with zinc and cadmium on other metals such as steel and iron, respectively, are preferred, and these can be coated with ferrite as disclosed in U.S. Pat. No. 3,963,527. It is easily chromate coated with chromic salts and strong mineral acids in the presence of salts such as ammonium hydrogenhydride, alkali chlorides and/or alkali sulfates.
このようなりロメート被覆は、必要な金属活性を付与す
るために、例えばｐＨ０，５〜３．５の強酸性浴から施
されねばならない。一方プラスチック被覆は、不安定に
なるのを防止するため特にアクリル酸エステル重合体類
又は共重合体類による被覆は、例えばｐＨ７，０〜９．
５の範囲の中性又はアルカリ性から適用されねばならな
い。Such romate coatings must be applied from strongly acidic baths, for example with a pH of 0.5 to 3.5, in order to impart the necessary metal activity. On the other hand, in order to prevent plastic coatings from becoming unstable, coatings with acrylic acid ester polymers or copolymers, for example, should have a pH of 7.0 to 9.
Must be applied from a neutral or alkaline range of 5.
それ故クロメート被覆に続いてプラスチック被覆を適用
するには注意深い中間の洗浄操作を使用する別の操作工
程があることのみを要求され、そのため特別の装置設備
と多量の作業時間と大容量の作業空間を必要とした。こ
の理由のため、この操作工程はしばしば他の会社及び／
又は別の場所で実施され、このことは被覆すべき金属物
品に対し付加的輸送コストを与える。Applying a plastic coating subsequent to a chromate coating therefore only requires a separate operating step with careful intermediate cleaning operations, requiring special equipment equipment and a large amount of working time and a large volume of work space. required. For this reason, this operating process is often carried out by other companies and/or
or carried out at another location, which imposes additional transportation costs on the metal articles to be coated.
Ｃ問題点を解決するための手段）
今や驚くべきことに、一定条件下に単一操作工程で亜鉛
又はカドミウム表面へクロメート被覆し、かつプラスチ
ック被覆を適用することが可能なことが見出された。It has now surprisingly been found that it is possible to apply a chromate coating and a plastic coating to zinc or cadmium surfaces in a single operating step under certain conditions. .
クロメート被覆可能な金属表面上に保護プラスチック被
覆のみならず無電解クロメート被覆を付与する方法は、
アクリル酸エステル又はメタクリル酸エステルの重合体
又は共重合体及び／又はアクリル酸エステル又はメタク
リル酸エステル−スチレン−共重合体のｐＨ１，０〜２
．０範囲の水性液中の分散体のみならず無電解クロメー
ト被覆浴に使用される第２クロム塩類と塩類と酸類を含
む浴にクロメート被覆とプラスチック被覆が夫々なさる
べき金属表面を浸漬することからなる。A method for applying electroless chromate coatings as well as protective plastic coatings on chromate-coatable metal surfaces is
pH 1,0-2 of polymer or copolymer of acrylic ester or methacrylic ester and/or acrylic ester or methacrylic ester-styrene-copolymer
．． It consists of immersing the metal surfaces to be coated with chromate and plastic coatings respectively in a bath containing dichromic salts, salts and acids used in electroless chromate coating baths as well as dispersions in aqueous liquids in the range 0. .
特に良好な結果は、亜鉛又はカドミウムの表面又は亜鉛
又はカドミウム被覆表面を有する他の金属の物品のクロ
メート被覆及びプラスチック被覆の両方において、この
表面又は物品を次の浴に浸漬することにより得られるこ
とが見出された。その浴はアクリル酸エステル又はメタ
クリル酸エステルの重合体又は共重合体又はアクリル酸
エステル又はメタクリル酸エステル−スチレン−共重合
体とクロム酸アルカリと濃塩酸とを分散し、次いで少な
くとも１２時間後に水酸化アルカリを加えてｐ）Ｉを１
．０〜１．２とすることにより得られる重合体または共
重合体の分散体のみならず第２クロム塩類、フン化水素
アンモニウムと硫酸及び／又は硝酸の各々０．１〜５０
ｇ１ｌ量含有するものであって、アクリル酸エステル重
合体又は共重合体の量は２０〜２００ ｇ／β、塩酸は
１０〜５０ｇ／ＩＶ、、及びクロム酸アルカリは０．２
〜５ｇ／ｊ２であり、クロメート処理浴とアクリル酸エ
ステル重合体又は共重合体の分散体の容量比は２：１〜
１：２、好適には１：１である。Particularly good results have been obtained both in chromate coatings and plastic coatings of zinc or cadmium surfaces or of other metal articles with zinc or cadmium coated surfaces by immersing this surface or article in the following baths. was discovered. The bath consists of dispersing a polymer or copolymer of acrylic ester or methacrylic ester or an acrylic ester or methacrylic ester-styrene-copolymer with alkali chromate and concentrated hydrochloric acid, followed by hydration after at least 12 hours. Add alkali and reduce p)I to 1
．． 0 to 1.2, as well as dispersions of polymers or copolymers, as well as dichromic salts, ammonium hydrogen fluoride, and sulfuric acid and/or nitric acid, each having a concentration of 0.1 to 50
The amount of acrylic acid ester polymer or copolymer is 20 to 200 g/β, the amount of hydrochloric acid is 10 to 50 g/IV, and the amount of alkali chromate is 0.2 g/l.
~5 g/j2, and the volume ratio of the chromate treatment bath and the dispersion of the acrylic acid ester polymer or copolymer is ~2:1.
The ratio is 1:2, preferably 1:1.
本発明において、好適なアルカリ塩類はナトリウム塩類
とカリウム塩類である。クロメート被覆浴は好適には硫
酸と硝酸のような強鉱酸を含む。クロメート被覆を与え
る成分として又Ｃｒ Ｑ ３もまた用いてよい。In the present invention, preferred alkali salts are sodium salts and potassium salts. The chromate coating bath preferably contains strong mineral acids such as sulfuric and nitric acids. CrQ3 may also be used as a component to provide a chromate coating.
アクリル酸エステル又はメタクリル酸エステルの重合体
又は共重合体は、メタノール、エタノール、プロパツー
ル及び各種ブタノール類のようなＣ５〜Ｃ４−アルカノ
ールとアクリル酸又はメタクリル酸のエステル類の、特
にアクリル酸又はメタクリル酸のメチル及びエチルエス
テルの重合体又は共重合体が好適である。Polymers or copolymers of acrylic acid esters or methacrylic acid esters are polymers or copolymers of acrylic acid or methacrylic acid with C5-C4 alkanols such as methanol, ethanol, propatool and various butanols, especially acrylic acid or methacrylic acid. Polymers or copolymers of methyl and ethyl esters of acids are preferred.
分散体において、アクリル酸エステル又はメタクリル酸
エステルの重合体又は共重合体又は ゛アクリル酸エス
テル又はメタクリル酸エステル−スチレン−共重合体は
好適には平均粒子径０．１μｍ、かさ密度約１．０４ｇ
／ｃＪ及びエプレヒト粘度計ＳＴＶ、プローブＣ，ステ
ップ■を使用して測定した時の粘度が０．８〜１．８
ＰａＸ ｓを有する。このような分散体は、例えばノ＼
スフ社から商標アクロナールのもとに市場で入手可能で
ある。In the dispersion, the polymer or copolymer of acrylic ester or methacrylic ester or the acrylic ester or methacrylic ester-styrene copolymer preferably has an average particle diameter of 0.1 μm and a bulk density of about 1.04 g.
/cJ and the viscosity when measured using Epprecht Viscometer STV, Probe C, Step ■ is 0.8 to 1.8.
It has PaX s. Such a dispersion can be used, for example, in
It is available on the market under the trademark Acronal from the company Sufu.
本発明に係る方法を実施する時、普通の無電解クロメー
ト被覆方法で知られる通常の１〜３００秒の適用時間内
において、黄、オリーブ又は黒の色彩の陰影を得ること
が出来、クロメート層はアクリル酸エステル又はメタク
リル酸エステルの重合体又は共重合体またはアクリル酸
エステル又はメタクリル酸エステル−スチレン−共重合
体の一面に薄（おおった被覆により保護されている。When carrying out the method according to the invention, yellow, olive or black color shading can be obtained within the usual application times of 1 to 300 seconds known in common electroless chromate coating methods, and the chromate layer is It is protected by a thin coating of an acrylic ester or methacrylic ester polymer or copolymer or an acrylic ester or methacrylic ester-styrene-copolymer.
プラスチック被覆を浴に染料又は顔料を添加することに
より任意的に着色してもよい。無色被覆を着色ラッカー
又はワニス塗膜により被覆してもよい。The plastic coating may optionally be colored by adding dyes or pigments to the bath. The colorless coating may also be covered with a colored lacquer or varnish coating.
本発明の先記以上に重要な目的は浴の提供であって、こ
の浴はアクリル酸又はメタクリル酸のＣ１〜Ｃ４−アル
カノールエステルの重合体又は共重合体及び／又はアク
リル酸又はメタクリル酸のＣ１〜Ｃ４−アルカノールエ
ステル−スチレン−共重合体の塩酸を含みｐＨ１，０〜
１．２のクロム酸アルカリ中の分散体のみならず、無電
解クロメート被覆浴が公知の少なくとも１種の第２クロ
ム塩と塩類と酸類、好適にはフッ化水素アンモニウムと
硫酸及び／又は硝酸を含有するものである。An overriding object of the invention is the provision of a bath comprising a polymer or copolymer of a C1-C4 alkanol ester of acrylic acid or methacrylic acid and/or a C1-C4 alkanol ester of acrylic acid or methacrylic acid. ~ Contains hydrochloric acid of C4-alkanol ester-styrene-copolymer, pH 1.0 ~
In addition to the dispersion in alkali chromate of 1.2, the electroless chromate coating bath contains at least one known secondary chromium salt, salts and acids, preferably ammonium hydrogen fluoride and sulfuric acid and/or nitric acid. It contains.
好適にはクロメート被覆浴の重合体又は共重合体分散体
に対する容量比は２：１〜１：１、特に約１：１であり
、第２クロム塩、塩例えばフン化水素アンモニウム及び
酸、例えば硫酸及び／又は硝酸の含量は各々０．１〜５
０ｇ／βであり、アクリル酸エステル重合体又は共重合
体の含量は２０〜２００ ｇ／βであり、ＨＣＩの含量
は１０〜５０ｇ／Ａであり、クロム酸アルカリの含量は
０．２〜５ｇ／Ａである。Preferably the volume ratio of the chromate coating bath to the polymer or copolymer dispersion is from 2:1 to 1:1, in particular about 1:1, and the volume ratio of the chromate coating bath to the polymer or copolymer dispersion is preferably from 2:1 to 1:1, in particular about 1:1, and contains a chromate salt, a salt such as ammonium hydrogen fluoride and an acid, such as The content of sulfuric acid and/or nitric acid is 0.1 to 5 each.
The content of acrylic acid ester polymer or copolymer is 20-200 g/β, the content of HCI is 10-50 g/A, and the content of alkali chromate is 0.2-5 g. /A.
本発明の浴で処理された表面を有する物品は、普通の無
電解クロメート被覆方法で先ず処理し次いで比較できる
ワニス又はラッカーでワニスを塗布する２工程方法で処
理した表面と比較する時、全く劣ってない性質を示す。Articles having surfaces treated with the baths of the present invention are significantly inferior when compared to surfaces treated with a two-step process, first treated with a conventional electroless chromate coating process and then varnished with a comparable varnish or lacquer. It shows a characteristic that is not true.
本発明の方法においては従来の無電解クロメート被覆方
法を変えなくてよい。水洗並びに熱風乾燥でさえプラス
チック被覆に全く影響することなく適用できる。しかし
、プラスチック被覆は大気中の保存に対し、従来のワニ
ス塗膜と同じく硬化する。The method of the present invention does not require any changes to conventional electroless chromate coating methods. Even water washing and hot air drying can be applied without any effect on the plastic coating. However, plastic coatings harden on storage in the atmosphere in the same way as traditional varnish coatings.
本発明方法の驚くべき利益は、亜鉛や他の金属類に対す
るアクリル酸エステル又はメタクリル酸エステルの重合
体又は共重合体分散体の公知の敏感さが全く見当らない
という事実に帰する。The surprising benefits of the process of the invention are due to the fact that the known sensitivity of polymeric or copolymer dispersions of acrylic or methacrylic esters to zinc and other metals is completely absent.
本発明を次の実施例により更に説明する。 The invention is further illustrated by the following examples.
実施例１ 無電解クロメート被覆用の浴は次により調製された。Example 1 A bath for electroless chromate coating was prepared as follows.
Ｃｒ ０３ １．Ｏｇ／β
（ＮＨ４） ＨＦ２． １．４ ｇ／ＲＨ２ＳＯ４１，
Ｏｇ／β
ＨＮＯ３、８，０ｇ／β
別にアクリル酸エチルエステル−スチレン−共重合体（
エプレヒト粘度計ＳＴＶ、プローブＣ，ステップ■で測
定した時の粘度ｌＰａＸ５）、５０％固体含量の分散形
態における２０℃のかさ密度１．０８ｇ ／ ｃｒｌ、
平均粒子大きさ０．１μｍ（商標アクロナール２９０Ｄ
）を濃塩酸２Ｑｃ＋ｄとクロム酸ナトリウム１ｇと混合
し２４時間放置後、か性ソーダ溶液をｐＩ（１，１にな
るまで添加した。次いで分散体を水で１βまで稀釈した
。Cr 03 1. Og/β (NH4) HF2. 1.4 g/RH2SO41,
Og/β HNO3, 8,0g/β Separately, acrylic acid ethyl ester-styrene-copolymer (
Viscosity when measured with an Epprecht viscometer STV, probe C, step ■ lPaX5), bulk density at 20 °C in dispersion form with 50% solids content 1.08 g / crl,
Average particle size 0.1 μm (trademark Acronal 290D
) was mixed with 2Qc+d of concentrated hydrochloric acid and 1g of sodium chromate, and after standing for 24 hours, caustic soda solution was added to pI (1,1).The dispersion was then diluted to 1β with water.
ｐｌ＋は１．０となった。pl+ was 1.0.
両方の溶液各々１１を混合し、亜鉛めっき鉄管をこの混
合溶液中に２０秒浸漬した。鉄管は共重合体被覆を伴な
った青色のクロメート被覆がなされ、これは耐食性を有
し、蒸留水で洗浄し熱風乾燥後に耐摩耗性を有した。Both solutions were mixed in 11 parts each, and a galvanized iron pipe was immersed in this mixed solution for 20 seconds. The iron tube was coated with a blue chromate coating with a copolymer coating, which was corrosion resistant and abrasion resistant after washing with distilled water and hot air drying.
実施例２ 次の組成の浴を調製した。Example 2 A bath with the following composition was prepared.
Ｃｒ ０３ １−９．４ ｇ／ ｊ！
ＮａＣ］ ９．６ｇ／ｎ
Ｎａ２３０４ １．０ ｇ／ １２
実施例１のアクリル酸エステル−スチレン−共重合体分
散体を添加した。Cr 03 1-9.4 g/j! NaC] 9.6 g/n Na2304 1.0 g/12 The acrylic acid ester-styrene-copolymer dispersion of Example 1 was added.
この溶液に亜鉛めっき鉄管を浸漬した。A galvanized iron pipe was immersed in this solution.
２０秒後に共重合体被覆を伴なった黄色クロメート被覆
が得られ、これは蒸留水で洗浄し熱風乾燥した後耐食性
、耐摩耗性であった。After 20 seconds a yellow chromate coating with a copolymer coating was obtained, which after washing with distilled water and drying with hot air was corrosion and abrasion resistant.
特許出願人
工しクトローブリテ ゲゼルシャフト
ミソト ベシュレンクテル ハフツンダウント コンパ
ニー
コマンデソトゲゼルシャフトPatent application for patent applications
Claims (7)
電解クロノート被覆及び同時にプラスチック被覆する方
法において、前記物品を酸水性浴に１〜２００秒間浸漬
し、前記浴は無電解クロメート被覆浴類に使用されるよ
うな少なくとも１種の第２クロム塩と塩類と酸類と、更
にアクリル酸エステル又はメタクリル酸エステルの重合
体又は共重合体及び／又はアクリル酸エステル又はメタ
クリル酸エステル−スチレン−共重合体のｐＨ１〜２に
おける分散体とを含有することを特徴とする被覆方法。(1) In a method of electroless chromat coating and simultaneous plastic coating of an article having a surface capable of being coated with chromate, the article is immersed in an acid aqueous bath for 1 to 200 seconds, and the bath is replaced with an electroless chromate coating bath. at least one secondary chromium salt, salts and acids as used, and also polymers or copolymers of acrylic esters or methacrylic esters and/or acrylic ester or methacrylic ester-styrene-copolymers. and a dispersion at a pH of 1 to 2.
うな少なくとも１種の第２クロム塩と他の塩類と鉱Ｗｉ
類とを夫々０．１〜５０ｇ／Ａ含む以外に更に、アクリ
ル酸又はメタクリル酸のｃ、−Ｃ４アルカノールエステ
ルの重合体又は共重合体及び／又はアクリル酸又はメタ
クリル酸のＣ４〜Ｃ４アルカノールエステル−スチレン
−共重合体とクロム酸アルカリと塩酸とを分散し、水酸
化アルカリを加えてｐｌ＋を１．０〜１．２とすること
により得られる分散体を含み、重合体又は共重合体量は
２０〜２００ｇ／ＩＨｃＩ量は１．０〜５０ｇ／＃及び
クロム酸アルカリ量は０６２〜５ｇ／β、更にクロメー
ト浴とアクリル酸エステル重合体又は共重合体分散体の
容量比は２：１〜１：２であることを特徴とする特許請
求の範囲第１項記載の被覆方法。(2) The bath contains at least one chromic salt and other salts such as those used in electroless chromate coating baths.
In addition to containing 0.1 to 50 g/A of acrylic acid or methacrylic acid, c, -C4 alkanol ester polymer or copolymer and/or acrylic acid or methacrylic acid C4 to C4 alkanol ester - It includes a dispersion obtained by dispersing a styrene copolymer, an alkali chromate, and hydrochloric acid, and adding an alkali hydroxide to adjust the pl+ to 1.0 to 1.2, and the amount of the polymer or copolymer is 20-200g/IHcI amount is 1.0-50g/#, chromate alkali amount is 062-5g/β, and the volume ratio of chromate bath and acrylic ester polymer or copolymer dispersion is 2:1-1 The coating method according to claim 1, characterized in that: :2.
アンモニウム及び硫酸及び／又は硝酸を夫々０．１１５
０ｇ／Ａを含む以外に更にアクリル酸又はメタクリル酸
のＣ１〜Ｃ４アルカノールエステルの重合体又は共重合
体及び／又はアクリル酸又はメタクリル酸の０１ ・〜
Ｃ４アルカノールエステル−スチレン−共重合体の２０
〜２００ ｇ／１２でｐＨ１，０〜１．２の分散体を含
み、クロメート浴とアクリル酸エステルの重合体又は共
重合体の分散体の容量比は約１：１であることを特徴と
する特許請求の範囲第２項記載の被覆方法。(3) The bath contains at least one chromic salt, ammonium hydrogen fluoride and 0.115% each of sulfuric acid and/or nitric acid.
In addition to containing 0g/A, a polymer or copolymer of C1-C4 alkanol ester of acrylic acid or methacrylic acid and/or 01 ・~ of acrylic acid or methacrylic acid
20 of C4 alkanol ester-styrene-copolymer
~200 g/12 containing a dispersion with a pH of 1.0 to 1.2, characterized in that the volume ratio of the chromate bath to the dispersion of a polymer or copolymer of an acrylic acid ester is approximately 1:1. A coating method according to claim 2.
体又は共重合体の分散体又はアクリル酸又はメタクリル
酸のエステル−スチレン−共重合体の分散体は平均粒子
径０．１μｍ、かさ密度的１．０４ｇ／ｃＪ及びエプレ
ヒト粘度計ＳＴＶ。 プローブＣ，ステップ■で測定した時の粘度０．８〜１
．８ ＰａＸ ｓ である特許請求の範囲第１項乃至第
３項のいずれか１項に記載の被覆方法。(4) The dispersion of a polymer or copolymer of ester of acrylic acid or methacrylic acid or the dispersion of ester of acrylic acid or methacrylic acid-styrene-copolymer has an average particle diameter of 0.1 μm and a bulk density of 1. 04g/cJ and Epprecht Viscometer STV. Viscosity 0.8-1 when measured with probe C, step ■
．． 8 PaX s The coating method according to any one of claims 1 to 3.
ムで被覆された表面を有する他金属の物品のための同時
にクロメート被覆とプラスチック被覆を施す浴において
、 （Ａ）第２クロム塩、他の塩類及び鉱酸類を夫々０．１
〜５０ｇ／β量含む溶液と （Ｂ）アクリル酸又はメタクリル酸のＣ１〜Ｃ４アルカ
ノールエステルの重合体又は共重合体、又はアクリル酸
又はメタクリル酸の自 〜Ｃ４アルカノールエステル−
スチレン−共重合体の２０〜２００ｇ／ｌ、クロム酸ア
ルカリ０．２〜５ ｇ ／ ｊ２及び濃塩酸１０〜５０
ｇ／βを分散し、少なくとも１２時間後に、ｐＨ１，０
〜２．０が得られる量で水酸化アルカリを加えて得られ
る重合体又は共重合体の分散体で、クロメート浴＜Ａ）
と分散体の容量比が２：１〜１：２である分散体と からなることを特徴とする浴。(5) In baths for simultaneously applying chromate coatings and plastic coatings for articles of zinc or cadmium or articles of other metals having surfaces coated with zinc or cadmium: (A) chromium salts, other salts and minerals; 0.1 each of acids
A solution containing ~50 g/β amount and (B) a polymer or copolymer of a C1-C4 alkanol ester of acrylic acid or methacrylic acid, or a ~C4 alkanol ester of acrylic acid or methacrylic acid.
20-200 g/l of styrene-copolymer, 0.2-5 g/j2 of alkali chromate and 10-50 g/l of concentrated hydrochloric acid
g/β and after at least 12 hours, at pH 1.0
A dispersion of a polymer or copolymer obtained by adding alkali hydroxide in an amount to obtain a chromate bath <A)
and a dispersion having a volume ratio of 2:1 to 1:2.
ニウムと硫酸及び／又は硝酸の各々１〜５０ｇ／１２か
らなる溶液である特許請求の範囲第５項記載の浴。(6) The bath according to claim 5, wherein the solution (A) is a solution containing 1 to 50 g/12 each of Cr 03 , ammonium hydrogen fluoride, sulfuric acid and/or nitric acid.
ｎ！ 。 平均粒子径０．１μｍ、エプレヒト粘度計ＳＴＶ。 プローブＣ，ステンプ■で測定した時の粘度０．８〜１
．８ Ｐａ ｘ ｓ を有するアクリル酸又はメタクリ
ル酸のＣ１〜Ｃ４アルカノールのエステルの重合体又は
共重合体及び／又はアクリル酸又はメタクリル酸のＣ（
〜Ｃ４アルカノールのエステル−スチレン−共重合体よ
りなるｐＨ，０〜１，２の分散体であることを特徴とす
る特許請求の範囲第５項記載の浴。(7) Dispersion (B) has a bulk density of 1.04 g/c
n! . Average particle size 0.1 μm, Epprecht viscometer STV. Viscosity 0.8 to 1 when measured with Probe C and Stemp ■
．． Polymers or copolymers of esters of C1-C4 alkanols of acrylic acid or methacrylic acid with 8 Pa x s and/or C(
6. The bath according to claim 5, wherein the bath is a dispersion of an ester-styrene copolymer of ~C4 alkanol and has a pH of 0 to 1.2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843407283 DE3407283A1 (en) | 1984-02-28 | 1984-02-28 | Method for the electroless application of chromium coatings and of plastic coatings onto chromatable metal surfaces and bath for carrying out the method |
| DE3407283.7 | 1984-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60258476A true JPS60258476A (en) | 1985-12-20 |
Family
ID=6229097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3669785A Pending JPS60258476A (en) | 1984-02-28 | 1985-02-27 | Electroless chromate coating, plastic coating process and bath therefor |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS60258476A (en) |
| DE (1) | DE3407283A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0222282A3 (en) * | 1985-11-04 | 1987-08-19 | HENKEL CORPORATION (a Delaware corp.) | Process for coating metal surfaces with organic layers |
| EP0264472A1 (en) * | 1986-10-21 | 1988-04-27 | Procoat, S.A. | Aqueous composition for the passivation of zinc and cadmium surfaces |
| DE3639417C1 (en) * | 1986-11-18 | 1987-11-26 | Mannesmann Ag | Process for encasing objects made of steel with plastic |
| NL9500250A (en) | 1995-02-10 | 1996-09-02 | Adw Chem Prod Bv | Coating composition for metal surface pretreatment and method using it. |
| CN109852958A (en) * | 2018-12-21 | 2019-06-07 | 南京沃尔德特钢有限公司 | A kind for the treatment of process of corrosion resistance seamless steel pipe |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE629606A (en) * | 1962-03-14 | |||
| DE2444028A1 (en) * | 1973-09-21 | 1975-03-27 | Metallgesellschaft Ag | PROCEDURE FOR APPLYING A COATING TO METALLIC SURFACES |
-
1984
- 1984-02-28 DE DE19843407283 patent/DE3407283A1/en not_active Withdrawn
-
1985
- 1985-02-27 JP JP3669785A patent/JPS60258476A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3407283A1 (en) | 1985-09-12 |
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