JPH09208859A - Composition for treating metal surface and surface-treated metal sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treatment bath without using chromium and to provide a surface-treated metal sheet excellent in the adhesion of a film, a naked corrosion resistance after processing, and the adhesion to a coating material. SOLUTION: This compsn, is prepd. by compounding 100 pts.wt. org. resin having 5wt.% or higher hydroxyl monomer units with 2-60 pts.wt phosphoric acid and 0.015-1.5g-ion of at least one kind of ion selected from among Mg<++> , Al<++> , Ba<++> , Ca<++> , Sr<++> , Fe<++> , Nb<+++> , Nb<++++> , Y<+++> , and Zn<++> and if necessary further with one of various colloids.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal such as a cold rolled steel sheet, a Zn plated steel sheet, a Zn alloy plated steel sheet, Ni, Cu, P.
b, Sn, Cd, Al, Ti, etc. Metal plate or a plated steel sheet of these metals or an alloy-plated steel sheet of these metals is applied and dried to form an anticorrosive film. The present invention relates to a metal surface treatment composition and a surface-treated metal plate having a rust preventive coating using the same.

[0002]

2. Description of the Related Art Cold rolled steel sheets, Zn plated steel sheets, Zn-Ni series, Zn
-Ni-Co series, Zn-Ni-Cr series, Zn-Fe series, Zn-Co series, Zn-Cr series
System, Zn-based alloy plated steel such as Zn-Mn system, Ni, Cu,
In order to improve the corrosion resistance of a metal plated steel sheet of Pb, Sn, Cd, Al, Ti or the like or an alloy plated steel sheet of these metals, a chromate film is generally formed by a chromate treatment.

However, as a recent tendency, due to environmental and pollution problems, regulations on chromium are being significantly strengthened. Accordingly, development of a corrosion-resistant coating composition that does not use chromium is also under consideration. For example, one that coats an emulsion polymer obtained by polymerizing a polymerizable unsaturated monomer containing a specific amount of unsaturated carboxylic acid (JP-A-5-222324), an aqueous dispersion of a synthetic resin containing a pendant acetoacetyl group. (Japanese Patent Laid-Open No. 5-148432), a substantially water-insoluble mono- or poly-basic salt of a special keto acid and a base selected from cations, amines, guanidines and amidines Coating a mixture of
(Japanese Unexamined Patent Publication No. 3-192166), which is coated with a copolymer resin of unsaturated carboxylic acid-unsaturated monomer containing glycidyl group-monomer copolymerized with alkyl acrylate and alkyl acrylate. Etc. can be given. All of them are coated with a special resin, but it is necessary to form a considerably thick film to secure the corrosion resistance. In addition, the adhesion to various metals such as iron and various plated steel sheets is not necessarily good, and the adhesion is remarkably lowered, especially in a wet environment, and the film peels off. There is no film that can maintain excellent adhesion even in a wet environment.

[0004]

On the other hand, the present invention solves the above-mentioned drawbacks of the prior art, cold rolled steel sheet or Zn or Zn-based alloy plated steel sheet, Ni, Cu, Pb, Sn, Cd, Al, Even if a very thin film is formed on a metal plate such as Ti, a plated steel sheet of these metals, or an alloy-plated steel sheet of these metals, it shows excellent adhesion to the material, and extremely excellent corrosion resistance and paint adhesion. The first object of the present invention is to provide a chromium-free surface treatment agent capable of ensuring the above. The second purpose is cold rolled steel sheet or Zn or Zn alloy plated steel sheet, Ni, C
u, Pb, Sn, Cd, Al, Ti, etc. metal plate or a plated steel sheet of these metals or an alloy-plated steel sheet of these metals with the above treatment agent, a film excellent in bare corrosion resistance after processing and paint adhesion The present invention provides a chromium-free surface-treated metal plate which is excellent in bare corrosion resistance and paint adhesion after processing in which a specific amount of is formed.

A third object is a cold rolled steel plate, a Zn or Zn alloy plated steel plate, a metal plate such as Ni, Cu, Pb, Sn, Cd, Al or Ti, or a plated steel plate of these metals or an alloy of these metals. A specific amount of a film with excellent paint adhesion is formed on the plated steel sheet with the above treatment agent, and a specific amount of a specific organic resin is applied on top of it to provide a chromium-free coating with excellent corrosion resistance and paint adhesion after processing. A surface-treated steel sheet is provided. The fourth purpose is to provide a cold-rolled steel plate, a Zn- or Zn-based alloy-plated steel plate, a metal plate such as Ni, Cu, Pb, Sn, Cd, Al, or Ti, a plated steel plate of these metals, or an alloy-plated steel plate of these metals. A specific amount of film with excellent scratch resistance and paint adhesion was formed on top of the above treatment bath, and SiO ₂ , Sn
_{O 2, Cr 2 O 3,} Fe 2 O 3, Fe 2 O 4, MgO, and a specific amount applying an organic resin mixed with colloid (sol) or the powder of Al ₂ O _3, highly corrosion resistance after processing Provided is a chromium-free surface-treated steel sheet having excellent paint adhesion.

[0006]

Means for Solving the Problems That is, the first invention
Is an organic resin containing 5% by weight or more of a hydroxyl group-containing monomer.
2 to 60 parts by weight of phosphoric acid is mixed with 100 parts by weight of fat.
And Mg⁺⁺, Ba⁺⁺, Al ⁺⁺⁺ , Ca⁺⁺, Sr⁺⁺, Fe⁺⁺, Nb
⁺⁺⁺⁺⁺ , Nb⁺⁺⁺ And Y⁺⁺⁺ 1 or 2 or more of 0.01
Metals characterized by containing 5 to 1.5 grams of ionic part
It is a composition for surface treatment. The second invention is a hydroxyl group-containing model.
100 parts by weight of organic resin containing 5% by weight or more of nomer
2 to 60 parts by weight of phosphoric acid, and Mg⁺⁺, Ba
⁺⁺, Al⁺⁺⁺ , Ca⁺⁺, Sr⁺⁺, Fe⁺⁺, Nb⁺⁺⁺⁺⁺ , Nb⁺⁺⁺ as well as
Y⁺⁺⁺ One or more of 0.015 to 1.5 grams io
Part of the mixture, and further SiO_Two, Cr_TwoO_Three , Fe_TwoO_Three , Fe_ThreeO_Four ,
MgO, ZrO_Two, SnO_Two, Al_TwoO_Three , Sb_TwoO_FiveColloid (sol)
Alternatively, 3 to 30 parts by weight of one or more powders are blended.
It is a composition for metal surface treatment characterized by the above. No.
Invention of 3 is metal, for example, cold rolled steel sheet, Zn plated steel sheet, Zn
System alloy plated steel sheet, gold such as Ni, Cu, Pb, Sn, Cd, Al, Ti
Metal plate, plated steel plate of these metals or combination of these metals
On the gold-plated steel sheet, the metal surface treatment shown in the first invention
The amount of coating formed by applying the composition for use is 0.1 to 3.
0 g / m^TwoIs a surface-treated metal plate.
A fourth invention is a metal, for example, a cold rolled steel plate, a Zn plated steel plate,
Zn-based alloy plated steel sheet, such as Ni, Cu, Pb, Sn, Cd, Al, Ti
Metal plate, plated steel of these metals or of these metals
On the alloy-plated steel sheet, the metal surface treatment shown in the second invention is applied.
The adhesion amount of the film formed by applying the theoretical composition is 0.1-
3.0 g / m^TwoIt is a surface-treated metal plate characterized by
You. The fifth invention is the surface treatment shown in the third or fourth invention.
Methyl methacrylate-
Butyl acrylate-styrene-glycidyl methacrylate
To-methacrylic acid-acrylic acid-organic phosphorus monomer-
1 or 2 from hydroxyethyl acrylate
Organic resin or olefin /
Acrylic acid copolymer resin, polyacrylic acid and its copolymer
Polymer resin, polyacrylic acid ester and its copolymer resin
Fat, polymethacrylic acid ester and copolymer resin thereof,
Polyacrylic ester and its copolymer resin, epoxy
Si resin, acrylic modified epoxy resin, ester modified EPO
Xy resin, urethane modified epoxy resin, urethane modified
Poxyester resin, vinyl modified epoxy resin, Bioni
There is one selected from among the modified epoxy ester resins.
Or a coating consisting of two or more kinds with a coating weight of 0.2-3.0 g / m^Twoso
Surface-treated metal characterized by being formed in a certain manner
Board. A sixth invention is the surface treatment according to the third or fourth invention.
Methyl methacrylate-
Butyl acrylate-styrene-glycidyl methacrylate
To-methacrylic acid-acrylic acid-organic phosphorus monomer-
1 or 2 from hydroxyethyl acrylate
Organic resin or olefin /
Acrylic acid copolymer resin, polyacrylic acid and its copolymer
Polymer resin, polyacrylic acid ester and its copolymer resin
Fat, polymethacrylic acid ester and copolymer resin thereof,
Polyacrylic ester and its copolymer resin, epoxy
Si resin, acrylic modified epoxy resin, ester modified EPO
Xy resin, urethane modified epoxy resin, urethane modified
Poxyester resin, vinyl modified epoxy resin, Bioni
There is one selected from among the modified epoxy ester resins.
Or 2 or more kinds of resin and 100 parts by weight of resin and SiO_Two, Cr_TwoO_Three , Fe_Two
O_Three, Fe_ThreeO_Four , MgO, ZrO_Two, SnO_Two, Al_TwoO_Three , Sb_TwoO_FiveThe sol
Or 10 to 1 or 2 or more selected from powders
The amount of coating containing 60 parts by weight is 0.2 to 3.0 g / m^TwoIn
Surface-treated metal plate characterized by being formed like
It is.

In the above-mentioned present invention, a surface-treated film containing a special organic resin, phosphoric acid, a special heavy metal as a component, or a special surface-treated film containing a special inorganic substance as a component is a cold-rolled steel plate or a Zn or Zn-based material. It is formed on various metals such as alloy-plated steel sheets, ensures extremely excellent adhesion with various metals, and has excellent bare corrosion resistance and paint adhesion after processing as well as adhesion with various organic resins. An extremely stable surface treatment bath that forms an excellent surface treatment film can be obtained. This extremely excellent adhesion with various metals is ensured depending on the combination of the special organic resin with phosphoric acid and special heavy metals. Further, extremely excellent bare corrosion resistance can be realized only by combining a special organic resin and a special heavy metal. Also, excellent paint adhesion is ensured by the combination of a special organic resin with phosphoric acid and a special heavy metal. Hereinafter, the contents of the special organic resin and the special heavy metal used in the present invention and the special organic resin,
It shows how the characteristics of the film formed by the combination of phosphoric acid and a special heavy metal compound change.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The organic resin referred to in the present invention means an organic resin containing a hydroxyl group-containing monomer as a component in an amount of 5% by weight or more (hereinafter referred to as the present organic resin). In addition, when only showing% and a part below, it means a weight% and a weight part, respectively. As the hydroxyl group-containing monomer component, (meth) acrylic acid-hydroxylethyl, (meth) hydroxypropyl acrylate, (meth) acrylic acid 3-hydroxybutyl, acrylate-2,2-bis (hydroxymethyl) ethyl, (meth) ) Acrylic-acid 2,3-dihydroxypropyl, (meth) acrylic acid-3-chloro-2-hydroxypropyl and other (meth) acrylic acid hydroxyesters, allyl alcohols and N-methylolacrylamide,
N-Butoxymethylol (meth) acrylamide and other alcohol amides containing reducing hydroxyl groups and glycidyl (meth) acrylate, allyl glycidyl ether, β-methylglycidyl, which can be expected to have the same reactivity as hydroxyl groups in acidic liquids (Meth) acrylate, 3,4-
Although a monomer having a glycidyl group such as epoxycyclohexylmethyl (meth) acrylate and a monomer having an aldehyde group such as acrolein can be used, particularly preferably -2-hydroxyethyl acrylate and -2-hydroxyethyl methacrylate. . In addition, (meth) acrylic acid ~ represents methacrylic acid ~ and / or acrylic acid ~. The present organic resin is a resin having the above hydroxyl group-containing monomer alone or a copolymer of the above hydroxyl group-containing monomer with another organic resin so that the hydroxyl group-containing monomer is 5% or more.

As the organic resin other than the present organic resin, it is desirable to use one or two of ethylenically unsaturated carboxylic acid and other ethylenically unsaturated compound at the same time. As the ethylenically unsaturated carboxylic acid component, for example, acrylic acid, methacrylic acid, ethylenically unsaturated monocarboxylic acid such as crotonic acid, itaconic acid, maleic acid, ethylenically unsaturated dicarboxylic acid such as fumaric acid, and those Alkali metal salts of carboxylic acids, ammonium salts and organic amine salts can be used. Further, the ethylenically unsaturated compound is an ethylenically unsaturated compound other than the examples of the ethylenically unsaturated carboxylic acid component and the hydroxyl group-containing monomer component, and the (meth) acrylic acid alkyl ester and its copolymer resin, and other Vinyl compounds such as aromatic vinyl compounds. In addition to the above, polyacrylic acid ester and its copolymer resin, polymethacrylic acid ester and its copolymer resin, epoxy and its copolymer resin, acrylic modified epoxy and its copolymer resin, ester modified epoxy and its copolymer It is also possible to use a coalescing resin, a urethane-modified epoxy resin and a copolymer resin thereof. One or two or more selected from these can be used in combination. Further, compounds other than the above-mentioned compounds may be contained within the range not impairing the object of the present invention.

As the special heavy metal, Mg, Al, Ba, Ca, Sr,
Fe, Nb, and Y, and these heavy metals must be present in the bath in the ionic state. Actual H ₂ O to these ions in aqueous solution, OH ^-, O ^-, etc. is or complexly bonded, or coordinated, while or adsorbed it at all no problem. It is necessary to mix 0.015 to 1.5 gram ion parts of one or more of the above heavy metal ions with 100 parts by weight of the present organic resin containing the hydroxyl group-containing monomer as a main component. Further, it is necessary to add 2 to 60 parts by weight of phosphoric acid to 100 parts by weight of the present organic resin containing the hydroxyl group-containing monomer as a main component.

Hereinafter, a bath in which the present organic resin, heavy metal ions and phosphoric acid coexist is prepared, and a film is formed on a plated steel sheet to show how the characteristics change. As the organic resin, 100 g / l (solid content 100% by weight) of a resin obtained by copolymerizing 40 parts of hydroxyethyl acrylate (hydroxyl group-containing monomer), 15 parts of methyl methacrylate and 20 parts of acrylic acid (hydroxyl group-containing monomer: 53%). Part) added. Phosphoric acid was added at 15 g / l (15 parts by weight), and Mg ++ was added at various ratios. When a surface treatment bath consisting of these aqueous liquids was created, it was applied to an electric Zn-plated steel sheet (Zn deposition amount: 30 g / m ² ) so that the total solid content was 0.30 g / m ^2, and dried to form Regarding the coating, it was investigated how the adhesion to the material (electrical Zn-plated steel sheet), paint adhesion, and bare corrosion resistance after processing change.

Here, the adhesion between the material and the surface-treated film according to the present invention is determined by immersing the film in boiling water for 30 minutes after drying, and then cutting the film on a 2 mm slot and peeling the tape to remove the coating film. Was evaluated. ◎: Film peeling area 0% ○: 〃 more than 0% to 1% △: 〃 more than 1% to 10% ×: 〃 more than 10% to 50% XX: more than 50%

Adhesion with the paint was applied by melamine-based low-temperature baking paint (baking temperature: 110 ° C on the surface-treated film obtained by spraying to 30 μm after baking, and then boiling water.
After being immersed for 30 minutes, the coating film was cut on a 2 mm goggle and the tape was peeled off to evaluate the peeled area of the coating film. ◎: Peeling area of coating film 0% ○: 〃 more than 0% to 1% △: 〃 more than 1% to 10% ×: 〃 more than 10% to 50% XX: more than 50%

The bare corrosion resistance after processing was evaluated by performing a cylindrical drawing process with a drawing depth of 50 mm and then performing a corrosion test, and the occurrence of red rust on the side surface subjected to the ironing process. Corrosion test is JI
In a salt spray test based on the SZ-2371 standard (salt water concentration 5%, bath temperature 35 ° C, spray pressure 20PSI), the rusting status after 1000 hours is shown, and there are 5 levels of ◎, ○, △, ×, XX. Evaluated with ◎
Is the best. ◎: Red rust occurrence rate 0% ○: 〃 more than 0% to 1% △: 〃 more than 1% to 10% ×: 〃 more than 10% to 50% XX: more than 50%

The adhesion of the formed film to the Zn-plated steel sheet depends on the concentration of coexisting Mg ⁺⁺ , and Mg ⁺⁺ is 0.015 gram ion / 1 (part) or more, 1.5 gram ion / 1
(Part) In the following, the adhesion of the film to the Zn-plated steel sheet is improved,
In the above test, the peeled area of the film was none (⊚).
If the Mg ^{++ is} less than 0.015 gram ion / l (part) and more than 1.5 gram ion / l (part), the adhesion will decrease. The adhesion between the coating of the formed film is affected by the concentration of Mg ^++, Mg ⁺⁺ is 0.015 g ion / 1 (parts) above, 1.5
It exhibits excellent paint adhesion at gram ion / part (1 part) or less, and there is no peeled area of the coating film (⊚) in the above test. If the amount is less than 0.015 gram ion / 1 (part) and exceeds 1.5 gram ion / 1 (part), the coating adhesion will decrease. The bare corrosion resistance of the formed film after processing depends on the concentration of Mg ⁺⁺ . When Mg ⁺⁺ is 0.015 g ion / l (part) or more and 1.5 g ion / l (part) or less, the bare corrosion resistance after processing is significantly improved. However, no red rust was generated (⊚) in the above test. 0.
015 gram ion / less than 1 (part) and 1.5 gram ion
/ More than 1 (part) reduces the bare corrosion resistance after processing.

Next, as the present organic resin, resins in which hydroxyethyl acrylate (hydroxyl group-containing monomer) was variously changed were prepared (hydroxyethyl acrylate (hydroxyl group-containing monomer) α part-methyl methacrylate 15 parts-acrylic acid
Resin (30 parts copolymerized) was added at 100 g / 1 (solid content) (100 parts by weight). In addition, an aqueous solution was prepared by adding 15 g / 1 (16 parts by weight) of phosphoric acid and 0.2 gram ion / l of Mg ⁺⁺ . A surface treatment bath consisting of these aqueous liquids was treated with electric Zn.
0.35 g / m ² of total solids content on plated steel sheet (Zn deposit: 30 g / m ² ).
It was investigated how the film formed by applying the above-mentioned coating and drying was changed in adhesion to the material (electrical Zn-plated steel sheet), paint adhesion, and bare corrosion resistance after processing.

The proportion of the hydroxyl group monomer in the present organic resin affects the adhesiveness between the formed film and the electric Zn-plated steel sheet, and improves when it is 5% or more (⊚). The proportion of the hydroxyl group monomer in the present organic resin affects the paint adhesion, and when it is 5% or more, the paint adhesion is remarkably improved, and no coating film peeling occurs in the above test (⊚). If it is less than 5%, the adhesiveness of the paint will be reduced. In addition, the proportion of hydroxyl monomer in this organic resin has a great effect on the bare corrosion resistance of the processed part,
As a result, the bare corrosion resistance of the worked part is significantly improved (⊚), and if it is less than 5%, the bare corrosion resistance of the worked part is reduced.

Next, as the organic resin, 100 g / l of a resin obtained by copolymerizing 20 parts of hydroxyethyl acrylate (monomer containing hydroxyl group) -30 parts of methyl methacrylate-40 parts of acrylic acid (monomer containing hydroxyl group: 22%) (Solid content) (100 parts by weight) was added, Mg ++ was added at 0.15 g ion / 1 (part), and phosphoric acid was added at various ratios. A surface treatment bath consisting of these aqueous liquids was prepared, and the electric Zn plated steel sheet (Zn
Coating weight: 30 g / m @ 2) on total solids. The coating is 0.35 g / m ^2, dried for coating when formed by material (electrical
It was investigated how the adhesiveness to a Zn-plated steel sheet, the adhesiveness to paint, and the bare corrosion resistance after processing changed. The concentration of phosphoric acid has a great influence on the adhesion between the formed film and the electric Zn plated steel sheet, and shows excellent adhesion at 2 to 60 parts by weight relative to 100 parts by weight of this organic resin. Is none (◎). If the amount is less than 2 parts by weight or more than 60 parts by weight, the adhesion of the coating is deteriorated. The concentration of phosphoric acid influences the adhesiveness of the paint, showing excellent adhesiveness at 60 parts by weight or less, and there is no peeling of the coating film in the above test (⊚). If it exceeds 60 parts by weight, the adhesiveness of the paint will be reduced. Further, the concentration of phosphoric acid does not significantly affect the corrosion resistance of the processed part. If it exceeds 60 parts by weight, the corrosion resistance of the work part will be slightly reduced.

From the above results, 5% of the hydroxyl group-containing monomer was added.
For every 100 parts by weight of organic resin contained above, 0.015 of Mg ++
~ 1.5g Ion part and 2 ~ 60 parts by weight of phosphoric acid are applied to the coated steel sheet for excellent adhesion to the coated steel sheet, as well as coating adhesion and bare corrosion resistance. Can form a film. here,
The reason why it is possible to form a film having excellent adhesion to a plated steel sheet by applying the above-mentioned aqueous liquid, and further, it is possible to form a film having extremely excellent paint adhesion and bare corrosion resistance of the processed part, but it is not clear as follows. Conceivable. That is, when the above-mentioned aqueous liquid is applied and dried to form a film, Mg ⁺⁺ oxidizes the OH group of the hydroxyl group-containing monomer contained in the organic resin, and itself plays a role of crosslinking between resin molecules. However, it seems that a very dense film is formed after the film formation. It is considered that the newly formed dense film further strengthens the adhesive force between the material and the film and ensures extremely excellent corrosion resistance. Further, it is considered that excellent paint adhesion is secured by the synergistic effect of the OH group remaining unoxidized by Mg ⁺⁺ and phosphoric acid. Furthermore, Mg ⁺⁺ and phosphoric acid coexist to form Mg ₃ (PO ₄ ) ₂ nH ₂ O, but a part of Mg is replaced with Zn to form Mg2Zn (PO4) 2nH2O, which forms the material and film. Adhesion seems to be stronger.

As a result of further investigations by the present inventors, A
I, Ba, Ca, Sr, Fe, Nb, Y and Zn ions also have hydroxyl groups.
When coexisting with resin containing limer, it has the same function as Mg ++.
It turned out to have. Each ion is Al⁺⁺⁺ , Ba⁺⁺,
Ca⁺⁺, Sr⁺⁺, Fe⁺⁺, Nb⁺⁺⁺ , Nb⁺⁺⁺⁺⁺ , Y⁺⁺⁺ , Zn⁺⁺But
desirable. That is, these ions are⁺⁺→ Mg, Al
⁺⁺⁺ → Al, Ba⁺⁺→ Ba, Ca⁺⁺→ Ca, Sr⁺⁺→ Sr, Fe⁺⁺→ F
e, Nb⁺⁺⁺ → Nb, Nb⁺⁺⁺⁺⁺ → Nb, Y⁺⁺⁺ → Y and
And Zn⁺⁺→ Change to Zn and oxidize the OH group of the hydroxyl group monomer,
In addition, each ion plays a role of crosslinking between the resins in the state of each element.
It turned out that a precise film can be formed. More than
From the results, in the present invention, a hydroxyl group-containing monomer is contained at 5% or more.
2 to 60 parts by weight of phosphoric acid based on 100 parts by weight of organic resin
Blended and Mg⁺⁺, Al⁺⁺⁺ , Ba⁺⁺, Ca ⁺⁺, Sr⁺⁺, F
e⁺⁺, Nb⁺⁺+, Nb⁺⁺⁺⁺⁺ , Y⁺⁺⁺And Zn⁺⁺One of
Special feature is to mix more than two kinds 0.015 to 1.5 grams ion part
The surface treatment composition liquid to be collected.

Next, 30 parts of hydroxyethyl acrylate-
Copolymer resin of 25 parts methyl methacrylate 25 parts butyl acrylate 15 parts methacrylic acid 30 parts (hydroxyl group-containing monomer: 30%) 100 parts by weight (67 g / l), phosphoric acid 15 parts by weight (10 g / l) ,
Mg ⁺⁺ 0.3 g ion part (0.21 g ion / l) Aqueous liquid mixed with colloidal silica at various ratios, and the coating after drying on an electric Zn plated steel sheet with a basis weight of 30 g / m ² is 0.
It is formed so as to be 35 g / m ^2, and the adhesion between the plating layer and the coating,
The paint adhesion and bare corrosion resistance after processing were investigated. Here, the evaluation method of the adhesion between the plating layer and the film and the paint adhesion is the same as above, but the bare corrosion resistance after processing is JIS-23.
In the salt spray test at 71, the rusting condition after 2000 hours was evaluated. The evaluation criteria are the same as above. If more than 30 parts of colloidal silica is added, the adhesion between the plating layer and the coating will be reduced. When the colloidal silica is 3 to 30 parts, the bare corrosion resistance after processing is further improved. Further, if the content of colloidal silica exceeds 30 parts, the coating adhesion tends to decrease. This tendency is that instead of colloidal silica, SiO ₂ powder or SnO ₂ , Cr ₂ O
Almost the same results were obtained by adding a colloid (sol) or powder of ₃ , Fe ₂ O ₃ , Fe ₃ O ₄ , MgO, Al ₂ O ₃ or ZrO ₂ . In addition, almost the same result was obtained by mixing two or more of these. Therefore, in the present invention, based on 100 parts by weight of an organic resin containing 5% or more of a hydroxyl group-containing monomer, 2 to 60 parts by weight of phosphoric acid is mixed, and Mg ⁺⁺ , Al ⁺⁺⁺ , B
a ⁺⁺ , Ca ⁺⁺ , Sr ⁺⁺ , Fe ⁺⁺ , Nb ⁺⁺⁺ , Nb ⁺⁺⁺⁺⁺ , Y ⁺⁺⁺ and Zn ⁺⁺ 1 type or 2 types or more 0.015 to 1.5 g ion part combination In a heated bath, SiO ₂ , SnO ₂ , Cr against 100 parts of organic resin
_{2 O 3, Fe 2 O 3} , Fe 3 O 4, MgO, Al 2 O 3, of ZrO ₂ colloid (sol) or one or surfaces of two or more characterized by blending 3 to 30 parts of the powder Use the treatment composition liquid.

Hydroxyethyl acrylate 40 parts-Methyl methacrylate 10 parts-Butyl acrylate 30 parts-Methacrylic acid 20 parts (hydroxyl group-containing monomer: 40%) 100 parts by weight of copolymer resin (60 g / l), 50 parts phosphoric acid (30 g / l), Mg ⁺⁺
An aqueous liquid mixed with 0.5 gram ion part (0.30 gram ion / l) was formed on an electric Zn-plated steel sheet with a basis weight of 30 g / m ² to form a film with various adhesion amounts, and the adhesion between the material and the film, the paint adhesion and After processing, the bare corrosion resistance was investigated. The evaluation method of the adhesion between the material and the film and the adhesion of the coating is the same as the above. The bare corrosion resistance after processing was evaluated by a salt spray test in the rust state after 1500 hours. The evaluation criteria are the same as above. As a result, at 0.1 g / m ² or higher, excellent film adhesion to materials, paint adhesion, and bare corrosion resistance after processing were exhibited. In addition, even when colloidal silica was added to the above-mentioned bath, 0.1 g / m ² or more showed excellent film adhesion to materials, paint adhesion, and bare corrosion resistance after processing. As a result, the coating amount of the surface treatment composition in the present invention is 0.1 g / m ² or more, and the upper limit is 3.0 g / m ² from the economical viewpoint.

Next, the surface treatment bath according to the present invention is a cold rolled steel sheet or a Zn or Zn alloy plated steel sheet, Ni, Cu, Pb, Sn,
Cd, Al, Ti, etc. metal plate or plated steel plate of these metals or alloy-plated steel plate of these metals, the surface shows excellent adhesion to materials, paint adhesion, and bare corrosion resistance after processing. A treatment film is formed. Since this surface treatment film has extremely excellent adhesion to other organic resins, various organic resins can be further applied thereon to produce an organic composite steel sheet. The organic resin applied to the upper layer is the present organic resin obtained by copolymerizing methyl methacrylate, butyl acrylate, methacrylic acid and hydroxyethyl acrylate, olefin / acrylic acid copolymer resin, polyacrylic acid and Use of its copolymer resin, polyacrylic acid ester and its copolymer resin, polymethacrylic acid ester and its copolymer resin, epoxy resin, acrylic modified epoxy resin, vinyl modified epoxy resin, vinyl modified epoxy ester resin, etc. You can

In addition, SiO ₂ , SnO ₂ , Cr ₂ O ₃ ,
One or more of colloids (sols) or powders of Fe ₂ O ₃ , Fe ₃ O ₄ , MgO, Al ₂ O ₃ and ZrO ₂ may be added and applied. At that time, it is desirable to add 10 to 60 parts of these sols or powders to 100 parts of the organic resin. The reason is that if it is less than 10 parts or more than 60 parts, the corrosion resistance is slightly reduced. Further, it was found that the effect can be more strongly obtained by using the sol or powder having a particle size of about 2 to 15 nm. Therefore, in the present invention, the particle size of the sol or powder is preferably 2 to 15 nm.

Further, when the organic resin or the mixture of the organic resin and the above-mentioned inorganic substance to be applied to the upper layer is applied, it is desirable that the applied amount is 0.2 to 3.0 g / m ² after drying. The reason is that if it is less than 0.2 g / m ² , the effect of the film formed in the upper layer cannot be sufficiently obtained, and if it exceeds 3.0 g / m ² , a bad effect appears in terms of weldability. Therefore, in the present invention, the film formed on the upper layer is set to 0.2 to 3.0 g / m ² .

The present invention has so far mainly described the case of treating an electric Zn plated steel sheet. However, the present invention
In addition to coated steel sheets, cold rolled steel sheets, hot-dip Zn coated steel sheets and Zn
-Ni system, Zn-Ni-Co system, Zn-Ni-Cr system, Zn-Fe system, Zn-Co
It can be used for electrical or hot-dip Zn alloy-plated steel sheets such as Zn-Cr alloys, Zn-Cr alloys, Zn-Mn alloys, Zn-Al alloys, and Zn-Mg alloys. Also, metal plates such as Ni, Cu, Pb, Cd, Sn, Al and Ti,
Alternatively, it can be used for a plated steel plate made of these metals or alloys of these metals. Further, in order to apply the surface treatment agent according to the present invention to various plated steel sheets, any coating method such as roll coating, spray coating, brush coating, dip coating and curtain flow may be used.

As described above, the surface treatment agent according to the present invention can be used as a substitute for so-called chromate agents such as coating chromate, electrolytic chromate, resin chromate and reaction chromate which are conventionally used as non-chromate agents not using chromium. At the same time, since it is a non-polluting surface treatment agent that does not use chromium, its use is expected to expand greatly for containers and toys.

[0028]

EXAMPLES Hereinafter, examples will be described in detail. The parts and% shown in the examples mean parts by weight and% by weight, respectively. Example 1 A Zn-plated steel sheet (weight per unit area: 20 g / m ² ) 40 parts of 2-hydroxybutyl acrylate-15 parts of methyl methacrylate-35 parts of butyl acrylate-20 parts of styrene-40 parts of methacrylic acid-
Copolymer resin of acrylic acid 3 parts-organic phosphorus monomer 2 parts (hydroxyl group-containing monomer: 25%) 60 g / l, phosphoric acid 10 g / l, Mg
⁺⁺ An aqueous solution containing 0.15 g ion / l was coated on a roll and dried at 120 ° C to form a film so that the total amount deposited would be 0.35 g / m ² .

Example 2 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 11.5%)
2-bis (hydroxymethyl) ethyl 15 parts-methyl methacrylate 35 parts-butyl acrylate 47 parts-glycidyl methacrylate 10 parts-methacrylic acid 30 parts-acrylic acid 3 parts-organophosphorus monomer 1 part Combined resin (hydroxyl group-containing monomer: 11%) 80g / l, phosphoric acid 25g / l, Fe ⁺⁺ 0.5g ion / l, colloidal silica 9g / l aqueous solution was coated with a roll and dried at 130 ° C. However, the total amount deposited is 0.45 g /
A film was formed so that the thickness was m ² .

Example 3 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.3%)
Of 2,3-dihydroxypropyl methacrylate 70 parts-methyl methacrylate 20 parts-butyl acrylate 45 parts-glycidyl methacrylate 20 parts-methacrylic acid 30 parts-acrylic acid 5 parts-organic phosphorus monomer 1 part Polymer resin (monomer containing hydroxyl group: 37%) 60g / l, phosphoric acid 15g / l, Al
⁺⁺⁺ 0.8g ion / l, 12g / l of colloidal silica was applied as an aqueous solution and dried at 60 ℃ to give a total adhesion of 0.45
A film was formed so as to have g / m ² . Furthermore, an organic resin obtained by copolymerizing 30 parts of methyl methacrylate, 37 parts of butyl acrylate, 10 parts of glycidyl methacrylate, 40 parts of methacrylic acid, 3 parts of acrylic acid, and 1 part of organic phosphorus monomer on it. The aqueous liquid was applied by a roll and dried at 150 ° C. to produce an organic composite plated steel sheet having a coating of 1.3 g / m ² .

Example 4 Zn-Fe alloy plated steel sheet (Basis weight: 20 g / m ² , Fe = 12.8%)
Acrylic acid hydroxy ester 80 parts-Methyl methacrylate 40 parts-Butyl acrylate 20 parts-Styrene 10 parts-Glycidyl methacrylate 15 parts-Methacrylic acid 20 parts-
Acrylic acid 10 parts-organic phosphorus monomer 1 part copolymer resin (hydroxyl group-containing monomer: 41%) 60 g / l, phosphoric acid 15 g / l, Ba
⁺⁺ An aqueous solution containing 0.6 g ion / l and 25 g / l of colloidal silica was applied by a roll and dried at 100 ° C. to form a film so that the total adhered amount was 0.25 g / m ² . On top of that, 10 parts of methyl methacrylate-butyl acrylate
An aqueous solution prepared by mixing 25 parts of colloidal silica with 100 parts of a copolymer resin of 40 parts-styrene 20 parts-glycidyl methacrylate 10 parts-methacrylic acid 40 parts-organophosphorus monomer 1 part was coated with a roll, and Organic resin dried at ℃ 1
A coating consisting of 00 parts and 25 parts colloidal silica 1.5g / m ²
The organic composite plated steel sheet having the above was manufactured.

Example 5 Zn-Mg alloy plated steel sheet (Basis weight: 30 g / m ² , Mg = 1.2%)
N-methyl acrylamide 25 parts-methyl methacrylate 25 parts-butyl acrylate 30 parts-styrene 5 parts-glycidyl methacrylate 20 parts-methacrylic acid 40 parts-acrylic acid 10 parts copolymer resin (hydroxyl group Contained monomers: 16
%) 60 g / l, phosphoric acid 20 g / l, Ca ⁺⁺ 0.1 g ion / l mixed with an aqueous solution, and dried at 150 ° C to give a total deposition of 0.35 g / m ^2. To form a film. Furthermore, to 100 parts of the olefin / acrylic acid copolymer resin, an aqueous liquid containing 25 parts of colloidal silica was coated with a roll and dried at 145 ° C to obtain 100 parts of the olefin / acrylic acid copolymer resin. An organic composite plated steel sheet having a film made of 25 parts of colloidal silica and 1.1 g / m ² was produced.

Example 6 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.4%)
Allyl glycidyl ether 80 parts-Methyl methacrylate 10 parts-Butyl acrylate 30 parts-Glycidyl methacrylate 15 parts-Methacrylic acid 40 parts-Acrylic acid 10 parts-Hydroxyethyl acrylate 15 parts Copolymer resin (containing hydroxyl groups Monomer-: 55%) 80 g / l, phosphoric acid 20 g / l, Sr ⁺⁺ 1.1
Apply an aqueous solution containing gram ion / l on a roll and
It was dried at ℃ and a film was formed so that the total amount of adhesion would be 0.55 g / m ² . Furthermore, to 100 parts of the olefin / acrylic acid copolymer resin, an aqueous liquid containing 20 parts of colloidal silica was coated with a roll and dried at 160 ° C to obtain 100 parts of the olefin / acrylic acid copolymer resin. An organic composite plated steel sheet having a coating consisting of 20 parts of colloidal silica at 1.35 g / m ² was produced.

Example 7 Zn-Mg based alloy plated steel sheet (Basis weight: 30 g / m ² , Mg = 1.2%)
Glycidyl methacrylate 35 parts-Ethyl methacrylate 20 parts-Butyl acrylate 25 parts-Methacrylic acid 35 parts-Hydroxyethyl acrylate 20 parts Copolymer resin (hydroxyl group containing monomer: 41%) 180 g / l, phosphoric acid 40g / l, Nb
⁺⁺⁺ 0.25 gram ion / l, colloidal silica 15g / l, Mg
An aqueous solution containing 3 g / l of O was applied by a roll and dried at 110 ° C. to form a film so that the total amount of adhesion was 0.45 g / m ² . Furthermore, 10 parts of methyl methacrylate-30 parts of butyl acrylate-15 parts of glycidyl methacrylate-
An aqueous solution of an organic resin obtained by copolymerizing 35 parts of methacrylic acid-10 parts of acrylic acid-15 parts of hydroxyethyl acrylate was applied by a roll and dried at 160 ° C to obtain the above organic resin. An organic composite plated steel sheet having a coating film of 1.2 g / m ² was produced.

Example 8 Zn-Ni alloy plated steel sheet (Basis weight: 30 g / m ² , Ni = 13.9%)
An organic resin obtained by copolymerizing 10 parts of glycidyl methacrylate with 50 parts of ethyl methacrylate, 35 parts of butyl acrylate, 40 parts of methacrylic acid and 30 parts of acrylic acid (hydroxyl group-containing monomer: 6%) 60 g / l, phosphoric acid 15g / l, Nb ⁺⁺⁺⁺⁺
0.25g ion / l, colloidal silica 15g / l, MgO 3g
An aqueous solution containing / l was coated on a roll and dried at 110 ° C. to form a film so that the total amount deposited was 0.60 g / m ² . On top of that, 100 parts of an organic resin obtained by copolymerizing 15 parts of methyl methacrylate, 35 parts of butyl acrylate, 15 parts of glycidyl methacrylate, 40 parts of methacrylic acid, and 5 parts of acrylic acid were mixed with Aerosil. An aqueous solution containing 25 parts was applied by a roll and dried at 160 ° C. to produce an organic composite plated steel sheet having a film consisting of 25 parts of the above-mentioned organic resin Aerosil at 1.1 g / m ² .

Example 9 Zn-Cr alloy plated steel sheet (Basis weight: 20 g / m ² , Cr = 10.8%)
Methacrylic acid-3-chloro-2-hydroxypropyl 40
Part-methyl acrylate 18 parts-butyl acrylate 30 parts-glycidyl methacrylate 20 parts-acrylic acid 41 parts organic resin obtained by copolymerization (hydroxyl group-containing monomer: 40
%) 60g / l, phosphoric acid 15g / l, Y ⁺⁺⁺ 0.30g ion / l,
An aqueous liquid containing 6 g / l of colloidal silica and 0.5 g / l of MgO was coated with a roll and dried at 110 ° C to give a total deposition of 0.15 g / m ²
A film was formed so that Furthermore, an aqueous solution of vinyl-modified epoxy resin was applied on a roll and dried at 135 ° C to form a film of vinyl-modified epoxy resin at 1.6 g /
An organic composite plated steel sheet having m ² was manufactured.

Example 10 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.1%)
An organic resin obtained by copolymerizing 45 parts of N-putoxymethylolmethacrylamide 45 parts of methyl methacrylate 15 parts of butyl acrylate 35 parts of methacrylic acid 40 parts of acrylic acid 5 parts of hydroxyethyl acrylate (Hydroxyl group-containing monomer: 42%) 100 g / l, phosphoric acid 40 g / l, Zn ⁺⁺ 0.35 g ion / l, colloidal silica 15 g / l Aqueous liquid was applied on a roll and dried at 90 ° C. Total deposition amount is 0.38 g /
A film was formed so that the thickness was m ² . Furthermore, 100 parts of urethane modified epoxy ester resin and 25 parts of Aerosil were mixed with an aqueous solution by a roll, and dried at 145 ° C. to obtain 100 parts of urethane modified epoxy ester resin and Aerosil.
An organic composite plated steel sheet having a coating consisting of 25 parts of 1.4 g / m ² was produced.

Example 11 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.1%)
Allyl glycidyl ether 50 parts-Methyl methacrylate 20 parts-Butyl acrylate 50 parts-Methacrylic acid 10 parts-
Organic resin obtained by copolymerizing 30 parts of hydroxyethyl acrylate (hydroxyl group-containing monomer: 50%) 80 g / l, phosphoric acid
20g / l, Mg ⁺⁺ 0.35g ion / l, colloidal silica 1
An aqueous solution containing 3 g / l was coated with a roll and dried at 115 ° C. to form a film so that the total amount of the coating was 0.45 g / m ² . Furthermore, urethane modified epoxy ester resin 100
Aqueous liquid containing 20 parts of Aerosil is coated on a roll and dried at 145 ° C to produce an organic composite plated steel sheet with a coating consisting of 100 parts of urethane modified epoxy ester resin and 20 parts of Aerosil 1.2 g / m ² did.

Example 12 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.1%)
45 parts of β-methylglycidyl acrylate-styrene 30
Part-butyl acrylate 60 parts-hydroxyethyl acrylate 10 parts-methacrylic acid 20 parts organic resin obtained by copolymerization (hydroxyl group-containing monomer: 33%) 90 g / l, phosphoric acid 25 g /
l, Al ⁺⁺⁺ 0.27 g ion / l, 10 g colloidal silica
An aqueous solution containing / l was applied on a roll and dried at 100 ° C to form a film so that the total amount of adhesion was 0.52 g / m ² . Furthermore, 100 parts of vinyl-modified epoxy ester resin is mixed with 25 parts of colloidal silica on an aqueous solution by a roll and dried at 155 ° C to form a film consisting of 100 parts of vinyl-modified epoxy ester resin and 25 parts of colloidal silica. 1.8 g
An organic composite plated steel sheet having / m ² was produced.

Example 13 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.8%)
60 parts of 3,4-epoxycyclohexyl methacrylate
Organic resin obtained by copolymerizing 35 parts of methyl methacrylate-45 parts of butyl acrylate-20 parts of styrene-15 parts of methacrylic acid-15 parts of hydroxyethyl acrylate (hydroxyl group-containing monomer: 39%) 80g / l, phosphoric acid 15g / l, Ba ⁺⁺ 0.30g ion / l, colloidal silica 9g / l was mixed with an aqueous solution, and dried at 90 ℃ to give a total adhesion of 0.35g / l.
A film was formed so that the thickness was m ² . Furthermore, 100 parts of olefin / acrylic acid copolymer resin and 25 parts of colloidal silica were mixed with an aqueous liquid by means of a roll and dried at 150 ° C, and 100 parts of olefin / acrylic acid copolymer resin and colloidal silica were coated. An organic composite plated steel sheet having a coating consisting of 25 parts and 1.6 g / m ² was produced.

Example 14 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 13.2%)
Acrylic acid-2-hydroxyethyl 50 parts-butyl acrylate 40 parts-methacrylic acid 35 parts-hydroxyethyl acrylate 25 parts organic resin obtained by copolymerization (hydroxyl group-containing monomer: 50%) 90 g / l, An aqueous solution containing 40 g / l of phosphoric acid, 0.35 g of Ca ⁺⁺ ion / l and 6 g / l of colloidal silica was applied on a roll and dried at 100 ° C to give a total adhesion of 0.27 g / l.
A film was formed so that the thickness was m ² . Furthermore, 100 parts of olefin / acrylic acid copolymer resin was mixed with 25 parts of colloidal silica on an aqueous solution by a roll, and dried at 150 ° C to dry 100 parts of olefin / acrylic acid copolymer resin and 100 parts of colloidal silica. An organic composite plated steel sheet having a coating consisting of 25 parts of 1.3 g / m ² was produced.

Comparative Example 1 20 g / l of chromic acid (hexavalent Cr 100% chromic acid) on a Zn-plated steel sheet
, Apply an aqueous solution containing 15 g / l phosphoric acid on a roll and
After drying at ℃, a chromate film with an adhesion amount of 57 mg / m ^{2 in} terms of Cr was formed.

Comparative Example 2 Zn-Ni alloy plated steel sheet (Basis weight: 20 g / m ² , Ni = 12.8%)
Chromic acid (hexavalent Cr 100% chromic acid) 20g / l, phosphoric acid 20g /
l, colloidal silica 10g / l aqueous solution is applied by roll,
It was dried at 190 ° C to form a chromate film with an adhesion amount of 52 mg / m ^{2 in} terms of Cr.

Comparative Example 3 Zn-Ni alloy plated steel sheet (adhesion amount: 20 g / m ² , Ni = 12.9%)
Chromic acid (hexavalent Cr 100% chromic acid) 20g / l, phosphoric acid 25g /
l, Aqueous liquid containing 100 g / l of acrylic emulsion was applied on a roll and dried at 160 ° C, and the adhesion amount was 55 m in terms of Cr.
A g / m ² chromate film was formed.

Comparative Example 4 Zn-Ni alloy plated steel sheet (adhesion amount: 20 g / m ² , Ni = 12.5
%) Acrylamide resin 80 g / l, phosphoric acid 15 g / l, Cu
⁺⁺ Aqueous liquid mixed with 0.25g ion / l and Aerosil 15g / l was coated with a roll and dried at 170 ° C to give a total deposition of 0.53.
A film was formed so as to have g / m ² .

Comparative Example 5 Zn-Ni alloy plated steel sheet (adhesion amount: 20 g / m ² , Ni = 12.3%)
Chromic acid (hexavalent Cr 100% chromic acid) 20g / l, phosphoric acid 10g /
l, an aqueous solution containing 80 g / l of an acrylic amide resin was applied by a roll and dried at 115 ° C. to form a film so that the total amount of adhesion was 0.48 g / m ² . Further, an aqueous solution of epoxy resin was coated on it with a roll and dried at 175 ° C. to produce an organic composite plated steel sheet having a coating of epoxy resin of 1.15 g / m ² .

Comparative Example 6 Zn-Ni alloy plated steel sheet (adhesion amount: 20 g / m ² , Ni = 12.9%)
Chromic acid (trivalent Cr / (trivalent Cr + hexavalent Cr) x 100 = 30 (%)) 30
g / l, phosphoric acid 15g / l, acrylic emulsion 80g / l, colloidal silica 15g / l blended aqueous solution on a roll and dried at 160 ° C to give a total deposit of 0.46g / m ^2. A film was formed. On top of that, an aqueous solution containing 25 parts of Aerosil was coated on 100 parts of the epoxy resin by brazing and dried at 185 ° C to obtain 100 parts of the epoxy resin and Aerosil.
An organic composite plated steel sheet having a coating consisting of 25 parts of 1.45 g / m ² was produced.

Table 1 shows the adhesion of the coatings of Examples 1 to 14 and Comparative Examples 1 to 6 treated with Zn or Zn alloy plated steel sheets after immersion in boiling water for 30 minutes, and bare corrosion resistance after processing by a salt spray test. And low temperature melamine type baking type (baking temperature: 110 ℃)
It shows the adhesion of the paint when 30μ is applied. As is clear from Table 1, when the surface treatment according to the present invention is performed on the Zn-plated steel sheet or the Zn-based alloy-plated steel sheet, the formed film has good adhesion and no peeling. When the surface treatment of the present invention is applied to a Zn-plated steel sheet, bare corrosion resistance after processing hardly changes after 1000 hours, and slight red rust occurs after 1500 hours. When the surface treatment according to the present invention is performed on the Zn-based alloy-plated steel sheet, bare corrosion resistance after processing hardly changes after 2000 hours, and only slight red rust occurs after 3000 hours. Further, in the case of an organic composite plated steel sheet which has been subjected to the surface treatment according to the present invention and further further subjected to the organic resin according to the present invention, bare corrosion resistance after processing may include slight red rust in 4000 hours. Not too much.

On the other hand, in the case of the known chromate film composition (Comparative Examples 1, 2, 3, 4, 5 and 6), the adhesion of the formed film was poor, and chromium was considerably eluted in boiling water, or The coatings are considerably peeled off by both treatment agents. In the case of inorganic chromate among the known chromate film compositions (Comparative Examples 1 and 2), the bare corrosion resistance after processing shows that a considerable amount of red rust occurred after 100 hours of SST. In the case of resin chromate (Comparative Examples 3 and 4), the bare corrosion resistance after processing shows that a considerable amount of red rust occurred after 400 hours of SST. Further, the adhesion of the coating film is also the same, and when the surface treatment agent according to the present invention is carried out or various organic coatings are further formed thereon, even the low temperature baking type (110 ° C baking) is difficult to obtain the adhesion of the coating material. Shows excellent adhesion. On the other hand, in the case of the known chromate film (Comparative Examples 1, 2, 3 and 4), the paint adhesion is extremely poor. Further, even when it is further coated with an organic resin (Comparative Examples 5 and 6), it is not always sufficient, and peeling of the coating film is observed.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

As described above, the surface treatment agent according to the present invention does not use chromium and is a so-called non-polluting non-chromating agent which has been conventionally used in the fields of automobiles, home appliances and building materials. And can be used as an alternative to all chromating agents such as reaction chromates. In addition, since it is a non-polluting surface treatment agent that does not use chromium, its use is expected to greatly expand to containers, tableware, toys, and indoor building materials.

[Procedure amendment]

[Submission date] February 7, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

As the special heavy metal, Mg, Al, Ba, Ca, Sr,
Fe, Nb, Y and Zn, which must be present in the bath in the ionic state of these heavy metals. Actual H ₂ O to these ions in aqueous solution, OH ^-, O ^-, etc. is or complexly bonded, or coordinated, while or adsorbed it at all no problem. To 100 parts by weight of the present organic resin containing the above hydroxyl group-containing monomer as a main component, 1 part of the above heavy metal ion is added.
It is necessary to mix 0.015 to 1.5 gram ion part of one kind or two or more kinds. Further, 2 to 60 parts by weight of phosphoric acid is added to 100 parts by weight of the organic resin containing the above hydroxyl group-containing monomer as a main component.
It is necessary to mix parts by weight.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

Hereinafter, a bath in which the present organic resin, heavy metal ions and phosphoric acid coexist is prepared, and a film is formed on a plated steel sheet to show how the characteristics change. As the organic resin, 100 g / l (solid content 100% by weight) of a resin obtained by copolymerizing 40 parts of hydroxyethyl acrylate (hydroxyl group-containing monomer), 15 parts of methyl methacrylate and 20 parts of acrylic acid (hydroxyl group-containing monomer: 53%). Part) added. Phosphoric acid was added at 15 g / l (15 parts by weight), and Mg ⁺⁺ was added at various ratios. When a surface treatment bath consisting of these aqueous liquids was created, it was applied to an electric Zn-plated steel sheet (Zn deposition amount: 30 g / m ² ) so that the total solid content was 0.30 g / m ^2, and dried to form Regarding the coating, it was investigated how the adhesion to the material (electrical Zn-plated steel sheet), paint adhesion, and bare corrosion resistance after processing change.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

Next, as the organic resin, 100 g / l of a resin obtained by copolymerizing 20 parts of hydroxyethyl acrylate (monomer containing hydroxyl group) -30 parts of methyl methacrylate-40 parts of acrylic acid (monomer containing hydroxyl group: 22%) (Solid content) (100 parts by weight), Mg ⁺⁺ at 0.15 g ion / 1 (part), and phosphoric acid at various ratios were added. A surface treatment bath consisting of these aqueous liquids was prepared, and the electric Zn plated steel sheet (Zn
Adhesion: 30 g / m ² ) so that the total solid content is 0.35 g / m ^2, and the film formed by drying the material (electrical
It was investigated how the adhesiveness to a Zn-plated steel sheet, the adhesiveness to paint, and the bare corrosion resistance after processing changed. The concentration of phosphoric acid has a great influence on the adhesion between the formed film and the electric Zn plated steel sheet, and shows excellent adhesion at 2 to 60 parts by weight relative to 100 parts by weight of this organic resin. Is none (◎). If the amount is less than 2 parts by weight or more than 60 parts by weight, the adhesion of the coating is deteriorated. The concentration of phosphoric acid influences the adhesiveness of the paint, showing excellent adhesiveness at 60 parts by weight or less, and there is no peeling of the coating film in the above test (⊚). If it exceeds 60 parts by weight, the adhesiveness of the paint will be reduced. Further, the concentration of phosphoric acid does not significantly affect the corrosion resistance of the processed part. If it exceeds 60 parts by weight, the corrosion resistance of the work part will be slightly reduced.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

From the above results, 5% of the hydroxyl group-containing monomer was added.
0.015 of Mg ⁺⁺ is added to 100 parts by weight of the above organic resin.
~ 1.5g Ion part and 2 ~ 60 parts by weight of phosphoric acid are applied to the coated steel sheet for excellent adhesion to the coated steel sheet, as well as coating adhesion and bare corrosion resistance. Can form a film. here,
The reason why it is possible to form a film having excellent adhesion to a plated steel sheet by applying the above-mentioned aqueous liquid, and further, it is possible to form a film having extremely excellent paint adhesion and bare corrosion resistance of the processed part, but it is not clear as follows. Conceivable. That is, when the above-mentioned aqueous liquid is applied and dried to form a film, Mg ⁺⁺ oxidizes the OH group of the hydroxyl group-containing monomer contained in the organic resin, and itself plays a role of crosslinking between resin molecules. However, it seems that a very dense film is formed after the film formation. It is considered that the newly formed dense film further strengthens the adhesive force between the material and the film and ensures extremely excellent corrosion resistance. Further, it is considered that excellent paint adhesion is secured by the synergistic effect of the OH group remaining unoxidized by Mg ⁺⁺ and phosphoric acid. Furthermore, Mg ⁺⁺ and phosphoric acid coexist to form Mg ₃ (PO ₄ ) ₂ nH ₂ O, but a part of Mg is replaced with Zn to form Mg ₂ Zn (PO ₄ ) ₂ nH ₂ O. It seems that the adhesion between the material and the film will be stronger.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 133/02 C09D 133/02 133/08 PFZ 133/08 PFZ 133/14 PGB 133/14 PGB 133 / 16 133/16 133/24 PFW 133/24 PFW 143/02 PGL 143/02 PGL 163/10 PDY 163/10 PDY 201/06 PDK 201/06 PDK C23C 22/07 C23C 22/07

Claims (6)

[Claims] 1. Containing 5% by weight or more of a hydroxyl group-containing monomer
2 to 60 parts by weight of phosphoric acid per 100 parts by weight of organic resin
Blended in parts and Mg⁺⁺, Ba⁺⁺, Al⁺⁺⁺ , Ca ⁺⁺, Sr⁺⁺,
Fe⁺⁺, Nb⁺⁺⁺⁺⁺ , Nb⁺⁺⁺ And Y⁺⁺⁺ 1 or 2 or more
Characterized by blending 0.015 to 1.5 grams of ionic component on the top
A composition for treating a metal surface. 2. Containing 5% by weight or more of a hydroxyl group-containing monomer
2 to 60 parts by weight of phosphoric acid per 100 parts by weight of organic resin
Blended in parts and Mg⁺⁺, Ba⁺⁺, Al⁺⁺⁺ , Ca ⁺⁺, Sr⁺⁺,
Fe⁺⁺, Nb⁺⁺⁺⁺⁺ , Nb⁺⁺⁺ And Y⁺⁺⁺ 1 or 2 or more
The upper part is blended with 0.015 to 1.5 grams ion part, and
O_Two, Cr_TwoO_Three , Fe_TwoO_Three , Fe_ThreeO_Four , MgO, ZrO_Two, SnO_Two, Al_TwoO
_Three , Sb_TwoO_FiveOne of the colloids (sols) or powders of
Gold characterized by mixing 3 to 30 parts by weight of two or more kinds
Metal surface treatment composition. 3. A coating film formed by applying the composition for metal surface treatment according to claim 1 on a metal plate, a metal-plated steel plate or a metal alloy-plated steel plate has an adhesion amount of 0.1 to 3.0 g /
A surface-treated metal plate characterized by being m ² . 4. The amount of a coating formed by applying the composition for metal surface treatment of claim 2 on a metal plate, a metal-plated steel plate or a metal alloy-plated steel plate is 0.1 to 3.0 g /
Surface-treated metal plate characterized by being m ² 5. The methylmethacrylate-butyl acrylate-styrene-glycidylmethacrylate-methacrylic acid-acrylic acid-organophosphorus monomer-hydroxy on the film of the surface-treated metal plate according to claim 3 or 4. Organic resin obtained by copolymerizing one or more of ethyl acrylate, olefin / acrylic acid copolymer resin, polyacrylic acid and its copolymer resin, polyacrylic acid ester and its copolymer resin , Polymethacrylic acid ester and its copolymer resin, polyacrylic acid ester and its copolymer resin, epoxy resin, acrylic modified epoxy resin, ester modified epoxy resin, urethane modified epoxy resin, urethane modified epoxy ester resin, vinyl modified epoxy Resin, bionyl modified epoxy ester resin A surface-treated metal sheet, characterized in that a coating containing one or more selected from the above is formed to have an adhesion amount of 0.2 to 3.0 g / m ² . 6. The methyl methacrylate-butyl acrylate-styrene-glycidyl methacrylate-methacrylic acid-acrylic acid-organophosphorus monomer-hydroxy on the film of the surface-treated metal plate according to claim 3 or 4. Organic resin obtained by copolymerizing one or more of ethyl acrylate, or olefin / acrylic acid copolymer resin, polyacrylic acid and its copolymer resin, polyacrylic acid ester and its copolymer Polymer resin, polymethacrylic acid ester and its copolymer resin, polyacrylic acid ester and its copolymer resin, epoxy resin, acrylic modified epoxy resin, ester modified epoxy resin, urethane modified epoxy resin, urethane modified epoxy ester resin, Vinyl modified epoxy resin, bionyl modified epoxy ester resin 100 parts by weight of resin and SiO ₂ , Cr ₂ O ₃ , Fe ₂ O ₃ ,
Fe ₃ O _4, MgO, the adhesion amount of the coating containing the _{ZrO 2, SnO 2, Al 2} O 3, Sb 2 O 1 kind selected from the sol or powder of ₅ or more 10 to 60 parts by weight A surface-treated metal plate characterized by being formed so as to have a concentration of 0.2 to 3.0 g / m ² .