JPS63295678A - Composition for treatment of aluminum surface - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in applicability and adhesion to aluminum, solvent resistance, etc., by mixing water-dispersible silica with three specified resin and a polyfunctional, aziridine compound. CONSTITUTION:0.1-10wt.% polymerizable unsaturated alkoxysilane compound (a), 0-20wt.% polymerizable unsaturated carboxylic acid (b), 20-99wt.% 1-8C alkyl (meth)acrylate (c) and 0-40wt.% monomer (d) copolymerizable therewith are subjected to multistage emulsion polymerization to obtain cationic and/or amphoteric acrylic resins (B) derived from a multilayer structure copolymer having a Tg of the core >=15 deg.C and Tg of the outermost shell <=10 deg.C. At most 700g of a mixture of 0.5-250g (in terms of SiO2) of a water-dispersible silica (A), 0.5-600g of component B, 0-600g of cationic and/or amphoteric carboxylated acrylic resins (C) of a Tg >=10 deg.C, and cationic and/or amphoteric carboxylated polylefin resins (D) is mixed with at most 10wt.%, based on the solid matter of components B-D, polyfunctional aziridine compound (E) and water (F) to obtain 1l of the title composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a composition for treating aluminum surfaces. Specifically, the present invention relates to an aluminum surface treatment composition that imparts high corrosion resistance and coating base properties to the aluminum surface, has excellent processing adhesion and solvent resistance, and has excellent blocking resistance.

(Prior Art) Conventionally, anodic oxidation treatment and chemical conversion coating treatment have been carried out for the purpose of imparting corrosion resistance to the aluminum surface and providing a coating base for improving adhesion with paint.

Among these, chemical conversion treatment has the advantages of faster film formation, lower treatment cost, and better paint adhesion than anodization treatment using electrical methods. Among these, chromate treatment is the mainstream in terms of performance, cost, and workability, but new surface treatment methods are desired because of the current situation where regulations on the amount of chromium in wastewater are being tightened.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing an aluminum surface treatment composition that imparts excellent corrosion resistance, coating base properties, etc. to aluminum plates, chemically treated aluminum plates, etc. This is what we provide.

(Means for Solving the Problems) The present invention provides that (A>water-dispersible silica (I>) is 0.0% in terms of SiO2 per layer of the composition for aluminum surface treatment.
(B) an alkoxysilane compound having a polymerizable unsaturated group (a) 0.1 to 10% by weight; a polymerizable unsaturated carboxylic acid (b) 0 to 20% by weight; (meth)acrylic acid alkyl ester (C) having 1 to 8 carbon atoms 20 to 99% by weight, monomer (d) copolymerizable with these 0 to 40% by weight [However, (a), (b) ), (c) and (d) are 100% by weight. The Tg of the core portion obtained by multistage emulsion polymerization of the monomer component consisting of
An amount in the range of 0.5 to 600 g of a cationic and/or amphoteric acrylic resin (II) derived from a multilayer structure copolymer whose outermost shell portion has a Tg of 10 ° C. or less, (C )'I'g is 10°C or higher and/or cationic and/or
or zwitterionic acrylic resin (III) from 0 to 60
L (D>II ionic and/or zwitterionic carboxylated polyolefin resin <IV) to the range of 0g from 0°5 to 60
0g (provided that the sum of (A), (B), (C) and (D) is
The present invention relates to an aluminum surface treatment composition containing (E) a compound having a polyfunctional aziridinyl group in a solid content ratio of 10% by weight or less to the resin.

The (A) water-dispersible silica (I) used in the present invention is:
It is a colloidal silica that is a condensation product of gaic acid that is commonly used, and preferably has a particle size of 2 to 50 mμ. Examples of such water-dispersible silica (I>) include commercially available products such as "Snowtex 0" and "Snowtex 0". Snowtex NJ
rSnowtex NC8” “Snowtex 20”
"Snowtex C", "Snowtex 3J rSnowtex SS", "Snowtex
rCataloid S! -350J rcat
aloidSi-500J (Catalyst Chemical Industry Co., Ltd.)
(manufactured by) etc. Also, surface-treated colloidal silica, such as rcataloldsA, which has not been treated with aluminic acid.
(manufactured by Catalysts Kasei Kogyo Co., Ltd.) etc. can also be used.

These may be used as they are, or in order to improve their dispersibility in the composition for aluminum surface treatment, they may be added with acrylic resin (II) or quaternary ammonium salt, etc., which are other essential components of the present invention. The water-dispersible silica (I) may be surface-treated in advance with an amine, or an aziridine derivative such as ethyleneimine may be crafted onto the surface of the water-dispersible silica (I).

Water-dispersible silica (I) is contained in an amount ranging from 0.5 to 250 g per 11 of the aluminum surface treatment composition of the present invention. If the amount is less than 0.5g, the effects such as corrosion resistance will be insufficient, and if it is used in excess of 250g, processability will deteriorate.
Neither is preferable.

The acrylic resin (II) (B) used in the present invention is an alkoxysilane compound having a polymerizable unsaturated group (a
) 0.1 to 10% by weight, polymerizable unsaturated carboxylic acid (b)
0 to 20% by weight, the number of carbon atoms in the alkyl group is 1 to 8 (
meth) acrylic acid alkyl ester (c) 20-99% by weight, monomer copolymerizable with these <d) 0-40% by weight (however, (a), (b), (c) and (d) The total of 100% by weight) is obtained by multi-stage emulsion polymerization of a monomer component consisting of Cationic and/or zwitterionic acrylic resins derived from polymers. The multistage emulsion polymerization referred to here is, first,
Among the monomer components, some components are selected according to the Tg of the polymer.
is selected so that the temperature is 15°C or higher, and this part of the components is emulsion polymerized by a known emulsion polymerization method as the first stage 11. In the presence of the obtained polymer (this is called the core part), the remaining monomers are This is a method in which emulsion polymerization in the second and subsequent stages is performed sequentially using polymeric components. At this time, from the second stage onward, the remaining monomer components used in the first stage may be used in their entirety to perform two-stage polymerization, or by appropriately dividing the polymerization to three or more stages.

In the present invention, the polymer having the composition of the final stage is referred to as the outermost shell portion. In the present invention, the Tg of the outermost shell portion must be 10° C. or less. Generally, two to three stages of polymerization are used as multistage emulsion polymerization, and the ratio of the core part to the other parts is 1.
It is preferable to polymerize at a weight ratio of 0:90 to 90=10.

A polymer obtained by such a method is referred to as a multilayer structure copolymer in the present invention.

Specific examples of polymer monomer components constituting the multilayer structure copolymer of the present invention include vinyldimethoxymethylsilane, vinyltris (β
-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like.

One type or a mixture of two or more of these monomers is used in an amount of 0.1 to 10% by weight based on the total monomer component. If the amount is less than 0.11i%, the adhesion to the substrate and crosslinking properties will be insufficient, and if the amount exceeds 10% by weight, crosslinking will proceed too much, adversely affecting processability and the like, making it uneconomical.

Typical examples of polymerizable unsaturated carboxylic acids (b) include:
Examples include acrylic acid, methacrylic acid, and itaconic acid. The zero-polymerizable unsaturated carboxylic acid, in which one or a mixture of two or more of these monomers is used in an amount of 0 to 20% by weight based on the total monomer, imparts amphoteric ionicity to the resin, and also provides cationic ions by post-reaction. It is used as a monomer to introduce properties, but if it exceeds 20% by weight, the water resistance of the resin will deteriorate, which is not preferable.

Typical examples of (meth)acrylic acid alkyl esters (C) in which the alkyl group has 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. methyl,
Examples include ethyl methacrylate, propyl methacrylate, and butyl methacrylate. One type or a mixture of two or more of these monomers accounts for 20% of the total monomer component.
~99% by weight is used.

Monomers (d) copolymerizable with these include α-olefins such as ethylene, propylene, and imbutylene; vinyl halides such as vinyl chloride and vinyl bromide; vinyl cyanides such as acrylonitrile and methacrylonitrile;
Vinyl esters such as vinyl acetate and vinyl propionate, aromatic vinyls such as styrene, vinyltoluene, and α-methylstyrene, vinylidene chloride, vinylidene fluoride, vinylidene halides, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethyl Examples include aminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl acrylate, acrylamide, methacrylamide, and N-methylolacrylamide. One or more of these monomers make the multilayer structure copolymer cationic and/or zwitterionic, and as necessary to satisfy the requirements for ]g in the core and outermost shell parts. 0 of all single components
~40% by weight is used. The multilayer structure copolymer is a special acrylic resin containing a hydrolyzable silicon compound in the molecule, and furthermore, the 'rg of the core portion is 15°C or higher,
In addition, it is important that the Tg of the outer shell portion is 10°C or less. The Tg shown here indicates the glass transition point of the copolymer, and it is preferable to actually measure its value, but another method is to use rBull from Fax.

It can be calculated as described in Am, Physics SOC, Vol. 41, No. 3, p. 123 (1956).

If the Tg of the core portion is less than 15°C, the strength of the resulting coating film will be low, and the coating film will tend to become too soft when heated. Therefore, the aluminum material coated with the composition is
For example, if it is an aluminum plate, it is likely to cause blocking when wound into a coil, which poses a problem in terms of work.

The outermost shell portion must have a Tg of 10°C or less.

Acrylic resin (U), when applied to aluminum materials at temperatures exceeding 10°C, tends to cause film defects and cannot be expected to provide sufficient performance when formed into a film at low temperatures. It has a cationic nitrogen in the molecule derived from a structural copolymer. Typical cationic resins include, for example, the resins listed in items (1) to (3) below.

(1) IN or 2! selected from vinyl compounds containing an amino ester group such as dialkylaminoalkyl (meth)acrylate, cationic nitrogen-containing vinyl compounds such as vinylpyridine, vinylimidazole, or their salts. ! ! A resin obtained by copolymerizing the above.

(2) A resin in which an acrylic resin copolymerized with glycidyl (meth)acrylate or chloromethyl methacrylate is cationized with dimethylamine, diethylamine, ethylenediamine, etc.

(3) A resin containing an aminomethyl group obtained by the reaction of an acrylic resin copolymerized with p-thalolmethylstyrene and an amine and/or a polyamine, and an amphoteric resin that has a cation in its molecule. A resin having nitrogen and an anionic carboxyl group, for example, the following (
The resins shown in each section of 4) to (6) can be mentioned.

(4) A resin in which a carboxyl group, which is an anionic group, is introduced into the cationic resin of items (1) to (3) above by a known method (for example, using chromium acetic acid or the like).

(5) Reaction of a carboxyl group-containing (meth)acrylic resin with a basic nitrogen-containing alkylating agent such as an aziridine compound such as ethyleneimine, propyleneimine, hydroxyethylethyleneimine, or cyanoethylethyleneimine, or glycidylamine or its container. Resin containing zwitterionic groups obtained by.

(6) 1 selected from basic nitrogen-containing vinyl compounds such as dialkylaminoalkyl (meth)acrylate, vinylpyridine, vinylimidazole, or their salts;
A copolymer obtained by using as essential components one or more carboxyl group-containing vinyl compounds such as <meth)acrylic acid, crotonic acid, or maleic acid.

etc. can be mentioned.

Among these acrylic resins (It), No.
The resins shown in Items and Items (5) are the resins (I) in the present invention.
It is particularly effective as I).

In the present invention, as the acrylic resin (I[),
Various cationic resins and/or amphoteric ionic resins can be used as exemplified in items (1) to (6) above.

However, in the case of a cationic resin, the amount of cationic nitrogen measured by a commonly known method such as colloid titration, conductivity titration, etc. is in the range of 90.01 to 5 mmol per 1 g of the resin. This is desirable.

In the case of an amphoteric ionic resin, the amount of cationic nitrogen and the amount of carboxyl groups that can be anionized (these amounts can also be measured by colloid titration, conductivity titration, etc.).

) is desirably in the range of 0.01 to 5 mmol per 1 g of the resin. If it deviates from this range, the effect as an aluminum surface treatment composition will be insufficient, and this is not preferred.

When using the acrylic resin (II) in the present invention,
It may be used as it is, or part or all of the cationic nitrogen may be used as a salt or quaternary ammonium salt of a mineral or organic acid such as hydrochloric acid, nitric acid, phosphoric acid, or formic acid,
Alternatively, a basic substance such as ammonia, amine, polyamine, etc. can be added and used. Acrylic resin (II
) is 0.5 to 600 g, preferably 1 to 400 g, per liter of the aluminum surface treatment composition of the present invention.
It is included.

Next, acrylic resin (III) added as necessary
is a cationic and/or amphoteric acrylic resin with a Tg of 10°C or higher, which can be obtained by various conventionally known emulsion polymerization methods, and typical examples include the above-mentioned (1) to The resins listed in each item (6) are used, but among them, the resins shown in item (1) or item (5) are preferable. However, the acrylic resin (
In acrylic resin (II[), which does not need to have a multilayer structure like II), the amount of cationic nitrogen is 1 g of the resin.
The amount is preferably in the range of 0.01 to 3 mmol, more preferably 0.01 to 1 mmol.

Further, in the case of an amphoteric ionic resin, the amount of cationic nitrogen and the amount of anionizable carboxyl group are each in the range of 0.01 to 3 mmol, more preferably 0.01 to 1 mmol, per 1 g of the resin. If the composition falls outside this range, the effect as an aluminum surface treatment composition will be insufficient and is not preferred.
) is 90 to 60 per liter of aluminum surface treatment composition.
Although it is contained in an amount in the range of 0g, it has the effect of improving blocking resistance when the treated aluminum plate is wound into a coil, and also has the effect of improving workability because it has little crosslinking and has thermoplasticity. be. It also works to improve the water resistance of the paint film.

The (D) carboxylated olefin resin (IV) used in the present invention includes (1) one or more ethylene hydrocarbons (e.g. ethylene, propylene, butene, isobutylene, etc.) and a carboxyl group-containing monomer. Copolymers (including block copolymers and random copolymers) containing one or more types of monomers (e.g. acrylic acid, methacrylic acid, maleic acid, etc.) as essential monomers
, or (2) a block copolymer of a carboxyl group-containing monomer polymer and an ethylene hydrocarbon polymer,
It is an olefin resin containing 3 to 30% by weight of carboxyl groups. Specifically, for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic acid copolymer, ethylene-vinyl alcohol-
Acrylic acid copolymer, ethylene-vinyl acetate-acrylic acid copolymer, ethylene-propylene-acrylic acid copolymer, ethylene-acrylic acid-methacrylic acid copolymer, propylene-acrylic acid copolymer, propylene-maleic acid Examples include copolymers, isobutylene-acrylic acid copolymers, and polyacrylic acid-polyethylene block copolymers. In such a copolymer, it is necessary that the carboxyl group content is set within a certain range as mentioned above; if it deviates from the above suitable range, a high degree of corrosion resistance cannot be obtained. It is thought that it is necessary to regulate the molecular weight range of
Since it is generally difficult to directly measure the molecular weight, it can be replaced by the melt index <Ml)fia, which is related to the molecular weight. However, this MID also varies depending on the type of copolymer, the type of carboxyl group-containing monomer, and the carboxyl group content, so it cannot be described in general, but for example, if the monomer ratio of acrylic acid is 20%, In the case of ethylene-acrylic acid copolymer, 1
MI value is 20 under the conditions of 90 parts 1°C 12160+10g
0 to 600 dg/min is suitable.

Carboxylated olefin resin (IV) is 065
1 in the range of ~600g. As for the mold layer used, it is easy to use a dispersion type that is water-dispersed.

In the present invention, (E) a compound having an aziridinyl group used as a crosslinking agent is a compound having two or more aziridinyl groups, such as 1,6-hexamethylene diethylene urea, diphenylmethane-bis-4,4--
N,N--diethyleneurea, 2,2-bishydroxymethylbutanol-tris(3-<1-aziridinyl)
10 bionate], triethylene melamine, tris-1
-aziridinylphosphine oxide, 2,4-diethyleneureatluidine, 2.4.6-(triethyleneimino)-sym-triazine, ω-aziridinylpropionic acid-2,2-dihydroxymethyl-butanol-triester , 2.4.6-tris(2-methyl-1-aziridyl)-sym=triazine, 2.4.6-tris(2-ethyl-1-aziridyl)-sym-triazine, bis(2-ethyl-1 -aziridyl)benzene-1゜3-dicarboxylic acid amide, tris(2-ethyl-1-aziridyl)benzene-1,3,5-tricarboxylic acid amide, bis(2-ethyl-1-aziridyl)sebacic acid amide, 2 .4-Diethyleneureidotoluene, 1.1-
monocarbonyl-b1s-ethyleneimine, polymethylene (C2-C4)-bis-ethylene urea, N, 'N-
-bis-(4,6-diethyleneimino-1,3,5
-triazin-2-yl)-hexamethylene diamino and the like.

The amount of the compound having an aziridinyl group to be added is 10% by weight or less as a solid content ratio to the resin, and is determined for each resin composition and for each compound having an aziridinyl group.

These crosslinking agents are used by reacting or mixing with the resin, and have the function of improving solvent resistance, water resistance, blocking resistance, etc. When the amount added exceeds 10'MJi%, solvent resistance, Water resistance, blocking resistance, etc. are greatly improved, but processing adhesion is poor, and it is not economical. Additives do not need to be added during advanced post-processing, and they can be used depending on the purpose of the surface-treated board. good.

The composition for aluminum surface treatment of the present invention can be used for aluminum, aluminum alloys, and aluminum treated with chemical conversion treatment or the like. Moreover, various shapes such as a plate shape, a pipe shape, and a line shape can be used as the shape of these objects to be coated.

The method for using the composition for aluminum surface treatment of the present invention is as follows:
After coating on the aluminum surface at room temperature to 150°C, preferably room temperature to 70°C, by bald coating, spray coating, roll coating, dipping, etc., it is only necessary to dry it at a temperature above room temperature for a few seconds to several minutes. At this time, the thickness of the resulting coating film was 0.
A sufficient effect can be obtained with a thin film of about 1 to 5 μm.

The aluminum surface treatment composition of the present invention is characterized in that it can be used for direct surface treatment of aluminum surfaces. Furthermore, it can be used as a sealant for anodic oxidation or chemical conversion treated plates to provide higher corrosion resistance and base properties for painting.

(Example) Hereinafter, the present invention will be explained in more detail using specific examples.
The present invention is not limited in any way by the examples.

Note that % in Production Examples and Examples indicates weight %.

Production example of zwitterionic acrylic resin (I[) Production example 1 Add 466 parts of deionized water and 2 parts of anionic emulsifier to a flask equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel. When the temperature is raised to 70"C,
After adding 2 parts of ammonium persulfate, styrene 28.0
A monomer mixture consisting of 27.5 parts of methyl methacrylate, 39 parts of butyl acrylate, 6 parts of acrylic acid, and 0.5 parts of vinyltrimethoxysilane was added over 1 hour to perform the first stage emulsion polymerization. . After further polymerization for 1 hour, 30 parts of styrene and 6 parts of butyl acrylate were added.
A monomer mixture consisting of 0 parts, 9 parts of acrylic acid, and 1 part of vinyldimethoxymethylsilane was added over 1 hour to perform emulsion polymerization of the second stage (constituting the outermost shell part), and the Tg of the core part was about 19. Next, 7 parts of ethyleneimine and 16 parts of deionized water were added to this polymer, and after reacting at 50°C for 3 hours, it was neutralized with ammonia. The pH was adjusted to 9.0 to obtain a zwitterionic acrylic resin (II) having a solid content of 30%.

Production Example 2 By the same method as Production Example 1, the first stage consisted of 54.5 parts of methyl methacrylate, 39 parts of butyl acrylate, 6 parts of acrylic acid, and 0.5 parts of γ-methacryloxyglopyltrimethoxysilane. , the second stage consists of 12 parts of methyl methacrylate, 81 parts of butyl acrylate, 6 parts of acrylic acid, and 1 part of γ-methacryloxypropyltrimethoxysilane, the Tg of the core part is about 21°C, and the outermost shell part has a Tg of about 21°C. After synthesizing the multilayer structure polymer at -36°C,
A cationization reaction was carried out with 3.6 parts of ethyleneimine, and after neutralization with ammonia, a zwitterionic acrylic resin (II>) having a solid content of 30% and a pH of 9.0 was obtained.

Production Example 3 By the same method as Production Example 1, the first stage consisted of 55 parts of methyl methacrylate, 39 parts of butyl acrylate, 5.5 parts of acrylic acid, and 0.5 parts of γ-methacrylate 17xyprobyltrimethoxysilane. , the second stage consists of 4 parts of methyl methacrylate, 81 parts of butyl acrylate, 14 parts of acrylic acid, and 1 part of γ-methacryloxypropyl 1-rimethoxysilane, the Tg of the core portion is about 24°C,
After synthesizing a multilayer structure polymer whose outermost shell has a nominal temperature of -35°C, a cationization reaction is performed with 6 parts of ethyleneimine, and after neutralization with ammonia, a zwitterionic 7°Crylic polymer with a solid content of 30% and a pH of 9°C is produced. A system resin (II) was obtained.

Manufacturing Example 4 of Zwitterionic Acrylic Resin <m> The 'rg obtained from 60 parts of methyl methacrylate, 38.8 parts of 2-ethylhexyl acrylate and 1.2 parts of acrylic acid is about 13°C. After reacting 100 parts of an emulsion polymer with a solid content of 40% and 0.28 parts of ethyleneimine, the mixture was neutralized with ammonia to obtain an amphoteric ionic acrylic resin (III) with a solid content of 40% and a pH of 8.5. .

Production Example 5 37 parts of 2-ethylhexyl acrylate, 58 parts of styrene
100 parts of an emulsion polymer having a solid content of 40% and having a Tg of about 15°C obtained from 5 parts of acrylic acid and 1 part of ethyleneimine.
．． After reacting with 1 part, neutralize with ammonia to reduce the solid content to 40%.
, pH 8.5 zwitterionic acrylic resin (III)
I got it.

Production Example 6 Emulsion polymer 1 with a solid content of 40% and a Tg of about 15°C obtained from 58.5 parts of methyl methacrylate, 37.5 parts of 2-ethylhexyl acrylate, and 4 parts of acrylic acid.
After reacting 0.00 parts with 0.95 parts of ethyleneimine, the mixture was neutralized with ammonia to obtain an amphoteric ionic acrylic resin (III) having a solid content of 40% and a pH of 8.5.

Zwitterionic carboxylated olefin resin (IV
) Production Example Production Example 7 Dice version of carboxylated polyethylene resin having a solid content of 25% and containing about 20 mol% of carboxyl groups (trade name: Zaixen A manufactured by Steel Chemical Industry Co., Ltd.) 10
After diluting 0 part with deionized water to a solid content of 20%, it was reacted with 1 part of ethyleneimine and neutralized with ammonia to a solid content of 20%.
%, pH 10.

0 zwitterionic carboxylated olefinic resin (I
V).

Production Example 8 Dispersion of carboxylated polyethylene resin containing 25% solids and 20 mol% carboxyl groups (
Product name: Slimacol 4983 (manufactured by Dow Chemical Co.)
After diluting 100 parts with deionized water to a solid content of 20%, it was reacted with 1 part of ethyleneimine, and neutralized with ammonia to obtain a zwitterionic carboxylated olefin resin (IV) of PHIO,O with a solid content of 20%. Obtained.

Production Example 9 Ethylene-methacrylic acid ionomer with a solid content of 27% (
Product name: Chemivar S-100 Mitsui Petrochemical Industries, Ltd.
After diluting 100 parts with deionized water to a solid content of 20%, it was reacted with 0.3 part of ethyleneimine and neutralized with ammonia to give a solid content of 20%. IV) was obtained.

Example 1 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 1 (I
I>15 parts, acrylic resin obtained in Production Example 4 (■)
and 11 parts of deionized water, then diphenylmethane-bis-4,4--N,N-
--Diethylene urea (product name: DZ-22N25%
Add 0.7 parts of white water (manufactured by Hon Shokubai Kagaku Kogyo Co., Ltd.) and react at 50°C for 12 hours.
) (Product name: Varnish Notex C, 5iO720% product) 3
3 parts were added to obtain a composition for aluminum surface treatment. This composition was applied to an aluminum plate with a thickness of 0.8 mm (JIS
H4000A1050P (Japan Test Panel) was spray coated to a film thickness of 2.0 μm, and then dried at 100° C. for 60 seconds to obtain a surface-treated board.

Example 2 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 2 (I
I) 15 parts, acrylic resin obtained in Production Example 5 (■)
4 parts and 11 parts of deionized water were mixed, and then 0.1 part of 1,6-hexamethylene diethylene urea (trade name: H2-22 manufactured by Nippon Shokubai Chemical Co., Ltd.) was added as a crosslinking agent. , after reaction at 50°C for 12 hours, water-dispersible silica (I
) (Product name: Cataloid 5i-35O3in
230% product) was added to obtain a composition for aluminum surface treatment. This composition was coated on an aluminum plate (JIS H4000A1050P: Japan Test Panel) with a thickness of 0°8 rLrm to a film thickness of 2. After spray coating to give a Q-noz, drying was performed at 100° C. for 60 seconds to obtain a surface-treated board.

Example 3 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 3 (I
I) 15 parts, acrylic resin obtained in Production Example 6 (■)
4 parts and 11 parts of deionized water, and then, as a crosslinking agent, 2,2-bishydroxymethylbutanol-trisE3-(1-aziridinyl)propionate (trade name, Pz-32 Nippon Shokubai Chemical Co., Ltd.) was mixed. Co., Ltd.) was added, and after reacting at 50°C for 12 hours, water-dispersible silica (trade name: Snowtex XS, Sio
220% product) was added to obtain a composition for aluminum surface treatment. This composition was applied to an aluminum plate (JIS H4000A1050P: Japan Test Panel) with a thickness of 0.8 mm. After spray coating to give AK2,0)t, drying was performed at 100°C for 60 seconds to obtain a surface-treated plate.

Example 4 Carboxylated olefin resin obtained in Production Example 8 (
IV) 70 parts, 7” grill resin obtained in Production Example 3
II) 15 parts, acrylic resin obtained in Production Example 5 (■
) and 11 parts of deionized water, and then 1,6-hexamethylene diethylene urea (
Product name: H2-22 (manufactured by Nippon Shokubai Chemical Co., Ltd.) 0.1
After reacting at 50°C for 12 hours, water-dispersible silica (I) (trade name Nisnortex X S, Si
0220% product) was added to obtain a composition for aluminum surface treatment. This composition was spray applied to a 0.8 m thick aluminum plate (JIS H4000A1050P: Japan Test Panel) to a film thickness of 2.0 μm, and then
Drying was performed at 00° C. for 60 seconds to obtain a surface-treated board.

Example 5 Carboxylated olefin resin obtained in Production Example 9 (
IV) 70 parts, acrylic resin obtained in Production Example 2 (I
I) 15 parts, acrylic resin obtained in Production Example 5 (■)
and 11 parts of deionized water, and then 0.15 parts of 2,4-diethyleneureatluidine as a crosslinking agent.
After reacting at 50°C for 12 hours, water-dispersible silica (1
) (trade name: Cataloid 5l-500 810220% product) was added thereto to obtain an aluminum surface treatment composition. This composition was applied to an aluminum plate with a thickness of 0°8 (JIS H4000A1050 P:
[1 test panel] After spray coating to a film thickness of 2.0 μm, drying was performed at 100° C. for 60 seconds to obtain a surface-treated board.

Example 6 Carboxylated olefin resin obtained in Production Example 7 (
■) 70 parts of the acrylic resin obtained in Production Example 2 (II
) 15 parts and the acrylic resin obtained in Production Example 5 (II
I) 4 parts and 11 parts deionized water;
Water-dispersible silica (■) (Product name: Varnish Notex X8
．． Add 33 parts of 510220% product) and # for aluminum surface treatment! 1. C) This composition was made into an aluminum plate (JIS H4000A1050P) with a thickness of 0.8.
: Japan Test Panel) to a film thickness of 2.0 μm, and dried at 100° C. for 60 seconds to obtain a surface-treated board.

Comparative Example 1 267 parts of acrylic resin (■) obtained in Production Example 3,
Acrylic resin (I[[>200
aluminum surface treatment by adding 200 parts of water-dispersible silica (trade name Nisnortex C, 0.220% Si product) and 10 parts of 5% chromic anhydride and bringing the total volume to 11 with deionized water. A composition for use was obtained. This composition was applied to an aluminum plate (JIS H
4000A1050P: Japan Test Panel) film thickness 2.
After spray coating so as to have a thickness of 0 μm, drying was performed at 100° C. for 60 seconds to obtain a surface-treated board.

Comparative Example 2 33 parts of the acrylic resin (II) obtained in Production Example 3, 25 parts of the acrylic resin (■) obtained in Production Example 4, 42 parts of deionized water, and 1 part of DZ-22N as a crosslinking agent. After adding .0 parts and reacting at 50°C for 12 hours, water-dispersible silica (1)
(Product name: Varnish Notex c, 5t0220% product) 3
3 parts were added to obtain a composition for aluminum surface treatment. This composition was applied to an aluminum plate with a thickness of 0.8 mm (JIS
H4000A1050P, Japan Test Panel) film thickness 2
After spray coating to give a thickness of 0.degree. C., the coating was dried at 100.degree. C. for 60 seconds to obtain a surface-treated board.

Comparative Example 3 Aluminum plate with a thickness of 0.8 mm (JISH11000A
1050P: Japan Test Panel) itself was used for evaluation.

Table 1 shows the test results of the surface-treated plates obtained in Examples and Comparative Examples.

The evaluation was performed as follows.

(1) Primary corrosion resistance: Salt spray tests were conducted for 500 and 1000 hours according to JIS Z-2371, and the area where white rust occurred was evaluated in %.

■Paint adhesion: Commercially available melamine-alkyd resin PWC
After baking 50% at 130℃ for 20 minutes to a film thickness of 25μ, insert a 1mm-wide 10XIO base hole, extrude EriRasen 6III+, press cellophane tape, and peel it off.10 points (full score) Evaluated by law.

■ Processing adhesion: (1) Erichsen test @: 17ma+ with Erichsen tester
After extrusion, the extruded Lofan chips were crimped and then peeled off and evaluated using a 10-point scale) method.

(2) IT bending processability: After a cellophane tape was crimped onto the folded surface, it was peeled off and evaluated using a 10-point (full score) method.

(3) DuPont? II impact: A 1 kir weight is dropped from a height of 50 cm using a 1/4φ punch from the back side (convex) and front side (concave) of the coating surface, and after applying an impact, apply cellophane tape to the impact area. After crimping it, peel it off and evaluate it using a 10-point scale.

■Gauze impregnated with solvent-resistant di-petroleum benzine, 5
A 10-reciprocating rubbing test was performed with a load of 0.00 g applied.

◎... No change, O... Scratches present, Δ... Partially eluted, X... Eluted ■ Blocking resistance: A treated board coated with an aluminum surface treatment composition on both sides, It was cut into a size of 50w x 50ma, stacked in four layers and pressed together at 50°C under a pressure of 1000kg/cd for 20 minutes, and then its blocking property was measured.

◎・・・No blocking, O...There is some blocking, Δ・・・Part of the coating film is blocking. It peels off. .

×・・・Full blocking ■Hardness: r1 brush hardness According to JIS K5400.

(Effects of the Invention) As is clear from the examples, the composition for aluminum surface treatment of the present invention has the following properties: (1) By introducing an olefin resin, the composition has improved paint adhesion, processing adhesion, solvent resistance, and blocking resistance; Surface-treated aluminum with extremely high performance that improves hardness and (2) improves solvent resistance and blocking resistance without reducing the performance of the pond by adding a compound having an aziridinyl group as a crosslinking agent. This has the effect that a plate can be manufactured.

Claims (1)

[Claims] (1) Per liter of aluminum surface treatment composition, (A)
Water-dispersible silica (I) converted to SiO_2 is 0.5
-250 g, (B) alkoxysilane compound having a polymerizable unsaturated group (a) 0.1 to 10% by weight, polymerizable unsaturated carboxylic acid (b) 0 to 20% by weight, carbon of the alkyl group (meth)acrylic acid alkyl ester having a number of 1 to 8 (c) 20 to 99% by weight, a monomer copolymerizable with these (d) 0 to 40% by weight [However, (a), (b) ), (c) and (d) are 100% by weight. ] A cationic copolymer derived from a multilayer structure copolymer whose core portion has a Tg of 15°C or more and an outermost shell portion has a Tg of 10°C or less and/or zwitterionic acrylic resin (II) from 0.5 to
(C) an amount of cationic and/or amphoteric acrylic resin (III) having a Tg of 10°C or more in a range of 0 to 600 g; (D) a cationic and/or amphoteric resin; Ionic carboxylated polyolefin resin (IV) in an amount ranging from 0.5 to 600 g (provided that the total of (A), (B), (C), and (D) is
(E) a compound having a polyfunctional aziridinyl group in an amount not exceeding 700 g in a solid content ratio of 10% by weight or less relative to the resin.