JPS63295677A - Composition for treatment of aluminum surface - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in applicability and adhesion to an aluminum surface, solvent resistance, etc., by mixing water-dispersible silica with three specified resins and a polyfunctional, epoxy compound. CONSTITUTION:0.1-10wt.% polymerizable unsaturated alkoxysilane compound (a), 0-2wt.% 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 coplymer having a Tg of the core >=15 deg.C and a Tg of the outermost shell >=10 deg.C. At most 700 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 0.5-600g of cationic and/or amphoteric carboxylated polyolefin resins (D) is mixed with at most 10wt.%, based on the solid matter of components B-D, polyfunctional epoxy compound (E) and water (F) to obtain 1l of the title composition.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a composition for treating aluminum surfaces. Specifically, the present invention relates to a composition for treating aluminum surfaces. This invention relates to an aluminum surface treatment composition that has excellent adhesion, solvent resistance, and blocking resistance. It is something.

(Prior Art) Conventionally, anodic oxidation treatment and chemical conversion coating treatment have been performed 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 compared to polar oxidation treatment using an electrical method. Among them, performance
Chromate treatment is mainstream from the viewpoint of 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) According to the present invention, (A) water-dispersible silica (I) is 0.0% in terms of SiO□ per 11 compositions 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 copolymerizable with these (d) 0 to 40% by weight [However, (a>, (b) ), (C) and (d) are 100% by weight.] The Tg of the core portion obtained by multi-stage emulsion polymerization of a 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 having a Tg of the outermost shell portion of 10 ° C. or less, (
C) an amount ranging from 0 to 600 g of cationic and/or zwitterionic acrylic resin (III), 1"g of which is 10°C or higher; (D) cationic and/or zwitterionic carboxylated polyolefin The amount of the system resin (1v) in the range of 0°5 to 600g [provided that the total of (A>(B)(C) and (I)) does not exceed 700g] (E) Polyfunctional epoxy The present invention relates to a composition for aluminum surface treatment, characterized in that it contains a compound having an I!! group in an amount of 10f!% or less in terms of solid content to fat.

The (A) water-dispersible silica (I) used in the present invention is:
Colloidal silica is a condensation product of silicic 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 O" and "Snowtex O". Snowtex N""
Snowtex NC8” “Snowtex 20” “
Snowtex C, Snowtex S, Snowtex SS, Snowtex
ataloid 81-350" rcataloi
d5l-500J (manufactured by Catalysts & Chemicals Co., Ltd.) and the like. Further, surface-treated colloidal silica such as ``catalolds A'' treated with aluminic acid (manufactured by Catalysts & Chemicals Co., Ltd.) can also be used. These may be used as such, and in order to improve their dispersibility in the composition for aluminum surface treatment, acrylic resin <II) or quaternary ammonium salt, etc., which are other essential components of the present invention, may be used. The water-dispersible silica (I) may be surface-treated in advance with an amine, or an aziridine derivative such as ethyleneimine may be grafted onto the surface of the water-dispersible silica (I).

The 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 (
20-99% by weight of meth)acrylic acid alkyl ester (C), 0-40% of monomer (d) copolymerizable with these (1 and 1% of (a), (b), (c) and The total of (d) is 100% by weight.) The Tg of the core portion obtained by multi-stage emulsion polymerization of the monomer component consisting of is 15 ° C. or higher,
It is a cationic and/or amphoteric acrylic resin derived from a multilayer structure copolymer whose outermost shell portion has a Tg of 10° C. or less. The multi-stage emulsion polymerization referred to here means that some of the monomer components are added to the T of the polymer.
g is selected so that it is 15°C or higher, and some of these components are added to the first
Emulsion polymerization is carried out using a known emulsion polymerization method as the second step, and in the presence of the resulting polymer (this is referred to as the core), the second and subsequent stages of emulsion polymerization are performed sequentially using the remaining monomer components. It's a method. 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 or 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-methacryloxyglobyltrimethoxysilane, 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 10ffi based on the total monomer components. If it is less than 0.1% stone, the adhesion to the base material and crosslinking properties are insufficient,
Moreover, if the amount exceeds 10% by weight, crosslinking will proceed too much and will adversely affect workability, etc., 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 monomers imparts zwitterionicity to the resin, and ) is used as a monomer to introduce cationic 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,
Examples include 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. One type or a mixture of two or more of these monomers accounts for 2% of the total monomer components.
It is used in an amount of 0 to 99% by weight.

Monomers (d) copolymerizable with these include α-olefins such as ethylene, propylene, and isobutylene; vinyl halides such as vinyl chloride and vinyl bromide; vinyl cyanides such as acrylonitrile and methacrylonitrile;
Vinyl esters such as vinyl acetate and vinyl 10 pionate, aromatic vinyls such as styrene, vinyltoluene and α-methylstyrene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, dimethylamine ethyl acrylate, diethylaminoethyl acrylate, Examples include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl acrylate, acrylamide, methacrylamide, and N-methylolacrylamide. One or more of these monomers make the multilayer structure copolymer cationic and/or amphoteric, and the monomer amount is adjusted as necessary to satisfy the requirements for Tg of the core portion and the outermost shell portion. Total body composition: 0
~40% by weight is used. The multilayer structure copolymer is a special acrylic resin containing a hydrolyzable silicon compound in its molecules, but it also has a Tg of 15°C or higher in the core and a Tg of 10°C or lower in the outermost shell. It is important that there be. Tg shown here indicates the glass transition point of the copolymer, and it is preferable to actually measure its value, but another method is rBull of Fox (Fax).

It can be calculated as described in Am, Physics SOC, Vol. J1, 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 (II), 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 cationic nitrogen in the molecule derived from such a multilayer structure copolymer. Typical cationic resins include, for example, the resins listed in items (1) to (3) below.

(1) One or more types selected from vinyl compounds containing an amino ester group such as dialkylaminoalkyl (meth)acrylate, and cationic nitrogen-containing vinyl compounds such as vinylpyridine, vinylimidazole, or their salts. A resin obtained by copolymerization.

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

(3) Resins containing aminomethyl groups obtained by the reaction of acrylic resins copolymerized with P-chloromethylstyrene and amines and/or polyamines, and amphoteric resins that contain cationic nitrogen in the molecule. 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) Carboxyl group-containing (meth)acrylic resins and basic nitrogen-containing alkylation compounds such as aziridine compounds such as ethyleneimine, propyleneimine, diroxyethylethyleneimine, cyanethylethyleneimine, glycidylamine or its salts, etc. Resin containing zwitterionic groups obtained by reaction with.

(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 types of carboxyl group-containing vinyl compounds such as (meth)acrylic acid, crotonic acid, or maleic acid.

Among these acrylic resins (I), the resins shown in items (1) and (5) are the resins (II) in the present invention.
) is particularly effective.

In the present invention, the acrylic resin (II) is
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 preferably in the range of 0.01 to 5 mmol per gram of the resin. If it is outside this range, the effect as an aluminum surface treatment composition will be insufficient, which is not preferable.

When using acrylic resin (I[> in the present invention,
The cationic nitrogen may be used up to
Part or all of it can 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, or it can be used with the addition of a basic substance such as ammonia, amine, polyamine, etc. Acrylic resin (I
I) is contained in an amount ranging from 0.5 to 600 g, preferably from 1 to 400 g, per 11 of the aluminum surface treatment composition of the present invention.

Next, acrylic resin (I[I) added as necessary
is a cationic and/or amphoteric acrylic resin with a Tg of 0°C or higher, which can be obtained by various conventionally known emulsion polymerization methods. ) to (6) are used, but among them, the resins shown in the above (1) or (5) are preferred; however, the acrylic resin (If) In the acrylic resin (I[), which does not need to have a multilayer structure like this, 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. It is preferable that acrylic resin (I[I
) is 90 to 60 per aluminum surface treatment composition 11
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 (1v) 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 as essential monomers one or more of acrylic acid, methacrylic acid, maleic acid, etc.
or (2) a block copolymer of a carboxyl group-containing monomer polymer and an ethylene hydrocarbon polymer,
3-30f carboxyl group! It is an olefin resin containing %. 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 combination, ethylene-10 pyrene-acrylic acid copolymer, ethylene-acrylic acid-methacrylic acid copolymer,
Examples include a 10-pyrene-acrylic acid copolymer, a propylene-maleic acid copolymer, an inbutylene-acrylic acid copolymer, and a polyacrylic acid-polyethylene block copolymer. 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
Melt index (MI) values related to molecular weight can be substituted. However, this MI value 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 2
In the case of 0% ethylene-acrylic acid copolymer, 19
MI value is 200~ under the conditions of 0±1℃ and 2160±10g
600dg/m1n is preferable. Ruru.

Carboxylated olefin resin (IV) is 0°5
~600 g. As for the form used, a dispersion type in which water is dispersed is easy to use.

In the present invention, (E) a compound having an epoxy group used as a crosslinking agent is preferably a compound having two or more epoxy groups, such as (1) ethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether. , detraethylene glycol diglycidyl ether, pentaethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, etc. Ethylene and polyethylene glycol diglycidyl ether, propylene and polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether , polyglycerol polyglycidyl ethers, (2) diglycidyl ethers of aliphatic diols such as butanediol, bentanediol, hexanediol and their isomers, (3) resorcinol, hydroquinone, virocax, saligenin, phloroglucinol, 1゜5-dihydroxynaphthalene, 1.6-dihydroxynaphthalene, 1.7
- glycidyl ether of polyvalent monocyclic and condensed ring phenols such as dihydroxynaphthalene, (4) following formula: % formula % [wherein R3 is 0 to 4 selected from the group consisting of halogens such as chlorine and bromine, and lower alkyl] substituents, A is R400 1II II -c-, -s-, -c-, -o-.

R50 and a linking group selected from a single covalent bond (R4 and R5 are each a group selected from hydrogen, lower alkyl, lower cycloalkyl, and aryl group)] Glycidyl of a non-fused polycyclic phenol represented by Ethers, such as 4,4-dihydroxydiphenylsulfone, 4,4-dihydroxybiphenyl, 4,4-dihydroxybenzophenone, di(4-hydroxyphenyl)methane (bisphenol F), 2,2-dihydroxybenzophenone, (4-hydroxyphenyl)butane (bisphenol B), 2.2
-di(4-hydroxyphenyl)propane (bisphenol A), 1,1-di(4-hydroxyphenyl)propane, 3,3-di(3-hydroxyphenyl)pentane, 2-(3-hydroxyphenyl) phenyl)-2-(4-hydroxyphenyl)butane, 1-phenyl-1-(2-hydroxyphenyl)-1-(3'-hydroxyphenyl)butane, 1-phenyl-1-(2-hydroxyphenyl) -1-(3--droxyphenyl)propane, 1
-phenyl-1,1-di(4-hydroxyphenyl)butane, 1-phenyl-1,1-di(4-hydroxyphenyl)pentane, 1-tolyl-1,1-di(4-hydroxyphenyl)ethane, Bis(3-bromo-4-hydroxyphenyl)methane, 2゜2-bis(3-bromo-4
-Droxyphenyl)propane, bis(3-bromo-
4-hydroxyphenyl)diphenylmethane, 1.1-
Bis(3-bromo-4-droxyphenyl)-1-2
,5-dibromophenyl)ethane, bis(3,5-bromo-4-droxyphenyl)methane, 2,2-bis(
3,5-dibromo-4-hydroxyphenyl)propane, bis(3,5-dibromo-4-hydroxyphenyl)
diphenylmethane, 1,1-bis(3,5-dibromo-
4-hydroxyphenyl)-1-(2,5-dibromophenyl)ethane, bis(3-bromo-4-hydroxyphenyl)sulfone, and bis(3,5-dibromo-4)
-hydroxyphenyl) sulfone and other bis(glycidyl ethers).

(5) Glycidyl ether of novolac resin.

etc. can be exemplified.

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

These crosslinking agents are used by reacting or mixing with the resin, but they work to improve solvent resistance, water resistance, blocking resistance, etc. If the amount added exceeds 10% by weight, solvent resistance and water resistance Although it greatly improves properties such as surface treatment and blocking resistance, it has poor processing adhesion and is not economical. Additives do not need to be added when performing advanced post-processing, and it is best to use them depending on the purpose of the surface-treated board. .

The composition for aluminum surface treatment of the present invention can be used for aluminum, aluminum alloys, and aluminum treated with these by chemical conversion treatment or the like. In addition, various shapes such as plate, pipe, and linear shapes can be used as the shape of the object to be coated.The aluminum surface treatment composition of the present invention can be used at room temperature to 150°C Preferably, after coating on the surface of aluminum at room temperature to 70°C by a method such as bald coating, spray coating, roll coating, or dipping, it is sufficient to dry it at a temperature above room temperature for a few seconds to several minutes. A sufficient effect can be obtained with a thin film of about 0.1 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) The present invention will be explained in more detail using specific examples below.
The present invention is not limited in any way by the examples; % in the examples does not indicate weight %.

Production example of zwitterionic acrylic resin (II) 1 part Production example 1 466 parts of deionized water and 2 parts of anionic emulsifier were placed in a flask equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet pipe and dropping funnel. Then, after adding 2 parts of ammonium persulfate, 28.0 parts of styrene, 27.5 parts of methyl methacrylate, 39 parts of butyl acrylate, 6 parts of acrylic acid and vinyltrimethoxysilane were added. A monomer mixture consisting of 0.5 parts was added over 1 hour to carry out the first stage of emulsion polymerization. After further polymerization for 1 hour, 30 parts of styrene and 60 parts of butyl acrylate were added.
A monomer mixture consisting of 9 parts of acrylic acid and 1 part of vinyldimethoxymethylsilane was added over 1 hour.
The emulsion polymerization of the stage (constituting the fi outer shell portion) was carried out to obtain a multilayered polymer having a Tg of approximately 19° C. in the core portion and approximately -12° C. in the outermost shell portion. 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 to a pH of 9.0. II) was obtained.

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-methacryloxypropyltrimethoxysilane, 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-methacryloxy 10 pyltrimethoxysilane, and has a Tg of about 21°C in the core part and about -36°C in the outer shell part. After synthesizing a poly71 structural polymer, a cationization reaction was performed with 3.6 parts of ethyleneimine, and after neutralization with ammonia, a zwitterionic acrylic resin (II) with a solid content of 30% and a pH of 9.0 was obtained. Ta.

Production Example 3 A method similar to Production Example 1 was used to prepare the first stage [55 parts of 1-methyl methacrylate, 39 parts of butyl acrylate, 5.5 parts of acrylic acid, and 0.5 parts of γ-methacryloxyglobil trimethoxysilane. 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-methacryloxypropyltrimethoxysilane. After synthesizing a multilayer structure polymer with an outer shell temperature of approximately -35°C, a cationization reaction was performed with 6 parts of ethyleneimine, and after neutralization with ammonia, a zwitterionic acrylic resin with a solid content of 30% and a pH of 9°C ( IF) was obtained.

Production example 4 during production of zwitterionic acrylic resin (II 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 produce an amphoteric ionic acrylic resin (I[[) with a solid content of 40% and a pH of 8.5. Don't get it.

Production Example 5 37 parts of 2-ethylhexyl acrylate, 58 parts of styrene
100 parts of an emulsion polymer with a solid content of 40% and 1 g of ethyleneimine at a temperature of about 15° C.
．． After reacting with 1 part, neutralize with ammonia to obtain solid content! 10
%, pH 8.5 zwitterionic acrylic resin (III
) was obtained.

Production Example 6 100 parts of an emulsion polymer with a solid content of 40% and having a 'rg 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, and ethylene After reacting with 0.95 parts of imine, the mixture was neutralized with ammonia to obtain a zwitterionic acrylic resin <III) having a solid content of 40% and a pH of 5.

Zwitterionic carboxylated olefin system t! 11 fat (
Production Example of IV) Production Example 7 Dispersion 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 ionic water to a solid content of 20%, it is reacted with 1 part of ethyleneimine, and neutralized with ammonia to obtain a zwitterionic carboxylated olefin resin system with a solid content of 20% and a pH of 10.0 ( IV) was obtained.

Production Example 8 100 parts of a carboxylated polyethylene resin dispersion (trade name: Slimacol 4983 manufactured by Dow Chemical Co., Ltd.) having a solid content of 25% and containing 20 mol% of carboxyl groups was reduced to a solid content of 20% with deionized water. After dilution, the mixture was reacted with 1 part of ethyleneimine and neutralized with ammonia to obtain a zwitterionic carboxylated olefin resin (IV) having a solid content of 20% and PHIO,O.

Production Example 9 Ethylene-methacrylic acid ionomer with a solid content of 27% (
Product name: Chemipearl S-10O Mitsui Petrochemical Industries, Ltd.
After diluting 100 parts of 20% solids with deionized water, it was reacted with 0.3 parts of ethyleneimine and neutralized with ammonia to give a solids content of 20% and a pH of 0. A zwitterionic carboxylated olefin resin (TV) of O was obtained.

Example 1 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 3 (I
t) 15 parts, acrylic resin obtained in Production Example 4 <I)
Then, 0.07 part of ethylene glycol diglycidyl ether (trade name: Bunacol EX-811 manufactured by Nagase Chemical Industries, Ltd.) was added as a crosslinking agent, and the mixture was heated at 50°C. After 12 hours of reaction, water-dispersible silica (■) (trade name Nisnortex C1S f
0220% product) was added to obtain a composition for aluminum surface treatment. This composition was spray applied to an aluminum plate (JIS H4000A1050P: Japan Test Panel) having a thickness of 0°81 WII+ to a film thickness of 2.0 μm, and then dried at 100°C for 60 seconds to obtain a surface-treated plate.

Example 2 Carboxylated olefin resin obtained in Production Example 8:
(IV) 70 parts of the acrylic resin obtained in Production Example 3 (
II) 15 parts, acrylic resin obtained in Production Example 6 (■
) and 11 parts of deionized water, and then, as a crosslinking agent, epoxy resin emulsion (trade name: Polsion EA-1 manufactured by Kanebo NSC Co., Ltd.) 0.0
After adding 8 parts of water and reacting at 50°C for 12 hours, water-dispersible silica (product name: Cataloid 5t-50O) was added.
5102 (20% product) was added to obtain a composition for aluminum surface treatment. This composition was spray applied to a 0.8-fin aluminum plate (JIS H4000A1050P: Japan Test Panel) to a film thickness of 2.0 μm, and then dried at 100° C. for 60 seconds to obtain a surface-treated plate.

Example 3 Carboxylated olefin resin obtained in Production Example 8 (
IV) 70 parts, acrylic resin obtained in Production Example 2 (I
) 15 parts, acrylic resin obtained in Production Example 5 (■) 4
and 11 parts of deionized water, and then, as a crosslinking agent, ethylene glycol diglycidyl ether (trade name: Bunacol EX-811 manufactured by Nagase Chemical Industries, Ltd.) was mixed.
After adding 0.07 parts and reacting at 50°C for 12 hours, water-dispersible silica (1) (trade name Nisnortex XS, S102
20% product) 33? I5 was added to obtain a composition for aluminum surface treatment. This composition was applied to an aluminum plate (JIS) (4000A1050) with a plate thickness of 0.8111111.
P: E1 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 plate.

Example 4 Carboxylated olefin resin obtained in Production Example 9 (
IV) 70 parts, acrylic resin obtained in Production Example 1 (I
I) 15 parts, acrylic resin obtained in Production Example 4 (■)
4 parts and 11 parts of deionized water, and then, as a crosslinking agent, glycerophorboliglycidyl ether (trade name: Bunacol EX-314 manufactured by Nagase Chemical Industries, Ltd.) 0
．． After reacting at 50°C for 12 hours, water-dispersible silica (I) (trade name Nisnortex XS, 5tO
720% product) was added to obtain a composition for aluminum surface treatment. After spraying this composition on an aluminum plate (JIS H4000A1050P: Japan Test Panel) with a thickness of 0.8m+n to a film thickness of 2.0μ,
Drying was performed at 100° C. for 60 seconds to obtain a surface-treated board.

Example 5 Carboxylated olefin resin obtained in Production Example 9:
(IV) 70 parts of the acrylic resin obtained in Production Example 3 (
If) 15 parts, acrylic resin obtained in Production Example 5 (■
) and 11 parts of deionized water, and then 0.0 parts of epoxy resin emulsion (trade name: Polsion EA-1 manufactured by Kanebo NSC Co., Ltd.) was mixed as a crosslinking agent.
After reacting at 50°C for 12 hours, water-dispersible silica (■) (trade name Nisnortex 88.51021) was added.
5% product) was added to obtain a composition for aluminum surface treatment. This composition was applied to an aluminum plate with a thickness of 0.8 m (
JIS lI4000A1050P: Japan Test Panel) film thickness 2. After spraying so that it becomes Onot, 10
Drying was performed at 0°C for 60 seconds to obtain a surface-treated board.

Example 6 70 parts of the carboxylated olefin resin (IV) obtained in M Preparation Example 7 was added to the acrylic resin (IV) obtained in Production Example 2.
II) 15 parts and the acrylic resin obtained in Production Example 5 (
ill) 4 parts and 11 parts deionized;
Water-dispersible silica (product name: Nisnortex XS,
5in220% product) was added to obtain a composition for aluminum surface treatment.

This composition was applied to an aluminum plate (J
IS H4000A1050P: Japan 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.

Comparative Example 1 267 parts of acrylic resin (■) obtained in Production Example 3,
Adding 200 parts of acrylic resin (DI > 200 parts), water-dispersible silica (1) (trade name Nisnortex C, 5in 220% product) obtained in Production Example 4, and 10 parts of 5% chromic anhydride. A composition for aluminum surface treatment was obtained by diluting the whole with deionized water to 1J.This composition was applied to an aluminum plate with a thickness of 0.8 mm (JIS H40
00A1050P: Japan Test Panel) film thickness 2.0μ
After spray coating, 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 ethylene glycol diglycidyl ether as a crosslinking agent. (Product name: Bunacol EX-811 manufactured by Nagase Kasei Kogyo Co., Ltd.) 0.07 parts was added, and after reacting at 50°C for 12 hours, 33 parts of water-dispersible silica (Product name: Nisnortex C9S i 02 20% product) was added. was added to obtain a composition for aluminum surface treatment. This composition is applied to a plate with a thickness of 0.
8 city aluminum plates (JIS H4000A105
After spray coating on 0P (Japan Test Panel) to a film thickness of 2.0 μm, drying was performed at 100° C. for 60 seconds to obtain a surface-treated board.

Comparative Example 3 Aluminum plate with a plate thickness of 0.8 mm (JIS H400
0A 1050 P: 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-23714, and the area where white rust occurred was evaluated in %.

■Paint adhesion: Commercially available melamine-alkyd e + fat PW
After baking C50% at 130°C for 20 minutes to a film thickness of 25μ, insert a 1mm wide 10XIO base hole, extrude Erichsen 6n++n, press cellophane tape, peel it off, and score 10 points ( Full score) method was used for evaluation.

■ Processing adhesion: (1) Erichsen test: After extruding 17 cocoons using an Erichsen tester, a cellophane chip was crimped and then peeled off and evaluated using a 10-point (full score) method.

(2) 1'I'' bending workability: After a cellophane tape was crimped onto the folded surface, it was evaluated using a 10-point scale (full score).

(3) DuPont*@: Drop a 1 kg weight from a height of 50 cm using a 1/4φ punch from the back side (convex) and front side (concave) of the coating surface, apply an impact, and then !7 After crimping a cellophane tube onto the striking part, it was peeled off and evaluated using the 10-point scale) method.

■Solvent resistance: Gauze impregnated with petroleum benzene,
Do a power bow 710 reciprocating rubbing test with a load of 00g.

◎... No change, ○... Scratches, △... Partial elution, ×... Elution ■ Blocking resistance A treated board coated with an aluminum surface treatment composition on both sides, The pieces were cut into pieces of 50 fins x 50 pieces, stacked in 4 pieces and pressed together at 50°C under a pressure of 1000 kg/c4 for 20 minutes, and then their blocking properties were measured.

◎・・・No blocking, O: Slight blocking, △・・・Part of the coating film is blocking. It peels off.

×・・・Full blocking ■Hardness: Lead cage 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; A surface-treated aluminum plate with extremely high performance that improves hardness and (2) improves solvent resistance and blocking resistance without deteriorating other properties by adding a compound having an epoxy group as a crosslinking agent. This has the effect of making it possible to create.

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 higher and an outermost shell portion has a Tg of 10°C or lower, which is obtained by multistage emulsion polymerization of a monomer component consisting of /or zwitterionic acrylic resin (II) from 0.5 to
(C) an amount in the range of 0 to 600 g of a cationic and/or amphoteric acrylic resin (III) with a Tg of 10°C or higher; (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
Range not exceeding 700 g] (E) An aluminum surface treatment composition comprising: (E) a compound having a polyfunctional epoxy group in a ratio of solids to resin of 10% by weight or less.