KR100497516B1 - A hydrophilic composition of organic type using hydrophilic handling the surface aluminium and it's manufacturing method - Google Patents

Abstract

The present invention relates to a hydrophilic composition of the organic material type used to impart hydrophilicity to the aluminum surface for fins used in home appliances or automobiles, and a method of manufacturing the same. More specifically, an outdoor unit or an indoor unit of an air conditioner and a heat exchanger of an automobile It can be applied to fin products made of aluminum and aluminum alloy used in manufacturing, and it is possible to harden high temperature baking as a thin film. In particular, it has excellent coating hardness and water resistance, and is excellent in workability. The present invention relates to a composition of an organic substance-type hydrophilic agent having improved adhesion and workability, and a method for producing the same.

Description

A hydrophilic composition of organic type using hydrophilic handling the surface aluminum and it's manufacturing method

The present invention relates to a hydrophilic composition of the organic material type used to impart hydrophilicity to the aluminum surface for fins used in home appliances or automobiles, and a method of manufacturing the same. More specifically, an outdoor unit or an indoor unit of an air conditioner and a heat exchanger of an automobile It can be applied to fin products made of aluminum and aluminum alloy used in manufacturing, and it is possible to harden high temperature baking as a thin film. In particular, it has excellent coating hardness and water resistance, and is excellent in workability. The present invention relates to a composition of an organic substance-type hydrophilic agent having improved adhesion and workability, and a method for producing the same.

Generally, aluminum or aluminum alloy, which is a material used in home appliances such as an outdoor unit or an indoor unit, or an automobile air conditioner, is often used by separately treating an anticorrosive agent.

This is because, in the case of aluminum or aluminum alloys, corrosion of aluminum may be promoted by acid rain resulting from nitric acid or sulfurous acid gas caused by air pollution and penetration by salts contained in the air under high temperature and high humidity conditions.

However, the anticorrosive applied to the surface of aluminum or aluminum alloy as described above increases the coating amount to increase the corrosion resistance of aluminum, resulting in poor interlayer adhesion with the paint, and thus the use of a very small amount or almost no use.

Therefore, in order to solve the above problems, a method of improving the corrosion resistance of the aluminum by adding hydrophilicity to the aluminum surface while using no or very small amount of corrosion inhibitors and at the same time developing methods for improving the interlayer adhesion between the hydrophilic agent and the corrosion inhibitor have been developed. And most representatively, methods using phosphate treatment or chromate treatment have been proposed.

However, such phosphate or chromate treatments generate a large amount of wastewater during the process, which is expensive, and affects the safety of the handler due to the carcinogenicity of the surface treatment agent itself. It is not used.

Therefore, in recent years, an organic type hydrophilic agent which uses a phosphate or chromate treatment is slightly inferior in corrosion resistance but obtains a coating film excellent in hydrophilicity, hydrophilic persistence, workability and processability.

Such an organic type hydrophilic agent is a hydrophilic material on the surface of the coating film during curing and drying, thereby making the hydrophilic and water resistant to water appear simultaneously. The contact angle with water on the surface of the coating film is low, and the film thickness is 1 to 1 on the aluminum plate. The main purpose is to obtain a clean film free of bubbles and streaks when performing a thin film operation, so-called PCM coating method with a reverse roll to be about 2㎛.

Therefore, since the hydrophilic agent of the organic type conventionally used contains a large amount of inorganic material, the inorganic material is arranged on the surface of the coating film after drying to maximize the hydrophilicity.

However, while the hydrophilic agent of the organic type has the characteristics that the coating film is excellent in rigidity, it is difficult to work and poor in workability, and the interlayer adhesion with the corrosion inhibitor for corrosion protection used in aluminum or aluminum alloy is somewhat poor. There was a problem that metal surface protection is difficult.

Therefore, the present invention is configured to solve the above problems, it is possible to harden the high temperature baking as a thin film during hydrophilic treatment of aluminum or aluminum alloy, in particular, the coating film hardness and water resistance, excellent workability, can be painted before the molding process It is also an object of the present invention to provide a hydrophilic composition of the organic material type which improves interlayer adhesion and workability with a corrosion inhibitor and a method for producing the same.

The present invention to achieve the above object,

1.0 to 20 parts by weight of the basic acrylic compound represented by the following formula (1), 1.0 to 5.0 parts by weight of the acrylic compound represented by the formula (2) to 100 parts by weight of the total copolymer composition 1.0 to 20 parts by weight, 1.0 to 15 parts by weight of the radical copolymerizable basic acrylic compound represented by the following formula (4), 1.5 to 30.0 parts by weight of the reactive emulsifier represented by the following formula (5), 0.5 to 0.5 to the compound represented by the formula (6) It can be achieved by providing a hydrophilic composition of the organic material type for hydrophilic treatment of aluminum surface, characterized in that 5.0 parts by weight and 0.02 to 0.05 parts by weight of the compound represented by the following formula (7).

CH ₂ = CR ¹ -NR ²

In Formula 1, R ¹ is hydrogen or a methyl group, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, and an aryl group containing basicity.

CH ₂ = CR ¹ COO (CH ₂ CH ₂ O) nR ³

In Formula 2, R ¹ is hydrogen or a methyl group, R ³ refers to a group which may be substituted with a methyl group or an aliphatic hydrocarbon group, nonyl phenol, octyl phenol, or phenol, and n is an integer of 1 to 80.

CH ₂ = CR ¹ COOR ²

In Formula 3, R ¹ is hydrogen or a methyl group, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, and an aryl group containing basicity.

CH ₂ = CHCONHR ² -R ⁴ -R ⁵

In Formula 4, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, an aryl group containing a basic, R ⁴ is a hydroxy group, R ⁵ is hydrogen, methyl It is a monomer containing a hetero group or an acid group containing the same.

In Formula 3, R ³ refers to a group which may be substituted with a methyl group or an aliphatic hydrocarbon group, nonyl phenol, octyl phenol, or phenol, and n is an integer of 1 to 80.

CH ₂ = CR ¹ COOR ² OH

In Formula 4, R ¹ is hydrogen or a methyl group, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, and an aryl group containing basicity.

CH ₂ = CR ¹ COO (CH ₂ CH ₂ O) _n OCR ¹ C = CH ₂ or CH ₂ = CR ¹ COOR ³ OOCR ¹ = CH ₂

In Formula 7, R ¹ is hydrogen or a methyl group, R ³ is a group which may be substituted with a methyl group or an aliphatic hydrocarbon group, nonylphenol, octylphenol, or phenol, and n is an integer of 1 to 80.

In addition, based on 100 parts by weight of the total copolymer composition 1.0 to 20 parts by weight of the basic acrylic compound represented by the formula (1), 1.0 to 5.0 parts by weight of the acrylic compound represented by the formula (2), acidic acrylic compound 1.0 represented by the formula (3) 20 parts by weight, 1.0 to 15 parts by weight of the radical copolymerizable basic acrylic compound represented by Formula 4, 1.5 to 30.0 parts by weight of the reactive emulsifier represented by Formula 5, 0.5 to 5.0 parts by weight of the compound represented by Formula 6, and 0.02 to 0.05 parts by weight of the compound represented by Chemical Formula 7 is added to 0.01 to 2.0 parts by weight of a water-soluble initiator in a completely dissolved solvent, and the emulsion is polymerized at 30 to 95 ° C. to obtain a solid content of 20 to 50% by weight. Provided is a method for preparing an organic hydrophilic composition for hydrophilic treatment.

The present invention also provides a hydrophilic coating composition comprising a hydrophilic agent prepared by the method for producing an organic material hydrophilic agent.

Hereinafter, the hydrophilic composition of the organic material type for hydrophilic treatment of aluminum surface of the present invention will be described in detail through the preparation method as follows.

The present invention is a basic acrylic compound represented by Formula 1, an acrylic compound represented by Formula 2, an acidic acrylic compound having an unsaturated double bond represented by Formula 3, a radical copolymerizable basic acrylic compound represented by Formula 4 In addition, at least one selected from the emulsifier represented by the formula (5), the compound represented by the formula (6) and the compound represented by the formula (7) is characterized in that the dispersing agent is added to the completely dissolved solvent and the polymerization reaction.

The compounds represented by Formula 1 and Formula 4 form basicity in the basic skeleton of the polymer to induce water dispersion more easily and to improve the durability and adhesion of the corrosion inhibitor when forming a coating film, The compound of Formula 1 is suitable for 1.0 to 20 parts by weight with respect to 100 parts by weight of the total copolymer composition, and the compound of Formula 4 is preferably 1.0 to 15 parts by weight.

In the above mixing ratio, when the compound of Formula 1 and Formula 4 is added less than the lower limit of the mixing ratio, the effect of the above-described compounds is too insignificant. On the contrary, when the compound is added beyond the upper limit, the color of the product is affected. This is because the workability is reduced due to the viscosity.

As the basic acrylic compound such as Chemical Formula 1, one or more selected from N-vinyl-2-pyrrolidone, 1-vinylimidazole, 2-vinylpyridine or acryloyl morpholine may be used. Radical copolymerizable basic acrylic compounds include acrylamide, methacrylamide, N-methol acrylamide, dimethyl amino ethyl methacrylate, tertiary amino amino methacrylate, diacetone acrylamide, acrylamide methyl propane sulfonic acid , Dimethyl amino neopentyl acrylate, N, N- dimethyl acrylamide and the like can be selected and used.

In addition, the compounds represented by the formula (2) and formula (3) plays an important role in the hydrophilicity of the hydrophilic agent as a component having excellent water solubility that acts as a basic skeleton of the polymer, the compound of the formula (2) is a total copolymer composition 100 1.0 parts by weight to 5.0 parts by weight is suitable, and the compound of Formula 3 is preferable for maintaining viscosity stability, hydrophilic ability, and storage property when mixing 1.0 to 20 parts by weight.

In this case, when the compound of Formula 2 is added in an amount of less than 1.0 part by weight based on 100 parts by weight of the total copolymer composition, water solubility may be degraded. In contrast, when the compound of Formula 2 is added in excess of 5.0 parts by weight, fine water may cause problems in water resistance. do. In addition, in the case of Formula 3, when the amount is less than 1.0 part by weight based on 100 parts by weight of the copolymer composition, the effect of Formula 3 is insignificant. On the contrary, when the amount is added in excess of 20 parts by weight, the polarity is increased to increase the viscosity. And storage stability tends to be poor depending on the amount of the curing agent added.

Examples of the acryl-based compound represented by Chemical Formula 2 include methoxy dieethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methoxy dieethylene glycol acrylate, methoxy polyethylene glycol acrylate, butoxy ethyl methacrylate, and phenoxy. At least one selected from carboxyl acrylate, phenoxy polyethylene glycol acrylate, nonyl phenol or octyl phenol-modified ethylene oxide acrylate, poly ethylene glycol acrylate, ethoxy diethylene glycol acrylate, and the like, can be used As the acidic acrylic compound having an unsaturated double bond, one or more selected from acrylic acid, methyl methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, and the like can be used.

The compound represented by the formula (5) is a reactive emulsifier in which an unsaturated group capable of radical polymerization is introduced into a hydrophobic group thereof as a basic structure of a sulfate ester salt having or without a very general polyethylene alkyl phenyl ether as an emulsifier for emulsion polymerization. Or a reactive surfactant exhibiting a similar structure.

The compound of the formula (5) is the most important part of the polymer backbone, not only maintains the hydrophilic performance of the entire polymer and the hydrophilic capacity after drying the coating film, but also maintains the adhesion to the corrosion inhibitor according to the amount used, and also maintains a low surface contact angle. Do it.

The compound of Formula 5 is suitable for 1.0 to 30.0 parts by weight with respect to 100 parts by weight of the copolymer composition, the water washing power is lowered if it exceeds this range, the hydrophilic performance tends to be somewhat weakened. It also affects particle stability during storage, so it should not be outside the formulation range.

Specific examples of such compounds of formula 5 include polyoxyethylene alkyl propenyl ether ammonium sulfate, polyoxyethylene alkyl propenyl ether sodium sulfate, polyoxyethylene alkyl propenyl ether ammonium phosphate, polyoxyethylene alkyl propenyl sodium One or more kinds can be selected and used in phosphate, sodium vinyl sulfonate, and the like.

The compound represented by the formula (6) is 0.5 ~ 5.0 parts by weight relative to 100 parts by weight of the copolymer as a reactive monomer, less than 0.5 parts by weight of the hydrophilic persistence is exhibited, on the contrary, if it exceeds 5.0 parts by weight, the curing reaction is increased and the coating film The degree of crosslinking may increase, resulting in poor workability.

As a specific example of the compound represented by the above formula (6), at least one selected from 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl methacrylate, and the like Can be used.

Compound represented by the formula (7) is a multifunctional monomer having at least two unsaturated groups capable of radical polymerization to give a constant degree of crosslinking to the polymer skeleton to increase the Tg of the polymer and improve the heat resistance and hydrophilic persistence.

The compound of the formula (7) is 0.02 ~ 0.05 parts by weight suitable for 100 parts by weight of the copolymer composition, if it exceeds this range, the viscosity rises during the production of synthetic resin is difficult to control the reaction is abnormal particles or high viscosity, if less than or not used heat resistance and Hydrophilic persistence is weakened.

Specific examples of the formula (7) are triethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, 1.6 hexanediol diacrylate, triethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1.6 hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like You can choose to use it.

In this way, at least one or more of each compound is selected and then polymerized to be added to a solvent in which a water-soluble initiator is dissolved. At this time, the water-soluble initiator is used in the aqueous solution of APS (Ammonium Phosphate), which is easy to generate free radicals by heat. Sodium Phosphate) or KPS (Potasium-Phosphate) may be selected, and the reaction may be smoothly performed by using 0.01 to 2.0 parts by weight based on 100 parts by weight of the copolymer composition.

In addition, the solvent used in the present invention is also preferable to add 100 to 500 parts by weight based on 100 parts by weight of the copolymer composition so that the solid content after the polymerization is 20 to 50% by weight based on 100% by weight of the copolymer is preferable.

At this time, the solvent used is butyl cellosol moiety, methanol, ethanol, isopropyl alcohol, ethyl cellosol moiety, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisobutyl ether, Ethylene Glycol Monotery Butyl Ether, Ethylene Glycol Isopropyl Ether, 3-methoxy Butanol, 3-Methyl 3-methoxy Butanol, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Mono Organic solvents such as butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like are contained in an amount of 5.0 to 30% by weight, and the remainder is made of ion-exchanged water.

In addition, 0.5 to 10.0 parts by weight of an emulsifier may be used based on 100 parts by weight of the total copolymer composition so that the functional monomer participating in the reaction may exhibit stable shelf life after polymer formation in the water phase. As the emulsifier used in the above-mentioned applications, nonionic emulsifiers with ethylene oxide added, which have antifoaming power and relatively good dispersion and chemical stability, are used.

It is most effective to react such a mixed copolymer composition by emulsion polymerization, and the reaction temperature and the amount of the initiator is preferably adjusted so that the copolymer produced has an average molecular weight ranging from 10,000 to 100,000.

This is because when the average molecular weight is less than 10,000, the durability of the coating film and the hydrophilic sustainability after curing tend to be lowered, and the adhesion with the anticorrosive agent is also insufficient, and when the average molecular weight is 100,000 or more, workability is deteriorated.

Therefore, the reaction temperature during the polymerization is suitable in the range 30 ~ 95 ℃ and if the appropriate temperature is determined according to the initiator and some water-soluble organic solvent can be prepared an organic material hydrophilic composition for hydrophilic treatment of aluminum surface.

In addition, in order to effectively control the molecular weight of the polymerized copolymer, a mercaptan-based polymerization regulator may be used. Specific examples of the regulator include n-butyl mercaptan, n-dodecyl mercaptan, 2-mercapto ethanol, and the like. Can be.

The hydrophilic composition of the organic material type prepared by the above method is a thin film during hydrophilic treatment of aluminum or aluminum alloy, has a polarity and has a reactive group in the molecular structure, has excellent adhesion to the coating material, and also has a molecular weight of the functional monomer Somewhat larger is included, which gives the polymer full flexibility.

Therefore, when the organic type hydrophilic composition of the present invention is used, it is possible to harden the high temperature baking in a short time, and excellent in workability and processability, such as a coil or sheet coating such as a continuous PCM method. It is possible to obtain both hydrophilicity and water resistance at the same time after curing, and to improve the interlayer adhesion with the corrosion inhibitor than the inorganic hydrophilic agent.

In another aspect, the present invention provides a hydrophilic coating composition comprising a hydrophilic composition of the organic type described above. That is, the present invention provides a coating composition having hydrophilicity, comprising 15 to 40% by weight of a hydrophilic composition of the above-described organic substance type in a conventional coating composition comprising a curing agent, a catalyst and a solvent which are generally used. to provide.

According to the present invention, the hydrophilic coating composition includes 15 to 40% by weight of the above-described hydrophilic composition. When the amount is less than 15% by weight, the hydrophilic persistence is lowered due to the lack of hydrophilic components. This is because the excess hydrophilic agent remaining after curing decreases the water resistance of the coating film.

Hydrophilic coating composition comprising a hydrophilic agent of the organic type as described above can bring excellent effects in terms of hydrophilicity and heat resistance, adhesion, corrosion resistance, hydrophilic retention, thermal shock compared to the prior art, because it has excellent odor and workability The working environment can be improved, thus improving the working efficiency.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention, but the present invention is not limited thereto.

Synthesis Example 1

Radical initiator and emulsifier in a state in which each compound was added together with the solvent according to the composition ratio as shown in the following Table 1 while supplying nitrogen to a four-necked flask equipped with a condenser and supplying and stirring nitrogen. After dissolving, the components were stirred and uniformly added dropwise for 3 hours, followed by maintaining the reaction for 2 hours while cooling at room temperature when the reaction rate was 98% or more to obtain a copolymer that is a water-soluble hydrophilic agent. In this case, the solid content of the copolymer was about 30% and the Brookefield viscosity was 2500 cps.

Synthesis Example 2

A solvent, a compound, a radical initiator, and an emulsifier were each selected as shown in Table 1 below, and synthesized in the same manner as in Synthesis Example 1 to obtain a copolymer that is a water-soluble hydrophilic agent. In this case, the solid content of the copolymer was about 30% and the Brookefield viscosity was 700 cps.

Synthesis Example 3

A solvent, a compound, a radical initiator, and an emulsifier were each selected as shown in Table 1 below, and synthesized in the same manner as in Synthesis Example 1 to obtain a copolymer that is a water-soluble hydrophilic agent. In this case, the solid content of the copolymer was about 30% and the Brookefield viscosity was 1100 cps.

division ingredient Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Solvent (g) water 60.0 65.0 55.0 Butyl-cellosolve 10.0 10.0 Methanol 5.0 5.0 Compound 1 (g) N-vinyl-2-pyrrolidone 4.5 4-vinylpyridine 4.5 1-vinylimidazole 4.5 Compound 2 (g) Methoxy Polyethylene Glycol Methacrylate 2.0 Octylphenoxy Polyethylene Glycol Methacrylate 2.0 Compound 3 (g) Acrylic acid 8.0 10.0 Methyl Methacrylic Acid 8.0 Compound 4 (g) Acrylamide 10.0 N-Methrol Acrylamide 10.0 Dimethyl Amino Ethyl Methacrylate 10.0 Compound 5 (g) Polyoxyethylene alkyl propenyl ether ammonium sulfate 3.5 Polyoxyethylene alkyl propenyl ether sodium sulfate 3.5 Sodium Vinyl Acrylate 3.5 Compound 6 (g) 2-hydroxy ethyl acrylate 0.5 2-hydroxy propyl acrylate 1.0 2-hydroxy propyl methacrylate 1.0 Compound 7 (g) Triethylene Glycol Diacrylate 0.02 Ethylene Glycol Dimethacrylate 0.02 Polyethylene Glycol Diacrylate 0.02 Radical initiator (g) Ammonium Persulfate 0.48 Sodium Persulfate 0.48 Potassium Persulfate 0.48 Emulsifier (g) Igepal CO897 from Rhodia 0.5 0.5 Teric X40L (Huntsman) 0.5 0.5 Sum 100.0 100.0 100.0

The following paint preparation examples were carried out using the water-soluble hydrophilic agents obtained in Synthesis Examples 1 to 3, and emulsion emulsions or epoxy modified resins generally used in the prior art were compared together as a comparative example.

<Example 1>

In a 200 ml beaker, 73.69 g of ion-exchanged water and 25 g of the hydrophilic agent of Synthesis Example 1 were mixed to make a uniform solution, and 1.11 g of hexamethoxymelamine resin (cymel 303, Cytec. Ind) was slowly stirred with a curing agent. Thereafter, polyether-modified tolydimethylsiloxane (BYK 333, Chemie) was added as an additive to prepare a coating composition for a hydrophilic agent. The prepared coating composition had a solids content of 8.5% and a viscosity of 11 seconds (pode cup # 4, 25 ° C).

<Example 2>

In a 200 ml beaker, 68.53 g of ion-exchanged water and 30 g of the hydrophilic agent of Synthesis Example 2 were mixed to make a uniform solution, and 1.27 g of hexamethoxymelamine resin (cymel 303, Cytec. Ind) was slowly stirred with a curing agent. Thereafter, polyether-modified tolydimethylsiloxane (BYK 333, Chemie) was added as an additive to prepare a coating composition for a hydrophilic agent. The prepared coating composition had a solid content of 10% and a viscosity of 12 seconds (pode cup # 4, 25 ° C).

<Example 3>

In a 200 ml beaker, 58.80 g of ion-exchanged water and 40.0 g of the hydrophilic agent of Synthesis Example 3 were mixed to make a homogeneous solution, and 1.11 g of hexamethoxymelamine resin (cymel 303, Cytec. Ind) was slowly stirred with a curing agent. Thereafter, polyether-modified tolydimethylsiloxane (BYK 333, Chemie) was added as an additive to prepare a coating composition for a hydrophilic agent. The prepared coating composition had a solid content of 13% and a viscosity of 10 seconds (pode cup # 4, 25 ° C).

Comparative Example 1

In a four-necked flask, 80 g of bisphenol A epoxy resin having an equivalent weight of 2500 to 3500 and 50 g of butylcellosol portion were mixed and completely dissolved at 110 ° C. Acrylamide, methylmethacrylic acid, styrene, butyl acrylate monomer and benzoyl 20 g of a peroxide mixture was added and the pH was adjusted to 8-9 with triethylamine at 80 ° C., followed by 20% solids with ion-exchanged water, and a viscosity of 25 seconds (pode cup # 4,25 ° C.). An acrylic modified epoxy resin composition was prepared.

350 g of the aqueous acrylic-modified epoxy resin composition prepared as described above was mixed with 638 g of ion-exchanged water in a 2000 ml beaker to make a uniform solution, and stirred while slowly injecting 10 g of hexamethoxymelamine resin (cymel 303, Cytec.Ind) as a curing agent. Thereafter, polyether-modified tolydimethylsiloxane (BYK 333, Chemie) was added as an additive to prepare a coating composition for a hydrophilic agent. The prepared coating composition had a solid content of 8.0% and a viscosity of 13 seconds (pode cup # 4, 25 ° C).

Comparative Example 2

In a four-necked flask, 80 g of bisphenol-A epoxy resin having an equivalent weight of 2500 to 3500 and 50 g of butylcellosol portion were mixed and completely dissolved at 110 ° C, followed by acrylamide, methylmethacrylic acid, styrene, butyl acrylate monomer and benzoyl. 20 g of the peroxide mixture was introduced and the grafting polymerization was carried out, followed by adjusting the pH to 8 to 9 with triethylamine at 80 ° C., 20% of solid content and 25 seconds of viscosity with ion-exchanged water (Pood Cup # 4, 25 ° C.) was prepared an aqueous acrylic modified epoxy resin composition.

350 g of the aqueous acrylic resin composition prepared as described above was mixed with 638 g of ion-exchanged water in a 2000 ml beaker to make a uniform solution, and stirred while slowly injecting 10 g of hexamethoxymelamine resin (cymel 303, Cytec. Ind) as a curing agent. Polyether-modified tolydimethylsiloxane (BYK 333, Chemie) was added as an additive to prepare a coating composition for a hydrophilic agent. The prepared coating composition had a solid content of 8.0% and a viscosity of 13 seconds (pode cup # 4, 25 ° C).

Experimental Example Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Synthesis Example 1 25.0 Synthesis Example 2 30.0 Synthesis Example 3 40.0 Styrene-acrylic emulsion resin 22.5 Acrylic Modified Epoxy Resin 35.0 Hardener 1.11 1.27 1.0 1.27 1.0 Additive BYK333 0.2 0.2 0.2 0.2 0.2 Ion exchange water 73.69 68.53 58.8 76.03 63.8 Sum 100.0 100.0 100.0 100.0 100.0

Experimental Example

The paints prepared by the methods of Examples 1 to 3 and Comparative Examples 1 and 2 were roll-coated on both sides so that 0.3 g / m 2 per unit area was coated on the surface of the aluminum coated with the anticorrosive (purity of 99% or more), and then 260. A steel sheet was prepared by drying at 20 ° C. for 20 seconds. Using the steel sheet thus prepared, the physical properties were measured in the following manners, and the results are shown in Table 3 below.

Corrosion Resistance

The double-coated aluminum steel sheet was sprinkled with 5% NaCl at 35 ± 2 ° C. and after 500 hours, abnormality of the coating was observed.

Adhesive

The coated double-coated aluminum sheet was made into a square having a size of 10 × 10 mm in width and length, and a cellophane tape was attached to the cross-cut specimen and then peeled off to evaluate the adhesion of the coating film.

Heat resistance

The double-coated aluminum steel sheet was cut to have a length of 100 mm and then left in a drying oven at 230 ° C. for 10 minutes to observe changes in color of the coated portion.

Hydrophilic

1) Initial Contact Angle: Cut both sides coated aluminum steel plate into 100 × 100mm size and drop 0.05cc of distilled water on the specimen at 20mm height by using contact angle tester. Thereafter, the contact angle was measured 20 seconds later.

2) Water flow: Cut the double coated aluminum sheet into 100 × 100mm size and maintain it at 45 degree angle (install it so that it is inclined at 200mm), mark the measuring section as 120mm and then use pipette 120 The flow time of arrival to the arrival point was measured by dropping 0.05 cc distilled water at a height of about 20 mm from the starting point of mm.

3) Water spreadability: The double-coated aluminum steel sheet was cut into 100 × 100 mm size, and the diameter of water droplets dropped on the specimen was measured by free-falling 0.05 cc of distilled water with a pipette at the height of 10 mm in the vertical direction of the specimen.

Hydrophilic oil retention

1) Immersion test: After coating the double-coated aluminum steel sheet in water at room temperature for 500 hours and drying for 8 hours at room temperature, the contact angle was measured.

2) Long-term maintenance test: The aluminum plate coated on both sides is immersed in a water tank (water pipe with a diameter of 10 mm) of size of 35 × 20 × 35cm with a flow rate of 6ℓ / min and left for 16 hours at room temperature. After 1 cycle and 24 replicates, the contact angle was measured.

Odor-

After drying the double-coated aluminum steel sheet to confirm the smell immediately after 10 minutes, the smell was confirmed again.

Thermal Shock

The double-coated aluminum steel sheet was repeatedly subjected to 10 times of 161 hours at -30 ° C. and 3 hours at 170 ° C., cut into squares having a size of 10 × 10 mm, and then subjected to a cross cutting test.

-Workability-

The workability is checked on the double-coated aluminium steel sheet with a circumferential speed ratio of 100 per minute and then coated with a natural coating.

Test Items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Corrosion resistance ◎ ◎ ◎ ◎ O Adhesive ◎ ◎ ◎ O △ Heat resistance ◎ ◎ ◎ ◎ △ Hydrophilic ◎ ◎ ◎ O X Hydrophilic ◎ ◎ ◎ O △ Workability ◎ ◎ ◎ O ◎ Odor ◎ ◎ ◎ X O Thermal shock ◎ ◎ ◎ O △

(◎ is very good, O is good, △ is usually, X means bad.)

As can be seen from Table 3, in the case of the coating composition containing a hydrophilic agent prepared by the present invention as in Examples 1 to 3 in Comparative Examples 1 or 2 which is a coating composition containing a conventionally used emulsion resin or epoxy modified water In comparison with the hydrophilicity and heat resistance, adhesion, corrosion resistance, hydrophilic maintenance, thermal shock it can be seen that excellent effects can be obtained.

In addition, in the case of Examples 1 to 3 according to the present invention, the work environment can be improved by showing excellent results of odor and workability as compared with the prior art, and thus, the work efficiency can be increased.

As described above, the organic type hydrophilic composition for the hydrophilic treatment of aluminum surface of the present invention and a method of manufacturing the same are thin films during hydrophilic treatment of aluminum or aluminum alloy, and can be baked at high temperature for a short time, and have excellent workability and workability. Coil or sheet coating like PCM method is possible, and hydrophilicity and water resistance can be obtained at the same time after curing, and it has the effect of improving the interlayer adhesion with the corrosion resistant agent than the inorganic hydrophilic agent. Is coming.

In addition, the present invention is to provide a coating composition having an excellent effect of preventing the adhesion of adhesion and cleaning effect by rain water by providing a hydrophilic coating composition comprising a hydrophilic composition of the organic material type.

Claims (14)

1.0 to 20 parts by weight of the basic acrylic compound represented by the following formula (1), 1.0 to 5.0 parts by weight of the acrylic compound represented by the formula (2) based on 100 parts by weight of the total copolymer composition, 1.0 to 20 of the acidic acrylic compound represented by the formula (3) Parts by weight, 1.0 to 15 parts by weight of the radical copolymerizable basic acrylic compound represented by the following formula (4), 1.5 to 30.0 parts by weight of the reactive emulsifier represented by the formula (5), 0.5 to 5.0 parts by weight of the compound represented by the formula (6) and the following formula 0.02 to 0.05 parts by weight of the compound represented by 7 0.01 to 2.0 parts by weight of a water-soluble initiator, 100 to 500 parts by weight of a completely dissolved solvent is added and the emulsion is polymerized at 30 to 95 ℃ so that the solid content is 20 to 50% by weight Manufacturing method of hydrophilic composition of organic material type for hydrophilic treatment of aluminum surface <Formula 1> CH ₂ = CR ¹ -NR ² In Formula 1, R ¹ is hydrogen or a methyl group, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, and an aryl group containing basicity. <Formula 2> CH ₂ = CR ¹ COO (CH ₂ CH ₂ O) nR ³ In Formula 2, R ¹ is hydrogen or a methyl group, R ³ refers to a group which may be substituted with a methyl group or an aliphatic hydrocarbon group, nonyl phenol, octyl phenol, or phenol, and n is an integer of 1 to 80. <Formula 3> CH ₂ = CR ¹ COOR ² In Formula 3, R ¹ is hydrogen or a methyl group, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, and an aryl group containing basicity. <Formula 4> CH ₂ = CHCONHR ² -R ⁴ -R ⁵ In Formula 4, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, an aryl group containing a basic, R ⁴ is a hydroxy group, R ⁵ is hydrogen, methyl It is a monomer containing a hetero group or an acid group containing the same. <Formula 5> In Formula 3, R ³ refers to a group which may be substituted with a methyl group or an aliphatic hydrocarbon group, nonyl phenol, octyl phenol, or phenol, and n is an integer of 1 to 80. <Formula 6> CH ₂ = CR ¹ COOR ² OH In Formula 4, R ¹ is hydrogen or a methyl group, R ² is hydrogen, one substituted or unsubstituted aliphatic hydrocarbon or selected from substituted hydrocarbon groups, and an aryl group containing basicity. <Formula 7> CH ₂ = CR ¹ COO (CH ₂ CH ₂ O) _n OCR ¹ C = CH ₂ or CH ₂ = CR ¹ COOR ³ OOCR ¹ = CH ₂ In Formula 7, R ¹ is hydrogen or a methyl group, R ³ is a group which may be substituted with a methyl group or an aliphatic hydrocarbon group, nonylphenol, octylphenol, or phenol, and n is an integer of 1 to 80. The method of claim 1, wherein the basic acrylic compound represented by the formula (1) is selected from N-vinyl-2-pyrrolidone, 1-vinylimidazole, 2-vinylpyridine or acryloyl morpholine alone or in combination Method for producing an organic material hydrophilic composition for hydrophilic treatment of aluminum surface The acryl-based compound represented by the formula (2) is methoxy dieethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methoxy dieethylene glycol acrylate, methoxy polyethylene glycol acrylate, butoxy Ethyl methacrylate, phenoxy ethyl acrylate, phenoxy polyethylene glycol acrylate, nonyl phenol or octyl phenol-modified ethylene oxide acrylate, poly ethylene glycol acrylate, ethoxy dieethylene glycol acrylate, characterized in that it is used alone or in combination Method for producing an organic material hydrophilic composition for hydrophilic treatment of aluminum surface  The aluminum surface hydrophilic acid of claim 3, wherein an acidic acrylic compound having an unsaturated double bond represented by Chemical Formula 3 is selected from acrylic acid, methyl methacrylic acid, maleic anhydride, fumaric acid, and itaconic acid alone or in combination. Process for preparing hydrophilic composition of organic material type for treatment The method according to claim 4, wherein the radical copolymerizable basic acrylic compound represented by the formula (4) is acrylamide, methacrylamide, N-methol acrylamide, dimethyl amino ethyl methacrylate, tertiary butyl amino ethyl methacrylate, Hydrophilic organic type for hydrophilic treatment of aluminum surface, characterized in that it is used alone or in combination of diacetone acrylamide, acrylamide methylpropane sulfonic acid, dimethyl amino neopentyl acrylate, N, N- dimethylacrylamide Method of Preparation of the Composition The method of claim 5, wherein the compound for emulsion polymerization represented by the formula (5) is polyoxyethylene alkyl propenyl ether ammonium sulfate, polyoxyethylene alkyl propenyl ether sodium sulfate, polyoxyethylene alkyl propenyl ether ammonium phosphate, polyoxy Method for producing an organic material type hydrophilic composition for hydrophilic treatment of aluminum surface, characterized in that the selected from ethylene alkyl propenyl sodium phosphate, sodium vinyl sulfonate alone or in combination The compound represented by the formula (6) is selected from 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl methacrylate alone Or a method for producing an organic material hydrophilic composition for hydrophilic treatment of aluminum surface, characterized in that used in combination The method of claim 7, wherein the compound represented by the formula (7) is triethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, 1.6 hexanediol diacrylate, triethylene Glycol Dimethacrylate, Polyethylene Glycol Dimethacrylate, Neopentyl Glycol Dimethacrylate, Ethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate, 1.6hexanediol Dimethacrylate, Trimethylol Propane Trimethacrylate Method for producing an organic material type hydrophilic agent for hydrophilic treatment of aluminum surface, characterized in that used in acrylates alone or mixed  The method of claim 8, wherein the solvent is butyl cellosol moiety, methanol, ethanol, isopropyl alcohol, ethyl cellosol moiety, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoter Sheryl Butyl Ether, Ethylene Glycol Isopropyl Ether, 3-methoxy Butanol, 3-Methyl 3-methoxy Butanol, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Propylene Method for producing an organic material type hydrophilic composition for hydrophilic treatment of aluminum surface, characterized in that the organic solvent selected from glycol monomethyl ether, dipropylene glycol monomethyl ether contains 5.0 to 30% by weight and the rest is made of ion-exchanged water The method according to claim 9, wherein the water-soluble initiator of the organic type hydrophilic composition for the aluminum surface hydrophilic treatment, characterized in that one selected from APS (Ammonium Phosphate), SPS (Sodium Phosphate) or KPS (Potasium-Phosphate) Manufacturing method The method of claim 1, wherein the nonionic emulsifier to which the ethylene oxide is added at the time of polymerization to include 0.5 to 10.0 parts by weight based on 100 parts by weight of the copolymer composition of the organic material type hydrophilic agent for hydrophilic treatment of aluminum surface Way The method according to claim 11, wherein the polymerization is obtained by including a polymerization regulator of the mercaptan system such as n-butyl mercaptan, n-dodecyl mercaptan, 2-mercapto ethanol and the like so that the average molecular weight of the copolymer obtained by the emulsion polymerization is 10,000 ~ 100,000 Method for producing an organic material hydrophilic agent for hydrophilic treatment of aluminum surface characterized in that Hydrophilic composition of the organic material type for hydrophilic treatment of aluminum surface, characterized in that the production method of claim 1 In a conventional coating composition comprising a curing agent, a catalyst and a solvent, a hydrophilic coating composition comprising 15 to 40% by weight of the organic material type hydrophilic composition prepared by the method of claim 1