JPH11293148A - Hydrophilic surface treating composition and hydrophilic surface treating membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrophilic surface treating composition and a hydrophilic surface treating membrane having no foaming during a hydrophilic treatment work, having no problems of mold abrasion and odor generation, and further capable of imparting excellent hydrophilicity and its durability to the surface of a material to be coated, especially the metal surface of a fin material for heat exchange or the like consisting of aluminum or its alloy, or the surface of various kinds of plastic products, glass products or the like for the purposes of antifog treatments, antistatic treatments or the like. SOLUTION: This hydrophilic surface treating composition contains (A) ammonium salt or amine salt of a water soluble carboxyl group-containing polymer molecule, (B) an imino group-containing polymer compound and (C) polyethylene glycol as active components, and these components A, B and C are preferably compounded in such a manner that the solid component's weight ratio of B/A is 0.01-0.5, and the solid component's weight ratio of C/A is 0.05 or more. Further, the hydrophilic surface treating membrane is formed by using said hydrophilic surface treating composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic surface treatment composition and a hydrophilic surface treatment film used for imparting hydrophilicity to the surface of various materials to be coated, and is not particularly limited. However, for example, a metal surface such as a fin material for heat exchange made of aluminum or an alloy thereof, or a plastic surface or a glass surface for the purpose of anti-fog treatment or antistatic treatment of various plastic products and glass products,
The present invention relates to a hydrophilic surface treatment composition for imparting excellent hydrophilicity and a hydrophilic surface treatment film.

[0002]

2. Description of the Related Art An air conditioner (air conditioner) having functions such as cooling, heating, and dehumidification is provided with a fin material for heat exchange in a heat exchange portion thereof. Excellent in heat resistance and heat conductivity,
It is formed of aluminum or its alloy.

When such an air conditioner is operated for cooling, the heat exchange portion on the indoor side becomes lower than the dew point of the moisture in the air, and the moisture in the air condenses on the fins used in the heat exchange portion. And adhere. The shape of the condensed water on the fin surface is determined by the wettability of the fin surface to water.On the fin surface with poor wettability, the condensed water becomes substantially hemispherical water droplets, and furthermore, water is formed between the fins. The bridge forms a bridge, which causes airflow resistance in the heat exchange portion, which impairs ventilation, causes noise, and in some cases, causes dew condensation to scatter and contaminate the surroundings.

Therefore, in order to solve such a problem,
Conventionally, the fin surface is subjected to a hydrophilic treatment. For example, a method using an inorganic hydrophilic treating agent containing water glass or the like as a main component (Japanese Patent Publication No. 2-42389, Japanese Patent Publication No. 3-77440). JP-A-1-299877, Japanese Patent Publication No. 3-475, and a method using an organic hydrophilic treating agent containing a resin having a hydrophilic group as a main component as a main component.
No. 70) and a method of using an organic hydrophilic treating agent having a surfactant added to impart resistance to volatile press oil (Japanese Patent Application Laid-Open No. 3-254864).

[0005] However, in the method using an inorganic hydrophilic treating agent, very good hydrophilicity is imparted to the fin surface, but the hydrophilic film formed on the fin surface mainly comprises silica (SiO ₂ ). It is a hard component and has the problem of severe wear of the mold during press working, and also has the property of easily adsorbing odor components in the environment, so there is also the problem that odor is felt at the beginning of cooling. is there.

In the method using the above-mentioned organic hydrophilic treating agent, there is no problem of mold abrasion or odor generation described above, but it is formed on the fin surface by volatile press oil used at the time of press working. The hydrophilic film is attacked,
There is another problem that the hydrophilicity is reduced.

Further, a method is proposed in which a surfactant is added to compensate for the drawbacks of the organic hydrophilic treating agent. However, when a surfactant is added, foaming occurs during the operation of the hydrophilic treatment and the hydrophilicity is increased. In addition to significantly reducing the workability of the water treatment, if dew water adheres to the fin surface during operation of an air conditioner, the surfactant starts to dissolve into the dew water from the hydrophilic film formed on the fin surface, and this dissolved surfactant However, there is also a serious problem that the drain pan deteriorates.

[0008]

Therefore, the present inventors have found that there is no foaming during the hydrophilic treatment operation, there is no problem of mold abrasion or odor generation, and further, the excellent hydrophilicity and the excellent As a result of intensive studies on a hydrophilic surface treatment composition and a hydrophilic surface treatment film that can impart durability, a water-soluble ammonium salt or amine salt of a carboxyl group-containing polymer, and an imino group-containing polymer compound, It has been found that a composition and a film containing polyethylene glycol achieve this object, and the present invention has been completed.

Accordingly, it is an object of the present invention to provide a heat exchange fin material which is free from foaming during a hydrophilic treatment operation, has no problem of mold wear and odor generation, and has a surface to be coated, particularly aluminum or an alloy thereof. Hydrophilicity that can impart excellent hydrophilicity and durability to these plastic surfaces and glass surfaces for the purpose of anti-fog treatment and antistatic treatment of various plastic products and glass products, etc. An object of the present invention is to provide a hydrophilic surface treatment composition and a hydrophilic surface treatment film.

[0010]

That is, the present invention provides a water-soluble ammonium salt or amine salt of a carboxyl group-containing polymer (A), an imino group-containing polymer compound (B), and polyethylene glycol as active ingredients. (C) and a hydrophilic surface-treated film containing such a component as an active ingredient.

In the present invention, the carboxyl group-containing polymer is obtained by homopolymerizing or copolymerizing one or more carboxyl group-containing monomers selected from acrylic acid, methacrylic acid and itaconic acid. Or a copolymer obtained by copolymerizing one or more of these carboxyl group-containing monomers with another copolymerizable monomer, or carboxymethyl cellulose. And cellulose derivatives such as alginic acid and derivatives thereof. One of these carboxyl group-containing polymers can be used alone, or a mixture of two or more thereof can be used.
The copolymer may be any as long as it has a carboxyl group and its ammonium salt or amine salt (A) shows water solubility, and may be a binary copolymer or a ternary copolymer. The above multi-component copolymer may be used.

In the present invention, such a carboxyl group-containing polymer may be an ammonium salt or an amine salt thereof (A).
This ammonium salt or amine salt refers to a salt obtained by neutralizing a carboxyl group of a carboxyl group-containing polymer with ammonia or an amine, and shows water solubility as these ammonium salts or amine salts. Things. Here, as the amine salt, for example, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a monoethylamine salt, a diethylamine salt, a triethylamine salt and the like are suitably used. When neutralizing the carboxyl group of the carboxyl group-containing polymer with ammonia or an amine, the carboxyl group may be neutralized using at least an equivalent or more of ammonia or an amine with respect to the carboxyl group. Is also good.

As the ammonium salt or amine salt (A) of the water-soluble carboxyl group-containing polymer used in the present invention,
Preferred specific examples include ammonium polyacrylate,
Polyammonium methacrylate, ammonium polyitaconate, ammonium polyacrylate-polyammonium methacrylate copolymer, ammonium polyacrylate-ammonium polyitaconate copolymer, ammonium polyacrylate-polyvinyl alcohol copolymer, ammonium polyacrylate- Examples include polystyrene sodium sulfonate copolymer, polyammonium methacrylate-polystyrene sodium sulfonate copolymer, ammonium alginate, and ammonium salts of carboxymethyl cellulose.

The imino group-containing polymer compound (B) used as an active ingredient in the present invention is a compound containing an imino group in the main chain or side chain, and is preferably a polyolefin imine such as polyethyleneimine or polypropyleneimine. And the like. These are high molecular weight polymers of branched olefin imines containing primary, secondary, or tertiary amino nitrogens, and various molecular weights can be obtained depending on the degree of polymerization. These polyolefin imines having different molecular weights may be appropriately contained.

Further, polyethylene glycol (C) used as an active ingredient in the present invention is a polymer of ethylene oxide, and can have various molecular weights depending on the degree of polymerization, but exhibits excellent hydrophilicity. From the viewpoint, those having a molecular weight of 200 to 20,000 are preferred. The polyethylene glycol may appropriately contain one having a different molecular weight.

The hydrophilic surface-treating composition of the present invention comprises a water-soluble carboxyl group-containing polymer ammonium salt or amine salt (A), an imino group-containing polymer compound (B), and polyethylene glycol (C). Weight ratio (B / A)
0.01 to 0.5, preferably 0.03 to 0.3 and a solid content weight ratio (C / A) of 0.05 or more, preferably 0.1
It is preferred that the content be 0 or more. This solid content weight ratio (B /
If A) is less than 0.01, the desired hydrophilicity is not exhibited. Conversely, if it is more than 0.5, the viscosity increases and coating becomes impossible, and the solid content weight ratio (C / A) is If it is less than 0.05, the hydrophilicity is not exhibited, and the moldability also decreases.

Further, regarding the mixing ratio of each component in the hydrophilic surface treatment composition of the present invention, the solid content weight ratio (B / A) and the solid content weight ratio (C / A) are maintained so that the composition can be used. And the type of the material to be coated, the method of application to the material to be coated, and further can be appropriately changed depending on the packaging of the hydrophilic surface treatment composition, but the mixing ratio when actually applied to the material to be coated is The amount of the water-soluble ammonium salt or amine salt (A) of a carboxyl group-containing polymer in an aqueous medium is 0.5 to 20% by weight, preferably 1 to 10% by weight, and the imino group-containing polymer compound (B) Is 0.005 to 1
0% by weight, preferably 0.05 to 5% by weight, and 0.025% by weight of polyethylene glycol (C).
It is preferably at least 0.5% by weight. If the compounding ratio of the water-soluble carboxyl group-containing polymer ammonium salt or amine salt (A) is less than 0.5% by weight, desired hydrophilicity may not be exhibited.
If the amount is more than the weight%, the viscosity increases and coating becomes impossible.
Also, when the blending ratio of the imino group-containing polymer compound (B) is less than 0.005% by weight, the desired hydrophilicity may not be exhibited. Conversely, if it exceeds 10% by weight, the viscosity increases. Coating becomes impossible. Further, if the blending ratio of polyethylene glycol (C) is less than 0.025% by weight, desired hydrophilicity may not be exhibited.

In the hydrophilic surface treatment composition of the present invention,
The aqueous medium used may be water itself, and, for the purpose of improving coating properties and preventing foaming when using a surfactant, preventing uneven coating, etc., as required, such as ethanol, isopropanol and isobutanol. Alcohols and polyhydric alcohols such as ethylene glycol and glycerin may be added.

The present invention comprises the above-mentioned water-soluble carboxyl group-containing polymer ammonium salt or amine salt (A), imino group-containing polymer compound (B), and polyethylene glycol (C) as main components. However, if necessary, a water-soluble polymer other than an ammonium salt or an amine salt (A) of a water-soluble carboxyl group-containing polymer, a surfactant, an antibacterial agent and the like may be used within a range not to impair the object of the present invention. Other additives can be added.

Examples of other water-soluble polymers added for the purpose of further improving the initial hydrophilicity and the effect of maintaining hydrophilicity include, for example, sodium salt of carboxymethylcellulose (CMC) and hydroxyethylcellulose (H
EC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC),
Examples include cellulose derivatives such as hydroxyethylmethylcellulose (HEMC) and hydroxypropylmethylcellulose (HPMC); polyalkylene glycols and derivatives thereof such as polypropylene glycol; and polyvinyl alcohol and derivatives thereof. As the surfactant used to obtain good coatability and better hydrophilicity against press oil, any type of anionic, cationic, nonionic, and amphoteric surfactants can be used. Sodium dialkyl sulfosuccinate, sodium dodecylbenzenesulfonate, etc., octadecylamine acetate, etc. as the cationic type, and polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, etc. as the nonionic type. However, as the amphoteric type, dimethylalkyl betaine and the like are preferably exemplified. Further, as an antibacterial agent added for the purpose of imparting antibacterial properties without impairing hydrophilicity, a benzimidazole compound, a nitrogen-containing sulfur compound, a quaternary ammonium salt, chitosan and chitosan can be obtained by chitinase treatment. Degradation products and the like.

The method for forming a hydrophilic film on the surface of the material to be coated using the hydrophilic surface treatment composition of the present invention is not particularly limited. It is as follows.

First, the surface (front and back) of an aluminum material having a thickness of, for example, 100 to 110 μm is degreased and dried, and then a corrosion resistant film is formed on the surface. The corrosion-resistant coating at this time is not particularly limited, and for example, an inorganic corrosion-resistant coating or an organic corrosion-resistant coating is formed by a chemical conversion treatment or a coating-type chromate treatment. Next, the hydrophilic surface treatment composition is applied on the corrosion-resistant coating by an appropriate application means such as a roll coating method, a bar coating method, a spraying method, a dipping method or the like, preferably at a heating temperature of 150 to 300. It heat-drys on conditions of 10 degreeC and the heating time of 10 to 60 seconds, and forms a hydrophilic surface treatment film. The fin material for heat exchange obtained in this way is subjected to forming processing such as slitting and corrugation by applying volatile press oil, and is used as a target fin material for heat exchange.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below based on examples and comparative examples.

Examples 1 to 35 and Comparative Examples 1 to 16 [Preparation of hydrophilic surface treatment composition] As a water-soluble carboxyl group-containing polymer, a weight average molecular weight (Mw) of 150,0 was used.
Polyacrylic acid (PA-150: Jurimer AC-10H manufactured by Nippon Pure Chemical Co., Ltd., solid content concentration: 20 wt%), polyacrylic acid having a weight average molecular weight (Mw) of 60,000 (PA-060: ROHM & Haas Accumer 1510, solids concentration: 25 wt
%), Polyacrylic acid having a weight average molecular weight (Mw) of 30,000 (PA-030: Jurimer AC-10L manufactured by Nippon Pure Chemical Co., Ltd., solid content concentration: 40 wt%), weight average molecular weight (Mw) of 5,000 Polyacrylic acid (PA-005: Jurimer manufactured by Nippon Pure Chemical Co., Ltd.)
AC-10S, solid content concentration: 40wt%), weight average molecular weight (Mw) 7
000 polymethacrylic acid (PM-070: Jurimer AC-30H manufactured by Nippon Pure Chemical Co., Ltd., solid content concentration: 20 wt%), polyacrylic acid-polymethacrylic acid having a weight average molecular weight (Mw) of 60,000 Polymer (PAPM-060: Jurimer AC-20H manufactured by Nippon Pure Chemical Co., Ltd., solid content concentration: 20 wt%), polyacrylic acid-polyitaconic acid copolymer (PAPI-020) having a weight average molecular weight (Mw) of 20,000 : Jurimar AC-5 manufactured by Nippon Pure Chemical Co., Ltd.
0P, solid content: 90 wt%), weight average molecular weight (Mw) 10
000 polyacrylic acid-polyvinyl alcohol copolymer (PAPV-100: Shin-Etsu Poval manufactured by Shin-Etsu Chemical Co., Ltd.)
SPC-20A, solid content concentration: 99 wt%), and poly (methacrylic acid-polystyrene sodium sulfonic acid copolymer) having a weight average molecular weight (Mw) of 50,000 (MSS-Na salt: Tosoh Corporation)
Manufactured, solid content concentration: 20 wt%).

As another ammonium salt of a water-soluble polymer having a carboxyl group, an ammonium salt of carboxymethyl cellulose (CMC-A: NH ₄ -CMC DL-10N manufactured by Daicel Chemical Industries, Ltd.) was used. Furthermore, carboxymethyl cellulose (CMC:
CMC 1290 manufactured by Daicel Chemical Industries, Ltd.) and polyvinyl alcohol (PVA: Shin-Etsu Poval manufactured by Shin-Etsu Chemical Co., Ltd.)
SMR-10HH) and chitosan oligosaccharide (CT: Yaizu Suisan Chemical Co., Ltd.) as an antibacterial agent that does not impair hydrophilicity
Was used.

Further, as the imino group-containing polymer compound,
Four kinds of polyethyleneimines having different weight average molecular weights (Mw), that is, polyethyleneimine having a weight average molecular weight (Mw) of 70,000 (PEI-70: Epomin P-1000 manufactured by Nippon Shokubai Chemical Co., Ltd., solid content concentration: 30 wt. %), Weight average molecular weight (M
w) 10,000 polyethyleneimines (PEI-10: Epomin P-200 manufactured by Nippon Shokubai Chemical Co., Ltd., solid content concentration: 98 wt.
%), Polyethyleneimine having a weight average molecular weight (Mw) of 1,200 (PEI-1.2: Epomin P-01 manufactured by Nippon Shokubai Chemical Co., Ltd.)
2, solid content concentration: 98wt%) and weight average molecular weight (Mw)
300 polyethyleneimines (PEI-0.3: Epomin P-003 manufactured by Nippon Shokubai Kagaku Co., Ltd., solid content concentration: 98 wt%) were used.

With respect to the water-soluble polymer having a carboxyl group, in Examples 1 to 16 and 18 to 35 and Comparative Examples 2, 4, 6, 9 and 11 to 16, equivalent amounts of ammonia, monoethanolamine, or , Neutralized with triethanolamine and used as an ammonium salt (AS salt), a monoethanolamine salt (ME salt), or a triethanolamine salt (TE salt). In Comparative Examples 7 and 8, the sodium salt ( Na salt).

Using water as an aqueous medium, water-soluble ammonium or amine salts of a carboxyl group-containing polymer in the proportions shown in Table 1, polyethyleneimine, polyethylene glycol (PEG) having a weight average molecular weight (Mw) shown in Table 1 ),
And the other water-soluble polymer was added and the bath was built, and the hydrophilic surface treatment composition of Examples 1-35 and Comparative Examples 1-16 was prepared.

[Formation of hydrophilic surface-treated film] A degreasing solution (concentration: 20 g / l, 60 ° C.) prepared using an alkaline degreasing agent (Surf Cleaner 53 manufactured by Nippon Paint Co., Ltd.)
Using an aluminum plate (JIS A 1100, thickness 105μ)
The surface of m) was degreased and washed for 5 minutes, then washed with water and dried. Next, a coating type chromate paint (Surfalcoat 427 manufactured by Nippon Paint Co., Ltd.) was applied to the degreased aluminum plate using a bar coater to a film thickness of 0.1 μm.
And then dried at 200 ° C. for 20 seconds to form a corrosion resistant film. The hydrophilic surface treatment composition of each of Examples 1 to 35 and Comparative Examples 1 to 16 was applied to an aluminum plate having a corrosion-resistant film obtained in this manner so that the film thickness after drying was 0.5 μm. Then 230 ° C
For 20 seconds to obtain test pieces having the hydrophilic surface-treated films of Examples 1 to 35 and Comparative Examples 1 to 16 on the corrosion-resistant film.

[Evaluation Test] The obtained hydrophilic surface-treated films of Examples 1 to 35 and Comparative Examples 1 to 16 were evaluated for initial hydrophilicity and durability of hydrophilicity. For the initial hydrophilicity, each test piece was immersed in a volatile press oil (Daphne Punch Oil AF2C manufactured by Idemitsu Kosan Co., Ltd.), pulled up, drained, dried at 180 ° C. for 3 minutes, and then measured with a contact angle meter. (CA-A type manufactured by Kyowa Interface Science Co., Ltd.) was used to measure and evaluate the contact angle by a droplet method.

The persistence of hydrophilicity can be determined by immersing a test piece in which the initial contact angle has been measured in pure water for 120 hours, drying it at room temperature, and measuring the contact angle with a contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.). (CA-A type) by the droplet method and evaluated.
Furthermore, the evaluation of hydrophilicity and its persistence was performed by a four-step evaluation in which the contact angle was 10 degrees or less, ◎; 11 to 30 degrees, ○; 31 to 40 degrees, Δ; The results are shown in Tables 1 to 3.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

As is clear from the results shown in Tables 1 to 3,
The hydrophilic surface-treated films formed by using the hydrophilic surface-treated compositions of the present invention shown in Examples 1 to 35 have an initial hydrophilicity and a sustainability of both ○ or more ◎.
And it was found to be excellent in hydrophilicity.

On the other hand, when a water-soluble polymer containing a carboxyl group not neutralized with ammonia was used (Comparative Examples 1, 3, and 5),
When neutralized with OH (Comparative Examples 7 and 8), the building bath was solidified and the coating operation became impossible.

When no PEG was added (Comparative Examples 2, 4 and 6), the hydrophilicity was very poor, and when no polyethyleneimine was added (Comparative Example 9), the hydrophilicity was poor. When no water-soluble ammonium salt of a carboxyl group-containing polymer was used (Comparative Example 10), it was found that the formed hydrophilic treated film was dissolved in water. Further, when the molecular weight of PEG exceeds 20,000 and is extremely large (Comparative Examples 15 and 16), the hydrophilicity decreases, and when the blending amount increases, the viscosity increases and coating becomes impossible.

[0038]

According to the hydrophilic surface treatment composition and hydrophilic surface treatment film of the present invention, there is no foaming during the hydrophilic treatment operation, no problem of mold abrasion and odor generation, and the surface of the material to be coated. In particular, metal surfaces such as fin materials for heat exchange made of aluminum or an alloy thereof, and various plastic products and glass products. Hydrophilicity and its durability can be imparted.

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Claims (8)

[Claims] 1. An active ingredient comprising a water-soluble ammonium salt or amine salt of a carboxyl group-containing polymer (A), an imino group-containing polymer compound (B), and polyethylene glycol (C). And a hydrophilic surface treatment composition. 2. A water-soluble ammonium salt or amine salt of a carboxyl group-containing polymer (A), an imino group-containing polymer compound (B), and polyethylene glycol (C) having a solid weight ratio (B / A) of 0. The hydrophilic surface treatment composition according to claim 1, wherein the composition is contained in an amount of 0.01 to 0.5 and a solid content weight ratio (C / A) of 0.05 or more. 3. The water-soluble carboxyl group-containing polymer,
Acrylic acid, methacrylic acid, and a homopolymer or copolymer obtained by homopolymerizing or copolymerizing one or more carboxyl group-containing monomers selected from itaconic acid,
The hydrophilic surface according to claim 1 or 2, wherein the hydrophilic surface is a copolymer obtained by copolymerizing one or more of these carboxyl group-containing monomers with another copolymerizable monomer. Treatment composition. 4. The water-soluble ammonium salt or amine salt of a carboxyl group-containing polymer is selected from the group consisting of ammonium polyacrylate, polyammonium methacrylate, ammonium polyitaconate, ammonium polyacrylate-polyammonium polymethacrylate, and polyacrylic. Ammonium acrylate-ammonium polyitaconate copolymer, ammonium polyacrylate-polyvinyl alcohol copolymer, ammonium polyacrylate-polystyrene sodium sulfonate copolymer, or polyammonium methacrylate-polystyrene sodium sulfonate copolymer The hydrophilic surface treatment composition according to claim 1. 5. The polymer compound having an imino group having a molecular weight of 3
A polyethyleneimine having a molecular weight of from 00 to 70,000.
5. The hydrophilic surface treatment composition according to any one of items 1 to 4. 6. Polyethylene glycol having a molecular weight of 2
The hydrophilic surface treatment composition according to any one of claims 1 to 5, wherein the number is from 00 to 20,000. 7. A hydrophilic surface-treated film comprising, as active ingredients, a water-soluble ammonium salt or amine salt of a carboxyl group-containing polymer, an imino group-containing polymer compound, and polyethylene glycol. 8. A hydrophilic surface-treated film according to claim 7, which is formed on the surface of a material to be coated by using the hydrophilic surface-treated composition according to any one of claims 1 to 6.