JP3403906B2 - Manufacturing method of highly hydrophilic paint - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the production of a highly hydrophilic paint .
Regarding the manufacturing method . More specifically, the present invention relates to a method for producing a highly hydrophilic coating that imparts a high degree of hydrophilic persistence and corrosion resistance to the aluminum fin surface of a heat exchanger for an air conditioner. More specifically, the present invention relates to a method for producing a highly hydrophilic coating material that retains a high degree of hydrophilicity even when a contaminant is adsorbed on the surface layer and is excellent in stain resistance.

[0002]

2. Description of the Related Art Conventionally, aluminum and its alloys have been widely used for heat exchangers of air conditioners because of their excellent workability and thermal conductivity. The configuration basically has multiple adjacent fins (relatively thin plates).

In a heat exchanger of an air conditioner, it is unavoidable that condensed water generated during cooling is attached as water droplets to fins.
The water droplets tend to form a water bridge between the adjacent fins. In that case, the water bridge blocks ventilation, increases ventilation resistance, and deteriorates the heat exchange rate. Therefore, the surface of the fin material is hydrophilized to suppress / prevent the formation of bridges due to water droplets and maintain a good heat exchange rate.

On the other hand, in recent years, home appliances are strongly required to be downsized, and air conditioners are no exception. In particular, the heat exchanger, which occupies a large volume among air conditioners, is required to be the strongest and downsized.
It is desired that the fin shape is complicated and the fin interval is narrowed, and the fin material is required to have higher hydrophilicity.

As a method for imparting hydrophilicity to the aluminum fin, there are methods such as chemical conversion treatment and coating with a hydrophilic paint.

The former chemical conversion treatment generally has a drawback that it is inferior in productivity because it is performed after fining such as making holes for passing a pipe through which a refrigerant flows.

In order to solve this problem, a method has been proposed in which the fins are coated with water glass or a hydrophilic paint before fin processing. Examples of such a coating agent include a coating material made of an organic hydrophilic resin and a coating material containing inorganic particles such as synthetic silica.

However, when an organic hydrophilic resin such as water-based nylon, water-based acrylic resin, polyvinyl alcohol or polyvinylpyrrolidone is used, the hydrophilicity and the adhesion are insufficient, or the hydrophilicity and the corrosion resistance are balanced. There was a problem that it could not be removed. On the other hand, when a coating containing synthetic silica or the like is used to impart hydrophilicity, the hydrophilicity and corrosion resistance are superior to those using an organic hydrophilic resin, but the coating is hard There are problems that the molds and machining tools used for machining such as voids are severely worn and the life of the tools is shortened, and that the odor suppression (prevention) effect is insufficient.

Further, when a water glass-based paint is applied, as in the case of using a paint containing synthetic silica or the like, there is a problem in that the mold, the working tool, etc. are greatly worn and the life of the tool is shortened. , Or slipperiness is poor, and as a result,
There were problems that frictional heat was generated between the tool and the coating film, seizure, continuous processing became impossible, and a smell of silica was generated when the air conditioner was used.

Furthermore, when an air conditioner using fins coated with water glass paint is installed in a new house, the problem of water splash (that is, water splash) between the fins has increased in recent years.

The cause is that the plasticizer contained in the interior wall material of the new house or the wax component contained in the floor polish is photo-decomposed to have a low molecular weight and volatilized to be adsorbed and contaminated by the fins. This is probably because the hydrophilicity of the surface was significantly impaired.

[0012] In order to impart the stain resistance to such contaminants to the fin, it has been proposed to use an organic hydrophilic paint which gradually releases the cleaning component, but the hydrophilicity persistence,
The adhesion to the base material is insufficient.

[0013]

The object of the present invention is to provide excellent hydrophilicity, corrosion resistance, stain resistance, adhesion and slipperiness, and
It is an object of the present invention to provide a method for producing a non-silica-based or non-aqueous glass-based highly hydrophilic coating capable of forming a coating film that is less likely to cause wear of molds and processing tools and is less likely to generate odor.

[0014]

Means for Solving the Problems That is, the first invention
Is an alumina sol (a) and a water-soluble acrylic resin (b)
, Then polyethylene glycol, polyethylene
Modified ethylene glycol, ethylene oxide and propylene
Copolymer with ethylene oxide, and ethylene oxide
And modified propylene oxide copolymer
Weight average molecular weight selected from the group is 2000 to 50,000
0, a hydroxyl group, a glycidyl group or a terminal functional group
Is one or more selected from blocked isocyanates
Add at least one compound (c) having the above functional group
A method for producing a highly hydrophilic paint characterized by adding and mixing
Is.

The second invention relates to the above-mentioned alumina sol (a).
The primary particles are feathery, rod-shaped or dendritic.
It has a shape and form, and its average particle size is 0.5 to 20 μm.
A method for producing a highly hydrophilic paint according to the first invention, characterized in that
It is a manufacturing method.

A third invention is the solid content 1 of the highly hydrophilic coating material.
30 to 60% by weight of the compound (c) in 100% by weight.
A high according to the first or second invention, characterized in that
It is a method for producing a hydrophilic paint.

A fourth invention is the water-soluble acrylic resin.
(B) has a sulfonic acid or sodium sulfonate group
1 to 80% by weight of the α, β unsaturated monomer (A)
5 to 5 α, β unsaturated monomer (B) having a rubonic acid group
0% by weight, α-, β-unsaturated monounsaturated with alcoholic hydroxyl groups
5 to 50% by weight of the monomer (C) is copolymerized (only
And, (A), (B) , the total is 100 wt%) This (C)
And the high invention according to any one of the first to third inventions,
It is a method for producing a hydrophilic paint.

A fifth invention is the polyethylene glycol
Or ethylene oxide and propylene oxide
The melting point of the copolymer is 50 ° C or higher.
Of the highly hydrophilic paint according to any one of the first to fourth inventions
It is a manufacturing method.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The alumina sol (a) used in the present invention is an aqueous dispersion in which particles of an alumina hydrate (arbitrary shape) are dispersed in water. i) Anions in water (eg OH ⁻ , S
O ₄ ⁻ , Cl ⁻ , NO ₄ ⁻ , CH ₃ COO ⁻ ) dispersed as a stabilizer and having a colloidal size of about 2 to 100 nm, or ii) the colloidal size obtained by various methods. The average particle size (average major axis) is 0.5.
The particles are aggregated to about 20 μm, and the latter is preferable. In particular, it is preferable that the agglomerated particles are not substantially spherical and have a surface area as large as possible in the same volume, for example, those having a feather-like, rod-like or dendritic shape / morphology in view of exerting high hydrophilicity.

As the alumina sol (a) utilizing the above i), "Cataloid AS-" manufactured by Catalysts & Chemicals Co., Ltd. is used.
1 ”: average particle size 0.2 μm,“ Cataloid AS-2 ”:
Average particle size 0.2 μm, “Alumina sol-100” manufactured by Nissan Chemical Industries, Ltd .: Average particle size 0.2 μm, “Alumina sol-2”
00 ”: average particle size 0.2 μm,“ alumina sol-52 ”
0 ”: average particle size 0.02 μm,“ alumina clear sol ”manufactured by Kawaken Fine Chemical Co., Ltd .: average particle size 0.02
μm, “aluminum sol-10”: An alumina sol in which particles having an average particle diameter of 2 to 200 nm, such as an average particle diameter of 0.02 μm, are dispersed in water.

Although such an alumina sol can be used alone, the average particle size exemplified immediately after this is 0.5 to 20 μm.
It is preferably used in combination with alumina sol, which is a dispersion of feather-like, rod-like, or dendritic agglomerated particles aggregated to about m.

The alumina sol, which is a dispersion of feather-like, rod-like or dendritic agglomerated particles aggregated to have an average particle diameter of about 0.5 to 20 μm, is, for example, “Cataloid AS-” manufactured by Catalyst Kasei Kogyo Co., Ltd. 3 ”can be used. Also,
A powder obtained by spray-drying "Cataloid AS-3", "Cataloid AP-3", dispersed in water can be used. In the case of "Cataloid AP-3", it exhibits an average particle size of 50 to 60 µm in a dry state, but it is easily redispersed in water and the average particle size of the dispersed particles at that time is "Cataloid AS-3" before drying. Similarly, it is 0.8 μm.

Such an alumina sol has a larger surface area for contact with water by roughening the cured coating film than the above-described alumina sol having relatively small dispersed particles, and the coating by the capillary phenomenon due to its complicated form. It is preferable because the wettability of the film with water can be improved.

If the average particle diameter is larger than 20 μm, the surface roughening effect is great, but coating defects such as spots are likely to occur, which is not preferable.

Alumina sol (a) used in the present invention
Is in the stage where the dispersed particles are transferred from the amorphous gel to boehmite, and this state does not change during the aggregation process and the usual baking conditions of the coating film (for example, 250 ° C. × 20 seconds).

The dispersed particles of alumina sol at the stage of the transition from the amorphous gel to boehmite are softer than those of colloidal silica, and therefore, the blade of a press machine or the like when processing a film containing this alumina sol. Very little tool wear.

The water-soluble acrylic resin (b) used in the present invention is an acrylic resin having a polar group (for example, sulfonic acid group, monovalent salt of sulfonic acid such as sodium, potassium and lithium, hydroxyl group and carboxyl group). It is a polymer, and preferably an acrylic copolymer (the partner monomer of the copolymer is arbitrary as long as the effects of the present invention are exhibited, but for example, acrylamide, N-methylolacrylamide, N-methoxy). A monomer having an amino group such as methylol acrylamide is preferred).
This water-soluble acrylic resin (b) forms a hydrophilic coating film on aluminum as a base material, and further undergoes a cross-linking reaction with dispersed particles in the alumina sol (a) to give an alumina sol (a) in the coating film. It has the function of fixing the dispersed particles inside.

The water-soluble acrylic resin (b) is preferably 1 to 80% by weight (more preferably 30 to 50) of the α, β unsaturated monomer (A) having a sulfonic acid group or a sodium sulfonate group. % By weight), 1 to 50% by weight (more preferably 20 to 50% by weight) of an α, β unsaturated monomer having a carboxylic acid group (more preferably 20 to 50% by weight), and an α, β unsaturated monomer having an alcoholic hydroxyl group. 1 to 50% by weight (more preferably 20 to 40% by weight) of the monomer (C) is copolymerized (however, the total of (A), (B) and (C) is 100% by weight). is there.

The α, β unsaturated monomer (A) having a sulfonic acid group or a sodium sulfonate group exhibits strong anionic hydrophilicity and improves the wettability of the surface of the formed film with water. Examples of the component (A) include vinyl sulfonic acid, aryl sulfonic acid, and 2-acrylamide-2.
—Methyl sulfonic acid, styrene sulfonic acid, methacryloyloxyethyl sulfonic acid and all of these sodium salts, potassium salts, lithium salts and the like.

The α, β-unsaturated monomer (B) having a carboxylic acid group bears some hydrophilicity and adhesion to an aluminum substrate. Examples of the component (B) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and the like.

The α, β-unsaturated monomer (C) having an alcoholic hydroxyl group is responsible for some hydrophilicity and cross-linking with the active hydroxyl group on the alumina sol particles, and the water-soluble acrylic resin is used as the alumina sol particles. It is responsible for fixing to. Examples of the component (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide and the like.

At least one selected from the group consisting of polyethylene glycol, a modified product of polyethylene glycol, a copolymer of ethylene oxide and propylene oxide, and a modified product of a copolymer of ethylene oxide and propylene oxide used in the present invention. The compound (c) (hereinafter also referred to as polyethylene glycol (c)) is a component that cleans contaminants, and considers the balance between the sustained release property from the coating film and the cleanability of contaminants and the upper limit of paint viscosity. And the weight average molecular weight is 2000 to 50,000.
The range of 0 is preferable.

That is, when the molecular weight is small, the viscosity tends to be low, and the lower the viscosity is, the more easily it is washed away by dew condensation water and the like, and the cleaning ability is easily attenuated.

The above-mentioned modified product is one in which a functional group other than a hydroxyl group is bonded to the terminal, and examples thereof include those having a glycidyl group, an oxime-blocked isocyanate group, and the like. Those having two or more are preferable. When such a functional group is present, the water-soluble acrylic resin (b) reacts with the functional group or the functional groups react with each other, so that it is difficult to wash away with dew condensation water or the like,
Although the cleaning ability is easily maintained, it is preferable, but on the other hand, it tends to be difficult to remove the pollutant, and therefore it is preferable to select it in consideration of the weight average molecular weight and the like.

In the case of not having the functional group as described above, that is, in the case of polyethylene glycol or a copolymer of ethylene oxide and polypropylene oxide, the melting point is preferably 50 ° C. or higher. That is, when the melting point is 50 ° C. or higher, it is difficult to wash away with dew condensation water and the like, the cleaning ability is easily maintained, and at the same time, the pollutant is easily removed. It is also preferable because the slipperiness of the surface of the coating film is improved. The higher the melting point is, the more preferable it is. However, the melting point of about 70 ° or less is easily available.

Commercially available products of polyethylene glycol include "PEG6000" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (weight average molecular weight 6000, melting point: 50 to 53 ° C), "PEG20000" manufactured by Sanyo Kasei Co., Ltd. (weight average molecular weight 200).
00, melting point 56 to 62 ° C.), “Paogen EP-15” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (weight average molecular weight 120000 to 1)
30,000, melting point 55 ° C.) and the like.

Commercially available products of modified polyethylene glycol include "Denacol" series having a glycidyl group and manufactured by Nagase Chemicals Co., Ltd., and Daiichi Kogyo Seiyaku Co., Ltd. having a blocked isocyanate group. "Elastron" series can be mentioned.

As a copolymer of ethylene oxide and polypropylene oxide, "Paogen PP-15" (weight average molecular weight of 12 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can be used.
0000 to 130000, melting point 55 ° C.) and the like.

In the present invention, the alumina sol (a) is
It is necessary to mix with water-soluble acrylic resin (b) before adding and mixing polyethylene glycol etc. (c).
It is important .

When the dispersed particles of the alumina sol (a) are relatively small and have a size of about 2 to 200 nm, a water-soluble acrylic resin (b) is prepared by using a high-share dispersing / mixing machine such as a homogenizer. It is preferable to mix with.

In the case of the alumina sol (a) having a relatively large dispersed particle size and an average particle size of about 0.5 to 20 μm and having a feather-like, rod-like or dendritic shape / form, a ball mill is used. It is preferable to use a sand mill, an attritor, a mycoloider, a three-roll mill, a Henschel mixer, a kneader, or other relatively low-share dispersing / mixing machine to mix with the water-soluble acrylic resin (b).

As described above, the water-soluble acrylic resin (b) undergoes a curing / crosslinking reaction with the dispersed particles in the alumina sol (a) in the coating film to fix the dispersed particles in the alumina sol (a) in the coating film. Is responsible for the function. However, alumina sol (a) and water-soluble acrylic resin (b)
When polyethylene glycol etc. (c) which is responsible for stain resistance are simply mixed, polyethylene glycol etc. (c) penetrates into the interface between the dispersed particles in the alumina sol (a) and the water-soluble acrylic resin (b), and the alumina sol ( There is a tendency that the curing / cross-linking reaction between the dispersed particles in a) and the water-soluble acrylic resin (b) is hindered, and the adhesion with the aluminum substrate is lowered. In some cases, it can make it much worse.

Therefore, polyethylene glycol or the like (c)
By mixing the alumina sol (a) and the water-soluble acrylic resin (b) prior to addition and mixing of the water-soluble acrylic resin (b), adsorption of the water-soluble acrylic resin (b) on the surface of the dispersed particles in the alumina sol (a) or By promoting the penetration of the water-soluble acrylic resin (b) into the dispersed particles in the alumina sol (a), it is possible to always prevent the above-mentioned curing / crosslinking reaction from being hindered and the poor adhesion.

As a result, a large amount of polyethylene glycol or the like (c), which is responsible for stain resistance, is added, for example, to a coating solid content of 1
It has become possible to add nearly 60% by weight in 00% by weight, and it has become possible to obtain a highly hydrophilic coating having excellent stain resistance.

Since the highly hydrophilic coating material of the present invention further improves the adhesion of the baked coating film to the aluminum base material, polyethylene glycol or the like (c) is mixed with alumina sol (a) and a water-soluble acrylic resin ( It is preferable to apply and bake after not adding too much time after adding and mixing to the mixture with b).

The baking coating film using the highly hydrophilic coating material of the present invention, particularly the highly hydrophilic coating material prepared by specifying the mixing order of the components, is prepared by dispersing dispersed particles from the alumina sol (a) into a water-soluble acrylic resin ( b) coated with polyethylene glycol or a modified polyethylene glycol (c) on the outside
It has a three-layer structure in which the cleaning component of 1. exists. That is,
By using dispersed particles in the alumina sol (a), the surface of the hydrophilic coating film having a film thickness of 0.5 to 2 μm is roughened to increase the contact surface area with water, and the outermost layer is a cleaning component. It succeeded in forming a coating film having a three-layer structure of covering with polyethylene glycol or the like (c).

With this structure, various pollutants discharged from a new house, for example, DOP contained in interior building materials
(Dioctyl phthalate), stearic acid or the like, or higher fatty acid contained in the floor polish which is photolyzed to have a low molecular weight, is volatilized and adheres to the aluminum fin, but the alumina sol (a) of The cleaning component such as polyethylene glycol (c) existing in the gap of the complicated fractal surface structure of the dispersed particles is entangled with the dispersed particles of the alumina sol (a), and is not washed away by the condensed water during the cooling operation at one time, and it can be used for a long time. Since it is released, the cleaning component such as polyethylene glycol (c) can sequentially wash away the contaminants as described above.

Further, in the baking coating film using the highly hydrophilic coating material of the present invention, after the construction of the building, a lapse of time and after the volatilization of pollutants is completed, that is, the content of the cleaning component in the coating film is reduced. After that, the water-soluble acrylic resin having a strong anionic hydrophilic group appeared on the surface of the coating film and succeeded in maintaining the hydrophilicity for a long period of time.

Polyethylene glycol (c), which is responsible for stain resistance, accounts for 5 to 60% by weight in 100% by weight of the coating solid content.
It is preferably contained, more preferably 30 to 60% by weight, further preferably 40 to 50% by weight. If the content is less than 5% by weight, the cleaning ability for pollutants tends to be insufficient, while if it exceeds 60% by weight, even if the alumina sol (a) and the water-soluble acrylic resin (b) are premixed, As a result, the water-soluble acrylic resin (b) is reduced and the adhesion may be impaired.

The dispersed particles in the alumina sol (a) and the water-soluble acrylic resin (b) were 100% by weight of the coating solid content.
It is desirable to contain 40 to 95% by weight, more preferably 40 to 70% by weight, and further preferably 50 to 6% by weight.
It is preferable to contain 0% by weight. If it is less than 40% by weight, the content of the cleaning component such as polyethylene glycol (c) becomes relatively large and the adhesion tends to deteriorate. On the other hand, when it exceeds 95% by weight, the content of the cleaning component such as polyethylene glycol becomes relatively small, and the stain resistance tends to be insufficient.

Further, dispersed particles in alumina sol (a) /
The water-soluble acrylic resin (b) is preferably mixed in a weight ratio of 1/1 to 1/3.

When the content of the dispersed particles in the alumina sol (a) increases, the viscosity of the coating material increases and the coatability deteriorates. On the other hand, when the content of the dispersed particles in the alumina sol (a) becomes small, the hydrophilicity tends to be insufficient.

In addition to the above components (a), (b) and (c), the highly hydrophilic coating composition of the present invention comprises a cellulose type, a polyurethane type, a polyester type, a polyether polyol type, a polyamide type, One or more water-soluble resins or water-dispersible resins such as epoxy resin, and, if necessary, a surfactant, hydrophilic organic particles or inorganic particles,
You may mix | blend an antibacterial agent, a lubricant, a coloring agent, an antioxidant, a solvent, etc.

[0056]

The present invention will be described below with reference to examples. Synthesis Example 1 A 500 cc three-necked flask was charged with 220 g of deionized water.
Keep at 0 ° C and stir. 0.4 g of ammonium persulfate was charged, and 160 g of a 50% aqueous solution of 2-acrylamido-2-methylpropanesulfonic acid (2AA2MPSA) and 2
A mixed solution of 10 g of hydroxyethyl acrylate (HEA), 10 g of acrylic acid (AA) and 20 g of a 10% aqueous solution of sodium hypophosphite is added dropwise over 1 hour. Ammonium persulfate (10% aqueous solution) 0.4 is added 4 times every 50 minutes, and the temperature of the reaction system is raised to 80 ° C. during the second addition. The nonvolatile matter was confirmed and the polymerization was completed to obtain a water-soluble acrylic resin.

Synthesis Examples 2 to 4 (Water-soluble acrylic resin-
Synthesis Example) Aqueous solution polymerization was performed in the same manner as in Synthesis Example 1 with the composition (weight ratio) shown in Table 1 to obtain water-soluble acrylic resin.

[0058]

[Table 1]

Example 1 40 parts by dry weight of the water-soluble acrylic resin obtained in Synthesis Example 1, "Cataloid AS-3" (average particle size 0.8 μm)
20 parts of m) by dry weight are mixed under stirring and mixed with glass beads in a red devil paint conditioner 2 times.
Time dispersed.

Next, polyethylene glycol (weight average molecular weight 6000, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., "PEG60"
(00 ″) aqueous solution was added in an amount of 40 parts by dry weight, and the mixture was stirred and diluted with ion-exchanged water to prepare a hydrophilic coating material having a nonvolatile content of 10%.

The particle size of the dispersed particles of alumina sol dispersed in this coating material is Microtrack MK-II manufactured by Nikkiso Co., Ltd.
When measured with a particle size analyzer, the average particle size is 0.8 μm.
Met. After coating the above coating with a bar coater No. 6 on an aluminum plate which has been subjected to phosphoric acid chromate treatment in advance, 25
It was baked for 20 seconds in a 0 ° C. gas oven (wind speed: 2 m / sec) to obtain an aluminum coating material having a coating film thickness of about 1 μm.

Example 2 "Cataloid AP-3" manufactured by Catalysts & Chemicals Industry Co., Ltd. having an average particle size of 50 to 60 μm in a dry state, a water-soluble acrylic resin and polyethylene glycol (weight average molecular weight of 20,000, according to Synthesis Example 1) Dai-ichi Kogyo Seiyaku Co., Ltd. "PE
G2000 ") was used and otherwise the same as in Example 1 to prepare a hydrophilic coating material.

The particle size of the alumina sol dispersed in this paint was measured with a Microtrac MK-II particle size analyzer manufactured by Nikkiso Co., Ltd., and it was found that the average particle size was 2 μm.

Using this coating composition, an aluminum coating material was obtained in the same manner as in Example 1.

Examples 3 to 6 In the same manner as in Example 1, except that the type and mixing ratio of "Cataloid AS-3" and other alumina sols were changed, the water-soluble acrylic resin according to Synthesis Example 1 was used. A hydrophilic coating material was prepared in the same manner as in 1. to obtain an aluminum coating material.

In Example 3, "Cataloid AS-3" and "Cataloid AS-1" manufactured by Catalyst Kasei Co., Ltd.
2 μm) in a dry weight ratio of 14/6 parts, and in Example 4, “Cataloid AS-3” and “Alumina sol-200” (average particle size 0.2 μm) manufactured by Nissan Chemical Industries, Ltd. in a dry weight ratio of 1 were used.
4 parts / 6 parts, Example 5 was "Cataloid AS-3" and "Alumina sol-200" manufactured by Nissan Chemical Industries, Ltd. in a dry weight ratio of 10 parts / 10 parts, and Example 6 was "Cataloid AS-3".
And Kawaken Fine Chemicals Co., Ltd. "Alumina sol-1"
0 "(average particle size 0.02 μm) in a dry weight ratio of 14 parts /
6 parts were mixed and used.

The average particle size of each alumina sol mixture particle in the paint after being made into a paint is 6 μm, 6 μm, 18 μm and 3 μm, respectively.
It was m.

Examples 7 to 8 Hydrophilic paints were prepared by changing the composition ratios of "Cataloid AS-3" and the water-soluble acrylic resin according to Synthesis Example 1 to obtain aluminum coating agents.

In Example 7, the dry weight of "Cataloid AP-
3 parts, 59 parts of a water-soluble acrylic resin and 40 parts of "PEG6000" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and Example 8 is water-soluble with 50 parts of "Cataloid AP-3" by dry weight. 20 parts of acrylic resin and 3 parts of "PEG6000"
0 parts were mixed, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.

Examples 9 to 11 Example 1 was repeated except that the water-soluble acrylic resins obtained in Synthesis Examples 2 to 4 were used in place of the water-soluble acrylic resin.
A hydrophilic coating material was prepared in the same manner as in 1. to obtain an aluminum coating material.

Example 12 The dry weight of the water-soluble acrylic resin of Synthesis Example 1 was 40%.
20 parts by weight of “Cataloid AP-3” in dry weight were mixed under stirring and dispersed with glass beads in a Red Devil Paint Conditioner for 2 hours. "PEG600
0 "30 parts, hydroxyethyl cellulose (SP-2
50: 10 parts of Daicel Chemical Industries Ltd.) was added and mixed by stirring, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.

Example 13 Instead of PEG6000, a weight average molecular weight of 12-13
A hydrophilic coating material was prepared in the same manner as in Example 1 except that polyethylene-polypropylene glycol (“PAOGEN PP-15” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used to obtain an aluminum coating material.

Example 14 The water-soluble acrylic resin according to Synthesis Example 1 was used in a dry weight of 40.
Parts, "Cataloid AP-3" is 10 parts by dry weight, and talc (Fuji Talc Industry Co., Ltd. "LMS-30" having an average particle size of 10 μm or more and a minimum particle size of 1.3 μm.
0 ") is mixed under stirring with 10 parts by weight of red devil.
Disperse with glass beads in paint conditioner for 2 hours. 40 parts of "PEG6000" was added and mixed by stirring, and then a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.

Example 15 The dry weight of the water-soluble acrylic resin according to Synthesis Example 1 was 40%.
Part, "Cataloid AP-3" is 10 parts by dry weight, aluminum hydroxide which is a flat particle having an average particle size of 10 μm or more and a minimum particle size of 3 μm (Showa Denko KK “Hijilite H”).
-42M ") was mixed with stirring by 10 parts by weight and dispersed with a glass bead in a Red Devil paint conditioner for 2 hours. 40 parts of "PEG6000" was added and mixed by stirring, and then a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.

Example 16 The water-soluble acrylic resin of Synthesis Example 1 was used in a dry weight of 40.
Part, "Cataloid AP-3" in 15 parts by dry weight, bentonite which is a flat particle having an average particle diameter of 10 µm or more and a minimum particle diameter of 0.2 µm ("Bengel S" manufactured by Toyonyo Yoko Co., Ltd.).
H ”) by weight, and mixing 5 parts by weight with red devil.
Disperse with glass beads in paint conditioner for 2 hours. 40 parts of "PEG6000" was added and mixed by stirring, and then a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material.

Comparative Example 1 In the same manner as in Example 1, the water-soluble acrylic resin obtained in Synthesis Example 1 was applied and baked on a phosphoric acid chromate-treated aluminum plate to obtain an aluminum coating material.

Comparative Example 2 70% by dry weight of the water-soluble acrylic resin obtained in Synthesis Example 1
30 parts by weight of "Cataloid AS-3" in dry weight were mixed under stirring, and a hydrophilic coating material was prepared in the same manner as in Example 1 to obtain an aluminum coating material. Comparative Example 3 (simultaneous mixing) A water-soluble acrylic resin having the same composition as in Example 1 was dried and dried.
40 parts by weight and 20 "Cataloid AS-3" by dry weight
Parts and 40 parts of "PEG6000" by stirring and mixing,
A hydrophilic paint was prepared in the same manner as in Example 1
The um coating material was obtained.

The compositions of the hydrophilic paints of Examples 1 to 16 and Comparative Examples 1 to 3 are shown in Table 2.

[0082]

[Table 2]

For each of the obtained aluminum coating materials (hydrophilic coating film), a hydrophilic continuation test, an adhesion test, and
A corrosion resistance test was conducted.

(1) Hydrophilicity sustaining test A coated aluminum plate was immersed in tap water (1 liter / min / min of water flow in a 30 liter plastic container) for 8 hours and then in an electric oven at 80 ° C. for 16 hours. The drying was taken as one cycle, and the water contact angle was measured continuously for up to 14 cycles.

The water contact angle was measured by placing the sample horizontally, dropping 5 μl of pure water on it, and using a contact angle meter (CA-Z: manufactured by Kyowa Interface Science Co., Ltd.). The evaluation is as follows.

[0086] ◎: less than 5 ° ○: 5 ° or more and less than 20 ° △ 20 ° or more and less than 30 ° ×: 30 ° or more

(2) Contamination resistance test After immersing the coated aluminum plate in the press oil "Finstock RF-190" manufactured by Showa Shell Sekiyu KK, 1
Dry at 50 ° C for 5 minutes, and tap water (running rate of 1 liter / min per 30 liter plastic container) for 12 minutes.
It was immersed for 0 hours.

DOP on an aluminum dish with a diameter of 5 cm and a depth of 1 cm.
(Dioctyl phthalate), stearic acid, palmitic acid, stearyl alcohol 4 kinds of pollutants of 3 g each are put, and placed on a hot plate inside the frame with a rectangular steel frame having a height of 10 cm.

The liquid surface of the mixture of pollutants was heated to 200 ° C., and the aluminum-coated plate which had been subjected to the above treatment was left still on the steel frame downward for 1 minute and exposed to the vapor of the pollutants to contaminate it. After that, the water contact angle was measured.

[0090] ◎: less than 5 ° ○: 5 ° or more and less than 20 ° △ 20 ° or more and less than 30 ° ×: 30 ° or more

(3) Adhesion test The coated aluminum plate was wiped with a paper towel moistened with water and evaluated.

[0092] ◎: Cannot be wiped off ◯: The surface layer can be wiped off, but one layer remains on the substrate Δ: About 50% can be wiped off from the substrate.

[0093] ×: Can be wiped off

(4) Corrosion resistance test The coated aluminum plate was subjected to a salt spray test 40 times.
The operation was performed for 0 hours, and the area ratio of the corroded portion was evaluated.

[0095] ◎: 0% or more and less than 1% Good: 1% or more and less than 5% X: 5% or more

(5) After dipping the aluminum plate coated with slipperiness in "Finstock RF-190" manufactured by Showa Shell Sekiyu KK, three points with three 13-inch diameter steel balls as contacts with the coating film The dynamic friction coefficient of the coating film was measured by the supporting method. (Load 1 kg,
Moving speed: 10 mm / min) ◎: 0.1 or less ○: 0.11 or more and 0.2 or less ×: 0.21 or more

The results of tests (1) to (5) are shown in Table 3.

[0098]

[Table 3]

[0099]

According to the present invention, the hydrophilicity, the corrosion resistance, the stain resistance, the adhesion, and the slidability are excellent, the mold and the processing tool are not easily worn, the odor is not easily generated, and the stain resistance is excellent. It has become possible to obtain a non-silica-based or non-aqueous glass-based highly hydrophilic coating capable of forming a coating film.

Front page continuation (51) Int.Cl. ⁷ identification code FI C09D 175/04 C09D 175/04 (72) Inventor Koichi Otomi 85 Hiramatsu, Susono City, Shizuoka Prefecture Mitsubishi Aluminum Co., Ltd. Technology Development Center (72) Inventor Masashi Kato 85 Hiramatsu, Susono, Shizuoka Prefecture, Mitsubishi Aluminum Co., Ltd. Technology Development Center (72) Inventor Ken Katsumata, 85, Hiramatsu, Susono City, Shizuoka Mitsubishi Aluminum Co., Ltd. (56) References JP-A-51-81877 (JP, A) JP-A-57-119974 (JP, A) JP-A-8-104828 (JP, A) JP-A-9-78002 (JP, A) JP-A-9-3397 (JP , A) JP 8-291269 (JP, A) JP 8-313191 (JP, A) JP 7-109436 (JP, A) JP 7-41696 (JP, A) JP 10-72566 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 1/00-201/10 C09K 3/18 C09K 3/00 C08L 33/00-33/26

Claims (5)

(57) [Claims] 1. Alumina sol (a) and a water-soluble acrylic resin
Mixing with fat (b), then polyethylene glycol,
Modified product of polyethylene glycol, ethylene oxide
And propylene oxide copolymer, and ethylene
Modification of Copolymer of Oxide and Propylene Oxide
The weight average molecular weight selected from the group consisting of
500000, and the terminal functional group is a hydroxyl group or glycine.
Selected from zyl group or blocked isocyanate
At least one compound having one or more functional groups
Highly hydrophilic coating characterized by adding (c) and mixing
Manufacturing method. 2. In the alumina sol (a),
Secondary particles have feather-like, rod-like or dendritic shape / morphology
And its average particle size is 0.5 to 20 μm.
The method for producing a highly hydrophilic paint according to claim 1. 3. The solid content of the highly hydrophilic coating is 100% by weight.
Containing 30 to 60% by weight of the compound (c)
The highly hydrophilic paint according to claim 1 or 2,
Build method. 4. The water-soluble acrylic resin (b) is a
Α, β-containing phosphonic acid or sodium sulfonate groups
1 to 80% by weight of a saturated monomer (A) and a carboxylic acid group
5 to 50% by weight of α, β unsaturated monomer (B)
The α, β unsaturated monomer (C) having a colloidal hydroxyl group is added to 5
To 50% by weight (provided that (A),
(The total of (B) and (C) is 100% by weight)
The production of the highly hydrophilic paint according to any one of claims 1 to 3.
Method. 5. The polyethylene glycol or ethylene
Of the copolymer of ren oxide and propylene oxide
2. The melting point is 50 ° C. or higher.
The method for producing the highly hydrophilic paint according to any one of item 4.