JP6064088B1 - Water-based surface treatment agent, film production method and surface treatment material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous surface treatment agent capable of forming a film excellent in molding processability and hydrophilic sustainability without irradiating energy rays, a method for producing a film using the aqueous surface treatment agent, and To provide a surface treatment material having a film formed by the method for producing a film. SOLUTION: Hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (except polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil) ( The above-described problems can be solved by using an aqueous surface treating agent containing C). [Selection figure] None

Description

  The present invention is formed by an aqueous surface treatment agent capable of forming a film excellent in moldability and hydrophilic sustainability, a method for producing a film using the aqueous surface treatment agent, and a method for producing the film. The present invention relates to a surface treatment material having a film.

  Various techniques have been proposed in the past for imparting various properties such as hydrophilicity to the fin material used in the heat exchanger of an air conditioner. For example, Patent Document 1 discloses a water-soluble and / or water-dispersible polymer compound (A), a water-soluble and / or water-dispersible polymer compound or oligomer (B) having energy beam curability, and energy beam curability. A technology relating to an energy ray-curable hydrophilic surface treating agent containing a hydrophilic monomer (C) having a hydrogen atom has been proposed. According to this technique, a film excellent in molding processability and hydrophilic sustainability can be formed by energy beam irradiation.

JP 2004-339345 A

  The present invention provides an aqueous surface treatment agent capable of forming a film excellent in molding processability and hydrophilic sustainability without irradiation with energy rays, a method for producing a film using the aqueous surface treatment agent, and It aims at providing the surface treatment material which has a membrane | film | coat formed by the manufacturing method of this membrane | film | coat.

  As a result of intensive studies to solve the above problems, the present inventors have found that a hydrophilic film-forming component, polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil The water-based surface treatment agent containing a nonionic surfactant was found to be able to form a film excellent in molding processability and hydrophilic sustainability without irradiating energy rays, and completed the present invention. .

That is, the present invention
(1) Hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (except polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil) (C Water-based surface treatment agent containing
(2) The aqueous surface treating agent according to the above (1), wherein the hydrophilic film forming component (A) contains at least one water-soluble organic polymer;
(3) The aqueous surface treating agent according to (2), wherein the hydrophilic film-forming component (A) further contains a crosslinking agent;
(4) A method for producing a film on the surface of an aluminum material or an aluminum alloy material or a plating material thereof, and bringing the aqueous surface treating agent according to any one of (1) to (3) into contact with the surface A method for producing a film, comprising a step and a step of drying the surface in contact with the aqueous surface treatment agent;
(5) A surface treatment material having a film formed by the method for producing a film according to (4) above;
Etc.

  According to the present invention, an aqueous surface treatment agent capable of forming a film excellent in moldability and hydrophilic sustainability without irradiation with energy rays, a method for producing a film using the aqueous surface treatment agent, And the surface treatment material which has a membrane | film | coat formed by the manufacturing method of this membrane | film | coat can be provided.

[Aqueous surface treatment agent]
The aqueous surface treatment agent according to the present invention comprises a hydrophilic film-forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), nonionic interface other than polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil. And an active agent (C). By including these components, the aqueous surface treating agent according to the present invention is excellent in liquid stability and can be stored for a long period (at least 3 months). In addition, even if an aqueous surface treatment agent immediately after preparation is used or an aqueous surface treatment agent stored for a certain period (for example, 3 months) is used, a film excellent in molding processability and hydrophilic sustainability is similarly formed on a metal substrate. Can be formed. Therefore, the aqueous surface treatment agent according to the present invention is useful as an aqueous metal surface treatment agent.

  The aqueous surface treatment agent can be prepared, for example, by adding the above components (A) to (C) one by one or simultaneously while stirring the solvent (liquid medium).

  As a solvent (liquid medium) used for the water-based surface treatment agent, water is a main component (for example, water is 70% by mass or more based on the mass of the total solvent). In order to improve the state, water-soluble alcohols such as methanol and ethanol, water-soluble ketones such as acetone, and water-soluble solvents such as cellosolve such as methyl cellosolve and ethyl cellosolve are within the scope of the present invention and do not impair the film performance And may be used in any proportion.

  The hydrophilic film forming component (A) is not particularly limited as long as it can form a hydrophilic film, and examples thereof include known water-soluble organic polymers or hydrophilic film forming compositions.

  The water-soluble organic polymer is not particularly limited as long as 1 g or more can be dissolved in 100 g of water at 20 ° C., for example, a (meth) acrylic acid polymer or copolymer, polyvinyl alcohol, or modified Examples include polyvinyl alcohol, a polymer or copolymer of a cellulose derivative, and the like. These may be used alone or in combination of two or more. When the water-soluble organic polymer is a non-self-curing type, it is preferable to use a combination of crosslinking agents. In addition, even if a water-soluble organic polymer is a self-hardening type, you may use it combining a crosslinking agent. The water-soluble organic polymer preferably has a weight average molecular weight of 1000 or more. The weight average molecular weight is a value measured by GPC.

  Examples of the hydrophilic film-forming composition include, but are not limited to, a mixture of two or more water-soluble organic polymers described above, a mixture of one or more water-soluble organic polymers and a crosslinking agent described above, and the like. In order to improve hydrophilicity, for example, organoalkoxysilicates such as silicate compounds such as alkali silicates, colloidal silica, and colloidal silica having an organic functional group (for example, glycidyl group, vinyl group, amino group, etc.) An inorganic compound modified with silane may be blended in the mixture.

  Examples of (meth) acrylic acid polymers include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamidoethylsulfone. Acid, vinyl sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , Monomers such as 2-methoxyethyl acrylate and acrylamide, or a polymer of a salt thereof can be used. Moreover, as a (meth) acrylic-acid type copolymer, the copolymer which combined the said monomer or its salt suitably can be mentioned, for example.

  Examples of polyvinyl alcohol include polyvinyl alcohol having a saponification degree of 70 mol% or more, preferably 90 mol% to 100 mol%. The degree of saponification is a value measured according to JIS K6726.

  Examples of the modified polyvinyl alcohol include an anion-modified PVA having a carboxyl group, a sulfone group, a phosphono group, a cation-modified PVA having an amino group, and an acetoacetyl group-modified PVA having an acetoacetyl group.

  Examples of the cellulose derivative include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and the like.

  Examples of the water-soluble organic polymer include, in addition to those described above, a polymer or copolymer of polyvinylpyrrolidone, polyacrylamide, polyamide, polyethylene glycol, chitosan derivative, and the like.

  The cross-linking agent is a component different from the water-soluble organic polymer and is not particularly limited as long as it is used for forming a hydrophilic film. A salt, glyoxal, isocyanate, block isocyanate, carbodiimide, etc. can be mentioned. The molecular weight of the crosslinking agent is preferably less than 1000.

  Examples of the polyvalent carboxylic acid include isophthalic acid, adipic acid, pyromellitic acid, maleic acid, itaconic acid, fumaric acid, 1,2,4-trimellitic acid, 1,2,3,4-butanetetracarboxylic acid. , 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and other compounds having two or more carboxyl groups Can be mentioned. These may be used alone or in combination. Examples of the polyvalent carboxylic acid salt include salts of sodium, potassium, lithium, ammonium and the like.

  As a compounding quantity of a crosslinking agent (a1), it is the quantity from which the solid content mass ratio (a1 / a2) of a crosslinking agent (a1) and a water-soluble organic polymer (a2) becomes the range of 0.01-0.7. It is preferable. By adjusting the solid content mass ratio (a1 / a2) within this range, the hydrophilic durability and molding processability of the formed film can be further improved.

  The polyoxyethylene castor oil or the polyoxyethylene hydrogenated castor oil (B) is not particularly limited as long as it is obtained by polymerizing and adding ethylene oxide to castor oil, or by polymerizing and adding ethylene oxide to hydrogenated castor oil. Although not used, it is preferable to use one having an HLB (depending on the Griffin method) of 2.5 to 13. By blending polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil whose HLB is within the above numerical range with an aqueous surface treatment agent, molding is performed while maintaining the hydrophilicity of the film formed by the hydrophilic film forming component (A). Workability can be further improved. In the present specification, “castor oil” is a non-drying oil extracted from castor bean seeds, and is mainly composed of triglyceride of ricinoleic acid.

  The blending amount of the polyoxyethylene castor oil or the polyoxyethylene hydrogenated castor oil (B) is 1% by mass to 15% by mass in terms of the mass in terms of solid content with respect to the total mass of the solid content in the aqueous surface treatment agent. preferable. By adjusting the blending amount within this range, it is possible to obtain a film with improved moldability while maintaining the hydrophilicity of the film formed by the hydrophilic film forming component (A).

The nonionic surfactant (C) is not particularly limited as long as it is other than polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, but polyalkylene oxide chain [specifically, polyoxyethylene chain {( CH ₂ CH ₂ O) _m }, polyoxypropylene {(CH ₂ CH (CH ₃ ) O) _n } and polyoxyethylene {(CH ₂ CH ₂ O) _i }, etc.], and an alkyl group ( It is preferably selected from polyoxyalkylene alkyl ethers composed of an ether bond with C _n H _{2n + 1} ), particularly polyoxyethylene alkyl ethers. Examples of polyoxyalkylene alkyl ethers include polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene lauryl ether, and the like. Examples of polyoxyethylene alkyl ethers include polyoxyethylene isopropyl ether. Examples include decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, and polyoxyethylene tridecyl ether. These may be used alone or in combination of two or more.

  The total solid mass of the polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B) and the nonionic surfactant (C) to be added to the aqueous surface treatment agent is based on the total mass of the solid content in the aqueous surface treatment agent. Thus, it is preferable to adjust the amount so as not to exceed 25% by mass and to blend such that the total HLB is 13 or more. As described above, the storage stability of the water-based surface treatment agent is further improved by adjusting the total solid mass of the component (B) and the component (C) and the total HLB of these components within a predetermined numerical range. Or the hydrophilicity of the film formed by the hydrophilic film forming component (A) can be maintained.

Here, the total HLB of the component (B) and the component (C) is calculated as a weighted average of each HLB. For example, the HLB of the component (B) is 12.5, the ratio of the solid content converted mass of the component (B) to the total solid mass of the component (B) and the component (C) is 42 mass%, the HLB of the component (C) 16.8, and the total HLB when the ratio of the solid content converted mass of the component (C) to the total solid mass of the components (B) and (C) is 58% by mass is as follows.
(12.5 × 0.42) + (16.8 × 0.58) = 15.0

  In the above, in addition to the solvent, the hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (however, polyoxyethylene castor oil and polyoxyethylene are used). (Excluding hardened castor oil) The water-based surface treatment agent containing only (C) has been described. To impart various performances to the film formed by the water-based surface treatment agent, antioxidants, antifoaming agents, and leveling agents are used. An agent, a rust inhibitor, an antibacterial agent, an antifungal agent, an antibacterial antifungal agent, a colorant, and the like may be further blended at an arbitrary ratio as long as the gist of the present invention and the film performance are not impaired.

[Film Production Method and Surface Treatment Material]
The surface treatment material according to the present invention can be obtained by producing a film on the surface of a metal substrate such as a heat exchanger fin material using the aqueous surface treatment agent.

  The method for producing the film is particularly limited as long as it includes a step of bringing the aqueous surface treatment agent into contact with the surface of the metal substrate and a step of drying the metal substrate surface in contact with the aqueous surface treatment agent. However, before the aqueous surface treatment agent is brought into contact with the surface of the metal substrate, a step of performing a degreasing treatment, a step of forming a corrosion-resistant film, and the like may be included.

  Examples of the method for bringing the aqueous surface treatment agent into contact include methods such as roll coater treatment, spray treatment, airless spray treatment, roller coating, brush coating, bar coater treatment, shower squeezing, and immersion treatment.

  The metal substrate surface can be dried by, for example, a convection type using hot air or a radiation type oven using an electric heating tube. As a drying temperature, it is preferable that the highest temperature reached by the metal substrate is 150 ° C to 250 ° C.

The adhesion amount of the film produced as described above is in the range of 0.05 g / m ^{2 to 20} g / m ² from the viewpoint of the uniformity of the film on the surface of the metal substrate, and workability and productivity. it is ^preferable, more preferably in the range of ^{0.2g / m 2 ~10g / m 2} .

  As a metal base material, an aluminum material, an aluminum alloy material, or those plating materials can be mentioned, for example. Examples of the aluminum material include a 1000 series pure aluminum material defined in JIS H4000, and examples of the aluminum alloy material include a 3000 series or 8000 series aluminum alloy material, but are not limited thereto. Is not to be done. Examples of the type of plating material of aluminum material or aluminum alloy material include, for example, a hot-dip aluminum-plated steel sheet specified in JIS G3314, a molten 55% aluminum-zinc alloy-plated steel sheet specified in JIS G3321, It is not limited to these.

  As the degreasing treatment on the surface of the metal substrate, there is no repellency, so long as the oil on the surface of the metal substrate can be removed to such an extent that the aqueous surface treatment agent and the surface treatment agent for forming a corrosion-resistant film can be applied. Any method may be applied. For example, a known degreasing treatment method using an alkaline or acid degreasing agent may be applied.

  Examples of the method of forming the corrosion-resistant film include a chemical conversion treatment method such as a coating type chromate treatment, a phosphoric acid chromate treatment, a zirconium chemical conversion treatment, a titanium chemical conversion treatment, or a surface containing an acrylic resin, a urethane resin, an epoxy resin, or the like. A known method such as a method of applying a treatment agent can be used, but it is not limited to these methods.

  As described above, by forming a film on the surface of a metal substrate using the aqueous surface treatment agent according to the present invention, a surface treatment material having both hydrophilic sustainability and molding processability can be obtained. In addition, the method for producing a film according to the present invention can produce a surface treatment material excellent in hydrophilic sustainability and molding processability without forming a lubricating film on the upper layer of the hydrophilic film. The fin material can be manufactured efficiently.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. These examples are described for the purpose of illustrating the present invention and are not intended to limit the present invention in any way.

[Preparation of test plate]
(1) Test material By spraying an alkali degreasing agent (2% aqueous solution of Fine Cleaner FC-4477: manufactured by Nihon Parkerizing Co., Ltd.) for 15 seconds at 60 ° C. on an aluminum material of JIS A1050 and plate thickness 0.26 mm. Degreasing was performed. Then, it washed with water, drained, and what dried the surface was used as a test material.

(2) Preparation of aqueous surface treatment agent Table 1 shows the composition of each aqueous surface treatment agent used for preparing test plates of Examples 1 to 19 and Comparative Examples 1 to 3 described later. The compounding amount of each component in Table 1 indicates a mass ratio (%) to the total solid mass of the aqueous surface treatment agent. In addition, each symbol shown in the type column in Table 1 means the substance shown in Table 2. In addition, all the solid content in an aqueous surface treating agent was 10 mass%. The aqueous surface treatment agent was prepared by sequentially adding each component while stirring water as a solvent.

(3) Formation of film An acrylic corrosion-resistant paint containing acrylic resin and ammonium zirconium carbonate was applied to the surface of the test material with a bar coater # 5 and dried in a hot air circulation drying furnace to form a corrosion-resistant film. Subsequently, each aqueous surface treatment agent was applied on the corrosion-resistant film with a bar coater # 5, and dried in a hot air circulation type drying furnace to form a hydrophilic film. Examples 1 to 19 and Comparative Examples 1 to 3 A test plate was prepared. The following performance evaluation was performed using these test plates.

[Performance evaluation]
(1) Hydrophilicity 10 μL of pure water is dropped on the surfaces of the test plates of Examples 1 to 19 and Comparative Examples 1 to 3, and the contact angle of the water drops is an automatic contact angle meter “DM-501” manufactured by Kyowa Interface Science Co., Ltd. Then, the hydrophilicity was evaluated based on the following evaluation criteria. In this evaluation, each test plate immediately after the formation of the hydrophilic film (initial hydrophilicity) and “treatment of dipping in 0.5 L / min of flowing water for 8 hours and then drying at 80 ° C. for 16 hours” are defined as 5 cycles. The test was repeated for each test plate (hydrophilic after cycle).
<Evaluation criteria>
◎ ・ ・ ・ Contact angle less than 10 ° ○ ・ ・ ・ 10 ° or more and less than 30 ° △ ・ ・ ・ 30 ° or more and less than 40 ° × ... 40 ° or more

(2) Molding processability The following evaluation was carried out in order to evaluate molding processability.

[Evaluation 1]
The dynamic friction coefficient of each test plate surface was measured using a surface property measuring instrument “HEYDON TYPE: 14FW” manufactured by Shinto Kagaku Co., Ltd., and the lubricity was evaluated based on the following evaluation criteria.
<Test conditions>
Load: 200 g, steel ball: 3 mmφ, stroke: 10 mm, sliding speed: 10 mm / sec, number of sliding times: 30 reciprocations <Evaluation criteria>
◎ ・ ・ ・ Friction coefficient less than 0.2 ○ ・ ・ ・ 0.2 or more and less than 0.3 Δ ・ ・ ・ 0.3 or more and less than 0.5 × ・ ・ ・ 0.5 or more

[Evaluation 2]
Surface stickiness, which is a problem in handling the test plate (including processing), was evaluated based on the following evaluation criteria. Specifically, a finger was lightly pressed against the surface of each test plate placed horizontally, and the determination was made based on the feeling when the finger was moved in the horizontal direction.
<Evaluation criteria>
○ ・ ・ ・ You can move your finger smoothly without feeling sticky.
Δ: Feels a little sticky immediately after touching the finger, but moves the finger almost without resistance.
X: The finger is sticky and the finger is difficult to move.

(3) Storage stability Each water type surface treating agent used in order to produce the test plates of Examples 1 to 19 and Comparative Examples 1 to 3 was sealed in a plastic container and allowed to stand at 25 ° C. for 3 months. The state was observed and storage stability was evaluated based on the following evaluation criteria.
<Evaluation criteria>
○: No aggregation or precipitation is observed.
X: Aggregation or precipitation was observed.

  As shown in Table 3, the examples of the present invention (Examples 1 to 19) are superior to the comparative examples (Comparative Examples 1 to 3) in terms of storage stability, and even if stored for a certain period of time, they are almost the same as immediately after preparation. A film excellent in molding processability and hydrophilic sustainability can be formed.

Claims (5)

  Hydrophilic film forming component (A), polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil (B), and nonionic surfactant (excluding polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil) (C) Contains an aqueous surface treatment.   The aqueous surface treating agent according to claim 1, wherein the hydrophilic film forming component (A) contains at least one water-soluble organic polymer.   The aqueous surface treatment agent according to claim 2, wherein the hydrophilic film forming component (A) further comprises a crosslinking agent. A method for producing a film on the surface of an aluminum material or an aluminum alloy material or a plating material thereof,
The manufacturing method of the membrane | film | coat including the process of making the surface contacted with the aqueous surface treating agent as described in any one of Claims 1-3, and the process of making the said surface contacted with the aqueous surface treating agent.   The surface treatment material which has a membrane | film | coat formed by the manufacturing method of the membrane | film | coat of Claim 4.