WO2016021071A1 - アルミニウム含有金属材料用親水化処理剤 - Google Patents
アルミニウム含有金属材料用親水化処理剤 Download PDFInfo
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- WO2016021071A1 WO2016021071A1 PCT/JP2014/071103 JP2014071103W WO2016021071A1 WO 2016021071 A1 WO2016021071 A1 WO 2016021071A1 JP 2014071103 W JP2014071103 W JP 2014071103W WO 2016021071 A1 WO2016021071 A1 WO 2016021071A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/642—Aluminium treated with inorganic compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/644—Aluminium treated with organic compounds, e.g. polymers
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
Definitions
- the present invention relates to a hydrophilic treatment agent for an aluminum-containing metal material, a hydrophilic treatment method for an aluminum-containing metal material, a method for producing a hydrophilized aluminum-containing metal material, and the like. More specifically, the present invention relates to a hydrophilizing agent for forming a film capable of imparting and sustaining excellent hydrophilicity to an aluminum-containing metal material used in a heat exchanger or the like.
- heat exchangers used in air conditioners and air conditioners for automobiles are often formed of aluminum-containing metal materials because of their superior workability and thermal conductivity.
- the spacing between aluminum-containing metal materials (commonly called fins) is designed to be very narrow.
- the air conditioner when the air conditioner is operated (cooled), moisture in the atmosphere condenses on the fins, resulting in condensation, and the condensed water becomes bulky water droplets as the hydrophobicity of the fin surface increases. Clogging is likely to occur. When clogging occurs, ventilation resistance increases, heat exchange efficiency decreases, and the original performance of the heat exchanger cannot be obtained. Moreover, the noise at the time of ventilation may increase by clogging.
- Patent Document 1 Patent Document 2
- Patent Document 3 Patent Document 1
- a hydrophilic treatment agent containing an inorganic substance as a main component (hereinafter referred to as an inorganic hydrophilic treatment agent) (see Patent Document 1, Patent Document 2, and Patent Document 3), polyvinyl.
- a hydrophilization treatment agent (hereinafter, referred to as an organic hydrophilization treatment agent) mainly composed of a resin such as alcohol, polyvinylpyrrolidone, or polyacrylic acid, or an organic substance (hereinafter referred to as an organic hydrophilization treatment agent) has been proposed and implemented (Patent Document 4, Patent Document 5) , Patent Literature 6, Patent Literature 7, and Patent Literature 8).
- aluminum-containing metal materials and heat exchangers imparted with hydrophilicity using an inorganic hydrophilic treatment agent can maintain high hydrophilicity for a long period of time and have excellent durability.
- a film odor peculiar to inorganic substances There is a problem with odor such as dusty odor.
- an organic hydrophilic treatment agent when used, the problem of dust odor is reduced, but the organic substance, which is a hydrophilic component, tends to flow out, making it difficult to maintain high hydrophilicity for a long period of time, making it durable. There's a problem.
- the present invention solves the above-mentioned problems of the prior art, and its purpose is to impart excellent hydrophilicity, hydrophilicity sustainability and odor to aluminum-containing metal materials used in heat exchangers and the like.
- An object of the present invention is to provide a hydrophilic treatment agent for an aluminum-containing metal material for forming a film.
- Another object of the present invention is to provide a method for hydrophilizing an aluminum-containing metal material, a method for producing a hydrophilized aluminum-containing metal material, and a heat exchange using the hydrophilized aluminum-containing metal material or the material. Is to provide a vessel.
- This invention (1) is chosen from 1 or more types chosen from water-soluble resin (A) which has a hydroxyl group, 1 or more types chosen from a water poorly soluble inorganic oxide (B), and organoalkoxysilane (C).
- One or more surfactants (D) and (C) / ⁇ (B) + (D) ⁇ are 0.001 to 1.0 and (A) / ⁇ (B ) + (C) + (D) ⁇ is obtained by blending so that 0.1 to 5.0, and water, and the organic-inorganic composite particles have a total solid mass.
- Is a hydrophilization treatment agent for an aluminum-containing metal material characterized by being 40 to 100% by mass based on A film formed by contacting and drying the hydrophilizing agent on an aluminum-containing metal material has improved odor problems such as dust odor and can maintain excellent hydrophilicity.
- this film is applied to, for example, an aluminum-containing metal material or a heat exchanger constituting a heat exchanger or the like, problems such as a decrease in heat exchange efficiency due to clogging of condensed water and noise can be solved.
- the water-soluble resin (A) having the hydroxyl group may be polyvinyl alcohol and / or a derivative of polyvinyl alcohol, and the component (a) having a saponification degree of 90 mol% or more.
- the surface tension of the surfactant (D) may be 15 to 65 mN / m (25 ° C., 0.1% by mass aqueous solution, Wilhelmy method).
- the surfactant (D) may be a nonionic surfactant.
- the blending ratio of (D) / ⁇ (A) + (B) + (C) + (D) ⁇ may be 0.0001 to 0.03 in each solid content weight ratio.
- 0.01 to 1.0 may be sufficient as the compounding ratio of (C) / ⁇ (B) + (D) ⁇ in each solid content weight ratio.
- the water-soluble resin (A) having a hydroxyl group may have a weight average molecular weight of 5,000 to 50,000.
- the organoalkoxysilane (C) may contain at least a component having one or more glycidyl groups. Further, the hardly water-soluble inorganic oxide (B) may be an inorganic oxide having Si.
- the present invention (2) is a method for hydrophilizing an aluminum-containing metal material, comprising the step of bringing the hydrophilizing agent into contact with the aluminum-containing metal material and then drying it. More specifically, in the present hydrophilization treatment method, the aluminum-containing metal material is not treated, or after cleaning and / or rust prevention treatment, the aluminum-containing metal material is partially or entirely applied to the present invention. After making the hydrophilic treatment agent for aluminum containing metal materials which concerns contact, it includes the process of drying and forming a membrane
- This invention (3) is a manufacturing method of the hydrophilized aluminum containing metal material characterized by including the process of making it dry after making the said hydrophilization treatment agent contact an aluminum containing metal material.
- This invention (4) is the hydrophilized aluminum containing metal material obtained by the said manufacturing method. More specifically, the present aluminum-containing metal material is characterized in that a hydrophilic film obtained from the hydrophilic treatment agent for an aluminum-containing metal material according to the present invention is formed on a part or the entire surface thereof. .
- the present invention (5) is a heat exchanger in which the hydrophilic aluminum-containing metal material is used.
- the present heat exchanger is characterized in that a hydrophilic film obtained from the hydrophilic treatment agent for an aluminum-containing metal material according to the present invention is formed on a part or the entire surface thereof.
- the present invention (6) is a method for hydrophilizing a heat exchanger characterized by comprising the step of drying the hydrophilizing agent after contacting the heat exchanger (that is, a completed heat exchanger). Dipping method).
- the present invention (7) is a method for producing a hydrophilized heat exchanger comprising the step of drying the hydrophilizing agent after bringing it into contact with the heat exchanger (that is, a completed heat exchanger) A method for producing a hydrophilized heat exchanger by dipping.
- the present invention (8) is a hydrophilized heat exchanger obtained by the production method.
- the film formed by contacting and drying the hydrophilizing agent for an aluminum-containing metal material of the present invention on an aluminum-containing metal material has excellent hydrophilicity and odor. Therefore, if this hydrophilization treatment is applied to, for example, an aluminum-containing metal material or a heat exchanger that constitutes a heat exchanger or the like, excellent hydrophilicity that solves the problem of noise reduction due to clogging of condensed water and heat exchange efficiency Can be given. Furthermore, the hydrophilic film formed by the hydrophilic treatment method of the present invention can maintain excellent hydrophilicity and odor even during long-term use.
- the aluminum-containing metal material of the present invention is applied to a heat exchanger because a hydrophilic film having excellent hydrophilicity that solves problems such as reduction in heat exchange efficiency due to clogging of condensed water and noise is formed.
- the practical value of the case is extremely high, and it is not only highly adaptable to heat exchangers, but can also be applied to a wide range of other uses.
- hydrophilization treatment agent the hydrophilization treatment method, the hydrophilization treated aluminum-containing metal material and the heat exchanger of the present invention will be described in more detail with reference to embodiments. It should be noted that “from” indicating a numerical range in the present specification and claims includes an upper limit value and a lower limit value unless otherwise specified. For example, the range “X to Y” means X or more and Y or less unless otherwise specified.
- hydrophilic treatment agent for an aluminum-containing metal material of the present invention
- hydrophilic treatment agent includes at least one selected from water-soluble resins (A) having a hydroxyl group, and a poorly water-soluble inorganic oxide.
- One or more types selected from (B), one or more types selected from organoalkoxysilane (C), and surfactant (D) are each in a weight ratio of (C) / ⁇ (B) + (D) ⁇ is an organic-inorganic obtained by blending so that 0.001 to 1.0 and (A) / ⁇ (B) + (C) + (D) ⁇ are 0.1 to 5.0 It contains at least composite particles and water, and contains 40 to 100% by mass of the organic-inorganic composite particles based on the total solid mass.
- each component of the hydrophilic treatment agent will be described in detail.
- the organic-inorganic composite particles contained in the hydrophilic treatment agent are at least one selected from water-soluble resins (A) having a hydroxyl group, one or more selected from poorly water-soluble inorganic oxides (B), organo One or more selected from the alkoxysilane (C) and the surfactant (D) have a weight ratio of (C) / ⁇ (B) + (D) ⁇ of 0.001 to 1.0. And (A) / ⁇ (B) + (C) + (D) ⁇ is a component obtained by blending so that the ratio is 0.1 to 5.0.
- the essential raw materials (A) to (D) will be described first, and then the mixing ratio of the essential raw materials and the method for producing the organic-inorganic composite particles will be described.
- the water-soluble resin (A) having a hydroxyl group is not particularly limited as long as it has a hydroxyl group in terms of dehydration condensation with an organoalkoxysilane, and examples thereof include polyvinyl alcohol and polyvinyl alcohol. Derivatives, polyethylene glycol and polyethylene glycol derivatives, cellulose and cellulose derivatives, chitosan and chitosan derivatives, and the like.
- a water-soluble resin having a high hydroxyl group density is preferred in terms of maintaining hydrophilicity and odor for a long period of time, and it is at least one selected from polyvinyl alcohol and / or a derivative of polyvinyl alcohol, and has a saponification degree. It is preferable that it is 90 mol% or more.
- water-soluble means a polymer substance having a solubility of 0.1% by mass or more with respect to water at room temperature of 20 ° C., and the solubility is preferably 0.5% by mass or more, particularly 1% by mass. % Or more is more preferable.
- the weight average molecular weight of the water-soluble resin (A) having a hydroxyl group is not particularly limited as long as the surface of the poorly water-soluble inorganic oxide can be coated, but the weight average molecular weight is 5,000 to 100 in terms of sufficient coating. 5,000 is preferable, and 5,000 to 50.000 is more preferable. In particular, the weight average molecular weight is more preferably 30,000 or less (the lower limit is not particularly limited, but is, for example, 5,000).
- the weight average molecular weight is 30,
- the lower limit is not particularly limited, but is, for example, 5,000.
- the weight average molecular weight here refers to a weight average molecular weight obtained by a measuring method such as GPC method or viscosity method.
- the weight average molecular weight of the water-soluble resin in the present invention was measured by GPC-LALLS method. The measurement was performed under the following conditions.
- GPC Apparatus Waters type 244 gel permeation chromatography column: Tosoh TSK (inner diameter 8 mm, length 30 cm, 2 pieces) Solvent: 0.1 M Tris buffer (pH 7.9) Flow rate: 0.5 ml / min Temperature: 23 ° C Sample concentration: 0.04% Filtration: 0.45 ⁇ m Mysori disk W-25-5 made by Tosoh Injection volume: 0.2ml 2) LALLS Apparatus: Chromatrix KMX-6 type low angle laser light scattering photometer Temperature: 23 ° C Wavelength: 633nm Second virial coefficient ⁇ concentration: 0 mol / g Refractive index density change (dn / dc): 0.159 / g Filter: MILIPORE 0.45 ⁇ m filter HAWPO1300 Gain: 800mV
- the water-insoluble inorganic oxide is not particularly limited as long as it is a water-insoluble inorganic oxide.
- zinc oxide, cerium (IV) oxide, titanium oxide (IV), tin oxide (II), oxidation Zirconium (IV), silicon oxide (IV), aluminum oxide (III), cobalt oxide (II), nickel oxide (II), ruthenium oxide (IV), palladium oxide (II), vanadium oxide (V), lithium oxide, Niobium oxide (V), zinc oxide (II), silicon oxide (IV) aluminum oxide (III) composite oxide, titanium oxide (IV) aluminum oxide (III) composite oxide, iron (III) oxide, magnesium oxide (II) ) Etc. can be used.
- organoalkoxysilane and water-soluble resin having a hydroxyl group are complexed on the surface of a poorly water-soluble inorganic oxide, and Ce, Ti, Sn, Zr, It is preferably at least one selected from inorganic oxides having at least one element selected from Si, Al, and Zn, and more preferably at least one selected from inorganic oxides having Si.
- the “poorly water-soluble” means that the solubility in water at 20 ° C. is 1% by mass or less.
- the mode of the poorly water-soluble inorganic oxide is not particularly limited, and can be used in any state such as a solid powder state or a sol state dispersed in a solvent.
- the particle diameter of the poorly water-soluble inorganic oxide is not particularly limited as long as organoalkoxysilane and a water-soluble resin having a hydroxyl group are combined on the surface of the poorly water-soluble inorganic oxide.
- the composite particles are preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, in that the composite particles are stably dispersed in an aqueous solvent to obtain superior hydrophilicity. As the particle diameter of the poorly water-soluble inorganic oxide is larger, precipitation may occur during long-term storage.
- the “particle diameter” in the present invention refers to a cumulative average system (Median diameter) measured by a dynamic light scattering method regardless of primary particles and secondary particles.
- An example of a measuring instrument based on the dynamic light scattering method is UPA-EX150 manufactured by Nikkiso Co., Ltd.
- the dynamic scattering method uses the fact that the speed of movement (Brownian motion) differs depending on the size of particles in the solution.
- the solution is irradiated with laser light, the scattered light is observed with a photon detector, and frequency analysis is performed. Thus, a particle size distribution can be obtained.
- the particle size in the present invention was measured under the following conditions. (Particle size measurement conditions) Measuring device: UPA-EX150 manufactured by Nikkiso Co., Ltd.
- Light source Semiconductor laser 780nm, 3mW
- Light source probe Preparation of internal probe type measurement sample: After dilution with deionized water so that the solid content concentration of the poorly water-soluble inorganic oxide (B) was about 0.01%, the mixture was well stirred and dispersed. Measurement time: 180 seconds Circulation: None Transmittance: Transmission shape: Aspherical refractive index: 1.81 (default setting of the device) Solvent: Water Solvent Refractive Index: 1.333
- organoalkoxysilane is not particularly limited as long as it is dehydrated and condensed with a poorly water-soluble inorganic oxide and a water-soluble resin having a hydroxyl group.
- a silane coupling agent can be used.
- it is preferably at least one selected from alkoxysilanes having one or more glycidyl groups, from the viewpoint of excellent compounding of a poorly water-soluble inorganic oxide and a water-soluble resin having a hydroxyl group.
- the surfactant (D) suppresses agglomeration when the water poorly water-soluble inorganic oxide, the organoalkoxysilane, and the water-soluble resin having a hydroxyl group are mixed to form a composite, and improves the stability of the obtained particles. If it does not inhibit, it will not specifically limit, For example, a nonionic surfactant, anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used.
- Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene Derivatives, oxyethylene / oxypropylene block copolymers, sorbitan monolaurate, sorbitan monostearate, sorbitan fatty acid esters such as sorbitan trioleate, glycerin fatty acid esters, polyoxyethylene fatty acid esters, fluorine-based compounds, and the like.
- Anionic surfactants include fatty acid salts such as sodium stearate and potassium oleate, alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, Examples thereof include alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate ester salt, fluorine series, and silicone series.
- fatty acid salts such as sodium stearate and potassium oleate
- alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate and ammonium lauryl sulfate
- alkylbenzene sulfonate alkyl naphthalene sulfonate
- cationic surfactants include alkylamine salts such as stearylamine acetate and stearylamine hydrochloride, quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and distearyldimethylammonium, laurylbetaine, stearylbetaine, and the like. Alkylbetaines, amine oxides, fluorine-based, silicone-based and the like.
- amphoteric surfactants examples include imidazoline type amphoteric surfactants, imidazoline type amphoteric surfactants, glycine type amphoteric surfactants, and amine oxide type amphoteric surfactants.
- the surface tension of the surfactant (D) (25 ° C., 0.1 mass% aqueous solution, wilhelmy method) is obtained by mixing the poorly water-soluble inorganic oxide, the organoalkoxysilane, and the water-soluble resin having a hydroxyl group. It is not particularly limited as long as it does not inhibit aggregation at the time of complexing and inhibit the stability of the obtained particles, but it suppresses aggregation at the time of complexing and the resulting film is hydrophilic over a long period of time.
- the surface tension of the surfactant (D) is preferably 15 to 65 mN / m, more preferably 15 to 55 mN / m, and more preferably 15 to 45 mN / m. More preferably it is.
- the surface tension is lower than 15 mN / m, the retention of the composite particles in the resulting film may be lowered, and the hydrophilicity may be lowered after the durability test.
- the surface tension is higher than 65 mN / m, the aggregation suppression at the time of compounding may be insufficient, and the odor of the resulting film may be lowered.
- the surfactant (D) suppresses aggregation when the water-insoluble inorganic oxide, the organoalkoxysilane, and the water-soluble resin having a hydroxyl group are mixed to form a composite, and the odor property is further improved. It is preferable that it is 1 or more types chosen from a nonionic surfactant in the point which raises.
- the surface tension in the present invention is one of the characteristics of a surfactant and refers to a value measured by the wihelmy method.
- a measuring instrument by the Wilhelmy method for example, CBVP surface tension meter A3 type manufactured by Kyowa Interface Science Co., Ltd. may be mentioned.
- the Wilhelmy method means that when a probe (hereinafter referred to as a plate) touches the surface of the liquid, the liquid wets the probe and surface tension acts along the periphery of the plate, and the plate tries to be pulled into the liquid. .
- the surface tension can be measured by reading the pulling force.
- the surface tension in the present invention was measured under the following conditions.
- (Mixing ratio) (C) / ⁇ (B) + (D) ⁇ is 0.001 to 1.0, preferably 0.01 to 1.0, and more preferably 0.01 to 0.5. .
- the solid content weight ratio of (C) / ⁇ (B) + (D) ⁇ is less than 0.001, it has an organoalkoxysilane (C) and a hydroxyl group with respect to the surface of the poorly water-soluble inorganic oxide (B).
- Organic-inorganic composite particles in which the water-soluble resin (A) is insufficiently combined are formed, and the resulting film causes the water-soluble resin having a hydroxyl group to flow away in long-term use, and dust odor is generated.
- (A) / ⁇ (B) + (C) + (D) ⁇ is 0.1 to 5.0, preferably 0.1 to 2.5, and preferably 0.1 to 1.0. More preferably.
- the amount of the water-soluble resin (A) having a hydroxyl group is too small. Compounding of the water-soluble resin (A) having a hydroxyl group with respect to the surface of the oxide (B) becomes insufficient, and the resulting film generates dust odor.
- the organic-inorganic composite particles are sufficiently complexed, but there are many water-soluble resins having hydroxyl groups that are not involved in the formation of the organic-inorganic composite particles, and the durability is poor because they are washed away by water.
- (D) / ⁇ (A) + (B) + (C) + (D) ⁇ is a composite obtained by mixing the poorly water-soluble inorganic oxide, an organoalkoxysilane, and a water-soluble resin having a hydroxyl group.
- the agglomeration is not particularly limited as long as it suppresses aggregation and does not inhibit the stability of the obtained particles, but is preferably 0.0001 to 0.03, and 0.001 to 0.03. More preferably, it is more preferably 0.001 to 0.01.
- the organic-inorganic composite particles are formed by combining a water-soluble resin having an organoalkoxysilane and a hydroxyl group on the surface of a poorly water-soluble inorganic oxide. More specifically, they are combined through dehydration condensation between the surface hydroxyl group of the poorly water-soluble inorganic oxide and the organoalkoxysilane, and dehydration condensation of the organoalkoxysilane and a water-soluble resin having a hydroxyl group.
- the method of compositing is not particularly limited as long as a dehydration condensation reaction occurs, and it may be blended and stirred.
- the heating method is more preferable in that acids, alkalis, catalysts, and the like are not present together with the organic / inorganic composite particles as a film component.
- the heating temperature is preferably 50 ° C to 90 ° C.
- the catalyst examples include inorganic compounds such as sodium hydroxide, potassium hydroxide, sulfuric acid, nitric acid, and phosphoric acid that promote dehydration condensation, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate, and methylaluminum bis (2,6-di-). metal complexes such as tert-butyl-4-methylphenoxide).
- the hydrophilic treatment agent for an aluminum-containing metal material of the present invention is a water-soluble or water-dispersible resin, a rust preventive agent such as a metal compound, a cross-linking agent, an antibacterial / anti-fungal agent, and the like within the scope of the present invention and film performance. Agents, surfactants, colorants and the like may be added.
- the liquid medium of the hydrophilic treatment agent for an aluminum-containing metal material of the present invention is basically water (preferably 90% by mass or more based on the mass of the entire liquid medium). However, it may contain a water-miscible liquid medium such as alcohol.
- the content of the organic-inorganic composite particles in the hydrophilic treatment agent for an aluminum-containing metal material of the present invention is 40 to 100% by mass, preferably 50 to 100% by mass, more preferably based on the total solid mass. Is 60 to 100% by mass.
- the content of the additive in the hydrophilic treatment agent for an aluminum-containing metal material of the present invention is 0 to 60% by mass based on the total solid mass.
- hydrophilizing agents for aluminum-containing metal materials [Uses of hydrophilizing agents for aluminum-containing metal materials] Next, the use of the hydrophilic treatment agent for an aluminum-containing metal material of the present invention will be described.
- the treatment agent of the present invention is useful for hydrophilizing part or all of the surface of the aluminum-containing metal material.
- the application in other words, a method for hydrophilizing an aluminum-containing metal material and a method for producing a hydrophilized aluminum-containing metal material
- the aluminum-containing metal material to be hydrophilized in the present invention is not particularly limited as long as it contains aluminum, and is made of an aluminum material, for example, a pure aluminum series 1000 series material, aluminum, or an aluminum alloy. Plated metal materials and aluminum-containing alloy materials such as aluminum-copper alloys (eg Al-Cu 2018), aluminum-manganese alloys (eg Al-Mn 3003), aluminum-magnesium alloys (eg Al-Mg-based 5052), aluminum-magnesium-silicon-based alloys (for example, Al-Mg-Si-based 6063), and the like.
- aluminum-copper alloys eg Al-Cu 2018
- aluminum-Mn 3003 aluminum-magnesium alloys
- Al-Mg-based 5052 aluminum-magnesium-silicon-based alloys
- Al-Mg-Si-based 6063 aluminum-magnesium-silicon-based alloys
- the treatment method with the hydrophilic treatment agent is not particularly limited as long as the hydrophilic treatment agent of the present invention and the object to be treated can be brought into contact with each other by an appropriate means, and examples thereof include roll coating, spraying, and dipping method.
- the drying after contacting a hydrophilic treatment agent will not be specifically limited if the water which a hydrophilic treatment agent contains volatilizes, and it is made to dry by heat drying etc.
- the temperature of the heat drying is not particularly limited, but it is preferable to dry in the range of 80 ° C. to 250 ° C. for 5 seconds to 120 minutes, more preferably 100 ° C. to 200 ° C.
- Aluminum-containing metal materials and heat exchangers are preferably cleaned beforehand with an alkaline or acidic cleaning agent to remove dirt on the surface, but should be cleaned if cleaning is not required. It may be omitted. Moreover, you may give a rust prevention process before processing with the hydrophilization processing agent which concerns on this invention in the unprocessed state or after cleaning as needed.
- the antirust treatment is not particularly limited, and examples thereof include known chromate, zinc phosphate, titanium-based, zirconium-based chemical conversion treatments, and corrosion-resistant coatings (chemical conversion-treated coatings or corrosion-resistant primer coatings) such as organic coatings.
- the hydrophilized aluminum-containing metal material of the present invention has a hydrophilic film on part or all of its surface.
- the weight of the film obtained with the hydrophilizing agent is not particularly limited as long as the hydrophilicity and odor properties which are the objects of the present invention can be obtained, but it is 0.1 to 3.0 g / m 2. Is preferable, and the range of 0.1 to 2.0 g / m 2 is more preferable.
- the coating amount is 0.1 g / m 2 or more, the coating of the metal material is sufficient, and the hydrophilicity and odor properties that are the object of the present invention are obtained. Moreover, it is economical if the coating amount is 3.0 g / m 2 or less.
- a preferred example of a product incorporating a hydrophilized aluminum-containing metal material is a heat exchanger.
- the hydrophilic film according to the present invention has excellent hydrophilicity and odor. Therefore, when applied to the aluminum-containing metal material constituting the heat exchanger, problems such as a decrease in heat exchange efficiency due to clogging of condensed water and noise can be solved. Furthermore, the hydrophilic film according to the present invention can maintain excellent hydrophilicity and odor even during long-term use.
- Tables 1 to 5 show the raw materials used in the hydrophilization treatment agents of Examples and Comparative Examples.
- Table 1 is a list of water-soluble resins (A) used in Examples and Comparative Examples.
- Table 2 is a list of the poorly water-soluble inorganic oxides (B) used in Examples and Comparative Examples.
- Table 3 is a list of organoalkoxysilanes (C) used in Examples and Comparative Examples.
- Table 4 is a list of surfactants (D) used in Examples and Comparative Examples.
- Table 5 is a list of additives (E) used in Examples and Comparative Examples.
- Hydrophilic treatment agents used in Examples and Comparative Examples are a water-soluble resin (A) having a hydroxyl group, a poorly water-soluble inorganic oxide (B), an organoalkoxysilane (C), and a surfactant (D).
- the additive (E) was measured using an electronic balance so that the solid content weight (g) of each raw material had the composition shown in Tables 6 to 9, and water was further added to make the total liquid weight 100 g. Thereafter, it was prepared by stirring.
- ⁇ Test material> An aluminum test piece (A1050 manufactured by Partec Co., Ltd., dimensions: 70 mm ⁇ 150 mm, plate thickness: 0.8 mm) was used.
- test material was immersed for 3 minutes in a treatment bath in which an alkaline degreasing agent “Fine Cleaner 315” (manufactured by Nihon Parkerizing Co., Ltd.) was adjusted to a chemical concentration of 20 g / L and a bath temperature of 60 ° C., and adhered to the surface. After removing dust and oil, the alkali remaining on the surface was washed with tap water.
- an alkaline degreasing agent “Fine Cleaner 315” manufactured by Nihon Parkerizing Co., Ltd.
- the contact angle of the evaluation sample cooled to room temperature after the hydrophilic treatment was initially hydrophilic, and after the evaluation sample was immersed in deionized water for 600 hours, it was dried in a blow dryer adjusted to 50 ° C. for 1 hour and cooled to room temperature.
- the contact angle was made hydrophilic after durability.
- the obtained contact angle was rated according to the following criteria, and three or more points in the rating were regarded as acceptable as the hydrophilicity that is the object of the present invention.
- ⁇ Hydrophilic rating criteria 5 points: less than 10 ° 4 points: 10 ° or more, less than 20 ° 3 points: 20 ° or more, less than 30 ° 2 points: 30 ° or more, less than 40 ° 1 point :: 40 ° or more
- ⁇ Odor evaluation method> After subjecting the test material to hydrophilic treatment, the odor of the evaluation sample immediately cooled to room temperature is the initial odor, the evaluation sample is immersed in deionized water for 600 hours, and then dried in an air dryer adjusted to 50 ° C. for 1 hour. The odor after cooling to room temperature was defined as the odor after durability. The obtained odor was rated according to the criteria shown below, and a rating of 3 or more was rated as the odor property of the present invention.
- ⁇ Durability rating standards 5 points: 90% or more 4 points: 80% or more, less than 90% 3 points: 70% or more, less than 80% 2 points: 50% or more, less than 70% 1 point: less than 50%
- the evaluation sample was immersed in deionized water for 100 hours, then dried in a blow dryer adjusted to 50 ° C. for 1 hour, cooled to room temperature, and used for evaluation.
- the evaluation sample is affixed to a cooling plate installed vertically in a constant temperature and humidity layer having an atmosphere of 2 ° C. and a relative humidity of 80%, cooled at ⁇ 10 ° C. for 30 minutes, cooled, and left for 10 minutes. Then, it cooled again for 15 minutes on the said conditions, and the generation
- the ratio of the generated frost (generated area ratio) to the surface area of the evaluation sample was rated according to the following criteria, and the rating of 3 or more was determined as the frost resistance that is the object of the present invention.
- ⁇ Dispersion stability evaluation method> The hydrophilizing agent was stored in a constant temperature bath at 40 ° C. for 1 week, the liquid appearance after storage was visually confirmed, and the following ratings were performed. In addition, even if precipitation was generated, the dispersion stability was determined to be acceptable if it was used after thoroughly stirring and dispersing and other performance evaluation results were acceptable.
- ⁇ Distribution stability rating criteria 5 points: No precipitation 3 points: A small amount of precipitation occurs at the bottom of the container 1 point: A large amount of precipitation occurs at the bottom of the container
- Tables 10 and 11 show the evaluation results of the hydrophilizing agents shown in the examples and comparative examples.
- the aluminum-containing metal material treated with the hydrophilizing agent for aluminum-containing metal material of the present invention As described above, the aluminum-containing metal material treated with the hydrophilizing agent for aluminum-containing metal material of the present invention, the heat exchanger in which those materials are assembled, and further the treatment with the hydrophilizing agent of the present invention. It is clear that heat exchangers have excellent hydrophilicity, odor and their durability.
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Abstract
Description
ここで、前記ヒドロキシル基を有する水溶性樹脂(A)が、ポリビニルアルコール及び/又はポリビニルアルコールの誘導体であり、且つ、けん化度が90mol%以上である成分(a)であってもよい。
また、前記界面活性剤(D)の表面張力が、15から65mN/m(25℃、0.1質量%水溶液、wilhelmy法)であってもよい。
また、前記界面活性剤(D)が、ノニオン系界面活性剤であってもよい。
また、(D)/{(A)+(B)+(C)+(D)}の配合比が、それぞれの固形分重量比で0.0001から0.03であってもよい。
また、(C)/{(B)+(D)}の配合比が、それぞれの固形分重量比で0.01から1.0であってもよい。
また、前記ヒドロキシル基を有する水溶性樹脂(A)の重量平均分子量が、5,000から50,000であってもよい。
また、前記オルガノアルコキシシラン(C)が、グリシジル基を1つ以上有する成分を少なくとも含んでいてもよい。
また、前記水難溶性無機酸化物(B)が、Siを有する無機酸化物であってもよい。
本発明(2)は、前記親水化処理剤をアルミニウム含有金属材料に接触させた後に乾燥させる工程、を含むことを特徴とするアルミニウム含有金属材料の親水化処理方法である。より具体的には、本親水化処理方法は、アルミニウム含有金属材料を無処理、或いは清浄化処理及び/又は防錆処理した後、前記アルミニウム含有金属材料の一部又は全面に、前記本発明に係るアルミニウム含有金属材料用親水化処理剤を接触させた後、乾燥して皮膜を形成する工程を含む。
本発明(3)は、前記親水化処理剤をアルミニウム含有金属材料に接触させた後に乾燥させる工程、を含むことを特徴とする親水化アルミニウム含有金属材料の製造方法である。
本発明(4)は、前記製造方法により得られた親水化アルミニウム含有金属材料である。より具体的には、本アルミニウム含有金属材料は、前記本発明に係るアルミニウム含有金属材料用親水化処理剤から得られる親水性皮膜が、その一部又は全面に形成されていることを特徴とする。
本発明(5)は、前記親水化アルミニウム含有金属材料が用いられている熱交換器である。より具体的には、本熱交換器は、前記本発明に係るアルミニウム含有金属材料用親水化処理剤から得られる親水性皮膜が、その一部又は全面に形成されていることを特徴とする。
本発明(6)は、前記親水化処理剤を熱交換器に接触させた後に乾燥させる工程、を含むことを特徴とする熱交換器の親水化処理方法である(即ち、完成した熱交換器を浸漬処理する方法)。
本発明(7)は、前記親水化処理剤を熱交換器に接触させた後に乾燥させる工程、を含むことを特徴とする親水化熱交換器の製造方法である(即ち、完成した熱交換器を浸漬処理して親水化熱交換器を製造する方法)。
本発明(8)は、前記製造方法により得られた親水化熱交換器である。
本発明のアルミニウム含有金属材料用親水化処理剤(以下、「親水化処理剤」と略す。)は、ヒドロキシル基を有する水溶性樹脂(A)から選ばれる1種以上と、水難溶性無機酸化物(B)から選ばれる1種以上と、オルガノアルコキシシラン(C)から選ばれる1種以上と、界面活性剤(D)とを、それぞれの固形分重量比で(C)/{(B)+(D)}が0.001から1.0、及び(A)/{(B)+(C)+(D)}が0.1から5.0となるよう配合して得られた有機無機複合粒子と、水とを少なくとも含有し、全固形分質量を基準として前記有機無機複合粒子を40から100質量%含有する。以下、当該親水化処理剤の各成分について詳述する。
まず、有機無機複合粒子について説明する。親水化処理剤に含まれる有機無機複合粒子は、少なくとも、ヒドロキシル基を有する水溶性樹脂(A)から選ばれる1種以上と、水難溶性無機酸化物(B)から選ばれる1種以上と、オルガノアルコキシシラン(C)から選ばれる1種以上と、界面活性剤(D)とを、それぞれの固形分重量比で(C)/{(B)+(D)}が0.001から1.0、且つ(A)/{(B)+(C)+(D)}が0.1から5.0となるよう配合して得られた成分である。以下、必須原料である(A)~(D)についてまず説明し、次いで必須原料の配合比、当該有機無機複合粒子の製造方法について説明する。
ヒドロキシル基を有する水溶性樹脂(A)は、オルガノアルコキシシランと脱水縮合する点で、ヒドロキシル基を有していれば特に限定されるものではなく用いることができ、例えば、ポリビニルアルコール及びポリビニルアルコールの誘導体、ポリエチレングリコール及びポリエチレングリコールの誘導体、セルロース及びセルロース誘導体、キトサン及びキトサン誘導体などが挙げられる。中でも親水性と臭気性を長期にわたり持続する点で、ヒドロキシル基密度が高い水溶性樹脂であることが好ましく、ポリビニルアルコール及び/又はポリビニルアルコールの誘導体から選ばれる1種以上で、且つケン化度が90mol%以上であることが好ましい。尚、「水溶性」とは、室温20℃で水に対して0.1質量%以上の溶解性を有する高分子物質を表し、該溶解性は0.5質量%以上が好ましく、特に1質量%以上がより好ましい。
1)GPC
装置:Waters製244型ゲル浸透クロマトグラフィー
カラム:東ソー製TSK(内径8mm、長さ30cm、2本)
溶媒:0.1M―トリス緩衝液(pH7.9)
流速:0.5ml/min
温度:23℃
試料濃度:0.04%
ろ過:東ソー製0.45μmマイショリディスクW-25-5
注入量:0.2ml
2)LALLS
装置:Chromatrix製KMX-6型低角度レーザー光散乱光度計
温度:23℃
波長:633nm
第2ビリアル係数×濃度:0mol/g
屈折率濃度変化(dn/dc):0.159/g
フィルター:MILLIPORE製0.45μmフィルターHAWPO1300
ゲイン:800mV
次に、水難溶性無機酸化物(B)について説明する。水難溶性無機酸化物は、水に難溶な無機酸化物であれば特に限定されるものではなく、例えば、酸化亜鉛、酸化セリウム(IV)、酸化チタン(IV)、酸化スズ(II)、酸化ジルコニウム(IV)、酸化ケイ素(IV)、酸化アルミニウム(III)、酸化コバルト(II)、酸化ニッケル(II)、酸化ルテニウム(IV)、酸化パラジウム(II)、酸化バナジウム(V)、酸化リチウム、酸化ニオブ(V)、酸化亜鉛(II)、酸化ケイ素(IV)酸化アルミニウム(III)複合酸化物、酸化チタン(IV)酸化アルミニウム(III)複合酸化物、酸化鉄(III)、酸化マグネシウム(II)などを用いることができる。中でも、オルガノアルコキシシランと、ヒドロキシル基を有する水溶性樹脂が水難溶性無機酸化物の表面に複合化し、有機無機複合粒子が水溶媒中で安定に分散する点で、Ce、Ti、Sn、Zr、Si、Al、Znから選ばれる少なくとも1種以上の元素を有する無機酸化物から選ばれる1種以上であることが好ましく、Siを有する無機酸化物から選ばれる1種以上であることがより好ましい。尚、「水難溶性」とは、20℃での水への溶解度が1質量%以下のものをいう。
(粒子径測定条件)
測定装置:日機装株式会社製UPA-EX150
光源:半導体レーザー780nm、3mW
光源プローブ:内部プローブ方式
測定サンプルの調整:水難溶性無機酸化物(B)の固形分濃度が0.01%程度になるよう脱イオン水で希釈した後、良く攪拌分散させた。
測定時間:180秒
循環:なし
子透過性:透過
形状:非球形
屈折利率:1.81(装置のデフォルト設定)
溶媒:水
溶媒屈折率:1.333
次にオルガノアルコキシシラン(C)について説明する。オルガノアルコキシシランは、水難溶性無機酸化物、及びヒドロキシル基を有する水溶性樹脂と脱水縮合すれば特に限定されるものではなく、例えばシランカップリング剤を用いることができる。但し、水難溶性無機酸化物とヒドロキシル基を有する水溶性樹脂との複合化に優れる点で、グリシジル基を1つ以上有するアルコキシシランから選ばれる1種以上であることが好ましく、例えば2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリメトキシシラン等が挙げられる。
次に界面活性剤(D)について説明する。前記界面活性剤(D)は、前記水難溶性無機酸化物、及びオルガノアルコキシシラン及びヒドロキシル基を有する水溶性樹脂を混合して複合化する際の凝集を抑制し、得られた粒子の安定性を阻害しなければ特に限定されるものではなく、例えばノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤を用いることができる。
(表面張力測定条件)
測定装置:協和界面科溶解学株式会社製CBVP式表面張力計A3型
測定子(プレート):白金製プレート
測定サンプルの調整:界面活性剤(D)の固形分濃度が0.1質量%になるよう脱イオン水で希釈した後、良く攪拌して水溶液とした。
測定温度:25℃
(C)/{(B)+(D)}は、0.001から1.0とし、0.01から1.0とすることが好ましく、0.01から0.5とすることがより好ましい。(C)/{(B)+(D)}の固形分重量比が0.001より少ないと、水難溶性無機酸化物(B)の表面に対してオルガノアルコキシシラン(C)とヒドロキシル基を有する水溶性樹脂(A)の複合化が不十分な有機無機複合粒子となり、得られる皮膜は長期の使用においてヒドロキシル基を有する水溶性樹脂が流去してしまい埃臭気が発生する。(C)/{(B)+(D)}の固形分重量比が1.0より多いと水難溶性無機酸化物の表面に対して、オルガノアルコキシシランとヒドロキシル基を有する水溶性樹脂の複合化は十分に進むが、水難溶性無機酸化物と水溶性樹脂との結合点が多すぎるため、得られる皮膜の親水性が不十分となる。
前記有機無機複合粒子は、水難溶性無機酸化物の表面にオルガノアルコキシシラン及びヒドロキシル基を有する水溶性樹脂が複合化されてなる。更に述べるならば、水難溶性無機酸化物の表面水酸基とオルガノアルコキシシランの脱水縮合、オルガノアルコキシシランとヒドロキシル基を有する水溶性樹脂の脱水縮合を介して複合化されてなる。複合化の方法としては、脱水縮合反応が起これば特に限定されるものではなく、配合して攪拌しておけばよいが、効率良く有機無機複合粒子を得る点では、pH調整、加熱、触媒添加等を行い攪拌する方法が好ましい。中でも、有機無機複合粒子と共に皮膜成分として酸やアルカリ、触媒などが共存しない点では加熱法がより好ましい。加熱温度としては、50℃から90℃が好ましい。
本発明のアルミニウム含有金属材料用親水化処理剤は、本発明の趣旨や皮膜性能を損なわない範囲で、水溶性又は水分散性樹脂、金属化合物などの防錆剤、架橋剤、抗菌・抗黴剤、界面活性剤、着色剤等を添加してもよい。
本発明のアルミニウム含有金属材料用親水化処理剤の液体媒体は、基本的には水である(好適には、全液体媒体の質量を基準として90質量%以上)。但し、アルコール等の水混和性液体媒体を含有していてもよい。
(有機無機複合粒子)
本発明のアルミニウム含有金属材料用親水化処理剤における有機無機複合粒子の含有量は、全固形分質量を基準として40から100質量%であり、好適には50から100質量%であり、より好適には60から100質量%である。
本発明のアルミニウム含有金属材料用親水化処理剤における添加剤の含有量は、全固形分質量を基準として0から60質量%である。
次に、本発明のアルミニウム含有金属材料用親水化処理剤の用途を説明する。本発明の処理剤は、アルミニウム含有金属材料の表面の一部又は全部を親水化させるために有用である。以下、当該用途(換言すれば、アルミニウム含有金属材料の親水化処理方法、親水化アルミニウム含有金属材料の製造方法)を説明する。
本発明での親水化対象となるアルミニウム含有金属材料は、アルミニウムを含有している限りその種類に格別の制限はなく、アルミニウム材料、例えば純アルミニウム系の1000番系材料、アルミニウム、又はアルミニウム合金によりメッキされた金属材料、及びアルミニウム含有合金材料、例えばアルミニウム-銅系合金(例えばAl-Cu系の2018)、アルミニウム-マンガン系合金(例えばAl-Mn系の3003)、アルミニウム-マグネシウム系合金(例えばAl-Mg系の5052)、アルミニウム-マグネシウム-シリコン系合金(例えばAl-Mg-Si系の6063)などを包含する。
本発明のアルミニウム含有金属材料用親水化処理剤の使用方法(換言すれば、アルミニウム含有金属材料の親水化処理方法、親水化アルミニウム含有金属材料の製造方法)は、親水化処理剤をアルミニウム含有金属材料に接触させる工程、当該接触後に乾燥させる工程と、を含む。以下、各工程を詳述する。
無処理、又は清浄化処理、防錆処理を適宜施したアルミニウム含有金属材料や熱交換器の表面の一部又は全部に、必要な皮膜量が得られるよう親水化処理剤で処理する。親水化処理剤での処理方法は特に限定されず適当な手段で本発明の本親水処理薬剤と被処理物が接触できれば良く、例えば、ロールコート、スプレー、及び浸漬法等が挙げられる。
親水化処理剤を接触させた後の乾燥は、親水化処理剤が含有する水が揮散すれば特に限定されるものではなく、加熱乾燥等により乾燥させる。加熱乾燥の温度は特に限定されるものではないが、80℃から250℃の範囲で5秒から120分間乾燥することが好ましく、100℃から200℃がより好ましい。
尚、アルミニウム含有金属材料や熱交換器は、予めアルカリ性又は酸性の洗浄剤によって、表面の汚れを取り除き清浄化することが好ましいが、清浄化を必要としない場合には清浄化を省略してもよい。また、必要に応じて、無処理の状態で、又は清浄化した後、本発明に係る親水化処理剤で処理する前に、防錆処理を施してもよい。防錆処理としては、特に限定されるものではなく、公知のクロメート、りん酸亜鉛、チタン系、ジルコニウム系化成処理、有機皮膜等の耐食皮膜(化成処理皮膜又は耐食プライマー皮膜)が挙げられる。
本発明の親水化アルミニウム含有金属材料は、その表面の一部又は全部に親水性皮膜を有する。ここで、前記親水化処理薬剤により得られた皮膜重量は、本発明の目的である親水性と臭気性が得られれば特に限定されるものではないが、0.1から3.0g/m2の範囲が好ましく、0.1から2.0g/m2の範囲がより好ましい。皮膜量が0.1g/m2以上であれば、金属材の被覆が十分となり、本発明の目的である親水性や臭気性が得られる。また、皮膜量が3.0g/m2以下であれば経済的である。
親水化アルミニウム含有金属材料が組み込まれた製品の好適例は熱交換器である。本発明に係る親水性皮膜は、優れた親水性及び臭気性を有する。したがって、熱交換器を構成するアルミニウム含有金属材料に適用すれば、結露水の目詰まりによる熱交換効率の低下、騒音等の問題を解決できる。更に、本発明に係る親水性皮膜は、長期の使用時においても優れた親水性と臭気性を持続することができる。
表1~表5に実施例、比較例の親水化処理剤に用いた原料を示す。ここで、表1は、実施例及び比較例に用いた水溶性樹脂(A)の一覧である。また、表2は、実施例及び比較例に用いた水難溶性無機酸化物(B)の一覧である。また、表3は、実施例及び比較例に用いたオルガノアルコキシシラン(C)の一覧である。また、表4は、実施例及び比較例に用いた界面活性剤(D)の一覧である。また、表5は、実施例及び比較例に用いた添加剤(E)の一覧である。
アルミニウム製テストピース(株式会社パルテック製A1050、寸法:70mm×150mm、板厚:0.8mm)を用いた。
前記の試験材を、アルカリ系脱脂剤「ファインクリーナー315」(日本パーカライジング株式会社製)を薬剤濃度20g/L、浴温度60℃に調整した処理浴に3分間浸漬処理し、表面に付着しているゴミや油を除去した後、表面に残存しているアルカリ分を水道水により洗浄した。
前記洗浄された試験材を、表6~表9に示す親水化処理剤中にそれぞれ浸漬した後、任意の温度に調整した送風乾燥機内で吊るして6分間加熱乾燥したものを以下の評価試験に用いる評価サンプルとした。
評価サンプル上に2μlの脱イオン水を滴下し、形成された水滴の接触角を接触角計(協和界面科学株式会社製:DM-501)により測定した。親水性処理後に室温まで冷却した評価サンプルの接触角を初期親水性、評価サンプルを脱イオン水に600時間浸漬した後、50℃に調整した送風乾燥機内で1時間乾燥させ室温まで冷却した後の接触角を耐久後親水性とした。得られた接触角は以下に示す基準でレーティングを行い、レーティングで3点以上を本発明の目的である親水性として合格とした。
5点:10°未満
4点:10°以上、20°未満
3点:20°以上、30°未満
2点:30°以上、40°未満
1点::40°以上
試験材を親水性処理した後、室温まで冷却して直ぐの評価サンプルの臭気を初期臭気、評価サンプルを脱イオン水に600時間浸漬した後、50℃に調整した送風乾燥機内で1時間乾燥させ室温まで冷却した後の臭気を耐久後臭気とした。得られた臭気は以下に示す基準でレーティングを行い、レーティングで3点以上を本発明の目的である臭気性として合格とした。
5点:ほとんど臭いを感じない
4点:かすかに臭いを感じる
3点:はっきりと臭いを感じる
2点:強いにおいを感じる
1点:非常に強いにおいを感じる
評価サンプルを脱イオン水に600時間浸漬した後、50℃に調整した送風乾燥機内で1時間乾燥させ室温まで冷却した評価サンプルの重量を測定し、式1より各例の皮膜残存率を求め、以下に示すレーティングを行った。
[式1]
皮膜残存率(%)=[耐久性試験後評価サンプル重量(g)-親水化処理前試験材重量(g)]÷[親水化処理後試験材重量(g)-親水化処理前試験材重量(g)]×100
得られた皮膜残存率を以下に示す基準でレーティングを行い、レーティングで3以上を本発明の目的である耐久性として合格とした。
5点:90%以上
4点:80%以上、90%未満
3点:70%以上、80%未満
2点:50%以上、70%未満
1点:50%未満
評価サンプルは脱イオン水に100時間浸漬させた後、50℃に調整した送風乾燥機内で1時間乾燥させ室温まで冷却して評価に用いた。前記評価サンプルを雰囲気2℃、相対湿度80%の恒温恒湿層内に鉛直方向に設置した冷却板に貼り付け、-10℃で30分間冷却し、冷却を止めて10分間放置する。その後、再び前記条件にて15分間冷却を行い、15分後の霜の発生面積を目視にて観察した。評価サンプルの表面積に対して、発生した霜の割合(発生面積率)を以下に示す基準でレーティングし、本発明の目的である耐着霜性としてレーティングで3以上を合格とした。
5点:霜発生面積率 20%未満
4点:霜発生面積率 20~40%未満
3点:霜発生面積率 40%以上、60%未満
2点:霜発生面積率 60%以上、80%未満
1点:霜発生面積率 80%以上
親水化処理剤を40℃の恒温槽に1週間保管し、保管後の液外観を目視にて確認し以下に示すレーティングを行った。尚、分散安定性は沈殿発生が有っても、良く攪拌、分散した後に用いて他の性能評価結果が合格であれば合格とした。
5点:沈殿なし
3点:容器底部に微量な沈殿発生
1点:容器底部に多量に沈殿発生
上記評価に基づき、実施例、比較例に示した親水化処理剤の総合評価を行った。総合評価に関しては、「総合評価の点数={親水性(初期)の点数}+{親水性(耐久後)の点数}×2+{臭気性(初期)の点数}+{臭気性(耐久後)の点数}×2+(耐久性の点数)+(耐着霜性の点数)×2+(分散安定性の点数)」として得点化を行った。
Claims (16)
- ヒドロキシル基を有する水溶性樹脂(A)から選ばれる1種以上と、水難溶性無機酸化物(B)から選ばれる1種以上と、オルガノアルコキシシラン(C)から選ばれる1種以上と、界面活性剤(D)とを、それぞれの固形分重量比で(C)/{(B)+(D)}が0.001から1.0、(A)/{(B)+(C)+(D)}が0.1から5.0となるよう配合して得られた有機無機複合粒子と、水と、を含有し、前記有機無機複合粒子が全固形分質量を基準として40から100質量%であることを特徴とする、アルミニウム含有金属材料用親水化処理剤。
- 前記ヒドロキシル基を有する水溶性樹脂(A)が、ポリビニルアルコール及び/又はポリビニルアルコールの誘導体であり、且つ、けん化度が90mol%以上である成分(a)である、請求項1記載の親水化処理剤。
- 前記界面活性剤(D)の表面張力が、15から65mN/m(25℃、0.1質量%水溶液、wilhelmy法)である、請求項1又は2記載の親水化処理剤。
- 前記界面活性剤(D)が、ノニオン系界面活性剤である、請求項1~3のいずれか一項記載の親水化処理剤。
- (D)/{(A)+(B)+(C)+(D)}の配合比が、それぞれの固形分重量比で0.0001から0.03である、請求項1~4のいずれか一項記載の親水化処理剤。
- (C)/{(B)+(D)}の配合比が、それぞれの固形分重量比で0.01から1.0である、請求項1~5のいずれか一項記載の親水化処理剤。
- 前記ヒドロキシル基を有する水溶性樹脂(A)の重量平均分子量が、5,000から50,000である、請求項1~6のいずれか一項記載の親水化処理剤。
- 前記オルガノアルコキシシラン(C)が、グリシジル基を1つ以上有する成分を少なくとも含む、請求項1~7のいずれか一項記載の親水化処理剤。
- 前記水難溶性無機酸化物(B)が、Siを有する無機酸化物である、請求項1~8のいずれか一項記載の親水化処理剤。
- 請求項1~9のいずれか一項記載の親水化処理剤をアルミニウム含有金属材料に接触させた後に乾燥させる工程、を含むことを特徴とするアルミニウム含有金属材料の親水化処理方法。
- 請求項1~9のいずれか一項記載の親水化処理剤をアルミニウム含有金属材料に接触させた後に乾燥させる工程、を含むことを特徴とする親水化アルミニウム含有金属材料の製造方法。
- 請求項11記載の製造方法により得られた親水化アルミニウム含有金属材料。
- 請求項12記載の親水化アルミニウム含有金属材料が用いられている熱交換器。
- 請求項1~9のいずれか一項記載の親水化処理剤を熱交換器に接触させた後に乾燥させる工程、を含むことを特徴とする熱交換器の親水化処理方法。
- 請求項1~9のいずれか一項記載の親水化処理剤を熱交換器に接触させた後に乾燥させる工程、を含むことを特徴とする親水化熱交換器の製造方法
- 請求項15記載の製造方法により得られた親水化熱交換器。
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WO2023189618A1 (ja) * | 2022-03-28 | 2023-10-05 | 日本パーカライジング株式会社 | 表面処理剤 |
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KR20240014112A (ko) | 2022-07-22 | 2024-02-01 | 전남대학교산학협력단 | 금속재료용 항곰팡이성 친수화처리제, 이를 포함하는 항곰팡이성 친수화처리액, 그 제조방법 및 항곰팡이성 친수피막형성방법 |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2018012381A1 (ja) * | 2016-07-11 | 2018-01-18 | 株式会社クラレ | 水生生物忌避用塗料組成物 |
JPWO2018012381A1 (ja) * | 2016-07-11 | 2019-05-16 | 株式会社クラレ | 水生生物忌避用塗料組成物 |
US10829661B2 (en) | 2016-07-11 | 2020-11-10 | Kuraray Co., Ltd. | Aquatic organism repellent paint composition |
WO2023189618A1 (ja) * | 2022-03-28 | 2023-10-05 | 日本パーカライジング株式会社 | 表面処理剤 |
Also Published As
Publication number | Publication date |
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EP3178897A4 (en) | 2018-05-02 |
US10221318B2 (en) | 2019-03-05 |
CN106661420B (zh) | 2019-02-05 |
TW201610133A (zh) | 2016-03-16 |
CN106661420A (zh) | 2017-05-10 |
KR20170038047A (ko) | 2017-04-05 |
JP6116695B2 (ja) | 2017-04-19 |
JPWO2016021071A1 (ja) | 2017-04-27 |
US20170226345A1 (en) | 2017-08-10 |
EP3178897A1 (en) | 2017-06-14 |
TWI665295B (zh) | 2019-07-11 |
KR101868762B1 (ko) | 2018-07-17 |
MX2017001755A (es) | 2017-04-27 |
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