CN110506085B - Hydrophilizing agent and method for forming hydrophilic coating film - Google Patents

Hydrophilizing agent and method for forming hydrophilic coating film Download PDF

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CN110506085B
CN110506085B CN201880022515.8A CN201880022515A CN110506085B CN 110506085 B CN110506085 B CN 110506085B CN 201880022515 A CN201880022515 A CN 201880022515A CN 110506085 B CN110506085 B CN 110506085B
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carboxylic acid
monomer
acid group
fine particles
containing polymer
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CN110506085A (en
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梅田真纱子
松崎正干
齐藤宏一
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Nippon Paint Surf Chemicals Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention provides a hydrophilizing agent capable of forming a coating film excellent in hydrophilicity and water droplet removability, and a method for forming a hydrophilic coating film. The hydrophilization treatment agent comprises an aqueous resin dispersion (A) and crosslinkable fine particles (B), wherein the aqueous resin dispersion (A) comprises an ethylene-vinyl alcohol copolymer (A1) and a carboxylic acid group-containing polymer (A2) having a structural unit derived from a radical polymerizable carboxylic acid monomer, the mass ratio (A1)/(A2) of the ethylene-vinyl alcohol copolymer (A1) to the mass of the carboxylic acid group-containing polymer (A2) is 0.43 to 2.33, and the mass ratio (B)/(A1+ A2) of the crosslinkable fine particles (B) to the total amount of the ethylene-vinyl alcohol copolymer (A1) and the carboxylic acid group-containing polymer (A2) is 0.11 to 1.

Description

Hydrophilizing agent and method for forming hydrophilic coating film
Technical Field
The present invention relates to a hydrophilizing agent comprising an aqueous resin dispersion and crosslinkable fine particles, and a method for forming a hydrophilic coating film.
Background
Conventionally, a technique of hydrophilizing a surface of a metal substrate is known. For example, in a heat exchanger using aluminum, in order to prevent problems such as noise generation due to condensed water adhering to the fin surface and contamination due to splashing of water droplets, the fin surface may be subjected to a hydrophilization treatment.
As a hydrophilization treatment agent used for hydrophilization treatment, a hydrophilization treatment agent containing a modified polyvinyl alcohol resin having an acetoacetyl group and an oxyalkylene group and a crosslinking agent has been proposed (for example, see patent document 1). By using the hydrophilization treatment agent described in patent document 1, a film having excellent hydrophilicity and water resistance can be formed.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-141625
Disclosure of Invention
Problems to be solved by the invention
However, it is considered that the more excellent the hydrophilicity is, the more stable the condensed water is on the substrate and the more difficult it is to remove. That is, it is considered that the more excellent the hydrophilicity is, the more the water droplet removing property is deteriorated. Therefore, even when the hydrophilization treatment agent described in patent document 1 is used, it is difficult to form a film having excellent water droplet removal properties.
The purpose of the present invention is to provide a hydrophilizing agent capable of forming a film having excellent hydrophilicity and water droplet removability, and a method for forming a hydrophilic film.
Means for solving the problems
The present invention relates to a hydrophilization treatment agent comprising an aqueous resin dispersion (A) and crosslinkable fine particles (B), wherein the aqueous resin dispersion (A) comprises an ethylene-vinyl alcohol copolymer (A1) and a carboxylic acid group-containing polymer (A2) having a structural unit derived from a radical polymerizable carboxylic acid monomer, the mass ratio (A1)/(A2) of the ethylene-vinyl alcohol copolymer (A1) to the mass of the carboxylic acid group-containing polymer (A2) is 0.43 to 2.33, and the mass ratio (B)/(A1+ A2) of the crosslinkable fine particles (B) to the total amount of the ethylene-vinyl alcohol copolymer (A1) and the carboxylic acid group-containing polymer (A2) is 0.11 to 1.
Further, it is preferable that: the aqueous resin dispersion (a) further contains a polymer (A3), the polymer (A3) being at least one of a polymer (A3-1) and a hydrophilic compound (A3-2), the polymer (A3-1) having a structural unit derived from at least one monomer selected from the group consisting of a radically polymerizable sulfonic acid monomer (A3-1-1) and a radically polymerizable monomer (A3-1-2) having no carboxylic acid group and no sulfonic acid group, and the mass ratio (A3)/(a1+ a2+ B) of the polymer (A3) to the total amount of the ethylene-vinyl alcohol copolymer (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) being 0.43 or less.
Further, it is preferable that: further comprising a hydrophilic compound (C), wherein the mass ratio (C)/(A1+ A2+ B) of the hydrophilic compound (C) to the total amount of the ethylene-vinyl alcohol copolymer (A1), the carboxylic acid group-containing polymer (A2) and the crosslinkable fine particles (B) is 0.2 or less.
Further, it is preferable that: further comprising a crosslinking agent (D), wherein the mass ratio (D)/(A1+ A2+ B) of the crosslinking agent (D) to the total amount of the ethylene-vinyl alcohol copolymer (A1), the carboxylic acid group-containing polymer (A2) and the crosslinkable fine particles (B) is 0.15 or less.
The crosslinkable fine particles (B) are preferably obtained by copolymerizing a monomer (B1) represented by the following formula (c), a monomer (B2) having a polyoxyalkylene chain and a polymerizable double bond, and another polymerizable monomer (B3).
[ solution 1]
Figure BDA0002219053870000021
[ in the formula (c), R 1 Represents hydrogen or methyl. R 2 Represents CH 2 Or C 2 H 4 。]
The present invention also relates to a method for forming a hydrophilic coating film, which comprises a step of applying the hydrophilizing agent to the surface of an aluminum substrate.
Effects of the invention
According to the present invention, a hydrophilizing agent capable of forming a film excellent in hydrophilicity and water droplet removability and a method for forming a hydrophilic film can be provided.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.
The hydrophilization treatment agent according to the present embodiment includes an aqueous resin dispersion (a) and crosslinkable fine particles (B). The aqueous resin dispersion (a) contains an ethylene-vinyl alcohol copolymer (hereinafter, also referred to as "EVOH") (a1) and a carboxylic acid group-containing polymer (a 2). When the mass ratio of each component of the EVOH (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) is set to an appropriate value, a film having excellent hydrophilicity and water droplet removability can be formed. In the present embodiment, the hydrophilization treatment agent includes the hydrophilic compound (C) and the crosslinking agent (D), and the aqueous resin dispersion (a) includes the polymer (a 3).
The following describes the respective configurations of the hydrophilizing agents. The hydrophilizing agent can form a film excellent in hydrophilicity and water droplet removability on various substrate surfaces without limiting the type of substrate, and an example of the case where the hydrophilizing agent is used on an aluminum substrate will be described below.
< aqueous resin Dispersion (A) >)
The aqueous resin dispersion (a) according to the present embodiment contains EVOH (a1) and a carboxylic acid group-containing polymer (a 2). In the present embodiment, the aqueous resin dispersion (a) further contains a polymer (A3) in addition to the EVOH (a1) and the carboxylic acid group-containing polymer (a 2).
The EVOH (a1) is a component that imparts hydrophobicity to the film. The EVOH (a1) has an ethylene structural unit and a vinyl alcohol structural unit. The content of the ethylene structural unit in the EVOH (A1) is preferably 25 to 44 mol%. When the content of the ethylene structural unit is within this range, the aqueous resin dispersion (A) having excellent dispersion stability can be obtained while maintaining the characteristics of EVOH itself.
As the EVOH (A1), a commercially available EVOH can be used. Examples thereof include "EVAL" manufactured by Colorado and "SOARNOL" manufactured by Nippon synthetic chemical industries, Inc.
The carboxylic acid group-containing polymer (a2) is a component that imparts hydrophilicity to the film. The carboxylic acid group-containing polymer (a2) has a structural unit derived from a radically polymerizable carboxylic acid monomer. That is, the carboxylic acid group-containing polymer (a2) is obtained by radical polymerization of a radical polymerizable monomer containing a radical polymerizable carboxylic acid monomer as an essential component.
Examples of the radical polymerizable carboxylic acid monomer of the carboxylic acid group-containing polymer (a2) include: unsaturated monocarboxylic acids such as itaconic acid, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and chloromaleic acid, and anhydrides thereof; monoesters of unsaturated dicarboxylic acids such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate and the like. These may be used alone or in combination of two or more. Further, metal salts, ammonium salts, and the like thereof may also be used. Among them, itaconic acid, acrylic acid and methacrylic acid are particularly preferable.
The polymer (A3) is a component that imparts hydrophilicity to the film, similarly to the carboxylic acid group-containing polymer (a 2). The polymer (A3) is at least one of a polymer (A3-1) and a hydrophilic compound (A3-2). The polymer (A3-1) has a structural unit derived from at least one monomer selected from the group consisting of a radically polymerizable sulfonic acid monomer (A3-1-1) and a radically polymerizable monomer (A3-1-2) having no carboxylic acid group or sulfonic acid group.
Examples of the radical polymerizable sulfonic acid monomer (a3-1-1) include a methacrylic acid ester sulfonic acid monomer, an acrylamide sulfonic acid monomer, an allyl sulfonic acid monomer, a vinyl sulfonic acid monomer, and a styrene sulfonic acid monomer. These monomers may be used alone or in combination of two or more. Further, metal salts thereof and the like may also be used. Among them, HAPS (sodium salt of 3-allyloxy-2-hydroxy-1-propanesulfonic acid) and AMPS (2-acrylamido-2-methylpropanesulfonic acid) are particularly preferable.
Examples of the radically polymerizable monomer (A3-1-2) having no carboxylic acid group or sulfonic acid group include the following radically polymerizable monomers (A3-1-2a) to (A3-1-2 c). The radically polymerizable monomers (A3-1-2a) to (A3-1-2c) may be used alone or in combination of two or more.
Examples of the radical polymerizable monomer (a3-1-2a) include radical polymerizable monomers represented by the following formula (a).
CH 2 ＝C(R 1 )CO-(OCH 2 CH 2 ) m -OR 2 … type (a)
[ in the formula (a), R 1 Represents hydrogen or methyl. R 2 Represents hydrogen or methyl. m is an integer of 1 to 200.]
That is, the polymer (a3-1) is (poly) ethylene glycol mono (meth) acrylate or methoxypolyethylene glycol (meth) acrylate in which m is an integer of 1 to 200, as represented by the above formula (a), or may have an amide bond. This can impart hydrophilicity and dispersion stability to the coating film.
The radically polymerizable monomer (a3-1-2b) may be at least one radically polymerizable monomer selected from the group consisting of (meth) acrylamide, N-vinylformamide, N-vinylacetamide, and N-vinylpyrrolidone. These monomers may be used alone or in combination of two or more. Among them, N-vinylformamide (NVF) and acrylamide (AAm) are particularly preferable.
Examples of the radical polymerizable monomer (A3-1-2c) include: radical polymerizable hydroxyl group-containing monomers such as hydroxypropyl (meth) acrylate; radically polymerizable amide group-containing monomers such as N-methylol (meth) acrylamide and N, N-dimethyl (meth) acrylamide; radical polymerizable silyl group-containing monomers such as γ - (meth) acryloyloxypropyltrimethoxysilane; radical polymerizable epoxy group-containing monomers such as glycidyl methacrylate; radical polymerizable ester group-containing monomers such as methyl (meth) acrylate and ethylene glycol dimethacrylate; and vinyl group-containing monomers such as vinyl acetate, styrene, acrylonitrile, and divinylbenzene. These monomers may be used alone or in combination of two or more. Among them, N-Dimethylacrylamide (DMAA) and Glycidyl Methacrylate (GMA) are particularly preferable. By having the radical polymerizable monomer (a3-1-2c), hydrophilicity, dispersion stability, or crosslinkability can be imparted to the film.
The hydrophilic compound (A3-2) may be at least one hydrophilic compound (A3-2) selected from the group consisting of a compound having a structure represented by the following formula (b) and a compound having a polyvinylpyrrolidone (PVP) structure.
R 3 O(CH 2 CH 2 O) n - … formula (b)
[ in the formula (b), R 3 Represents hydrogen or methyl. n is an integer of 2 to 100,000.]
Examples of the compound having the structure represented by the formula (b) include polyethylene glycol, polyethylene oxide, and polyoxyethylene-containing polyvinyl alcohol. Examples of the compound having a polyvinylpyrrolidone (PVP) structure include PVP, PVP-modified PVA, and the like. These monomers may be used alone or in combination of two or more. Among them, polyethylene glycol (PEG), polyethylene oxide (PEO), polyvinyl alcohol containing polyoxyethylene group (EO-PVA) are particularly preferable. By containing the hydrophilic compound (a3-2), excellent dispersion stability can be imparted and hydrophilicity can be imparted to the film.
< method for producing aqueous resin Dispersion (A) >
The method for producing the aqueous resin dispersion (a) may comprise the steps of: the radical polymer was obtained by (co) polymerization in a solution containing EVOH (a 1).
When the hydrophilic compound (a3-2) is contained in the aqueous resin dispersion (a), it preferably includes the following steps: a radical polymer is obtained by (co) polymerizing an EVOH (A1) and, if necessary, a hydrophilic compound (A3-2) in a solution.
The radical polymerization method may be a conventionally known method, and a conventionally known polymerization initiator may be used as the radical polymerization initiator.
When the carboxylic acid group-containing polymer (a2) is a (co) polymer of the 1 st monomer group, it is preferable to add the 1 st monomer group to a solution containing EVOH (a1) and, if necessary, a hydrophilic compound (A3-2) and copolymerize the monomer group.
Similarly, when the carboxylic acid group-containing polymer (a2) is a copolymer of the 1 st monomer group and the 2 nd monomer group, the 1 st monomer group and the 2 nd monomer group are simultaneously added to a solution containing EVOH (a1) and, if necessary, a hydrophilic compound (A3-2) to copolymerize, or the 1 st monomer group may be added first to (co) polymerize, and then the 2 nd monomer group may be added to (co) polymerize.
In the production method of the present embodiment, instead of performing the (co) polymerization reaction in the solution containing the EVOH (a1), the carboxylic acid group-containing polymer (a2) may be obtained by mixing the (co) polymer of the 1 st monomer group and the (co) polymer of the 2 nd monomer group in the solution. For example, the aqueous resin dispersion (a) may be prepared by (co) polymerizing the 1 st monomer group in the presence of EVOH (a1), adding another (co) polymer (B2) obtained by polymerizing the 2 nd monomer group thereto, and stirring and mixing the resulting mixture.
An example of the method for producing the aqueous resin dispersion (a) according to the present embodiment will be described below.
First, a mixed solution of an appropriate amount of water and methanol was added to EVOH in pellet form (A1). After the addition, the EVOH was heated at a temperature not lower than the glass transition point of the EVOH and not higher than the boiling point of the solvent, and stirred for a predetermined time, thereby obtaining a solution of EVOH (A1).
Subsequently, a hydrophilic compound (A3-2) is dissolved in an EVOH (A1) solution as needed, and a solution containing a radical polymerization initiator and a liquid obtained by mixing a monomer solution containing a monomer of the carboxylic acid group-containing polymer (A2) as an essential component and a monomer of an arbitrary polymer (A3-1) and a solution containing a radical polymerization initiator are added dropwise under a nitrogen atmosphere to perform a reaction.
Subsequently, a base (preferably aqueous ammonia) equivalent to the acid equivalent of the monomer to be blended is added dropwise to neutralize the monomer. Then, methanol was distilled off while supplementing water under heating, and the medium was replaced with water.
Then, the aqueous resin dispersion (a) of EVOH (a1) having excellent dispersion stability of the present embodiment is obtained by cooling and filtering.
< crosslinkable Fine particles (B) >)
The crosslinkable fine particles (B) in the present invention are resin particles having an average particle diameter of 200 to 400nm, and are obtained by copolymerizing monomer components containing a monomer (B1) represented by the following formula (c), a monomer (B2) having a polyoxyalkylene chain and a polymerizable double bond, and another polymerizable monomer (B3). In the crosslinkable fine particles (B), the methylol group and the hydroxyethyl group of (B1) are reacted with a functional group such as a carboxyl group and a hydroxyl group of (B2), or the methylol group and the hydroxyethyl group are condensed with each other, or reacted with a carboxyl group and a hydroxyl group of (B3). Therefore, when the crosslinkable fine particles (B) are used as a component of the hydrophilization treatment agent, a water-insoluble strong hydrophilic film can be formed on the surface of the substrate. Since the crosslinkable fine particles (B) have high hydrophilicity and many unreacted functional groups, when used as a component of a hydrophilizing agent, the hydrophilic property can be greatly improved without impairing the hydrophilicity by reacting with another hydrophilic resin, and the hydrophilicity persistence after the contaminants are adhered thereto can be greatly improved. Further, since the swelling ratio of the crosslinkable fine particles (B) with respect to water is small, the formed hydrophilic film can be suppressed from dissolving in water.
[ solution 2]
Figure BDA0002219053870000071
[ in the formula (c), R 1 Represents hydrogen or methyl. R 2 Represents CH 2 Or C 2 H 4 。]
The monomer (b1) represented by the above formula (c) is N-methylolacrylamide, N-methylolmethacrylamide, N-hydroxyethylacrylamide or N-hydroxyethylmethacrylamide. When a hydrophilization treatment agent containing the crosslinkable fine particles (B) obtained when the monomer (B1) represented by the formula (c) is used, a hydrophilic film having excellent hydrophilic durability and adhesion can be formed. These may be used alone or in combination of two or more.
The crosslinkable fine particles (B) are obtained by copolymerizing a monomer component containing 30 to 95 mass% of a monomer (B1) represented by the formula (c). If the mass is less than 30, the hydrophilic coating may have a reduced hydrophilic durability after the contaminants have adhered thereto. If it exceeds 95 mass, the manufacture may become difficult. Since the monomer (b1) represented by the above formula (c) is blended in the above range, it functions as a crosslinking component and also functions as a main component of the hydrophilic film-forming component. That is, in the case of blending in order to exhibit only the function as a crosslinking component, the blending amount is usually less than the above range, but in the crosslinkable fine particles (B) of the present invention, by using the monomer (B1) represented by the above formula (c) in the blending amount within the above range, hydroxymethyl groups and hydroxyethyl groups remain in the crosslinkable fine particles even after copolymerization. Therefore, when a hydrophilic coating film is formed using a hydrophilizing agent containing the crosslinkable fine particles (B), it can react with another hydrophilic resin to obtain strong adhesion and hydrophilic durability. Therefore, even after a plastic lubricant such as palmitic acid, stearic acid, or paraffin acid, or a contaminant such as diisooctyl phthalate adheres to the formed hydrophilic coating, the hydrophilicity of the hydrophilic coating can be sufficiently maintained.
In addition, the crosslinking degree of the crosslinkable fine particles obtained by blending the monomer (b1) represented by the above formula (c) is increased by the increase in the blending amount. Therefore, the formed hydrophilic film can be inhibited from dissolving due to moisture, and a film having excellent adhesion (adhesion when the film is exposed to moisture) can be formed.
< hydrophilic Compound (C) >
The hydrophilic compound (C) according to the present embodiment is a component that imparts hydrophilicity to the coating film. Examples of the hydrophilic compound (C) include resins having a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, or a hydroxyl group. Specifically, there may be mentioned: modified polyvinyl alcohols such as polyvinyl alcohol (PVA) and ethylene oxide-modified polyvinyl alcohol (EO-PVA), polyacrylic acid (PAA), polyacrylamide (PAAm), carboxymethyl cellulose (CMC), polyvinyl pyrrolidone (PVP), polyalkylene ether (PAE), N-methylolacrylamide (NMAM), poly-N-vinyl formamide (PNVF), acrylic acid copolymers, sulfonic acid copolymers, amide copolymers, and the like. These may be used alone or in combination of two or more.
< crosslinking agent (D) >)
The crosslinking agent (D) according to the present embodiment is a component that imparts mechanical strength to the coating film. Examples of the crosslinking agent (D) include melamine resins and silane coupling agents. Specific examples of the melamine resin include "CYMEL 370N" manufactured by Cytec Industries, japan. Further, as the silane coupling agent, "KBM-403" manufactured by shin-Etsu chemical Co., Ltd. These may be used alone or in combination of two or more.
The hydrophilization treatment agent of the present embodiment may further contain a rust preventive material. Examples of the rust preventive material include a zirconium compound, a vanadium compound, a titanium compound, a niobium compound, a phosphorus compound, a cerium compound, and a chromium compound. These may be used alone or in combination of two or more.
< mass ratio of each component >
By setting the mass ratios of the respective components of the aqueous resin dispersion (a), the crosslinkable fine particles (B), the hydrophilic compound (C), and the crosslinking agent (D) contained in the hydrophilizing agent described above to appropriate values, the hydrophilizing agent according to the present embodiment can form a film having excellent hydrophilicity and water droplet removability.
Specifically, the mass ratio (A1)/(A2) of the EVOH (A1) to the carboxylic acid group-containing polymer (A2) is 0.43 to 2.33 (preferably 0.75 to 2.33). The mass ratio (B)/(A1+ A2) of the crosslinkable fine particles (B) to the total amount of the EVOH (A1) and the carboxylic acid group-containing polymer (A2) is 0.11 to 1 (preferably 0.43 to 1).
When the mass ratio (a1)/(a2) is less than 0.43, the EVOH (a1) has a small mass, and therefore the water repellency of the film is low. Therefore, it is difficult to form a coating film having excellent water droplet removability. On the other hand, when the mass ratio (a1)/(a2) exceeds 2.33, the carboxylic acid group-containing polymer (a2) has a small mass, and thus the hydrophilicity of the film is low. Therefore, it is difficult to form a film having excellent hydrophilicity.
When the mass ratio (B)/(a1+ a2) is less than 0.11, the number of particles of the crosslinkable fine particles (B) on the surface of the coating film is small, and therefore a coating film having a smooth surface is easily formed. On the other hand, when the mass ratio (B)/(a1+ a2) exceeds 1, the crosslinkable fine particles (B) have a large number of particles, and therefore a rough surface film is easily formed.
Here, the smoother the substrate surface, the smaller the contact area between the substrate surface and the water droplets, and therefore it is difficult to hold the water droplets on the substrate surface (low hydrophilicity). Conversely, the rougher the substrate surface, the more difficult it is to remove water droplets from the substrate surface (water droplet removability is low).
Therefore, when the mass ratio (B)/(a1+ a2) is less than 0.11, the hydrophilicity of the substrate surface becomes low because a smooth surface film is formed. On the other hand, when the mass ratio (B)/(a1+ a2) exceeds 1, a coating film having a rough surface is formed, and thus the water droplet removability of the substrate surface is lowered.
In the present embodiment, the mass ratio (A3)/(a1+ a2) of the polymer (A3) to the total amount of the EVOH (a1) and the carboxylic acid group-containing polymer (a2) is 45/100 or less. When the mass ratio (A3)/(a1+ a2) exceeds 45/100, it is difficult to form a film having excellent water droplet removability.
In the present embodiment, the mass ratio (C)/(a1+ a2+ B) of the hydrophilic compound (C) to the total amount of the EVOH (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) is 0.2 or less. When the mass ratio (C)/(a1+ a2+ B) exceeds 0.2, it is difficult to form a coating film having excellent water droplet removal performance.
In the present embodiment, the mass ratio (D)/(a1+ a2+ B) of the crosslinking agent (D) to the total amount of the EVOH (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) is 0.15 or less. When the mass ratio (D)/(a1+ a2+ B) exceeds 0.15, it is difficult to form a film having excellent water droplet removal performance.
< hydrophilic film formation >
The method for forming a hydrophilic film according to the present embodiment includes a step of applying the hydrophilizing agent to the surface of an aluminum substrate. Specifically, the hydrophilizing agent is applied to the surface of an aluminum substrate and dried to form a hydrophilic coating film. Examples of methods for applying the hydrophilizing agent include roll coating, bar coating, dipping, spraying, and brushing. After the coating, the coating is dried at a temperature of, for example, 120 to 300 ℃ and calcined for 3 seconds to 60 minutes, whereby a hydrophilic coating film can be obtained. If the calcination temperature is less than 120 ℃, sufficient film-forming properties cannot be obtained, and the film may dissolve after immersion in water. If the temperature exceeds 300 ℃, the resin is decomposed, and the hydrophilicity of the hydrophilic coating may be impaired.
The thickness of the hydrophilic coating is preferably 0.05g/m 2 More preferably 0.1 to 2g/m 2 . If the film thickness of the coating film is less than 0.05g/m 2 The durability of the hydrophilicity, processability, adhesion, and corrosion resistance of the film may become insufficient.
As described above, the hydrophilization treatment agent of the present embodiment comprises an aqueous resin dispersion (a) containing an ethylene-vinyl alcohol copolymer (a1) and a carboxylic acid group-containing polymer (a2) having a structural unit derived from a radical polymerizable carboxylic acid monomer, wherein the mass ratio (a1)/(a2) of the ethylene-vinyl alcohol copolymer (a1) to the mass of the carboxylic acid group-containing polymer (a2) is 0.43 to 2.33, and the mass ratio (B)/(a1+ a2) of the crosslinkable fine particles (B) to the total amount of the ethylene-vinyl alcohol copolymer (a1) and the carboxylic acid group-containing polymer (a2) is 0.11 to 1.
By setting the mass ratio of each component of the EVOH (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) contained in the hydrophilizing agent to an appropriate value, the hydrophilizing agent according to the present embodiment can form a film having excellent hydrophilicity and water droplet removability.
The aqueous resin dispersion (a) further contains a polymer (A3), wherein the polymer (A3) is at least one of a polymer (A3-1) and a hydrophilic compound (A3-2), the polymer (A3-1) has a structural unit derived from at least one monomer selected from the group consisting of a radically polymerizable sulfonic acid monomer (A3-1-1) and a radically polymerizable monomer (A3-1-2) having no carboxylic acid group and no sulfonic acid group, and the mass ratio (A3)/(a1+ a2+ B) of the polymer (A3) to the total amount of the ethylene-vinyl alcohol copolymer (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) is 0.43 or less.
The hydrophilization treatment agent according to the present embodiment can form a film having more excellent water droplet removal properties by setting the mass ratio of each component of EVOH (a1), carboxylic acid group-containing polymer (a2), polymer (A3), and crosslinkable fine particles (B) contained in the hydrophilization treatment agent to an appropriate value.
The hydrophilization treatment agent further comprises a hydrophilic compound (C), and the mass ratio (C)/(a1+ a2+ B) of the hydrophilic compound (C) to the total amount of the ethylene-vinyl alcohol copolymer (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) is 0.2 or less.
The hydrophilization treatment agent according to the present embodiment can form a film having more excellent water droplet removal properties by setting the mass ratio of each component of EVOH (a1), carboxylic acid group-containing polymer (a2), crosslinkable fine particles (B), and hydrophilic compound (A3-2) contained in the hydrophilization treatment agent to an appropriate value.
The hydrophilization treatment agent further comprises a crosslinking agent (D), and the mass ratio (D)/(a1+ a2+ B) of the crosslinking agent (D) to the total amount of the ethylene-vinyl alcohol copolymer (a1), the carboxylic acid group-containing polymer (a2) and the crosslinkable fine particles (B) is 0.15 or less.
The hydrophilization treatment agent according to the present embodiment can form a film having more excellent water droplet removal properties by setting the mass ratio of each component of the EVOH (a1), the carboxylic acid group-containing polymer (a2), the crosslinkable fine particles (B), and the crosslinking agent (D) contained in the hydrophilization treatment agent to an appropriate value.
The crosslinkable fine particles (B) are obtained by copolymerizing a monomer (B1) represented by the following formula (c), a monomer (B2) having a polyoxyalkylene chain and a polymerizable double bond, and another polymerizable monomer (B3).
[ solution 3]
Figure BDA0002219053870000111
[ in the formula (c), R 1 Represents hydrogen or methyl. R 2 Represents CH 2 Or C 2 H 4 。]
The hydrophilization treatment agent according to the present embodiment can form a coating film having more excellent hydrophilicity by using the crosslinkable fine particles (B) composed of the monomer.
The method for forming a hydrophilic film in the present embodiment includes a step of applying the hydrophilizing agent to the surface of the aluminum substrate. This makes it possible to form a film having excellent hydrophilicity and water droplet removability. The use of the aluminum substrate having such a hydrophilic film formed thereon is not particularly limited, and for example, when used in a heat exchanger, hydrophilicity and water droplet removability required for the heat exchanger can be satisfied at the same time.
The present invention is not limited to the above-described embodiments, and modifications and improvements within a range that can achieve the object of the present invention are also included in the present invention.
For example, an example in which a hydrophilic film is formed on the surface of an aluminum substrate by the hydrophilization treatment agent is described, but the present invention is not limited thereto. A hydrophilic coating may be formed on a metal substrate other than an aluminum substrate by using the hydrophilizing agent.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
< example 1 >
[ preparation of aqueous resin Dispersion (A) ]
A flask equipped with a stirrer, a cooler, a temperature controller, and a dropping funnel (2 pieces) was charged with 15 mass% of pelletized EVOH (a1) and a 9-fold mass% of a mixed solution of water and methanol (water: methanol: 1 by mass ratio), heated to 75 ℃ and vigorously stirred for 1 hour or more, thereby obtaining an EVOH (a1) solution.
Next, a solution of 10 mass% itaconic acid as a monomer of the carboxylic acid group-containing polymer (a2), a solution of 25 mass% acrylic acid and methanol, and an aqueous solution of 0.6 mass% ammonium persulfate were added to different dropping funnels, and added dropwise to a solution of EVOH (a1) under a nitrogen atmosphere. At this time, the liquid temperature was maintained at 75 ℃ and dropwise addition was carried out over 30 minutes, and after completion of the dropwise addition, stirring was continued at this temperature for 2 hours.
Then, ammonia water equivalent to carboxylic acid (diluted with methanol equivalent to water in ammonia water) was added dropwise over about 20 minutes to neutralize the reaction mixture. Then, a cooling tube for removing the solvent was attached, and the mixture was heated while supplementing water, thereby distilling off methanol and replacing the medium with water. Then, cooling and filtration were carried out to obtain the aqueous resin dispersion (a) of example 1.
[ preparation of crosslinkable Fine particles (B) ]
A monomer solution prepared by dissolving 70 parts by mass of N-methylolacrylamide and 30 parts by mass of methoxypolyethylene glycol monomethacrylate (polyethylene chain having a repeating unit number of 90) in 200 parts by mass of methoxypropanol, and a solution prepared by dissolving 1 part by mass of "ACVA" (azo initiator manufactured by Otsuka chemical Co., Ltd.) in 50 parts by mass of methoxypropanol were added dropwise to 150 parts by mass of methoxypropanol over 3 hours under a nitrogen atmosphere at 105 ℃ to polymerize the mixture, and the mixture was further heated and stirred for 1 hour to obtain crosslinkable fine particles (B). In the obtained dispersion, the average particle diameter of the crosslinkable fine particles was 250 nm.
To 50 mass% of the aqueous resin dispersion (A) of example 1 were added 50 mass% of the crosslinkable fine particles (B) and 2 mass% of a melamine resin as the crosslinking agent (D), to obtain 102 mass% of the hydrophilization treatment agent of example 1.
< example 2 to example 6 >
In examples 2 to 6, the EVOH (a1) was dissolved in the same manner as in example 1 according to the formulation shown in table 1, and mixed with the monomer of the carboxylic acid group-containing polymer (a2), an aqueous ammonium persulfate solution was added dropwise, the mixture was neutralized with aqueous ammonia, methanol was replaced with water, and then the mixture was cooled and filtered, thereby obtaining aqueous resin dispersions (a) of examples 2 to 6.
The crosslinkable fine particles (B) obtained in the same manner as in example 1 and the crosslinking agent (D) were added to the aqueous resin dispersion (a) of examples 2 to 6 in the blending amounts shown in table 1 to obtain hydrophilization treatment agents of examples 2 to 6.
[ Table 1]
Figure BDA0002219053870000131
< example 7 to example 19 >
In examples 7 to 19, the same procedure as in example 1 was repeated, except that EVOH (A1) was added in the formulation shown in Table 2, the hydrophilic compound (A3-2) was added and dissolved in the mixture of examples 17 to 19, the monomer of the carboxylic acid group-containing polymer (A2) was added and the monomer of the polymer (A3-1) was added and mixed in examples 7 to 16, an aqueous ammonium persulfate solution was added dropwise, the mixture was neutralized with aqueous ammonia, and methanol was replaced with water, followed by cooling and filtration to obtain aqueous resin dispersions (A) of examples 7 to 19.
The crosslinkable fine particles (B) obtained in the same manner as in example 1 and the crosslinking agent (D) were added to the aqueous resin dispersion (a) of examples 7 to 19 in the blending amounts shown in table 2 to obtain hydrophilization treatment agents of examples 7 to 19.
[ Table 2]
Figure BDA0002219053870000141
< example 20 to example 29 >
In examples 20 to 29, the same procedure as in example 1 was repeated, except that EVOH (a1) was dissolved in the formulation shown in table 3, and the resulting mixture was mixed with a monomer of the carboxylic acid group-containing polymer (a2), an aqueous ammonium persulfate solution was added dropwise, the mixture was neutralized with aqueous ammonia, methanol was replaced with water, and then the mixture was cooled and filtered, thereby obtaining aqueous resin dispersions (a) of examples 20 to 29.
The crosslinkable fine particles (B), the hydrophilic compound (C) and the crosslinking agent (D) obtained in the same manner as in example 1 were added to the aqueous resin dispersion (a) of examples 20 to 29 in the blending amounts shown in table 3 to obtain hydrophilization treatment agents of examples 20 to 29.
[ Table 3]
Figure BDA0002219053870000161
< embodiments 30 and 31 >
In examples 30 and 31, the same procedure as in example 1 was repeated, except that EVOH (a1) was dissolved in the formulation shown in table 4, and the resulting mixture was mixed with a monomer of the carboxylic acid group-containing polymer (a2), an aqueous ammonium persulfate solution was added dropwise, the mixture was neutralized with aqueous ammonia, methanol was replaced with water, and then the mixture was cooled and filtered to obtain aqueous resin dispersions (a) of examples 30 and 31.
Crosslinkable fine particles (B) obtained in the same manner as in example 1 and 2 mass% of a silane coupling agent as a crosslinking agent (D) were added to the aqueous resin dispersion (a) of example 30 in the proportions shown in table 4 to obtain a hydrophilization treatment agent of example 30. In addition, in the aqueous resin dispersion (a) of example 31, the crosslinkable fine particles (B) obtained in the same manner as in example 1, 13 mass% of a melamine resin as a crosslinking agent (D), and 2 mass% of a silane coupling agent were added in the blending amounts shown in table 4 to obtain a hydrophilization treatment agent of example 31.
[ Table 4]
Figure BDA0002219053870000171
< comparative example 1 to comparative example 4 >
Comparative examples 1 to 4 also obtained aqueous resin dispersions (a) of comparative examples 1 to 4 by dissolving EVOH (a1) in the formulation shown in table 5, mixing with the monomer of the carboxylic acid group-containing polymer (a2), dropping an aqueous ammonium persulfate solution, neutralizing with aqueous ammonia, replacing methanol with water, cooling, and filtering in the same manner as in example 1.
The crosslinkable fine particles (B), the hydrophilic compound (C), and the crosslinking agent (D) obtained in the same manner as in example 1 were added to the aqueous resin dispersion (a) of comparative examples 1 to 4 in the blending amounts shown in table 5 to obtain hydrophilization treatment agents of comparative examples 1 to 4.
[ Table 5]
Figure BDA0002219053870000181
The numerical values in tables 1 to 5 represent the content (% by mass) of each component in the solid content of the hydrophilization treatment agent.
In addition, as the aqueous resin dispersion (A) in tables 1 to 5, the following materials were used.
[ aqueous resin Dispersion (A) ]
HAPS: sodium salt of 3-allyloxy-2-hydroxy-1-propanesulfonic acid
AMPS: 2-acrylamido-2-methylpropanesulfonic acid
NVF: n-vinyl formamide
AAm: acrylamide
DMAA: n, N-dimethylacrylamide
GMA: glycidyl methacrylate
PEG: polyethylene glycol (weight average molecular weight: 20000)
PEO: polyethylene oxide (weight average molecular weight: 500000)
EO-PVA: polyoxyethylene-modified polyvinyl alcohol (weight-average molecular weight: 20000)
In addition, as the hydrophilic compound (C) in tables 1 to 5, the following materials were used.
[ hydrophilic Compound (C) ]
EO-PVA: ethylene oxide-modified PVA (weight-average molecular weight: 20000)
PVA: polyvinyl alcohol (weight average molecular weight: 20000, degree of saponification 98.5)
PAA: polyacrylic acid (weight average molecular weight: 20000, acid value 780mgKOH/g)
CMC: carboxymethyl cellulose (weight average molecular weight: 20000)
PVP: polyvinylpyrrolidone (weight average molecular weight: 20000)
PEG: polyethylene glycol (weight average molecular weight: 20000)
NMAM: n-methylolacrylamide
PNVF: Poly-N-vinylformamide (weight-average molecular weight: 100000)
Acrylic acid copolymer: sodium salt of acrylic acid/N-vinylformamide copolymer (weight-average molecular weight: 700000)
Sulfonic acid copolymer: 2-acrylamido-2-methylpropanesulfonic acid/acrylic acid
In addition, as table 1 ~ 5 in the cross-linking agent (D), using the following material.
[ crosslinking agent (D) ]
Melamine resin: "CYMEL 370N" manufactured by Cytec Industries, Japan "
Silane coupling agent: KBM-403 manufactured by shin-Etsu chemical Co., Ltd "
< production of test plate >
A1000 series aluminum substrate of 150 mm. times.200 mm. times.0.13 mm was degreased at 70 ℃ for 5 seconds using a 1% solution of Surf Cleaner EC370 manufactured by Nippon Paint Surf Chemicals. Subsequently, a 10% solution of Alsurf 407/47 manufactured by Nippon Paint Surf Chemicals was used to perform a phosphate chromate treatment at 40 ℃ for 5 seconds. Subsequently, the hydrophilization agents of examples and comparative examples were prepared to have a solid content of 5%, applied to the aluminum substrate by means of a bar coater #4, heated at 220 ℃ for 20 seconds, and dried to prepare test plates.
< evaluation of initial hydrophilicity >
The contact angle of the water drop to the test plate was evaluated, respectively. The water contact angle was measured using an automatic contact angle measuring instrument (model: DSA20E, manufactured by KRUSS). The contact angle measured is the contact angle of the test plate with a drop of water 30 seconds after the drop in the ambient environment at room temperature. The evaluation results are shown in tables 1 to 5. If the contact angle is 30 ° or less, the initial hydrophilicity is considered to be good.
(evaluation criteria)
4: water contact angle of 20 DEG or less
3: more than 20 DEG and not more than 30 DEG
2: more than 30 DEG and 50 DEG or less
1: over 50 DEG
< evaluation of hydrophilicity persistence >
The test panels were immersed in pure water for 240 hours, lifted and dried. Subsequently, the water contact angle of the test plate after drying with a water droplet was measured. The contact angle was measured by using an automatic contact angle measuring instrument (model: DSA20E, manufactured by KRUSS). The contact angle measured was the contact angle of the test plate with a water drop 30 seconds after dropping in a room temperature atmosphere. The evaluation results are shown in tables 1 to 5. If the water contact angle is 40 ° or less, the hydrophilicity persistence is considered to be good.
(evaluation criteria)
4: water contact angle of 30 DEG or less
3: more than 30 DEG and 40 DEG or less
2: more than 40 DEG and 50 DEG or less
1: over 50 DEG
< evaluation of WET Adhesivity >
The test plate was sprayed with pure water, and a load of 500g was applied to rub the coating film. One round was recorded as 1 time, and the test plate was rubbed at most 10 times until the base was exposed, and evaluated. The evaluation results are shown in tables 1 to 5. The WET adhesion was considered to be good if the number of times until the base of the test plate was exposed was 7 or more.
(evaluation criteria)
4: sliding times of 10 times and no peeling of hydrophilic coating
3: 7 or more and less than 10 sliding times to peel off the hydrophilic coating
2: 3 or more and less than 7 sliding times to peel off the hydrophilic coating
1: less than 3 sliding times, the hydrophilic coating is peeled off
< evaluation of Water droplet removability >
Will be the same as the test plateThe specimen having a size of 10cm × 10cm thus prepared was immersed in pure water for 60 minutes. The test piece was sufficiently dried at 40 ℃ until the moisture on the surface was volatilized, and the initial weight (W) of the test piece was measured 0 )。
Subsequently, the plate was immersed in pure water for 3 minutes. After the test plate was pulled out of the pure water, the coated plate was vertically erected, and water droplets accumulated on the lower end face were removed with a dust-free paper (Kimwipe). The time of lifting was set to 0 second, and the weight (W) after 60 seconds was measured 1 )。
The test piece was baked at 500 ℃ for 15 minutes in a muffle furnace, and the aluminum weight (W) of the test piece after burning off the coating was measured A )。
The residual water content (W) per unit film weight was calculated from the following formula (1). The evaluation results are shown in tables 1 to 5. When the residual water content is 60 or less, the adhesion is considered to be good.
W＝(W 1 -W 0 )÷(W 0 -W A )…(1)
(evaluation criteria)
4: the water residual amount per unit coating amount is 30 or less
3: more than 30 and 60 or less
2: more than 60 and 100 or less
1: over 100
As is clear from comparison between each example and each comparative example shown in tables 1 to 5, the hydrophilic film of each example was excellent in initial hydrophilicity, hydrophilicity-sustaining property, WET adhesion, and adhesion. Therefore, it was confirmed from the comparison between each example and each comparative example that the hydrophilization treatment agent according to the present embodiment can form a film having excellent hydrophilicity and water droplet removability by setting the mass ratio (a1)/(a2) of the ethylene-vinyl alcohol copolymer (a1) to the mass of the carboxylic acid group-containing polymer (a2) to 0.43 to 2.33 and the mass ratio (B)/(a1+ a2) of the crosslinkable fine particles (B) to the total amount of the ethylene-vinyl alcohol copolymer (a1) and the carboxylic acid group-containing polymer (a2) to 0.11 to 1.
As is clear from comparison between example 1 and examples 3 to 6 shown in table 1, the hydrophilic films of examples 3 to 6 had better WET adhesion. Accordingly, it was confirmed from the comparison between example 1 and examples 3 to 6 that the hydrophilization treatment agent according to the present embodiment can form a film having more excellent hydrophilicity and water droplet removal property by setting the mass ratio (a1)/(a2) of the ethylene-vinyl alcohol copolymer (a1) to the mass of the carboxylic acid group-containing polymer (a2) to 0.75 to 2.33.
As is clear from comparison between example 2 and examples 3 to 6 shown in Table 1, the hydrophilic coating films of examples 3 to 6 have better persistence of hydrophilicity. Therefore, it was confirmed from the comparison between example 1 and examples 3 to 6 that the hydrophilization treatment agent according to the present embodiment can form a film having more excellent hydrophilicity and water droplet removal property by setting the mass ratio (B)/(a1+ a2) of the crosslinkable fine particles (B) to the total amount of the ethylene-vinyl alcohol copolymer (a1) and the carboxylic acid group-containing polymer (a2) to 0.43 to 1.

Claims (4)

1. A hydrophilizing agent comprising an aqueous resin dispersion (A), crosslinkable fine particles (B), a hydrophilic compound (C) and a crosslinking agent (D),
the aqueous resin dispersion (A) comprises an ethylene-vinyl alcohol copolymer (A1) and a carboxylic acid group-containing polymer (A2) having a structural unit derived from a radically polymerizable carboxylic acid monomer,
the mass ratio (A1)/(A2) of the ethylene-vinyl alcohol copolymer (A1) to the carboxylic acid group-containing polymer (A2) is 0.43 to 1.14,
the mass ratio (B)/(A1+ A2) of the crosslinkable fine particles (B) to the total amount of the ethylene-vinyl alcohol copolymer (A1) and the carboxylic acid group-containing polymer (A2) is 0.11 to 1,
a mass ratio (C)/(A1+ A2+ B) of the hydrophilic compound (C) to the total amount of the ethylene-vinyl alcohol copolymer (A1), the carboxylic acid group-containing polymer (A2) and the crosslinkable fine particles (B) is 0.11 or less,
the mass ratio (D)/(a1+ a2+ B) of the crosslinking agent (D) to the total amount of the ethylene-vinyl alcohol copolymer (a1), the carboxylic acid group-containing polymer (a2), and the crosslinkable fine particles (B) is 0.15 or less.
2. The hydrophilization treatment agent according to claim 1, the aqueous resin dispersion (A) further comprising a polymer (A3),
the polymer (A3) is at least one of a polymer (A3-1) and a hydrophilic compound (A3-2), the polymer (A3-1) has a structural unit derived from at least one monomer selected from the group consisting of a radically polymerizable sulfonic acid monomer (A3-1-1) and a radically polymerizable monomer (A3-1-2) having no carboxylic acid group and no sulfonic acid group,
the mass ratio (A3)/(a1+ a2+ B) of the polymer (A3) to the total amount of the ethylene-vinyl alcohol copolymer (a1), the carboxylic acid group-containing polymer (a2) and the crosslinkable fine particles (B) is 0.43 or less.
3. The hydrophilization treatment agent according to claim 1 or 2, wherein the crosslinkable fine particles (B) are obtained by copolymerizing a monomer (B1) represented by the following formula (c), a monomer (B2) having a polyoxyalkylene chain and a polymerizable double bond, and another polymerizable monomer (B3),
Figure FDF0000016895220000011
in the formula (c), R 1 Represents hydrogen or methyl, R 2 Represents CH 2 Or C 2 H 4 。
4. A method for forming a hydrophilic film, comprising a step of applying the hydrophilization agent according to any one of claims 1 to 3 to the surface of an aluminum substrate.
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