WO2024252703A1 - 親水性持続効果及び/又は滑水性付与剤 - Google Patents
親水性持続効果及び/又は滑水性付与剤 Download PDFInfo
- Publication number
- WO2024252703A1 WO2024252703A1 PCT/JP2023/047171 JP2023047171W WO2024252703A1 WO 2024252703 A1 WO2024252703 A1 WO 2024252703A1 JP 2023047171 W JP2023047171 W JP 2023047171W WO 2024252703 A1 WO2024252703 A1 WO 2024252703A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- monomer
- mass
- water
- hydrophilicity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- 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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C09D201/08—Carboxyl groups
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- 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
- F28F13/04—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by preventing the formation of continuous films of condensate on heat-exchange surfaces, e.g. by promoting droplet formation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F17/00—Removing ice or water from heat-exchange apparatus
- F28F17/005—Means for draining condensates from heat exchangers, e.g. from evaporators
-
- 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
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
Definitions
- the present invention relates to an agent that provides sustained hydrophilicity and/or water slippage.
- Heat exchangers have heat exchange plates, such as aluminum fins (aluminum fins), for exchanging heat between the heat medium and the air.
- heat exchanger When the heat exchanger is in operation, moisture in the air can condense on the surface of the aluminum fins. If this causes the condensed water to turn into droplets and form bridges between the fins, problems such as increased power consumption due to ventilation resistance and water droplets scattering can occur.
- the surface of the fin material is often treated to make it hydrophilic.
- hydrophilization treatment a method is known in which a resin composition containing hydrophilic particles is applied to the surface of the fin material to form a hydrophilic coating film.
- inorganic particles such as silica and organic particles such as acrylic particles have been used as hydrophilic particles.
- Patent Documents 1 and 2 describe the use of hydrophilic cross-linked polymer fine particles as hydrophilic particles, which are made of a copolymer of (a) 2 to 50% by weight of a hydrophilic monomer having a polymerizable double bond and a polyoxyalkylene chain or a polyvinylpyrrolidone chain, (b) 20 to 97% by weight of a (meth)acrylamide monomer, (c) 1 to 30% by weight of a cross-linkable unsaturated monomer, (d) 2 to 50% by weight of a carboxyl group-containing polymerizable unsaturated monomer, and (e) 0 to 50% by weight of other polymerizable monomers.
- the aluminum fin surface may cause various problems such as a decrease in heat exchange efficiency, corrosion of the aluminum fin, proliferation of bacteria, frosting, etc.
- it is important that the condensation water on the aluminum fin surface is easily drained, that is, it is important to increase the water slippage of the aluminum fin surface.
- the aluminum fin surface is subjected to a water-repellent treatment in order to improve the drainage (water sliding) of the condensed water.
- Patent Document 3 discloses that a super water-repellent and oil-repellent heat exchanger member with excellent water sliding properties can be obtained by providing a plurality of confetti-shaped protrusions made of silica or the like on the surface of a substrate, and then forming a water-repellent, oil-repellent and dirt-resistant thin film on the surface of the substrate on which the confetti-shaped protrusions are formed.
- Patent Document 4 discloses that a heat exchanger member with excellent water repellency and water sliding properties can be obtained by applying a structure having a water-repellent layer containing a polymer having a polyethyleneimine skeleton, a fluorine-containing compound, and silica on a substrate.
- Patent Document 5 describes that by using a treatment agent obtained by mixing a specific water-soluble resin (A), colloidal silica (B), organoalkoxysilane and/or its hydrolyzate (C), a crosslinking agent (D) capable of crosslinking with the water-soluble resin (A), and water (E) in a specific ratio as a surface treatment agent for aluminum-containing metal heat exchangers, it is possible to make the aluminum fin surface hydrophilic, prevent bridges caused by condensed water, and also improve drainage.
- a treatment agent obtained by mixing a specific water-soluble resin (A), colloidal silica (B), organoalkoxysilane and/or its hydrolyzate (C), a crosslinking agent (D) capable of crosslinking with the water-soluble resin (A), and water (E) in a specific ratio as a surface treatment agent for aluminum-containing metal heat exchangers
- an object of the present invention is to achieve the following first and/or second problems.
- the hydrophilic coating film is required to have high hydrophilicity (initial hydrophilicity) immediately after the coating film is formed, and also to maintain the hydrophilicity.
- various tangible objects themselves or their surfaces may be required to have hydrophilicity (initial hydrophilicity) in various applications, and the hydrophilicity may also be required to be maintained.
- the fin material of a heat exchanger repeats a wet state in which condensed water is present on the fin material surface and a dry state in which the condensed water evaporates through long-term use. Therefore, it is required that the hydrophilicity of the tangible object, such as the hydrophilic coating film applied to the fin material of the heat exchanger, is maintained even after repeated adhesion and drying of condensed water.
- Patent documents 1 and 2 also state that hydrophilicity is maintained even after repeated application of tap water and drying.
- the condensed water that adheres to the fins of a heat exchanger has a low content of ionic components, similar to pure water (hereinafter referred to as "low ion water"), and when the hydrophilic particles described in Patent documents 1 and 2 are used, the hydrophilicity is not maintained sufficiently after repeated application of low ion water and drying.
- Patent Documents 1 and 2 require the use of an organic solvent in their production, and the (meth)acrylamide monomer that is the main component of the hydrophilic particles is highly toxic, which is undesirable from the viewpoints of reducing the environmental load and safety. Furthermore, since the techniques disclosed in Patent Documents 3 and 4 relate to a water-repellent treatment, the effect of sustained hydrophilicity cannot be expected. In addition, Patent Document 5 makes no consideration whatsoever about the sustainability of hydrophilicity after repeated adhesion and drying of condensed water.
- a first object of the present invention is to provide a hydrophilicity sustaining effect imparting agent capable of forming a hydrophilized tangible object (e.g., a coating film) having good hydrophilicity sustaining properties even after repeated application and drying of low ion water such as pure water (hereinafter sometimes referred to as "after wet/dry cycles").
- a hydrophilicity sustaining effect imparting agent capable of forming a hydrophilized tangible object (e.g., a coating film) having good hydrophilicity sustaining properties even after repeated application and drying of low ion water such as pure water (hereinafter sometimes referred to as "after wet/dry cycles").
- tangible objects placed in an indoor environment may have oily stains, the main components of which are oily components (e.g., higher fatty acids and higher alcohols) derived from floating matter volatilized and scattered from building materials, food, daily necessities, etc., attached to the surface of the tangible object, and it is required that the tangible object can exhibit good hydrophilicity even after such oily stains have attached to the surface of the tangible object. Therefore, a preferred but not essential object of the present invention is to provide a hydrophilicity sustaining effect imparting agent that provides good hydrophilicity to the surface of the tangible object (e.g., fin materials) even after the oily stains have attached to it.
- oily stains the main components of which are oily components (e.g., higher fatty acids and higher alcohols) derived from floating matter volatilized and scattered from building materials, food, daily necessities, etc.
- Patent Documents 1 and 2 make no consideration whatsoever about the water sliding properties of droplets.
- the water sliding property of droplets can be increased by increasing the water repellency of the substrate surface, but the large contact angle makes it easier for tall droplets to form in the direction perpendicular to the substrate, which causes the problem of bridging between the fins caused by the droplets.
- the fin spacing has become extremely narrow in order to improve the heat dissipation efficiency or cooling efficiency of heat exchangers, and it is necessary to achieve both hydrophilicity to suppress bridging between fins and water sliding to improve the drainage of droplets.
- the surface treatment agent described in Patent Document 5 is said to have achieved both hydrophilicity and drainage (water sliding) properties, but uses colloidal silica as hydrophilic particles, which tends to result in insufficient hydrophilicity.
- the second objective of the present invention is to provide a new water-slipping agent capable of forming a tangible object (e.g., a coating film) with good hydrophilicity and water-slipping properties.
- the present invention aims to solve at least one of the first and second problems, and in a preferred embodiment, to solve both the first and second problems.
- the inventors have found that the use of particles containing a crosslinked polymer having a specific functional group can enhance the sustained hydrophilicity after wet/dry cycles.
- the present inventors have also found that by using the particles, it is possible to enhance not only hydrophilicity but also water slippage.
- An agent for imparting hydrophilicity sustaining effect and/or water slipping comprising, as a constituent, particles containing a crosslinked polymer having a -COOR group (R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium) and a hydroxyl group.
- R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium
- the crosslinked polymer contains a structural unit derived from a monomer (AB1) having one or more -COOR groups, one or more hydroxyl groups, and one polymerizable group in one molecule, and a structural unit derived from a monomer (C) having two or more polymerizable groups in one molecule.
- [5] The agent for imparting hydrophilicity sustaining effect and/or water slipping property according to any one of [2] to [4], wherein the content of the structural unit derived from the monomer (AB1) in the crosslinked polymer is 5 mass% or more.
- [6] The agent for imparting hydrophilicity sustaining effect and/or water slipping property according to any one of [2] to [5], wherein the content of the structural unit derived from the monomer (C) in the crosslinked polymer is 0.01 to 70 mass%.
- a resin composition comprising the agent for imparting hydrophilicity sustaining effect and/or water slipping effect according to any one of [1] to [11] and a hydrophilic resin.
- the hydrophilic resin is a resin having at least one polar functional group selected from the group consisting of a carboxy group and a salt of a carboxy group, in a side chain.
- a method for imparting sustained hydrophilicity and/or water slippage to a tangible object comprising incorporating into the tangible object particles containing a crosslinked polymer having a -COOR group (R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium) and a hydroxyl group.
- R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium
- a method for imparting sustained hydrophilicity and/or water slippage to a substrate surface comprising applying to the substrate a composition containing particles comprising a crosslinked polymer having a -COOR group (R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium) and a hydroxyl group, thereby forming a coating film containing the particles on the substrate surface.
- the substrate is a fin material of a heat exchanger.
- the composition further contains a hydrophilic resin.
- the hydrophilic resin is a resin having at least one polar functional group selected from the group consisting of a carboxy group and a salt of a carboxy group, on a side chain.
- the composition further contains a crosslinking agent.
- crosslinked polymer contains a structural unit derived from a monomer (AB1) having one or more -COOR groups, one or more hydroxyl groups, and one polymerizable group in one molecule, and a structural unit derived from a monomer (C) having two or more polymerizable groups in one molecule.
- the present invention can provide the following first and/or second effects.
- First effect By using the particles of the present invention, the hydrophilicity of the resulting shaped object can be improved after wet/dry cycles, and preferably, the hydrophilicity of the shaped object after the adhesion of oily stains can also be improved.
- Second effect By using the particles of the present invention, it is possible to impart hydrophilicity and water-slip properties to the resulting tangible object.
- the agent for imparting hydrophilicity sustaining effect and/or water slipping property which comprises the particles of the present invention as a constituent component, is also preferable in that the production thereof does not necessarily require the use of organic solvents (particularly organic solvents that are immiscible with water) or highly toxic monomers.
- FIG. 1 is a schematic diagram showing a method for measuring a sliding angle.
- a coating film will be used as an example of a tangible object, but as will be described later, the tangible object is not limited to a coating film.
- the hydrophilicity sustaining effect and/or water slipping agent of the present invention is composed of particles (hereinafter, sometimes simply referred to as "polymer particles") containing a crosslinked polymer having a -COOR group (R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium) and a hydroxyl group.
- polymer particles containing a crosslinked polymer having a -COOR group (R represents a hydrocarbon group, a hydrogen atom, an alkali metal atom, or ammonium) and a hydroxyl group.
- the crosslinked polymer constituting the polymer particles has a -COOR group and a hydroxyl group, which makes it possible to exhibit excellent hydrophilic properties (initial hydrophilicity, hydrophilicity sustaining after wet/dry cycles, hydrophilicity after oil stain adhesion, etc.).
- the crosslinked polymer has a -COOR group and a hydroxyl group, which makes it possible to exhibit excellent hydrophilicity as well as excellent water slipping.
- the polymer having a -COOR group and a hydroxyl group is a crosslinked polymer, which makes it possible to prevent the hydrophilicity sustaining effect and/or water slipping agent from dissolving into water, and makes it possible to increase the sustaining of the hydrophilic properties and water slipping.
- the hydrophilicity sustaining effect and/or water slipping agent of the present invention is also preferable in that the above effects can be obtained without using silica particles that are likely to cause odor or mold wear.
- crosslinked polymer refers to a polymer having a crosslinked structure, and the crosslinked structure can be introduced into the crosslinked polymer by (co)polymerizing a monomer having two or more polymerizable groups in one molecule.
- a crosslinked polymer can be said to be a polymer containing structural units derived from a monomer having two or more polymerizable groups in one molecule.
- the hydrocarbon group represented by R may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.
- Examples of the aliphatic hydrocarbon group include Alkyl groups (preferably alkyl groups having 1 to 4 carbon atoms), such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group; alkenyl groups (preferably alkenyl groups having 2 to 6 carbon atoms) such as a vinyl group, an n-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, a 2-methyl-2-butenyl group, or a 3-methyl-1-butenyl group; cycloalkyl groups (preferably cycloalkyl groups having 3 to 8 carbon atoms) such as cyclopropyl group, cyclobutyl group
- the aromatic hydrocarbon group may, for example, be a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a 4-tert-butylphenyl group, a naphthyl group, etc., and is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.
- groups that combine an aliphatic hydrocarbon group and an aromatic hydrocarbon group include aralkyl groups such as benzyl and phenethyl groups, and preferably aralkyl groups having 7 to 12 carbon atoms.
- the hydrocarbon group represented by R is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, even more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.
- the alkali metal atom represented by R includes lithium, sodium, potassium, etc., with sodium and potassium being preferred, and sodium being more preferred.
- the ammonium represented by R is not limited to NH4 + , but is defined to include organic ammonium.
- organic ammonium include quaternary ammonium such as tetraalkylammonium (preferably tetra- C1-10 alkylammonium) such as tetramethylammonium and tetrabutylammonium; and ammonium (primary to tertiary ammonium) formed by protonating an amine.
- the amine examples include trialkylamine (preferably tri- C1-10 alkylamine) such as trimethylamine, triethylamine, tributylamine; and hydroxyalkylamine (preferably mono-, di- or tri-(hydroxy- C1-10 alkyl)amine) such as monoethanolamine, diethanolamine, triethanolamine.
- the ammonium represented by R includes NH4 + and primary to quaternary ammonium, and preferably includes tetraalkylammonium such as tetramethylammonium, tetrabutylammonium, etc.
- trialkylammonium such as trimethylammonium, triethylammonium, tributylammonium, etc. (preferably tri- C1-10 alkylammonium), hydroxyalkylammonium such as monoethanolammonium, diethanolammonium, triethanolammonium, etc. (preferably mono-, di- or tri-(hydroxy- C1-10 alkyl)ammonium), or NH4 + .
- the crosslinked polymer may have one type of -COOR group alone or multiple types.
- the R is preferably a hydrogen atom, an alkali metal atom, or ammonium, and more preferably an alkali metal atom or ammonium.
- the R is preferably a combination of one or more selected from hydrogen atoms, alkali metal atoms, and ammonium with a hydrocarbon group (particularly, an alkyl group having 1 to 4 carbon atoms), and more preferably a combination of one or more selected from alkali metal atoms and ammonium with a hydrocarbon group (particularly, an alkyl group having 1 to 4 carbon atoms).
- the total ratio of R that is a hydrogen atom, an alkali metal atom, or ammonium out of the total R 100 mol % contained in the crosslinked polymer (hereinafter referred to as the ionization rate) is, for example, 20 to 100 mol %, preferably 40 to 100 mol %, and more preferably 50 to 100 mol %.
- the upper limit of the ionization rate may be 95 mol% or less, or may be 90 mol% or less.
- the hydroxyl value of the crosslinked polymer is preferably from 20 to 500 mgKOH/g, more preferably from 40 to 480 mgKOH/g, and further preferably from 70 to 450 mgKOH/g.
- the hydroxyl value means the amount (mg) of potassium hydroxide having the same substance amount as the substance amount of hydroxyl groups contained in 1 g of the crosslinked polymer.
- the hydroxyl value of the crosslinked polymer can be calculated by determining the amount of hydroxyl groups contained in the monomer component used as the raw material of the crosslinked polymer.
- the hydroxyl value can also be determined by determining the amount (mg) of potassium hydroxide (KOH) required to neutralize acetic acid bonded to hydroxyl groups when 1 g of the crosslinked polymer is acetylated in accordance with JIS K0070.
- KOH potassium hydroxide
- the hydroxyl value of the crosslinked polymer can be easily adjusted by adjusting the amount of the hydroxyl-containing monomer contained in the monomer component used as the raw material for the crosslinked polymer.
- the proportion of -COOR groups contained in the crosslinked polymer is preferably 10 to 300 moles, more preferably 30 to 200 moles, even more preferably 50 to 150 moles, and particularly preferably 80 to 120 moles, per 100 moles of hydroxyl groups contained in the crosslinked polymer.
- the crosslinked polymer contains a structural unit derived from a monomer having two or more polymerizable groups in one molecule.
- the monomer having two or more polymerizable groups in one molecule includes a monomer having two or more ethylenically unsaturated bonds, and is preferably a monomer having two or more ethylenically unsaturated bonds at the terminal, that is, a monomer having two or more CH 2 ⁇ C ⁇ groups. That is, the polymerizable group is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group.
- monomers having two or more polymerizable groups in one molecule include the monomers exemplified below as monomer (A2), monomer (B2), monomer (AB2), and monomer (C), with monomer (C) being preferred.
- the content of structural units derived from a monomer having two or more polymerizable groups in one molecule (preferably structural units derived from monomer (C)) in the crosslinked polymer is, for example, 0.01 to 70% by mass, preferably 0.01 to 35% by mass, more preferably 1 to 25% by mass, and even more preferably 5 to 20% by mass.
- the crosslinked polymer is preferably a crosslinked polymer of any one of the following aspects 1 to 4, more preferably a crosslinked polymer of aspect 1, aspect 2, or aspect 4, and particularly preferably a crosslinked polymer of aspect 4.
- R in the -COOR group is the same as above, and the preferred aspects are also the same.
- a crosslinked polymer comprising a structural unit derived from a monomer having one or more -COOR groups and one polymerizable group in one molecule and no hydroxyl group (hereinafter, monomer (A1)), a structural unit derived from a monomer having one or more hydroxyl groups and one polymerizable group in one molecule and no -COOR group (hereinafter, monomer (B1)), and a structural unit derived from a monomer (C) having two or more polymerizable groups in one molecule (hereinafter, monomer (C)).
- a crosslinked polymer containing a structural unit derived from a monomer having one or more -COOR groups, one or more hydroxyl groups, and two or more polymerizable groups in one molecule hereinafter, monomer (AB2)).
- a crosslinked polymer comprising a structural unit derived from a monomer having one or more -COOR groups, one or more hydroxyl groups, and one polymerizable group in one molecule hereinafter, referred to as monomer (AB1)
- monomer (AB1) monomer
- C monomer
- structural unit derived from a specified monomer refers to a structural unit having the same structure as the structure formed by polymerization of the specified monomer, and is usually a structure in which the carbon-carbon double bond contained in the specified monomer is replaced with a carbon-carbon single bond and two bonds bonded to each carbon.
- the structural unit derived from the specified monomer does not necessarily have to be a structural unit formed by the actual polymerization of the specified monomer, and even if it is a structural unit formed by a method other than polymerization of the specified monomer (for example, a structural unit formed through a reaction such as hydrolysis or neutralization after polymerization) that has the same structure as the structure formed by polymerization of the specified monomer, it is included in the structural unit derived from the specified monomer.
- the number of --COOR groups contained in one molecule of the monomer (A1) is preferably 1 to 3, and more preferably 1.
- the polymerizable group contained in the monomer (A1) is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, and more preferably a (meth)acryloyl group.
- Examples of the monomer (A1) include carboxyl group-containing monofunctional monomers, salts of carboxyl group-containing monofunctional monomers, (meth)acrylate monomers, etc.
- carboxyl group-containing monofunctional monomer examples include unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and among these, unsaturated monocarboxylic acids are preferred, (meth)acrylic acid is more preferred, and acrylic acid is particularly preferred.
- unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid
- unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid
- unsaturated monocarboxylic acids are preferred, (meth)acrylic acid is more preferred, and acrylic acid is particularly preferred.
- Examples of the salt of the carboxyl group-containing monofunctional monomer include alkali metal salts of the carboxyl group-containing monofunctional monomer and ammonium salts of the carboxyl group-containing monofunctional monomer.
- specific examples of the alkali metal atom or ammonium that forms a salt with the carboxyl group-containing monofunctional monomer are the same as the examples of the alkali metal atom or ammonium represented by R described above, and the preferred embodiments are also the same.
- salts of unsaturated monocarboxylic acids are preferred, and salts of acrylic acid are more preferred.
- the (meth)acrylate monomer examples include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; and (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate.
- (meth)acrylic acid alkyl esters are preferred, (meth)acrylic acid C1-10 alkyl esters are more preferred, and (meth)acrylic acid C1-4 alkyl esters are even more preferred.
- the number of --COOR groups contained in one molecule of the monomer (A2) is preferably 1 to 3, and more preferably 1.
- the number of polymerizable groups contained in the monomer (A2) is preferably 2 to 6, and more preferably 2.
- the polymerizable group contained in the monomer (A2) is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, and more preferably a (meth)acryloyl group.
- Examples of the monomer (A2) include 1-benzyl-3,4-divinyl-1H-pyrrole-2,5-dimethyl dicarboxylate, 1,1'-[2-[(ethoxycarbonyl)oxy]-1,3-propanediyl]bis(2-methyl-2-propenoic acid ester), etc.
- the number of hydroxyl groups contained in one molecule of the monomer (B1) is preferably 1 to 3, and more preferably 1.
- the polymerizable group contained in the monomer (B1) is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, and more preferably a (meth)acryloyl group.
- the monomer (B1) include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
- (meth)acrylic acid C 1-8 hydroxyalkyl esters are preferred, and (meth)acrylic acid C 1-4 hydroxyalkyl esters are more preferred.
- the number of hydroxyl groups contained in one molecule of the monomer (B2) is preferably 1 to 3, and more preferably 1.
- the number of polymerizable groups contained in one molecule of the monomer (B2) is preferably 2 to 6, and more preferably 2.
- the polymerizable group contained in the monomer (B2) is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, and more preferably a (meth)acryloyl group.
- the monomer (B2) examples include esters of polyols having n hydroxyl groups (n is an integer of 3 or more, preferably an integer of 3 to 6), such as pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate, with 2 to n-1 (meth)acrylic acids, and divinyl compounds having hydroxyl groups as represented by the following formula:
- the polymerizable group contained in the monomer (C) is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, more preferably a vinyl group or a methacryloyl group, and particularly preferably a vinyl group.
- the molecular weight of the monomer (C) is preferably 50 or more and 1,000 or less, and more preferably 100 or more and 400 or less.
- the monomer (C) is preferably a polyfunctional ethylenically unsaturated monomer having two or more ethylenically unsaturated bond-containing groups, such as a hydrocarbon crosslinkable monomer, a divinyl ether monomer, a diallyl ether monomer, or a polyvalent (meth)acrylic acid ester.
- a polyfunctional ethylenically unsaturated monomer having two or more ethylenically unsaturated bond-containing groups such as a hydrocarbon crosslinkable monomer, a divinyl ether monomer, a diallyl ether monomer, or a polyvalent (meth)acrylic acid ester.
- hydrocarbon cross-linking monomers examples include aromatic hydrocarbon cross-linking monomers such as divinylbenzene, trivinylbenzene, divinylnaphthalene, divinyltoluene, and divinylxylene; alicyclic hydrocarbon cross-linking monomers such as trivinylcyclohexane; and linear hydrocarbon cross-linking monomers such as 1,3-butadiene.
- divinyl ether monomers include dialkylene glycol divinyl ethers such as diethylene glycol divinyl ether, dipropylene glycol divinyl ether, dibutylene glycol divinyl ether (preferably diC 1-4 alkylene glycol divinyl ether); polyalkylene glycol divinyl ethers such as polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polybutylene glycol divinyl ether (preferably polyC 1-4 alkylene glycol divinyl ether); etc.
- the number of repeating alkylene glycol units in the polyalkylene glycol divinyl ether is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5.
- diallyl ether monomers include dialkylene glycol diallyl ethers such as diethylene glycol diallyl ether, dipropylene glycol diallyl ether, dibutylene glycol diallyl ether (preferably di-C 1-4 alkylene glycol diallyl ether); polyalkylene glycol diallyl ethers such as polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, polybutylene glycol diallyl ether (preferably poly-C 1-4 alkylene glycol diallyl ether); etc.
- the number of repeating alkylene glycol units in the polyalkylene glycol diallyl ether is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5.
- polyfunctional (meth)acrylic acid esters include (meth)acrylic acid diesters of mono-, di-, or polyalkylene glycols such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate (preferably mono-, di-, or poly-C
- the (meth)acrylic acid diester of 2-4 alkylene glycol (meth)acrylic acid triesters of polyols such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, (meth)acrylic acid tetraesters of polyols such as pentaerythritol tetra(meth)acrylate, (meth)acryl
- the number of repeating alkylene glycol units in the (meth)acrylic acid diester of polyalkylene glycol is not particularly limited, but is preferably 3 to 10, and more preferably 3 to 5.
- polyvalent methacrylic acid esters such as methacrylic acid diesters of mono-, di-, or polyalkylene glycols, methacrylic acid triesters of polyols, methacrylic acid tetraesters of polyols, methacrylic acid pentaesters of polyols, and methacrylic acid hexaesters of polyols are preferred because they have high resistance to hydrolysis, prevent the elution of particle components such as hydrophilic components, and tend to enhance the hydrophilicity sustaining effect and/or water slipping property.
- hydrocarbon cross-linkable monomers and polyvalent (meth)acrylic acid esters are preferred.
- Hydrocarbon cross-linkable monomers and polyvalent methacrylic acid esters are more preferred because they are particularly resistant to hydrolysis and tend to further enhance the sustained hydrophilic effect and/or water slippage, while aromatic hydrocarbon cross-linkable monomers and methacrylic acid diesters of mono-, di-, or polyalkylene glycols are even more preferred, with divinylbenzene being particularly preferred.
- the number of --COOR groups contained in one molecule of the monomer (AB1) is preferably 1 to 3, and more preferably 1.
- the number of hydroxyl groups contained in one molecule of the monomer (AB1) is preferably 1 to 3, and more preferably 1.
- the monomer (AB1) is preferably a hydroxymethylacrylic acid monomer represented by the following formula (2):
- R 1 represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, an alkali metal atom, or ammonium.
- Examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 in the above formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc.
- an alkyl group having 1 to 2 carbon atoms is preferred, and a methyl group is more preferred.
- the alkali metal atom and ammonium represented by R 1 in the above formula (2) are the same as those exemplified for the alkali metal atom and ammonium represented by R above, and preferred embodiments thereof are also the same.
- the number of --COOR groups contained in one molecule of the monomer (AB2) is preferably 1 to 3, and more preferably 1.
- the number of hydroxyl groups contained in one molecule of the monomer (AB2) is preferably 1 to 3, and more preferably 1.
- the number of polymerizable groups contained in one molecule of the monomer (AB2) is preferably 2 to 6, and more preferably 2.
- the polymerizable group contained in the monomer (AB2) is preferably an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, and more preferably a (meth)acryloyl group.
- the monomer (AB2) examples include methyl 3,4-diethenyl-5-(hydroxymethyl)-1-(phenylmethyl)-1H-pyrrole-2-carboxylate, methyl 3-hydroxy-3-(2-propen-1-yl)-5-hexenoate, etc.
- the crosslinked polymer of the embodiment 1 may contain one or more structural units derived from the monomer (A1).
- the crosslinked polymer of the embodiment 1 may contain one or more structural units derived from the monomer (B1).
- the crosslinked polymer of the embodiment 1 may contain one or more structural units derived from the monomer (C).
- the content of the structural unit derived from the monomer (A1) in the crosslinked polymer of the embodiment 1 is preferably 1 to 98.99 mass %, more preferably 10 to 90 mass %, and even more preferably 10 to 50 mass %.
- the content of the structural unit derived from the monomer (B1) in the crosslinked polymer of the embodiment 1 is preferably 1 to 98.99 mass %, more preferably 10 to 90 mass %, and even more preferably 10 to 50 mass %.
- the content of the structural unit derived from the monomer (C) (preferably a polyfunctional ethylenically unsaturated monomer) in the crosslinked polymer of Aspect 1 is preferably 0.01 to 70 mass%, more preferably 0.01 to 35 mass%, and even more preferably 5 to 20 mass%.
- the total content of the structural units derived from the monomer (A1), the structural units derived from the monomer (B1), and the structural units derived from the monomer (C) is preferably 20 to 100 mass%, more preferably 30 to 100 mass%, and even more preferably 50 to 100 mass%.
- the crosslinked polymer of the embodiment 1 may further contain a structural unit derived from another monomer other than the monomer (A1), the monomer (B1), and the monomer (C).
- Examples of the other monomer include, in addition to the monomer (AB1), a polyoxyalkylene group-containing ethylenically unsaturated monomer, a styrene-based monomer, a vinyl ester-based monomer, a silane group-containing monomer, a nitrogen atom-containing monomer, an oxo group-containing monomer, a fluorine atom-containing monomer, an epoxy group-containing monomer, a light stabilizing monomer, and an ultraviolet absorbing monomer, which will be described later.
- the crosslinked polymer of the aspect 2 may contain one or more types of structural units derived from the monomer (A1).
- the crosslinked polymer of the aspect 2 may contain one or more types of structural units derived from the monomer (A2).
- the crosslinked polymer of the aspect 2 may contain one or more types of structural units derived from the monomer (B1).
- the crosslinked polymer of the aspect 2 may contain one or more types of structural units derived from the monomer (B2).
- the total content of the structural units derived from the monomer (A2) and the structural units derived from the monomer (B2) is preferably 0.01 to 70 mass%, more preferably 0.01 to 35 mass%, and even more preferably 5 to 20 mass%.
- the total content of the structural units derived from the monomer (A1), the structural units derived from the monomer (A2), the structural units derived from the monomer (B1) and the structural units derived from the monomer (B2) is preferably 20 to 100 mass%, more preferably 30 to 100 mass%, and even more preferably 50 to 100 mass%.
- the crosslinked polymer of the embodiment 2 may further contain a structural unit derived from another monomer other than the monomer (A1), the monomer (A2), the monomer (B1), and the monomer (B2).
- the other monomer may be a monomer (C) not included in the monomer (A2) and the monomer (B2), a monomer (AB1), a monomer (AB2), or a polyoxyalkylene group-containing ethylenically unsaturated monomer, a styrene-based monomer, a vinyl ester-based monomer, a silane group-containing monomer, a nitrogen atom-containing monomer, an oxo group-containing monomer, a fluorine atom-containing monomer, an epoxy group-containing monomer, a light stabilizing monomer, an ultraviolet absorbing monomer, or the like, which will be described later.
- a monomer (C) not included in the monomer (A2) and the monomer (B2) a monomer (AB1), a monomer (AB2), or a polyoxyalkylene group-containing ethylenically unsaturated monomer, a styrene-based monomer, a vinyl ester-based
- the crosslinked polymer of the embodiment 3 may contain one type of structural unit derived from the monomer (AB2) alone or two or more types.
- the content of the structural unit derived from the monomer (AB2) in the crosslinked polymer of the third embodiment is preferably 0.01 to 100% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 50% by mass.
- the crosslinked polymer of the third aspect may further contain a structural unit derived from a monomer other than the monomer (AB2).
- the monomer examples include the monomer (A1), the monomer (A2), the monomer (B1), the monomer (B2), the monomer (C), and the monomer (AB1), as well as a polyoxyalkylene group-containing ethylenically unsaturated monomer, a styrene-based monomer, a vinyl ester-based monomer, a silane group-containing monomer, a nitrogen atom-containing monomer, an oxo group-containing monomer, a fluorine atom-containing monomer, an epoxy group-containing monomer, a light stabilizing monomer, and an ultraviolet absorbing monomer, which will be described later.
- the crosslinked polymer of the present invention is preferably a crosslinked polymer of embodiment 4 containing a structural unit derived from monomer (AB1) and a structural unit derived from monomer (C), and particularly preferably a crosslinked polymer containing a structural unit derived from a hydroxymethylacrylic acid monomer represented by formula (2) and a structural unit derived from a polyfunctional ethylenically unsaturated monomer.
- the crosslinked polymer of embodiment 4 may contain one type of structural unit derived from monomer (AB1) alone or two or more types.
- the crosslinked polymer of embodiment 4 may contain one type of structural unit derived from monomer (C) alone or two or more types.
- the structural unit derived from the hydroxymethylacrylic acid monomer represented by formula (2) can be rephrased as the structural unit represented by the following formula (1), that is, among the crosslinked polymers of embodiment 4, a crosslinked polymer containing a structural unit represented by formula (1) and a structural unit derived from a polyfunctional ethylenically unsaturated monomer is particularly preferred.
- R 1 represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, an alkali metal atom, or ammonium.
- the alkyl group having 1 to 4 carbon atoms, the alkali metal atom, and ammonium represented by R 1 in the above formula (1) are the same as R 1 in the above formula (2), and preferred embodiments thereof are also the same.
- R 1 is an alkali metal atom, it is contained in the crosslinked polymer as an alkali metal salt of a carboxylic acid, and when R 1 is ammonium, it is contained in the crosslinked polymer as an ammonium salt of a carboxylic acid.
- the crosslinked polymer of the fourth aspect preferably has a plurality of structural units represented by formula (1), and the R 1s contained in the plurality of formulas (1) may be the same or different.
- R 1 is preferably a hydrogen atom, an alkali metal atom, or ammonium, and more preferably an alkali metal atom or ammonium.
- R 1 is preferably a combination of at least one selected from a hydrogen atom, an alkali metal atom, and ammonium with an alkyl group having 1 to 4 carbon atoms, and more preferably a combination of at least one selected from an alkali metal atom and ammonium with an alkyl group having 1 to 4 carbon atoms.
- the total ratio of R 1s that are hydrogen atoms, alkali metal atoms, or ammonium (hereinafter referred to as the ionization rate) in 100 mol % of all R 1s contained in the crosslinked polymer of the fourth aspect is, for example, 20 to 100 mol %, preferably 40 to 100 mol %, and more preferably 50 to 100 mol %.
- the upper limit of the ionization rate may be 95 mol % or less, or may be 90 mol % or less.
- the content of the structural unit derived from the above monomer (AB1) (particularly, the structural unit represented by formula (1)) in the crosslinked polymer of Aspect 4 is, for example, 5 to 99.9 mass%, preferably 10 to 99 mass%, more preferably 15 to 95 mass%, and even more preferably 15 to 90 mass%.
- the content of the structural unit derived from the above monomer (AB1) (particularly, the structural unit represented by formula (1)) in the crosslinked polymer of Aspect 4 is preferably 45 to 99.9 mass%, more preferably 65 to 99 mass%, and even more preferably 75 to 95 mass%.
- the structural unit represented by the formula (1) may be formed by polymerization of the hydroxymethylacrylic acid monomer represented by the formula (2), or may be formed by other methods.
- a monomer in which R 1 is an alkyl group having 1 to 4 carbon atoms is polymerized, and then a basic substance such as an alkali metal hydroxide, ammonia, or amine is added to hydrolyze the ester group, thereby forming a structural unit in which R 1 is an alkali metal or a structural unit in which ammonium is present in the formula (1).
- an acid may be appropriately added to neutralize the resulting mixture, thereby forming a structural unit in which R 1 is a hydrogen atom in the formula (1).
- the monomer represented by the formula (2) may be one type or two or more types.
- the crosslinked polymer of the embodiment 4 contains two or more types of structural units represented by the formula (1), it may be formed by polymerizing two or more types of monomers represented by the formula (2), or it may be formed by polymerizing a monomer represented by the formula (2) in which R 1 is an alkyl group having 1 to 4 carbon atoms, and then partially hydrolyzing the ester group or hydrolyzing it with two or more types of basic substances.
- the crosslinked polymer of aspect 4 has a structural unit derived from monomer (C), and preferably has a structural unit derived from a polyfunctional ethylenically unsaturated monomer.
- the crosslinked polymer of aspect 4 may contain one type of structural unit derived from monomer (C) alone, or may contain two or more types.
- Monomer (C) is as described above, and the preferred aspects thereof are also the same.
- the content of the structural unit derived from the monomer (C) is, for example, 0.01 to 70 mass%, preferably 0.01 to 35 mass%, more preferably 1 to 25 mass%, and even more preferably 5 to 20 mass%, in the crosslinked polymer of Aspect 4.
- the content of the structural unit derived from the monomer (C) (particularly, a polyfunctional ethylenically unsaturated monomer) in the crosslinked polymer of Aspect 4 may be 0.01 to 10 mass%, 0.02 to 8 mass%, or 0.04 to 6 mass%.
- the content of the structural unit derived from monomer (C) (particularly, the polyfunctional ethylenically unsaturated monomer) relative to 100 parts by mass of the structural unit derived from monomer (AB1) (particularly, the structural unit represented by formula (1)) is preferably 0.1 to 36 parts by mass, more preferably 2 to 26 parts by mass, and even more preferably 6 to 21 parts by mass.
- the total content of the structural units derived from monomer (AB1) and the structural units derived from monomer (C) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.
- the upper limit of the total content may be 99.9% by mass or 99% by mass.
- the crosslinked polymer of aspect 4 may further contain one or more structural units derived from a polyoxyalkylene group-containing ethylenically unsaturated monomer.
- structural units derived from a polyoxyalkylene group-containing ethylenically unsaturated monomer.
- polyoxyalkylene group-containing ethylenically unsaturated monomers examples include compounds having a polyoxyalkylene group with two or more repeating oxyalkylene units and an ethylenically unsaturated bond-containing group, and among these, compounds represented by the following formula (3) are preferred.
- R 31 represents a hydrogen atom or a methyl group
- R 32 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms
- m represents an integer of 1 to 4
- n represents an integer of 2 to 20.
- R 31 is preferably a methyl group
- R 32 is preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms represented by R 32 is the same as that explained for the alkyl group having 1 to 4 carbon atoms represented by R 1 .
- Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 32 include a phenyl group which may have one or more alkyl groups having 1 to 10 carbon atoms (provided that the total number of carbon atoms is 20 or less), and a naphthyl group which may have one or more alkyl groups having 1 to 10 carbon atoms (provided that the total number of carbon atoms is 20 or less).
- Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
- an alkyl group having 4 to 10 carbon atoms is preferable, and a nonyl group is more preferable.
- R 32 is preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a phenyl group which may have an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a phenyl group which may have a nonyl group.
- the structure represented by C m H 2m in formula (3) refers to an alkylene group, and the alkylene group may be linear or branched, but is preferably linear.
- the structures represented by multiple C m H 2m in formula (3) may be the same or different.
- -(C m H 2m O) n - in formula (3) is preferably a structure in which one or more -C 2 H 4 O- and one or more -C 3 H 6 O- are bonded in any order.
- n is preferably an integer from 2 to 4, more preferably 2 or 3, and even more preferably 2.
- n is preferably an integer from 2 to 15, and more preferably an integer from 2 to 10.
- the content thereof in the crosslinked polymer of Aspect 4 is preferably 0.1 to 30 mass %, more preferably 1 to 20 mass %, and further preferably 3 to 15 mass %.
- the content of the structural unit derived from the polyoxyalkylene group-containing ethylenically unsaturated monomer relative to 100 parts by mass of the structural unit derived from the monomer (AB1) (particularly, the structural unit represented by formula (1)) is preferably 0.2 to 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 5 to 16 parts by mass.
- the total content of the structural units derived from the monomer (AB1), the structural units derived from the monomer (C), and the structural units derived from the polyoxyalkylene group-containing ethylenically unsaturated monomer is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
- the upper limit of the total content may be 99.9% by mass or 99% by mass.
- the crosslinked polymer of the above-mentioned embodiment 4 may contain one or more structural units derived from a monomer having one polymerizable group such as a carbon-carbon double bond-containing group in one molecule (hereinafter referred to as "other monomer") other than the structural units derived from monomer (AB1), the structural units derived from monomer (C), and the structural units derived from the polyoxyalkylene group-containing ethylenically unsaturated monomer.
- other monomer a monomer having one polymerizable group such as a carbon-carbon double bond-containing group in one molecule
- Other monomers include, but are not limited to, (meth)acrylic monomers, styrene monomers, carboxyl group-containing monomers, salts of carboxyl group-containing monomers, vinyl ester monomers, silane group-containing monomers, hydroxyl group-containing monomers, nitrogen atom-containing monomers, oxo group-containing monomers, fluorine atom-containing monomers, epoxy group-containing monomers, light stabilizing monomers, ultraviolet absorbing monomers, etc.
- Examples of the (meth)acrylic monomer include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate.
- (meth)acrylic acid C1-10 alkyl esters are preferred, and (meth)acrylic acid C1-5 alkyl esters are more preferred.
- styrene-based monomer examples include styrene which may have one or more substituents such as a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g., a C1-4 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, etc.), etc.
- a halogen atom e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
- an alkyl group e.g., a C1-4 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl
- styrene-based monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, tert-butylstyrene, chlorostyrene, vinyltoluene, etc., and among these, styrene is preferable.
- carboxyl group-containing monomers examples include unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; and anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; among these, unsaturated monocarboxylic acids are preferred, (meth)acrylic acid is more preferred, and acrylic acid is particularly preferred.
- Examples of the salt of the carboxyl group-containing monomer include an alkali metal salt of the carboxyl group-containing monomer and an ammonium salt of the carboxyl group-containing monomer.
- specific examples of the alkali metal atom or ammonium that forms a salt with the carboxyl group-containing monomer are the same as the examples of the alkali metal atom or ammonium represented by R1 above, and the preferred embodiments are also the same.
- the salt of acrylic acid is preferred.
- vinyl ester monomers examples include esters of saturated fatty acids such as vinyl acetate and vinyl propionate with vinyl alcohol, and among these, esters of C1-5 saturated fatty acids with vinyl alcohol are preferred.
- silane group-containing monomers examples include alkoxysilyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, ⁇ -(meth)acryloyloxypropyltrimethoxysilane, and 2-styrylethyltrimethoxysilane, halogenated silyl group-containing silane coupling agents such as vinyltrichlorosilane, and silanol group-containing silane coupling agents such as ⁇ -(meth)acryloyloxypropylhydroxysilane and ⁇ -(meth)acryloyloxypropylmethylhydroxysilane.
- alkoxysilyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, ⁇ -(meth)acryloyloxypropyltrimethoxysilane, and
- hydroxyl group-containing monomer examples include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
- (meth)acrylic acid C 1-8 hydroxyalkyl esters are preferred, and (meth)acrylic acid C 1-4 hydroxyalkyl esters are more preferred.
- nitrogen atom-containing monomers examples include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N-vinylpyrrolidone, (meth)acrylonitrile, etc.
- An example of an oxo group-containing monomer is ethylene glycol methoxy(meth)acrylate.
- fluorine atom-containing monomer examples include (meth)acrylic acid fluorinated alkyl esters such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate.
- (meth)acrylic acid C1-10 fluorinated alkyl esters are preferred, and (meth)acrylic acid C1-5 fluorinated alkyl esters are more preferred.
- epoxy group-containing monomers examples include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and 2-glycidyloxyethyl (meth)acrylate.
- Examples of light stabilizing monomers include monomers having a 2,2,6,6-tetramethylpiperidine ring structure and a polymerizable group (e.g., an ethylenically unsaturated bond-containing group such as a (meth)acryloyl group or a vinyl group), such as 2,2,6,6-tetramethylpiperidine-4-(meth)acrylate and 1,2,2,6,6-pentamethyl-4-piperidyl(meth)acrylate.
- a polymerizable group e.g., an ethylenically unsaturated bond-containing group such as a (meth)acryloyl group or a vinyl group
- ultraviolet absorbing monomers examples include benzotriazole-based ultraviolet absorbing monomers and benzophenone-based ultraviolet absorbing monomers.
- a (meth)acrylic monomer, a styrene-based monomer, a carboxy group-containing monomer, a salt of a carboxy group-containing monomer, or a hydroxy group-containing monomer is preferable, a (meth)acrylic acid alkyl ester, (meth)acrylic acid, a salt of (meth)acrylic acid, or a styrene-based monomer is more preferable, an acrylic acid alkyl ester, acrylic acid, or a salt of acrylic acid is further preferable, and acrylic acid or a salt of acrylic acid is particularly preferable.
- the total content of the structural units derived from acrylic acid and the structural units derived from a salt of acrylic acid (in particular, the content of the structural units derived from a salt of acrylic acid) in the crosslinked polymer of Aspect 4 may be 0 to 40% by mass or may be 5 to 20% by mass.
- the content of structural units derived from other monomers in the crosslinked polymer of embodiment 4 is, for example, 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less or 10% by mass or less, and even more preferably 5% by mass or less or 3% by mass or less.
- the polymer particles may be entirely composed of the crosslinked polymer described above, or part of the polymer particles may be composed of the crosslinked polymer described above. That is, the polymer particles may have a single-layer structure or a multi-layer structure.
- the entire particle is composed of the crosslinked polymer described above
- the polymer particles have a multi-layer structure
- the outermost shell layer is composed of the crosslinked polymer described above.
- Making the polymer particles into a multi-layer structure, preferably a core-shell structure is also effective in further enhancing hydrophilicity and water slippage.
- the particles can be given high hydrophilicity and the resulting tangible object can be given water slippage, while by lowering the hydrophilicity of the inner layer such as the core part, the particles can be given low solubility and low swelling in water, and as a result, the deterioration and elution of the resulting coating film (tangible object) can be suppressed.
- the core-shell structure it is possible to give the particles higher hydrophilicity (especially initial hydrophilicity) and water slippage than in the case of a single layer.
- the fin material of the heat exchanger used in the outdoor unit, the car air conditioner, etc. may be exposed to pollutants such as carbon black contained in the exhaust gas of the automobile, etc., and the adhesion of such pollutants leads to a decrease in the hydrophilicity of the coating film (tangible object).
- the polymer particles have a multilayer structure such as a core-shell structure, the pollutants attached to the surface of the coating film (tangible object) tend to be more easily removed.
- the second polymer constituting layers other than the outermost shell is different from the cross-linked polymer.
- the second polymer preferably has one or more structural units composed of a non-aqueous monomer that does not have an acidic proton-containing group such as a carboxy group, a hydroxyl group, a thiol group, or a silanol group, and an amino group. This can reduce the hydrophilicity of the inner layer such as the core portion.
- the non-aqueous monomer is preferably a monomer composed of a hydrocarbon that may have one or more selected from an ester group, an ether group, an amide group, and a halogeno group, and more preferably a monomer composed of a hydrocarbon that may have an ester group.
- non-aqueous monomer examples include (meth)acrylic monomers, styrene monomers, vinyl ester monomers, oxo group-containing monomers, fluorine atom-containing monomers, and epoxy group-containing monomers.
- the (meth)acrylic monomers, styrene monomers, vinyl ester monomers, oxo group-containing monomers, fluorine atom-containing monomers, and epoxy group-containing monomers are the same as the monomers described in the crosslinked polymer above, and the preferred aspects of each monomer are also the same.
- the non-aqueous monomer is preferably a (meth)acrylic monomer or a styrene monomer, more preferably a (meth)acrylic acid alkyl ester or a styrene monomer, and even more preferably a (meth)acrylic acid C 1-5 alkyl ester or styrene.
- the content of structural units derived from non-aqueous monomers in the second polymer is preferably 40 to 99% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 80% by mass.
- the second polymer preferably further has one or more structural units derived from a polyfunctional ethylenically unsaturated monomer. This is expected to have the effect of further increasing the initial hydrophilicity, sustained hydrophilicity, and water slippage of the coating film (tangible object) surface.
- the polyfunctional ethylenically unsaturated monomer include the same monomers as the polyfunctional ethylenically unsaturated monomers described in the crosslinked polymer.
- hydrocarbon crosslinkable monomers and polyvalent (meth)acrylic acid esters are preferred, aromatic hydrocarbon crosslinkable monomers and (meth)acrylic acid diesters of mono-, di-, or polyalkylene glycols are more preferred, and divinylbenzene is even more preferred.
- the content of the structural unit derived from the polyfunctional ethylenically unsaturated monomer in the second polymer is preferably 1 to 50% by mass, more preferably 10 to 45% by mass, and further preferably 20 to 40% by mass.
- the content of the structural units derived from the polyfunctional ethylenically unsaturated monomer relative to 100 parts by mass of the structural units derived from the non-aqueous monomer is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 20 to 50 parts by mass.
- the total content of the structural units derived from the non-aqueous monomer and the structural units derived from the polyfunctional ethylenically unsaturated monomer is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
- the upper limit of the total content may be 99.9% by mass or 99% by mass.
- the second polymer may contain one or more structural units derived from the above-mentioned monomer (AB1) (particularly, the structural unit represented by formula (1)), but preferably does not contain any.
- the content (content ratio) of the structural unit derived from the monomer (AB1) (particularly, the structural unit represented by formula (1)) is preferably less than the content (content ratio) of the structural unit derived from the monomer (AB1) (particularly, the structural unit represented by formula (1)) in the crosslinked polymer, specifically, 10% by mass or less is preferable, and 5% by mass or less is more preferable.
- the second polymer may contain one or more structural units derived from a monomer having one polymerizable group, such as a carbon-carbon double bond-containing group, in one molecule other than the structural units derived from a non-aqueous monomer, the structural units derived from a polyfunctional ethylenically unsaturated monomer, and the structural units derived from the monomer (AB1) (hereinafter, "second other monomer").
- a monomer having one polymerizable group such as a carbon-carbon double bond-containing group
- the second other monomer may be a monomer having a carboxy group, a thiol group, a silanol group, an amino group, or the like, such as a carboxy group-containing monomer, a silane group-containing monomer, a hydroxyl group-containing monomer, a nitrogen atom-containing monomer, a light stabilizing monomer, or an ultraviolet absorbing monomer.
- a carboxy group-containing monomer, a silane group-containing monomer, a hydroxyl group-containing monomer, a nitrogen atom-containing monomer, a light stabilizing monomer, or an ultraviolet absorbing monomer are the same as the monomers described in the crosslinked polymer described above, and the preferred aspects of each monomer are also the same.
- the content of structural units derived from the second other monomer in the second polymer is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less or 3% by mass or less.
- the volume average particle diameter of the polymer particles is, for example, 10 nm to 10 ⁇ m, preferably 10 nm to 5 ⁇ m, more preferably 20 nm to 1 ⁇ m, and even more preferably 30 nm to 500 nm. From the viewpoint of further increasing hydrophilicity after adhesion of oil stains, it is preferably 10 nm to 500 nm, more preferably 15 nm to 300 nm, and even more preferably 20 nm to 100 nm.
- the volume average particle diameter can be measured, for example, by dynamic light scattering.
- the method for producing the polymer particles is not particularly limited, and a conventionally known method may be adopted, but it is preferable to produce the polymer particles by polymerizing the monomers constituting the polymer particles (hereinafter, these may be collectively referred to as "raw monomer components") in an aqueous solvent, and partially or completely hydrolyzing them as necessary.
- hydroxymethylacrylic acid monomers represented by formula (2) in which R 1 is an alkyl group having 1 to 4 carbon atoms (hereinafter, referred to as hydroxymethylacrylic acid ester), a polyfunctional ethylenically unsaturated monomer, a polyoxyalkylene group-containing ethylenically unsaturated monomer used as required, other monomers, non-aqueous monomers, and a second other monomer, in an aqueous solvent, and partially or completely hydrolyzing them as required.
- the product can be made into a particulate form even when polymerized in an aqueous solvent that does not require an organic solvent, which is preferable from the viewpoint of reducing environmental load.
- Polymerization methods include suspension polymerization, emulsion polymerization, dispersion polymerization, etc. Among them, emulsion polymerization is preferred in which the raw material monomer components are dispersed in an aqueous solvent in the presence of an emulsifier and a (radical) polymerization reaction is carried out. Emulsion polymerization may be carried out in only one stage or in multiple stages.
- a non-aqueous monomer, a polyfunctional ethylenically unsaturated monomer used as needed, a monomer (AB) (particularly a monomer represented by formula (2)), and a second other monomer are polymerized in an aqueous solvent to synthesize seed particles that become the core (i.e., the second polymer), and then in the second stage, monomers that constitute the crosslinked polymer (preferably hydroxymethyl acrylic acid ester, a polyfunctional ethylenically unsaturated monomer, and a polyoxyalkylene group-containing ethylenically unsaturated monomer and other monomers used as needed) are polymerized to synthesize a shell (i.e., the crosslinked polymer), thereby producing polymer particles having a core-shell structure.
- a crosslinked polymer preferably hydroxymethyl acrylic acid ester, a polyfunctional ethylenically unsaturated monomer, and a polyoxyalkylene group-containing ethylenically unsaturated
- the emulsifier may be one or more kinds, and may be a non-reactive surfactant that does not have a radically polymerizable group in the molecule, or a reactive surfactant that has a radically polymerizable group (e.g., an ethylenically unsaturated group) in the molecule.
- Non-reactive surfactants include anionic and non-ionic surfactants.
- non-reactive anionic surfactants include fatty acid salts, alkyl (aryl) sulfonates, alkyl sulfate ester salts, polyoxyethylene alkyl (phenyl) ether sulfate salts, etc.
- non-reactive nonionic surfactants include polyoxyethylene alkyl (phenyl) ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers, etc.
- Reactive surfactants include anionic and nonionic surfactants.
- Anionic reactive surfactants include, but are not limited to, ether sulfate reactive surfactants and phosphate ester reactive surfactants.
- the amount of emulsifier used is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 0.2 to 5 parts by mass, and particularly preferably 0.3 to 3 parts by mass, per 100 parts by mass of the total raw monomer components.
- the aqueous solvent may be water alone or a mixture of water and a water-miscible organic solvent.
- the aqueous solvent typically refers to a solvent having a water content of more than 50% by volume.
- water ion-exchanged water (deionized water), distilled water, pure water, etc.
- water-miscible organic solvent an organic solvent that can be mixed uniformly with water (for example, a lower alcohol such as a C 1-4 alkyl alcohol) can be used.
- an aqueous solvent in which 80% by volume or more of the aqueous solvent is water is preferred, an aqueous solvent in which 90% by volume or more of the aqueous solvent is water is more preferred, an aqueous solvent in which 95% by volume or more of the aqueous solvent is water is even more preferred, an aqueous solvent substantially composed of water (an aqueous solvent in which 99.5% by volume or more of water) is particularly preferred, and water alone is most preferred.
- a polymerization initiator for example, a polymerization initiator, irradiation with ultraviolet rays or radiation, application of heat, etc. are used. It is preferable to use a polymerization initiator, and from the viewpoint of efficiently reacting the raw monomer components and sufficiently reducing the remaining monomer, a polymerization initiator combining an oxidizing agent and a reducing agent (redox type polymerization initiator) is preferable.
- oxidizing agent examples include persulfates such as ammonium persulfate and potassium persulfate, and peroxide-based polymerization initiators such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
- peroxide-based polymerization initiators such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
- reducing agent examples include soluble sulfites and ascorbic acid.
- additives such as chain transfer agents, pH buffers, and chelating agents may be added in appropriate amounts to the reaction system in the above emulsion polymerization.
- the amount of additive varies depending on the type and cannot be determined in general, but is usually preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the raw material monomer components.
- the hydrolysis of the polymer particles can be carried out by adding an aqueous solution of an alkali metal hydroxide such as an aqueous solution of sodium hydroxide, an aqueous solution of an amine such as an aqueous solution of cyclohexylamine, or an aqueous solution containing a basic substance such as an aqueous solution of ammonia. Furthermore, partial or complete neutralization can be carried out by adding an appropriate acid to the solution after hydrolysis. By carrying out hydrolysis and neutralization, the group corresponding to R in the -COOR group contained in the polymer particles (particularly, the group corresponding to R 1 in formula (1)) can be converted to a hydrogen atom, an alkali metal atom, or ammonium.
- an alkali metal hydroxide such as an aqueous solution of sodium hydroxide
- an aqueous solution of an amine such as an aqueous solution of cyclohexylamine
- an aqueous solution containing a basic substance such as an
- the hydrolysis rate of the polymer particles of the present disclosure is, for example, 20 to 100%, preferably 40 to 100%, more preferably 50 to 100%, from the viewpoint of further enhancing hydrophilic properties and water sliding properties.
- the hydrolysis rate may be 95% or less, or may be 90% or less.
- the hydrolysis rate can be calculated from the amount (amount of substance) of the basic substance added to 100 mol% of the structural unit derived from the hydrolyzable monomer contained in the crosslinked polymer.
- the hydrolyzable monomer include acrylic monomers such as acrylic acid alkyl esters, and monomers represented by general formula (2).
- the hydrolysis rate can be calculated by assuming that all of the carboxylic acid groups in the hydrolyzable monomers such as the acrylic monomers and the monomers represented by formula (2) are present as esters.
- the agent for imparting hydrophilicity sustaining effect and/or water slipping property of the present invention essentially contains the polymer particles.
- the content of the polymer particles in the agent for imparting hydrophilicity sustaining effect and/or water slipping property of the present invention is, for example, 0.01% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 90% by mass or more, particularly preferably 98% by mass or more, and may be 100% by mass or 99.8% by mass or less.
- the hydrophilicity sustaining effect and/or water slipping agent of the present invention may contain components other than the polymer particles.
- components other than the polymer particles include, but are not limited to, solvents such as aqueous solvents.
- the obtained tangible object can be made hydrophilic for a sustained period of time.
- a tangible object having sustained hydrophilicity on the surface of the fin material in a heat exchanger it is possible to suppress bridges between fins caused by condensed water for a long period of time.
- the shaped object is preferably produced from a composition containing the above-mentioned polymer particles (i.e., a composition containing an agent for imparting hydrophilicity sustaining effect and/or water slipping).
- a composition containing an agent for imparting hydrophilicity sustaining effect and/or water slipping The composition and the shaped object will be described below in order.
- the composition of the present invention contains the above-mentioned polymer particles, i.e., contains the above-mentioned agent for imparting hydrophilicity sustaining effect and/or water slipping property.
- the content of the solid content of the agent for imparting hydrophilicity sustaining effect and/or water slipping property (preferably the above-mentioned polymer particles) in the composition is not particularly limited, but is, for example, 1 to 80 mass%, preferably 5 to 50 mass%, and more preferably 8 to 30 mass%, relative to 100 mass% of the solid content of the composition.
- the composition preferably further contains a resin different from the polymer particles.
- a composition containing a hydrophilicity sustaining effect and/or water slipping agent and a resin may be referred to as a resin composition.
- various resin compositions and tangible objects are included as described below, but here, a case where a hydrophilic coating film is formed using a resin composition containing a hydrophilicity sustaining effect and/or water slipping agent and a hydrophilic resin will be described.
- the hydrophilic resin is not particularly limited, but is preferably a resin having a polar functional group such as a carboxy group, a salt of a carboxy group, a hydroxy group, a sulfonic acid group, an amide group, or an amino group on the side chain, or a resin having a polyether skeleton and/or a polyamine skeleton on the main chain, and more preferably a resin having a polar functional group on the side chain.
- a polar functional group such as a carboxy group, a salt of a carboxy group, a hydroxy group, a sulfonic acid group, an amide group, or an amino group on the side chain
- a resin having a polyether skeleton and/or a polyamine skeleton on the main chain and more preferably a resin having a polar functional group on the side chain.
- the resin having a polar functional group in a side chain may have one type of polar functional group alone or two or more types.
- salt of a carboxy group refers to a functional group in which a hydrogen ion contained in a carboxy group (-COOH) is replaced with a monovalent cation, and is preferably -COOR a (R a represents an alkali metal atom or ammonium).
- R a represents an alkali metal atom or ammonium.
- the alkali metal atom and ammonium represented by R a are the same as the alkali metal atom and ammonium represented by R 1 in the above formula (1).
- R a is preferably an alkali metal atom or hydroxyalkylammonium, more preferably an alkali metal atom or mono-, di- or tri-(hydroxyC 1-10 alkyl)ammonium, and even more preferably sodium or mono(hydroxyC 1-5 alkyl)ammonium.
- the polar functional group is preferably a carboxy group or a salt of a carboxy group, more preferably a carboxy group or an alkali metal salt of a carboxy group, and further preferably a carboxy group or a sodium salt of a carboxy group.
- hydrophilic resin examples include carboxyl group-containing polymers such as (co)polymers of (meth)acrylic acid and (co)polymers of maleic acid; carboxyl group salt-containing polymers such as (co)polymers of (meth)acrylic acid salts and (co)polymers of maleic acid salts; hydroxyl group-containing polymers such as (co)polymers of hydroxy(meth)acrylate and (co)polymers of polyvinyl alcohol; sulfonic acid group-containing polymers such as (co)polymers of 2-acrylamido-2-methylpropanesulfonic acid; amide group-containing polymers such as (co)polymers of acrylamide and (co)polymers of N-vinyl-2-pyrrolidone; amino group-containing polymers such as (co)polymers of diethylaminoethyl(meth)acrylate; polyether-based (co)polymers such as polyethylene glycol; polyamine-based (co)
- the (co)polymer may be either a homopolymer or a copolymer.
- the hydrophilic resin may be a thermoplastic resin or a thermosetting resin, but is preferably a thermosetting resin. Since thermosetting resins have excellent mechanical strength and heat resistance, by using a thermosetting resin as the hydrophilic resin, the uneven shape of the surface of the resulting tangible object tends to be maintained, and the effect of improving the hydrophilic properties and water slippage tends to be further enhanced.
- the hydrophilic resins may be used alone or in combination of two or more types.
- the hydrophilic resin is more preferably a resin having at least one polar functional group selected from the group consisting of a carboxy group and a salt of a carboxy group in the side chain, and is even more preferably a (co)polymer of (meth)acrylic acid (salt).
- (meth)acrylic acid (salt) refers to (meth)acrylic acid and/or a salt of (meth)acrylic acid
- a copolymer of (meth)acrylic acid (salt) refers to a copolymer of (meth)acrylic acid (salt) and other copolymerizing monomers.
- other copolymerizing monomers include monomers other than (meth)acrylic acid and polyfunctional ethylenically unsaturated monomers among the other monomers constituting the polymer particles.
- (meth)acrylic monomers, styrene-based monomers, and hydroxyl group-containing monomers are preferred, and (meth)acrylic acid alkyl esters and styrene-based monomers are more preferred.
- the other copolymerizable monomers may be used alone or in combination of two or more.
- the total proportion of structural units derived from (meth)acrylic acid and salts of (meth)acrylic acid is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.
- the content of the solid content (preferably the polymer particles) of the hydrophilicity sustaining effect and/or water slipping agent in the resin composition is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the hydrophilic resin. By setting it within the above range, the hydrophilicity sustaining effect and/or water slipping property of the hydrophilic coating film tends to be further improved.
- the content of the solid content (preferably the polymer particles) of the hydrophilicity sustaining effect and/or water slipping property of the agent is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the hydrophilic resin.
- the upper limit of the content is not particularly limited, but is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less, per 100 parts by mass of the hydrophilic resin.
- the content is preferably 0.1 to 200 parts by mass, more preferably 5 to 200 parts by mass, even more preferably 15 to 200 parts by mass, still more preferably 40 to 200 parts by mass, particularly preferably 60 to 200 parts by mass, and most preferably 80 to 150 parts by mass, relative to 100 parts by mass of the hydrophilic resin.
- the weight average molecular weight of the hydrophilic resin is not particularly limited, but is, for example, 1,000 to 100,000, preferably 1,500 to 500,000, and more preferably 2,000 to 200,000.
- the composition preferably a resin composition
- the composition further contains a crosslinking agent.
- a crosslinking agent By containing a crosslinking agent, the strength of the hydrophilic coating film can be increased. Furthermore, by containing a crosslinking agent, the durability of the hydrophilic coating film is increased, and as a result, the hydrophilicity sustaining effect and the water slippage of the hydrophilic coating film after a heat cycle as shown in the examples described later are improved.
- the crosslinking agent may be used alone or in combination of two or more types.
- the crosslinking agent is preferably a compound having two or more groups in one molecule that can react with the polar functional group of the hydrophilic resin.
- Examples of the group that can react with the polar functional group include an epoxy group, an oxazoline group, a carbodiimide group, an isocyanate group, etc., and may be selected appropriately depending on the hydrophilic resin to be used.
- a resin having at least one polar functional group selected from the group consisting of carboxy groups and salts of carboxy groups in the side chain as the hydrophilic resin preferably a (co)polymer of (meth)acrylic acid (salt)
- it is preferable to use a crosslinking agent having two or more oxazoline groups in one molecule hereinafter, sometimes referred to as an oxazoline-based crosslinking agent
- an oxazoline-based crosslinking agent a crosslinking agent having two or more oxazoline groups in one molecule
- a crosslinking agent having two or more oxazoline groups in one molecule a water-soluble oxazoline compound is preferred from the viewpoint of excellent crosslinking performance, and an oxazoline group-containing polymer is also preferred.
- the oxazoline group-containing polymer can be produced by a conventionally known production method. For example, a method of polymerizing one or more types of addition polymerizable oxazolines, or a monomer component containing an addition polymerizable oxazoline and a monomer copolymerizable with the addition polymerizable oxazoline can be mentioned.
- addition-polymerizable oxazoline examples include compounds having a polymerizable unsaturated group and an oxazoline group in the molecule, such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
- 2-vinyl-2-oxazoline 2-vinyl-4-methyl-2-oxazoline
- 2-vinyl-5-methyl-2-oxazoline 2-isopropenyl-2-oxazoline
- 2-isopropenyl-4-methyl-2-oxazoline 2-isopropenyl-5-methyl-2-oxazoline
- the monomer copolymerizable with the addition-polymerizable oxazoline is preferably a monomer that does not have a functional group that reacts with an oxazoline group and is copolymerizable with the addition-polymerizable oxazoline, such as (meth)acrylic monomers such as alkyl (meth)acrylates, styrene-based monomers such as styrene, ⁇ -methylstyrene, and chloromethylstyrene, vinyl-based monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate, acrylonitrile, (meth)acrylamide-based monomers such as acrylamide, and olefin-based monomers such as ethylene and propylene.
- (meth)acrylic monomers such as alkyl (meth)acrylates
- styrene-based monomers such as styrene, ⁇ -methylstyrene, and chloromethylst
- water-soluble oxazoline group-containing polymers are preferred, and can be produced by the same method as the above-mentioned method for producing oxazoline group-containing polymers.
- water-soluble oxazoline group-containing polymers include polymers that have a (meth)acrylic resin or the like as the main chain and contain oxazoline groups in the side chains.
- Oxazoline group-containing polymers can also be commercially available products. Examples include water-soluble polymers such as EPOCROS WS-500 and EPOCROS WS-700 manufactured by Nippon Shokubai Co., Ltd., and emulsion-type polymers such as EPOCROS K-2010E, EPOCROS K-2020E, and EPOCROS K-2035E.
- water-soluble polymers such as EPOCROS WS-500 and EPOCROS WS-700 manufactured by Nippon Shokubai Co., Ltd.
- emulsion-type polymers such as EPOCROS K-2010E, EPOCROS K-2020E, and EPOCROS K-2035E.
- the content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the hydrophilic resin.
- the total content of the solids of the hydrophilicity sustaining effect and/or water slipping agent (preferably the polymer particles), the hydrophilic resin, and the crosslinking agent in 100% by mass of the solids of the composition (preferably the resin composition) is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 97% by mass or more, and may be 100% by mass.
- the composition may further contain a solvent.
- a solvent By containing a solvent, the composition (preferably a resin composition) has good coatability.
- the solvent is preferably an aqueous solvent.
- the aqueous solvent is the same as the aqueous solvent used in emulsion polymerization, and the preferred aspects thereof are also the same.
- the content of the solvent in the composition may be 0% by mass, preferably 0.1% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, and is preferably 99.9% by mass or less, and more preferably 99% by mass or less.
- the content of the solvent in the composition may be 0 to 99.9% by mass, preferably 0.1 to 99.9% by mass, more preferably 40 to 99.9% by mass, even more preferably 60 to 99.9% by mass, and particularly preferably 80 to 99% by mass.
- the composition may contain other additives within a range that does not impair the effects of the present invention.
- additives commonly used in this technical field may be used, and examples thereof include water-soluble low molecular weight compounds having a hydroxyl group, such as L-ascorbic acid, gallic acid, tannic acid, glucono- ⁇ -lactone, and gluconic acid, and compounds having a hydroxyl group, such as polymer compounds having a hydroxyl group, such as polyvinyl alcohol.
- the molecular weight of the water-soluble low molecular weight compound having a hydroxyl group is not particularly limited, but is, for example, 50 to 2,000, and preferably 100 to 2,000.
- the weight average molecular weight of the polymer compound having a hydroxyl group is not particularly limited, but is, for example, 3,000 to 100,000.
- the compound having a hydroxyl group is preferably a compound (A) that satisfies the following requirements 1 to 4.
- the composition preferably a resin composition
- the compound (A) contains the compound (A)
- the resulting tangible object is likely to have better hydrophilicity durability.
- the effect of improving hydrophilicity durability by the compound (A) is more likely to be exhibited when the composition contains the crosslinking agent described above, that is, the compound (A) is preferably used in combination with the crosslinking agent.
- the compound (A) is used in combination with the oxazoline-based crosslinking agent, the effect of improving hydrophilic properties is more likely to be greater.
- Requirement 1 Water solubility.
- Requirement 2 The acid dissociation constant pKa A (temperature: room temperature (25° C.), solvent: water) is 12 or less.
- Requirement 3 The compound has at least one hydroxyl group, and the total number of hydroxyl groups and carboxyl groups contained in one molecule is two or more.
- Requirement 4 The compound has at least one highly acidic group selected from a hydroxyl group and a carboxyl group, the acid dissociation constant of which is 12 or less (temperature: room temperature (25° C.), solvent: water).
- the compound (A) is a water-soluble compound.
- water-soluble means that the water solubility at 20°C (hereinafter, water solubility (20°C)) is 20 g/L or more, that is, the compound (A) can be said to have a water solubility (20°C) of 20 g/L or more.
- compound (A) in the present invention can be said to be a compound that, when 1 g of the compound is used in the measurement of the water solubility (20°C), the resulting solution is uniformly transparent. Note that uniform transparency means that no phase separation is observed by visual inspection and no cloudiness is observed.
- the acid dissociation constant pKa A in requirement 2 refers to a value measured at room temperature (25° C.) using water as a solvent.
- the acid dissociation constant pKa 1 of the first stage is taken as the acid dissociation constant pKa A.
- the pKa A of the compound (A) is preferably 11 or less, more preferably 10 or less, and even more preferably 5 or less.
- the compound (A) is a compound having at least one hydroxyl group, and the total number of hydroxyl groups and carboxyl groups contained in one molecule of the compound (A) is at least 2. That is, the compound (A) can be said to be a compound having two or more hydroxyl groups, or a compound having at least one hydroxyl group and at least one carboxyl group.
- the total number of hydroxyl groups and carboxy groups in one molecule of the compound (A) is, for example, 2 to 30, preferably 2 to 6, and more preferably 3 to 6.
- the compound (A) has at least one highly acidic group selected from a hydroxyl group (hereinafter sometimes referred to as a hydroxyl group (1)) having a pKa of 12 or less and a carboxy group.
- a hydroxyl group (1) having a pKa of 12 or less and a carboxy group.
- the compound (A) can react with the crosslinking agent (preferably an oxazoline-based crosslinking agent), and the compound (A) can easily achieve an effect of improving the sustained hydrophilicity.
- the pKa of the highly acidic group is preferably 11 or less, more preferably 10 or less, and further preferably 5 or less.
- the number of the highly acidic groups contained in one molecule of the compound (A) is preferably 1 to 3, and more preferably 1.
- the compound (A) satisfies the following requirement 5 in addition to the requirements 1 to 4.
- Requirement 5 The compound has at least one hydroxyl group having an acid dissociation constant pKa (temperature: room temperature (25° C.), solvent: water) of more than 12.
- the initial hydrophilicity and sustained hydrophilicity of the resulting tangible object can be further improved.
- the pKa of the hydroxyl group (2) is more preferably 14 or more, and further preferably 15 or more.
- the upper limit of the pKa of the hydroxyl group (2) is not particularly limited, but is preferably 20 or less.
- the number of the hydroxyl groups (2) per molecule of the compound (A) is preferably 1 to 20, and more preferably 3 to 5.
- L-ascorbic acid, gallic acid, tannic acid, and gluconic acid are preferred, L-ascorbic acid, gallic acid, and gluconic acid are more preferred, and L-ascorbic acid is particularly preferred.
- compound (A) When compound (A) is added to the composition, compound (A) may be added as is, or compound (B) that is modified to compound (A) in the composition may be added to the composition, thereby allowing compound (A) to be included in the composition.
- compound (B) include compounds that are modified to compound (A) by reacting with water at room temperature (25°C) and being hydrolyzed, such as glucono- ⁇ -lactone.
- the content of the compound having a hydroxyl group is not particularly limited, but is, for example, 0 to 100 parts by mass, preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the hydrophilic resin.
- the amounts of the compound (A) and compound (B) added are not particularly limited, but are, for example, 0 to 100 parts by mass, preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the hydrophilic resin.
- the total content of the solid content of the hydrophilicity sustaining effect and/or water slipping agent (preferably the polymer particles), the hydrophilic resin, the crosslinking agent (preferably the oxazoline-based crosslinking agent), and the compound having a hydroxyl group (preferably compound (A)) in 100% by mass of the solid content of the composition (preferably a resin composition) is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 97% by mass or more, and may be 100% by mass.
- the method for producing the composition of the present invention is not particularly limited, but may include, for example, a step of mixing a hydrophilicity sustaining effect and/or water slipping agent, as well as a hydrophilic resin, a crosslinking agent, a solvent, and other additives that are used as needed (also referred to as mixing step (A)).
- mixing step (A) for example, mixing may be performed in the presence of a solvent (preferably an aqueous solvent) or in the absence of a solvent.
- the crosslinking agent may be added after film formation, which will be described later.
- hydrophilic coating film as a tangible object
- the hydrophilic coating film as a tangible object formed from the composition contains the above-mentioned hydrophilicity sustaining effect and/or water slipping agent (particularly the above-mentioned polymer particles), and therefore has not only good hydrophilicity but also hydrophilicity sustaining effect and/or good water slipping property. Also preferably, the hydrophilicity of the coating film (tangible object) after the oil stain is attached is improved.
- the hydrophilicity sustaining effect and/or water slipping agent of the present invention is preferably used for tangible objects that require hydrophilicity as well as hydrophilicity sustaining effect and/or water slipping property, and is particularly preferably used for hydrophilic coating films applied to fin materials of heat exchangers.
- the tangible object when a tangible object such as a coating film exhibits a hydrophilicity sustaining effect, it is preferable that the tangible object satisfies, for example, the following (a) and (b).
- the initial contact angle ( ⁇ 0) measured by the method described in ⁇ Evaluation of initial hydrophilicity> in the Examples below is less than 40°.
- the contact angle ( ⁇ 2) after wet/dry cycles measured by the method described in ⁇ Evaluation 2 of hydrophilicity sustaining effect after wet/dry cycles> in the Examples below is less than 40°.
- the initial contact angle ( ⁇ 0) of the tangible object is preferably less than 35°, more preferably 30° or less, even more preferably 20° or less, and particularly preferably 15° or less or less than 15°. There is no particular lower limit to the initial contact angle ( ⁇ 0), but it is, for example, 5° or more.
- the contact angle ( ⁇ 2) of the tangible object is preferably less than 35°, more preferably 30° or less, even more preferably 26° or less, even more preferably 20° or less, and particularly preferably 15° or less or less than 15°.
- the lower limit of the contact angle ( ⁇ 2) is not particularly limited, but is, for example, 2° or more or 8° or more.
- the relationship between the initial contact angle ( ⁇ 0) and the contact angle ( ⁇ 2) on the tangible object satisfies the following (c) or (d).
- (d) Contact angle ( ⁇ 2)>initial contact angle ( ⁇ 0) and the absolute value of the difference between the contact angle ( ⁇ 2) and the initial contact angle ( ⁇ 0) is 20° or less.
- the absolute value of the difference between the contact angle ( ⁇ 2) and the initial contact angle ( ⁇ 0) is preferably any value, more preferably 1° or more, and even more preferably 3° or more.
- the upper limit of the absolute value of the difference is not particularly limited, but is, for example, 15° or less.
- the relationship between the initial contact angle ( ⁇ 0) and the contact angle ( ⁇ 2) on the tangible object satisfies (d) above, the smaller the absolute value of the difference between the contact angle ( ⁇ 2) and the initial contact angle ( ⁇ 0) the better, and specifically, it is 20° or less, preferably 15° or less, and more preferably 10° or less.
- the contact angle ( ⁇ 1) after wet/dry cycles measured by the method described in ⁇ Evaluation 1 of hydrophilicity sustaining effect after wet/dry cycles> in the examples described later is, for example, less than 40°, preferably less than 35°, more preferably 30° or less, even more preferably 26° or less, even more preferably 20° or less, and particularly preferably 15° or less or less than 15°.
- the lower limit of the contact angle ( ⁇ 1) is not particularly limited, but is, for example, 2° or more or 8° or more. Note that evaluation 1 of hydrophilicity sustaining effect after wet/dry cycles is performed under stricter conditions than evaluation 2 of hydrophilicity sustaining effect after wet/dry cycles, so the contact angle ( ⁇ 1) tends to be larger than the contact angle ( ⁇ 2).
- the relationship between the initial contact angle ( ⁇ 0) and the contact angle ( ⁇ 1) on the tangible object satisfies the following (e) or (f).
- (f) Contact angle ( ⁇ 1)>initial contact angle ( ⁇ 0) and the absolute value of the difference between the contact angle ( ⁇ 1) and the initial contact angle ( ⁇ 0) is 20° or less.
- the absolute value of the difference between the contact angle ( ⁇ 1) and the initial contact angle ( ⁇ 0) is preferably any value, more preferably 1° or more, and even more preferably 3° or more.
- the upper limit of the absolute value of the difference is not particularly limited, but is, for example, 15° or less.
- the absolute value of the difference between the contact angle ( ⁇ 1) and the initial contact angle ( ⁇ 0) is, the more preferable; specifically, it is 20° or less, preferably 15° or less, and more preferably 10° or less.
- the contact angle ( ⁇ 3) after adhesion of oil stains is preferably less than 35°, more preferably 30° or less, even more preferably 26° or less, and particularly preferably 15° or less or less than 15°.
- the lower limit of the contact angle ( ⁇ 3) is not particularly limited, but is, for example, 3° or more.
- the relationship between the initial contact angle ( ⁇ 0) and the contact angle ( ⁇ 3) on the tangible object satisfies the following (g) or (h).
- (h) Contact angle ( ⁇ 3)>initial contact angle ( ⁇ 0) and the absolute value of the difference between the contact angle ( ⁇ 3) and the initial contact angle ( ⁇ 0) is 20° or less.
- the absolute value of the difference between the contact angle ( ⁇ 3) and the initial contact angle ( ⁇ 0) is preferably any value, but more preferably 0.1° or more.
- the upper limit of the absolute value of the difference is not particularly limited, but is, for example, 15° or less.
- the absolute value of the difference between the contact angle ( ⁇ 3) of the tangible object and the initial contact angle ( ⁇ 0) is, the more preferable; specifically, it is 20° or less, preferably 15° or less, and more preferably 10° or less.
- the tangible object when a tangible object such as a coating film exhibits hydrophilicity as well as water-slip properties, for example, it is preferable that the tangible object satisfies the above-mentioned initial contact angle ( ⁇ 0) and the following (i).
- the sliding angle ( ⁇ s) measured by the method described in the ⁇ Evaluation of Water Slippage> in the Examples below is less than 30°.
- the sliding angle ( ⁇ s) of the material object is preferably 20° or less, more preferably 15° or less or less than 15°, even more preferably 12° or less, and particularly preferably 10° or less.
- the conventional measurement of the sliding angle did not take into account the influence of the wetting and spreading of the droplet due to the hydrophilicity of the measurement substrate surface. Therefore, in a hydrophilic tangible object, even if the sliding angle measured by the conventional measurement method is good, it does not necessarily mean that the water-slip property is good. That is, in the conventional method, the sliding angle was determined as the inclination angle of the tangible object when the droplet was placed on the tangible object and the droplet moved a certain distance in the sliding direction.
- an evaluation method is adopted that aims to extract the end point movement due to sliding by excluding the influence of the end point movement due to wetting and spreading from the end point movement of the water droplet in the sliding direction.
- the tangible object of the present invention that can reduce the sliding angle can be said to have good water sliding property while being hydrophilic.
- the present invention by incorporating the above-mentioned polymer particles into a tangible object, it is possible to impart good hydrophilicity to the tangible object as well as sustained hydrophilicity and/or water slippage. That is, in the present invention, by incorporating the above-mentioned polymer particles into a tangible object, it is possible to impart sustained hydrophilicity and/or water slippage to the tangible object.
- the shape of the tangible object does not have to be the above-mentioned coating film shape and is not particularly limited, but examples thereof include planar shapes (film-like, sheet-like, plate-like), granular, powder-like, block-like, particle aggregate-like, spherical, elliptical sphere-like, lenticular, columnar, rod-like, cone-like, cylindrical, needle-like, fibrous, fibrous aggregate-like (e.g., woven fabric, nonwoven fabric, etc.), hollow fiber-like, porous, etc. It is preferable that the tangible object of the present invention is a coating film.
- the thickness is not particularly limited, but is, for example, 0.1 to 80 ⁇ m, preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 10 ⁇ m, and even more preferably 0.3 to 5 ⁇ m.
- the method for producing the tangible object is not particularly limited, and a conventionally known method may be appropriately adopted.
- the tangible object can be obtained by molding or forming the above-mentioned composition (preferably a resin composition). Even when a resin composition is used, the resin contained in the resin composition is not limited to the hydrophilic resin described above, and various resins selected from thermoplastic resins and thermosetting resins can be used.
- a tangible object containing the polymer particles present on the surface of a tangible object that does not contain the above-mentioned polymer particles
- the molding or forming method is not particularly limited, and may be appropriately selected according to the type of composition used and the shape of the desired tangible object.
- molding or forming methods include a method of forming a film by applying a composition containing the polymer particles (preferably a resin composition) to a substrate by a method such as coating, spraying, printing, or impregnation; a method of forming a molded body by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like of a composition containing polymer particles (preferably a resin composition); and a method of laminating a tangible object containing polymer particles (such as a molded body) on the surface of a substrate.
- the resins constituting the resin composition used in the molding or formation include, in addition to the hydrophilic resins described above, for example, polyester, polyethylene, polypropylene, triacetyl cellulose, polystyrene, polycarbonate, polyether sulfone, cellophane, polyamide, polyvinyl alcohol, polyacetal, polyphenylene ether, polyphenylene sulfide, polyimide, polyamideimide, polyetherimide, polyether ether ketone, fluororesins such as polytetrafluoroethylene, ABS resin, Noryl resin, acrylic resin, epoxy resin, cellophane, etc.
- polyester polyethylene, polypropylene, triacetyl cellulose, polystyrene, polycarbonate, polyether sulfone, cellophane, polyamide, polyvinyl alcohol, polyacetal, polyphenylene ether, polyphenylene sulfide, polyimide, polyamideimide, polyetherimide, polyether ether ket
- materials constituting the substrate include inorganic materials such as glass, slate, and mortar; metals such as stainless steel plate, iron, copper, aluminum, magnesium, and zinc, and alloys thereof; and the like, but the present invention is not limited to only these examples.
- the substrate may be composed of only a single layer, or may have a laminated structure in which multiple layers are laminated.
- the substrate is preferably a fin material of a heat exchanger, and more preferably the fin material is made of aluminum.
- composition preferably a resin composition
- hydrophilic coating film a coating film
- a crosslinking agent if a crosslinking agent is applied to the hydrophilic coating film, it may be mixed in advance with the composition or may be added after the film is formed.
- the film When the shaped product (preferably a coating film) of the present invention is applied to a fin material (particularly an aluminum fin material) of a heat exchanger, the film may be formed directly on the surface of the fin material (particularly an aluminum plate constituting the aluminum fin material) (i.e., the fin material (particularly an aluminum plate constituting the aluminum fin material) and the shaped product may be directly laminated), or the film may be formed via a base layer such as a chemical conversion layer and/or a resin coating layer provided on the surface of the fin material (particularly an aluminum plate constituting the aluminum fin material) for the purpose of preventing corrosion of the fin material (particularly the aluminum constituting the aluminum fin material) (i.e., the fin material (particularly the aluminum plate constituting the aluminum fin material) and the shaped product may be laminated via a base layer).
- a base layer such as a chemical conversion layer and/or a resin coating layer provided on the surface of the fin material (particularly an aluminum plate constituting the aluminum fin material) for the purpose of preventing corrosion of the fin material (particularly
- the chemical conversion layer may be a layer made of an inorganic oxide or an inorganic-organic composite compound.
- the inorganic material constituting the inorganic oxide or inorganic-organic composite compound is preferably mainly composed of chromium, zirconium or titanium.
- the layer made of an inorganic oxide may be formed, for example, by subjecting the fin material (particularly the aluminum plate constituting the aluminum fin material) to a chromate phosphate treatment, a zirconium phosphate treatment, a zirconium oxide treatment, a chromate chromate treatment, a zinc phosphate treatment, a titanic acid phosphate treatment, or the like.
- the layer made of an inorganic-organic composite compound may be formed, for example, by subjecting the fin material (particularly the aluminum plate constituting the aluminum fin material) to a coating type chromate treatment or a coating type zirconium treatment.
- specific examples of such inorganic-organic composite compounds include, for example, acrylic-zirconium composites.
- the resin coating layer can be formed, for example, by applying a resin-containing resin paint to the fin material (particularly onto the aluminum plate or chemical conversion layer that constitutes the aluminum fin material) and solidifying it by drying or the like.
- a resin-containing resin paint to the fin material (particularly onto the aluminum plate or chemical conversion layer that constitutes the aluminum fin material) and solidifying it by drying or the like.
- the resin a conventionally known material can be used, and examples of the resin include various polyester-based, polyolefin-based, epoxy-based, urethane-based, and (meth)acrylic-based resins, and a mixture of one or more of these can be used.
- (meth)acrylic resins are preferred, and a polymer having a (meth)acrylic resin or the like as the main chain and containing an oxazoline group in the side chain can also be used.
- the resin coating layer may contain other optional components within the scope of the present invention, so long as the effects of the present invention are not impaired.
- Optional components include various paint additives for improving the paintability, workability, and physical properties of the coating, such as water-based solvents, crosslinking agents, surfactants, film-forming aids, surface conditioners, wetting and dispersing agents, anti-settling agents, antioxidants, defoamers, rust inhibitors, antibacterial agents, and anti-fungal agents.
- paint additives may be used alone or in combination of two or more types.
- the method for producing the hydrophilic coating film is not particularly limited, but may include a drying step or a curing step after the film-forming step such as coating, spraying, printing, or impregnation.
- the tangible objects were then removed, and excess moisture was removed by blowing air onto the contact angle measurement surface until no water droplets were visible to the naked eye, and the objects were dried at 80°C for 12 hours in an air atmosphere using a constant temperature incubator (Yamato Scientific Co., Ltd. "DNF400"). These operations were repeated five times to obtain tangible objects (film-formed samples) after wet/dry cycles.
- a 2 ⁇ L droplet of pure water was prepared under the condition of 25° C., and the droplet was placed on the surface of the tangible object (the coating surface of the film-formed sample) after the wet/dry cycle, and the contact angle was calculated by the ⁇ /2 method.
- the contact angle value 30 seconds after the droplet was placed was taken as the measured value, and five measurements were taken, and the average value of the three points excluding the maximum and minimum values was taken as the contact angle after the wet/dry cycle.
- the hydrophilicity sustaining effect of the tangible object (coating film) after the wet/dry cycle was quantitatively evaluated according to the following criteria. ⁇ : Contact angle after wet/dry cycle is less than 15° ⁇ : Contact angle after wet/dry cycle is 15° or more and less than 40° ⁇ : Contact angle after wet/dry cycle is 40° or more
- a 2 ⁇ L droplet of pure water was prepared under the condition of 25° C., and the droplet was placed on the surface of the tangible object (the coating surface of the film-formed sample) after the wet/dry cycle, and the contact angle was calculated by the ⁇ /2 method.
- the contact angle value 30 seconds after the droplet was placed was taken as the measured value, and five measurements were taken, and the average of the three measurements excluding the maximum and minimum values was taken as the contact angle after the submersion treatment.
- the hydrophilicity sustaining effect of the tangible object (coating film) after the wet/dry cycle was quantitatively evaluated according to the following criteria.
- ⁇ Contact angle after wet/dry cycle is less than 15°.
- ⁇ Contact angle after wet/dry cycle is 15° or more and less than 40°.
- ⁇ Contact angle after wet/dry cycle is 40° or more.
- the tangible object (specifically, the film-formed sample) prepared in Examples 1-1 to 1-5, 1-8 or Reference Example 1-1 was immersed in pure water for 6 hours, and then, in an environment of 25°C and 50% humidity, the removed tangible object (film-formed sample) was placed on a Kimwipe so that the contact angle measurement surface (if it was a film-formed sample, the coated surface of the sample) was the upper surface, and another Kimwipe was covered from above and maintained in that state for 5 seconds.
- the tangible object was then removed, and excess moisture was removed by blowing air onto the contact angle measurement surface until no water droplets were visible to the naked eye, and the tangible object (film-formed sample) was dried for 12 hours at 80°C in an air atmosphere using a constant temperature incubator (Yamato Scientific Co., Ltd. "DNF400") to obtain a tangible object (film-formed sample) after submersion treatment.
- a constant temperature incubator Yamato Scientific Co., Ltd. "DNF400"
- a constant temperature incubator manufactured by Yamato Scientific Co., Ltd., "DNF400
- RHMA 2-hydroxymethylmethyl methacrylate
- DVD810 divinylbenzene
- a polymer particle water dispersion (a1-2) in which hydrolyzed polymer particles (1-2) were dispersed was obtained in the same manner as in Production Example 1-1, except that the basic aqueous solution was changed to 1.4 parts by mass of an aqueous sodium hydroxide solution (concentration 20.0%).
- the volume average particle diameter of the obtained polymer particles (1-2) was 399 nm.
- ⁇ Production Example 1-3> In a stainless steel first reaction kettle equipped with a stirrer, a thermometer, and a cooler, 1128 parts by mass of deionized water and 1.05 parts by mass of ADEKA REASOAP SR-20 (active ingredient 100% by mass, manufactured by ADEKA Corporation), an anionic reactive emulsifier mainly composed of ether sulfate-type ammonium salt, diluted with ion-exchanged water to 10% by mass of active ingredient (hereinafter referred to as "SR-20 (active ingredient 10% by mass)”) were added, and the internal temperature was raised to 75°C and maintained at the same temperature.
- SR-20 active ingredient 10% by mass
- MMA methyl methacrylate
- DVB810 30 parts by mass of DVB810 were mixed to prepare 100 parts by mass of monomer composition A.
- 90 parts by mass of RHMA and 10 parts by mass of DVB810 were mixed to prepare 100 parts by mass of monomer composition B.
- the internal temperature of the first reaction kettle was kept at 75° C., and the reaction solution was kept at the same temperature for 2 hours for aging, and then cooled to obtain a polymer water dispersion 1-3 in which polymer particles were dispersed.
- 10 parts by mass of the polymer water dispersion 1-3 obtained above and 1.1 parts by mass of an aqueous ammonia solution (concentration: 25.0% by mass) as a basic aqueous solution were added to a first reaction kettle and stirred overnight at 25° C. to obtain an aqueous polymer particle dispersion (a1-3) in which partially hydrolyzed polymer particles (1-3) were dispersed.
- the volume average particle diameter of the obtained polymer particles (1-3) was 331 nm.
- the volume average particle diameter of the obtained polymer particles (1-4) was 58.4 nm.
- a polymer particle aqueous dispersion (a1-5) in which hydrolyzed polymer particles (1-5) are dispersed was obtained in the same manner as in Production Example 1-3, except that the monomer composition B was changed to 80 parts by mass of RHMA, 10 parts by mass of DVB810, and 10 parts of NOF Corp.'s Blenmer PME400 (hereinafter, PME400), the basic aqueous solution was changed to 1.2 parts by mass of an aqueous sodium hydroxide solution (concentration 20%), and the amount of reactive emulsifier was appropriately adjusted to obtain a target particle diameter.
- the volume average particle diameter of the obtained polymer particles (1-5) was 64.6 nm.
- ⁇ Production Example 1-6> In a stainless steel reaction kettle equipped with a stirrer, a thermometer, and a cooler, 832.0 parts by mass of deionized water and 0.96 parts by mass of SR-20 (active ingredient 25.0% by mass) were added, and the internal temperature was raised to 75° C. and maintained at that temperature. Meanwhile, in a vessel different from the reaction kettle, 180.0 parts by mass of RHMA and 20.0 parts by mass of DVB810 were mixed to prepare 200.0 parts by mass of a monomer composition.
- SR-20 active ingredient 25.0% by mass
- the remaining 160.0 parts by mass of the monomer composition, 479.0 parts by mass of hydrogen peroxide solution (hydrogen peroxide concentration 0.22% by mass), and 486.04 parts by mass of a mixed composition of 479.0 parts by mass of an aqueous L-ascorbic acid solution (L-ascorbic acid concentration 0.33% by mass) and 7.04 parts by mass of SR-20 (active ingredient 25.0% by mass) were uniformly dropped into the reactor from different inlets over 4 hours.
- the internal temperature was kept at 75° C. and the reaction solution was aged at the same temperature for 2 hours, and then cooled to obtain a polymer water dispersion 1-6 in which polymer particles were dispersed.
- the volume average particle diameter of the polymer particles was 221 nm. 100 parts by mass of the polymer particle aqueous dispersion 1-6 and 15 parts by mass of an aqueous sodium hydroxide solution (concentration: 20.0% by mass) as a basic aqueous solution were mixed and stirred overnight at 25° C. to obtain an aqueous polymer particle dispersion (a1-6) in which partially hydrolyzed polymer particles (1-6) were dispersed. The volume average particle diameter of the obtained polymer particles (1-6) was 389 nm.
- a polymer particle aqueous dispersion (a1-7) in which partially hydrolyzed polymer particles (1-7) were dispersed was obtained in the same manner as in Production Example 1-6, except that the sodium hydroxide aqueous solution was changed to 5 parts by mass of an aqueous ammonia solution (concentration: 25.0%).
- the volume average particle diameter of the obtained polymer particles (1-7) was 379 nm.
- the amount of basic aqueous solution added represents the number of moles of added base when the number of moles of RHMA in the polymer particles is taken as 100 mol%, i.e., it corresponds to the ionization rate and hydrolysis rate.
- Example 1-1 ⁇ Preparation of Film-Deposited Sample A1-1> Epocross K-2035E (manufactured by Nippon Shokubai Co., Ltd.; solid content 40 mass%) as a water-based resin and CS-12 (manufactured by JNC Corporation; active ingredient 100 mass%) as a film-forming aid were mixed in an active ingredient ratio (mass basis) of 100:25, and diluted with pure water to a final solid content of 10 mass%, to obtain a base coating composition.
- the base coating composition was applied to an aluminum plate (length: 150 mm, width: 60 mm, thickness: 0.100 mm) using a bar coater so that the film thickness after coating would be 1.1 ⁇ m, and the plate was dried at 160° C. for 11 seconds in an automatic discharge dryer (Tojo Netsugaku Co., Ltd.'s "AT-101 (standard type)") to obtain an aluminum plate with a base layer coating.
- an automatic discharge dryer Tojo Netsugaku Co., Ltd.'s "AT-101 (standard type)
- aqueous polyacrylic resin (weight average molecular weight: about 5000) which is a hydrophilic resin, an aqueous dispersion of polymer particles (a1-1), and an aqueous crosslinking agent ("Epocross WS-700" manufactured by Nippon Shokubai Co., Ltd.; solid content: 25% by mass) were mixed in a solid content ratio of 100:25:18 (by mass), and the mixture was diluted with pure water to a final solid content of 5% by mass, to obtain a coating composition A1-1.
- the coating composition A1-1 was applied to the undercoat layer coated surface of the undercoat layer coated aluminum plate prepared above using a bar coater so that the coating thickness after coating was 0.70 ⁇ m, and then dried at 200° C.
- Example 1-2 to 1-5 ⁇ Preparation of Film-Deposited Samples A1-2 to A1-5> Film-formed samples A1-2 to A1-5 were prepared in the same manner as in Example 1-1, except that the polymer particle aqueous dispersion to be blended was changed to that shown below, and the amount of each polymer particle added to 100 parts of the solid content of the aqueous polyacrylic acid resin was changed to that shown in Table 2. The evaluation results of the obtained film-formed samples are shown in Table 2.
- Example 1-3 Polymer particle water dispersion (a1-3)
- Comparative Examples 1-1 and 1-2 Film-formed samples B1-1 and B1-2 were prepared in the same manner as in Example 1-1, except that the polymer particle aqueous dispersion to be blended was changed to the following: Evaluation results of the obtained film-formed samples are shown in Table 2.
- Comparative Example 1-1 Silica particles (Nissan Chemical Industries, Ltd. "Snowtex N", average particle size 12 nm)
- Comparative Example 1-2 Acrylic particles ("Eposter MX100W” manufactured by Nippon Shokubai Co., Ltd., average particle size 150 nm)
- Example 1-1 A film-formed sample C1-1 was prepared in the same manner as in Example 1-1, except that the aqueous dispersion of polymer particles was not blended in. The evaluation results of the obtained film-formed sample are shown in Table 2.
- DNF400 To prepare an aluminum test panel with a modified surface.
- the coating composition was applied to the modified surface of the aluminum test panel prepared above with a bar coater so that the coating thickness after coating was 45.8 ⁇ m, and then dried at 200 ° C. for 1 minute in a constant temperature incubator (Yamato Scientific Co., Ltd. "DNF400”) to obtain a coating film-formed sample A1-6.
- the evaluation results of the obtained coating sample are shown in Table 2.
- Examples 1 to 7 A film-formed sample A1-7 was obtained in the same manner as in Example 1-6, except that the polymer particle aqueous dispersion was changed to the polymer particle aqueous dispersion (a1-7) and the polycarboxylic acid resin aqueous solution (Z-1a) and the polymer particle aqueous dispersion (a1-7) were blended so that the ratio of the resin (Z-1) to the polymer particles (1-7) was 100:20 in terms of solid content.
- the evaluation results of the obtained film-formed sample are shown in Table 2.
- Example 1-8 A film-forming sample A1-8 was obtained in the same manner as in Example 1-1, except that a film-forming composition A1-8 was used in place of the film-forming composition A1-1, which was a composition obtained by blending a hydrophilic resin, an aqueous polyacrylic acid resin (weight average molecular weight about 5000), a polymer particle aqueous dispersion (a1-5), an aqueous crosslinking agent ("Epocross WS-700" manufactured by Nippon Shokubai Co., Ltd.; solid content 25% by mass), and L-ascorbic acid in a solid content ratio of 100:100:18:20 (by mass), and diluting with pure water to a final solid content of 5% by mass.
- the evaluation results of the obtained film-forming sample are shown in Table 2.
- Example 1-2 A film-formed sample C-2 was prepared in the same manner as in Example 1-6, except that the aqueous dispersion of polymer particles was not blended in. The evaluation results of the obtained film-formed sample are shown in Table 2.
- particle addition amount refers to the amount of particles added (converted into solids) when the solids content of the hydrophilic resin is taken as 100 parts.
- the results in Table 2 show that the hydrophilicity sustaining effect and/or water slipping agent of the present invention, which contains specific particles as components, can provide a hydrophilicity sustaining effect to tangible objects such as coatings, such that hydrophilicity is sustained even after wet/dry cycles. It can also provide the effect of exhibiting good hydrophilicity even after the adhesion of oily stains.
- ⁇ Evaluation of hydrophilicity> The initial contact angle of the material (coating film) was determined in the same manner as in ⁇ Evaluation of initial hydrophilicity> in Experimental Example 1, and the hydrophilicity of the material (coating film) was quantitatively evaluated according to the following criteria.
- the sliding angle of a water droplet with respect to the surface of a material object was measured.
- the tangible object (film-formed sample) was immersed in running pure water for 1 hour under the condition of 25°C, and then, in an environment of 25°C and 50% humidity, the removed tangible object (film-formed sample) was placed on a Kimwipe so that the sliding angle measurement surface (if it was a film-formed sample, the coated surface of the sample) was the upper surface, and covered with another Kimwipe from above, and maintained in that state for 5 seconds.
- the tangible object was then removed, and the sliding angle measurement surface was subjected to air blowing until no water droplets were visible to the naked eye, thereby removing excess moisture, and the tangible object was dried at 80°C for 2 hours using a constant temperature incubator (Yamato Scientific Co., Ltd.'s "DNF400") to obtain a tangible object (film-formed sample) that reproduced the fin material (fin material after adhesion of condensed water and heat drying) when used in a heat exchanger.
- the tangible object subjected to the above treatment is referred to as the "tangible object after heat cycle" (specifically, the film-formed sample after heat cycle).
- a 10 ⁇ L droplet of pure water was prepared under the condition of 25° C., and the droplet was placed on the surface of a horizontally placed tangible object after heat cycle (the coating surface of a film-formed sample after heat cycle), and 0.1 seconds after the droplet was placed, the object was gradually tilted at a rate of 2°/sec in increments of 0.5°, and the angle at which the droplet started to move was taken as the measured value. Five measurements were taken, and the average of the three points excluding the maximum and minimum values was taken as the sliding angle ⁇ s.
- the water sliding property of the tangible object (coating) was quantitatively evaluated according to the following criteria.
- ⁇ sliding angle ⁇ s is less than 15°.
- ⁇ sliding angle ⁇ s is 15° or more and less than 30°.
- ⁇ sliding angle ⁇ s is 30° or more.
- the movement of the water droplet was determined as follows: as shown in FIG. 1, the end point of the water droplet (2a) on the opposite side to the sliding direction 0.1 seconds after it landed on the surface of the tangible object 1 was R0, and the end point on the sliding direction side was L0. The end point of the water droplet (2b) on the opposite side to the sliding direction at the inclination angle ⁇ was R ⁇ , and the end point on the sliding direction side was L ⁇ .
- , and the movement distance of the end point on the sliding direction side of the water droplet was dL
- the water droplet was determined to have moved when dR+dL>1.00 mm was first satisfied, and the inclination angle ⁇ at that time was defined as the sliding angle ⁇ s.
- This definition is an evaluation method intended to extract the end point movement due to sliding by excluding the effect of end point movement due to wetting and spreading from the end point movement of the water droplet in the sliding direction.
- ⁇ Production Example 2-2> A polymer particle aqueous dispersion (a2-2) in which hydrolyzed polymer particles (2-2) were dispersed was obtained in the same manner as in Production Example 2-1, except that the monomer composition B was changed to 80 parts by mass of RHMA, 10 parts by mass of DVB810, and 10 parts by mass of PME400, and the basic aqueous solution was changed to 1.2 parts by mass of an aqueous sodium hydroxide solution (concentration 20%). The volume average particle diameter of the obtained polymer particles (2-2) was 302 nm.
- the amount of basic aqueous solution added represents the number of moles of added base when the number of moles of RHMA in the polymer particles is taken as 100 mol%, i.e., it corresponds to the ionization rate and hydrolysis rate.
- Example 2-1 ⁇ Preparation of Film-Deposited Sample A2-1> An aqueous polyacrylic resin (weight average molecular weight: about 5000) which is a hydrophilic resin, an aqueous dispersion of polymer particles (a2-1), and an aqueous crosslinking agent ("Epocross WS-700" manufactured by Nippon Shokubai Co., Ltd.; solid content: 25% by mass) were mixed in a solid content ratio of 100:100:18 (by mass), and the mixture was diluted with pure water to a final solid content of 5.45% by mass, to obtain a coating composition A2-1.
- aqueous polyacrylic resin weight average molecular weight: about 5000
- a2-1 aqueous dispersion of polymer particles
- an aqueous crosslinking agent (“Epocross WS-700" manufactured by Nippon Shokubai Co., Ltd.; solid content: 25% by mass) were mixed in a solid content ratio of 100:100:18 (by mass), and the mixture was
- the coating composition A2-1 was applied to the surface of an aluminum plate (length: 150 mm, width: 60 mm, thickness: 0.100 mm) using a bar coater so that the coating thickness after coating would be 1.00 ⁇ m, and then dried at 200° C. for 1 minute in an automatic discharge dryer (Tojo Netsugaku Co., Ltd.'s "AT-101 (standard type)") to obtain a coating sample A2-1 having a coating layer.
- the evaluation results of the obtained coating sample are shown in Table 4.
- Example 2-2 ⁇ Film-formed sample A2-2> A film-formed sample A2-2 was prepared in the same manner as in Example 2-1, except that the polymer particle aqueous dispersion to be blended was changed to the polymer particle aqueous dispersion (a2-2). The evaluation results of the obtained film-formed sample are shown in Table 4.
- Example 2-1 A film-formed sample C2-1 was prepared in the same manner as in Example 2-1, except that the aqueous dispersion of polymer particles was not blended in. The evaluation results of the obtained film-formed sample are shown in Table 4.
- particle addition amount refers to the amount of particles added (converted into solids) when the solids content of the hydrophilic resin is taken as 100 parts.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
この凝結水の排水性(滑水性)を高めるために、アルミフィン表面に撥水処理を行うことも知られている。例えば特許文献3には、基材の表面に、シリカ等からなる複数の金平糖状の突起を設け、その後金平糖状の突起が形成された前記基材の表面に撥水撥油防汚性薄膜を形成することで、滑水性に優れた超撥水撥油性熱交換部材が得られることが開示されている。また特許文献4には、基材上にポリエチレンイミン骨格を有するポリマーと、含フッ素化合物と、シリカとを含む滑落撥水層を有する構造体を適用することで、撥水性と滑水性の両方に優れる熱交換機用部材が得られることが開示されている。
(第1の課題)
ところで上記親水性塗膜には、塗膜形成直後の塗膜の親水性(初期親水性)が高められていることはもちろんのこと、当該親水性が持続することも求められる。また、フィン材及びその表面に適用される塗膜等(以下、これら形状を有するものを有形物と称する)の親水化に限らず、様々な用途で各種有形物自体またはその表面の親水性(初期親水性)が求められることがあり、当該親水性が持続することも求められることがある。特に、熱交換器のフィン材は、長期間の使用を通して、凝縮水がフィン材表面に存在しているウェット状態と、該凝結水が蒸発するドライ状態とを繰り返すことになる。従って、熱交換器のフィン材に適用される親水性塗膜等の親水性有形物には、凝結水の付着及び乾燥を繰り返した後であっても、有形物の親水性が持続されることが求められる。
また、特許文献1~2には、水道水の付着及び乾燥を繰り返した後であっても親水性が持続することが記載されている。しかし、熱交換器のフィンに付着する凝結水は、純水と同様、イオン成分の含有量が少ないもの(以下、「低イオン水」という)であり、特許文献1~2に記載の親水性粒子を用いた場合には、低イオン水の付着及び乾燥を繰り返した後の親水持続性は不十分であった。
さらに、特許文献1~2に記載の親水性粒子は、その製造において有機溶媒を使用することが必須であり、また該親水性粒子の主成分である(メタ)アクリルアミド系モノマーは毒性が高く、環境負荷低減の観点及び安全性の観点からも好ましくない。
また、特許文献3~4は撥水処理に関する技術であるため、親水持続性の効果は見込めない。
加えて、特許文献5では、凝結水の付着及び乾燥を繰り返した後の親水持続性について一切検討されていない。
また、室内環境下に置かれる有形物(例えば熱交換器のフィン材)は、建材、食物、生活用品等から揮発、飛散した浮遊物に由来する油性成分(例えば、高級脂肪酸や高級アルコールなど)を主成分とする油汚れが前記有形物表面に付着する場合があり、このような油汚れが有形物表面に付着した後であっても、良好な親水性を発現できることが求められる。そのため、本発明の必須ではない好ましい課題は、油汚れ付着後であっても有形物(例えば、フィン材)表面の親水性が良好となる親水性持続効果付与剤を提供することにある。
上述の通り、熱交換器におけるアルミフィンには、液滴の排水性(滑水性)が良好であることが求められる場合がある。
しかしながら、特許文献1~2では、液滴の滑水性について一切検討されていない。
また、特許文献3~4に記載のように、基材表面の撥水性を高めることにより液滴の滑水性は高められるが、接触角が大きくなることで基材に対して垂直方向に背の高い液滴が生じやすくなり、該液滴によるフィン間のブリッジの問題が発生する。特に、近年、熱交換器の放熱効率或いは冷却効率の向上を目的として、フィン間隔が極めて狭くなっており、フィン間のブリッジ抑制のための親水性と、液滴の排水性向上のための滑水性との両立が求められる。
また、特許文献5に記載の表面処理剤は、親水性及び排水性(滑水性)の両立が達成できたとされているものの、親水性粒子としてコロイダルシリカを使用しており、この場合親水持続性が不足しやすい。また、シリカ特有の臭気や、硬質な無機系材料であるシリカに起因する金型摩耗性の懸念もあるため、新たな表面処理剤の開発が求められている。
また本発明者らは、当該粒子を用いることで、親水性と共に滑水性も高めることができることを見出した。
[1] -COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子を構成成分とする親水性持続効果及び/又は滑水性付与剤。
[2] 前記架橋重合体が、1分子中に1つ以上の-COOR基と1つ以上の水酸基と1つの重合性基とを有する単量体(AB1)に由来する構造単位と、1分子中に2つ以上の重合性基を有する単量体(C)に由来する構造単位とを含む、[1]に記載の親水性持続効果及び/又は滑水性付与剤。
[3] 前記単量体(AB1)に由来する構造単位が、下記式(1)で表される構造単位であり、前記単量体(C)に由来する構造単位が、多官能エチレン性不飽和単量体に由来する構造単位である、[2]に記載の親水性持続効果及び/又は滑水性付与剤。
[式(1)中、R1は、炭素数1~4のアルキル基、水素原子、アルカリ金属原子、又はアンモニウムを表す。]
[4] 前記架橋重合体が、前記式(1)で表される構造単位であって、R1がアルカリ金属原子又はアンモニウムであるものを含有する、[3]に記載の親水性持続効果及び/又は滑水性付与剤。
[5] 前記単量体(AB1)に由来する構造単位の含有量が、前記架橋重合体中、5質量%以上である、[2]~[4]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤。
[6] 前記単量体(C)に由来する構造単位の含有量が、前記架橋重合体中、0.01~70質量%である、[2]~[5]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤。
[7] 前記架橋重合体が、さらにポリオキシアルキレン基含有エチレン性不飽和単量体に由来する構造単位を含む、[2]~[6]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤。
[8] 前記粒子の体積平均粒子径が、10nm~10μmである、[1]~[7]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤。
[9] 前記粒子が前記架橋重合体を含む単層粒子であるか、前記架橋重合体をシェル層に含むコアシェル構造の粒子である、[1]~[8]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤。
[10] 熱交換器のフィン材用である、[1]~[9]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤。
[11] 前記フィン材がアルミニウム製のフィン材用である、[10]に記載の親水性持続効果及び/又は滑水性付与剤。
[12] [1]~[11]のいずれかに記載の親水性持続効果及び/又は滑水性付与剤と、親水性樹脂とを有する樹脂組成物。
[13] 前記親水性樹脂が、カルボキシ基及びカルボキシ基の塩よりなる群から選択される少なくとも1種の極性官能基を側鎖に有する樹脂である、[12]に記載の樹脂組成物。
[14] さらに架橋剤を含有する、[12]又は[13]に記載の樹脂組成物。
[15] -COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子を有形物に含有させる、有形物に、持続的親水化及び/又は滑水化を施す方法。
[16] -COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子を含有する組成物を、基材に塗工することにより、前記粒子を含む塗膜を基材表面に形成させる、基材表面に持続的親水化及び/又は滑水化を施す方法。
[17] 前記基材が、熱交換器のフィン材である、[16]に記載の方法。
[18] 前記組成物が、さらに親水性樹脂を含有する、[16]又は[17]に記載の方法。
[19] 前記親水性樹脂が、カルボキシ基及びカルボキシ基の塩よりなる群から選択される少なくとも1種の極性官能基を側鎖に有する樹脂である、[18]に記載の方法。
[20] 前記組成物がさらに架橋剤を含有する、[16]~[19]のいずれかに記載の方法。
[21] 前記架橋重合体が、1分子中に1つ以上の-COOR基と1つ以上の水酸基と1つの重合性基とを有する単量体(AB1)に由来する構造単位と、1分子中に2つ以上の重合性基を有する単量体(C)に由来する構造単位とを含む、[15]~[20]のいずれかに記載の方法。
[22] 前記単量体(AB1)に由来する構造単位が、下記式(1)で表される構造単位であり、前記単量体(C)に由来する構造単位が、多官能エチレン性不飽和単量体に由来する構造単位である、[21]に記載の方法。
[式(1)中、R1は、炭素数1~4のアルキル基、水素原子、アルカリ金属原子、又はアンモニウムを表す。]
[23] 前記架橋重合体が、前記式(1)で表される構造単位であって、R1がアルカリ金属原子又はアンモニウムであるものを含有する、[22]に記載の方法。
[24] 前記単量体(AB1)に由来する構造単位の含有量が、前記架橋重合体中、5質量%以上である、[21]~[23]のいずれかに記載の方法。
[25] 前記単量体(C)に由来する構造単位の含有量が、前記架橋重合体中、0.01~70質量%である、[21]~[24]のいずれかに記載の方法。
[26] 前記架橋重合体が、さらにポリオキシアルキレン基含有エチレン性不飽和単量体に由来する構造単位を含む、[21]~[25]のいずれかに記載の方法。
[27] 前記粒子の体積平均粒子径が、10nm~10μmである、[15]~[26]のいずれかに記載の方法。
[28] 前記粒子が前記架橋重合体を含む単層粒子であるか、前記架橋重合体をシェル層に含むコアシェル構造の粒子である、[15]~[27]のいずれかに記載の方法。
第1の効果:本発明の粒子を用いることで、得られる有形物のウェット/ドライサイクル後の親水持続性を高めることができる。また、好ましくは油汚れ付着後の有形物の親水性も高めることができる。
第2の効果:本発明の粒子を用いることで、得られる有形物に親水性を付与すると共に、滑水性を付与することができる。
さらに本発明の粒子を構成成分とする親水性持続効果及び/又は滑水性付与剤は、その製造において有機溶媒(特に水と混和しない有機溶媒)や毒性の高いモノマーの使用が必須でない点でも好ましい。
<重合体粒子>
本発明の親水性持続効果及び/又は滑水性付与剤は、-COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子(以下、単に「重合体粒子」という場合がある)を構成成分とする。前記重合体粒子を構成する架橋重合体が、-COOR基および水酸基を有することによって、優れた親水特性(初期親水性、ウェット/ドライサイクル後の親水性持続性、油汚れ付着後の親水性など)を示すことが可能となる。また、前記架橋重合体が-COOR基および水酸基を有することによって、優れた親水性と共に、優れた滑水性を示すことが可能となる。さらに、前記-COOR基および水酸基を有する重合体が架橋重合体であることによって、親水性持続効果及び/又は滑水性付与剤の水への溶出を防止でき、前記親水特性の持続性や滑水性を高めることが可能となる。加えて、本発明の親水性持続効果及び/又は滑水性付与剤は、臭気や金型摩耗の懸念のあるシリカ粒子を使用せずとも、上記効果が得られる点においても好ましい。
メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基等のアルキル基(好ましくは炭素数1~4のアルキル基);
ビニル基、n-プロペニル基、イソプロペニル基、1-ブテニル基、2-ブテニル基、1-ペンテニル基、2-ペンテニル基、2-メチル-1-ブテニル基、2-メチル-2-ブテニル基、3-メチル-1-ブテニル基等のアルケニル基(好ましくは炭素数2~6のアルケニル基);
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、3-メチルシクロヘキシル基、4-メチルシクロヘキシル基、4-エチルシクロヘキシル基等のシクロアルキル基(好ましくは炭素数3~8のシクロアルキル基);等が挙げられる。
前記水酸基価は、架橋重合体1gに含まれている水酸基の物質量と同じ物質量を有する水酸化カリウムの量(mg)を意味する。
架橋重合体の水酸基価は、その組成が判明している場合には、架橋重合体の原料として用いられる単量体成分に含まれる水酸基の量を求めることで算出することができる。例えば、水酸基を有する単量体として2-ヒドロキシエチルメタクリレート1質量%を含有する単量体成分を重合させることによって調製された架橋重合体を例にとると、当該架橋重合体の水酸基価は、
式:〔架橋重合体の水酸基価〕=〔0.01(架橋重合体の原料として用いられる単量体成分における2-ヒドロキシエチルメタクリレートの質量基準の含有率)/130(2-ヒドロキシエチルメタクリレートの分子量)×1(2-ヒドロキシエチルメタクリレート1分子中の水酸基の数)〕×56.1(水酸化カリウムの物質量)×1000=4.3mgKOH/gに基づいて求めることができる。
また、架橋重合体の組成が判明していない場合には、JIS K0070に準拠して、当該架橋重合体1gをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウム(KOH)の量(mg)を求めることで水酸基価を決定することもできる。
架橋重合体の水酸基価は、当該架橋重合体の原料として用いられる単量体成分に含まれる水酸基を有する単量体の量を調節することによって容易に調整することができる。
態様1:1分子中に1つ以上の-COOR基と1つの重合性基とを有し且つ水酸基を有さない単量体(以下、単量体(A1))に由来する構造単位と、1分子中に1つ以上の水酸基と1つの重合性基とを有し且つ-COOR基を有さない単量体(以下、単量体(B1))に由来する構造単位と、1分子中に2つ以上の重合性基を有する単量体(C)(以下、単量体(C))に由来する構造単位とを含む架橋重合体
態様2:単量体(A1)及び/又は1分子中に1つ以上の-COOR基と2つ以上の重合性基とを有し且つ水酸基を有さない単量体(以下、単量体(A2))に由来する構造単位と、単量体(B1)及び/又は1分子中に1つ以上の水酸基と2つ以上の重合性基とを有し且つ-COOR基を有さない単量体(以下、単量体(B2))に由来する構造単位とを含む架橋重合体であって、少なくとも単量体(A2)及び/又は単量体(B2)に由来する構造単位を含む架橋重合体
態様3:1分子中に1つ以上の-COOR基と1つ以上の水酸基と2つ以上の重合性基とを有する単量体(以下、単量体(AB2))に由来する構造単位を含む架橋重合体
態様4:1分子中に1つ以上の-COOR基と1つ以上の水酸基と1つの重合性基とを有する単量体(以下、単量体(AB1))に由来する構造単位と、単量体(C)に由来する構造単位とを含む架橋重合体
前記単量体(A1)に含まれる重合性基は、ビニル基、アリル基、(メタ)アクリロイル基等のエチレン性不飽和結合含有基が好ましく、より好ましくは(メタ)アクリロイル基である。
前記単量体(A2)に含まれる重合性基の数は、2~6個であることが好ましく、2個であることがより好ましい。
前記単量体(A2)に含まれる重合性基は、ビニル基、アリル基、(メタ)アクリロイル基等のエチレン性不飽和結合含有基が好ましく、より好ましくは(メタ)アクリロイル基である。
前記単量体(B1)に含まれる重合性基は、ビニル基、アリル基、(メタ)アクリロイル基等のエチレン性不飽和結合含有基が好ましく、より好ましくは(メタ)アクリロイル基である。
前記単量体(B2)1分子に含まれる重合性基の数は、2~6個であることが好ましく、2個であることがより好ましい。
前記単量体(B2)に含まれる重合性基は、ビニル基、アリル基、(メタ)アクリロイル基等のエチレン性不飽和結合含有基が好ましく、より好ましくは(メタ)アクリロイル基である。
中でも、加水分解への耐性が高く、親水成分等の粒子の構成成分の溶出を防ぎ、親水性持続効果及び/又は滑水性を高める傾向にあることから、モノ、ジ、又はポリアルキレングリコールのメタクリル酸ジエステル、ポリオールのメタクリル酸トリエステル、ポリオールのメタクリル酸テトラエステル、ポリオールのメタクリル酸ペンタエステル、ポリオールのメタクリル酸ヘキサエステル等の多価メタクリル酸エステルが好ましい。
前記単量体(AB1)1分子に含まれる水酸基の数は、1~3個であることが好ましく、1個であることがより好ましい。
前記単量体(AB1)に含まれる重合性基は、ビニル基、アリル基、(メタ)アクリロイル基等のエチレン性不飽和結合含有基が好ましく、より好ましくは末端にエチレン性不飽和基を有する基(CH2=C<を有する基)、さらに好ましくは(メタ)アクリロイル基である。
前記単量体(AB2)1分子に含まれる水酸基の数は、1~3個であることが好ましく、1個であることがより好ましい。
前記単量体(AB2)1分子に含まれる重合性基の数は、2~6個であることが好ましく、2個であることがより好ましい。
前記単量体(AB2)に含まれる重合性基は、ビニル基、アリル基、(メタ)アクリロイル基等のエチレン性不飽和結合含有基が好ましく、より好ましくは(メタ)アクリロイル基である。
前記単量体(A1)に由来する構造単位の含有量は、前記態様1の架橋重合体中、好ましくは1~98.99質量%、より好ましくは10~90質量%、さらに好ましくは10~50質量%である。
前記単量体(B1)に由来する構造単位の含有量は、前記態様1の架橋重合体中、好ましくは1~98.99質量%、より好ましくは10~90質量%、さらに好ましくは10~50質量%である。
前記単量体(C)(好ましくは多官能エチレン性不飽和単量体)に由来する構造単位の含有量は、前記態様1の架橋重合体中、好ましくは0.01~70質量%、より好ましくは0.01~35質量%、さらに好ましくは5~20質量%である。
前記態様1の架橋重合体中、単量体(A1)に由来する構造単位と、単量体(B1)に由来する構造単位と、単量体(C)に由来する構造単位との合計含有量は、好ましくは20~100質量%、より好ましくは30~100質量%、さらに好ましくは50~100質量%である。
前記態様1の架橋重合体は、さらに単量体(A1)、単量体(B1)、及び単量体(C)以外のその他単量体に由来する構造単位を含んでいてもよい。前記その他単量体としては、単量体(AB1)の他、後述のポリオキシアルキレン基含有エチレン性不飽和単量体、スチレン系単量体、ビニルエステル系単量体、シラン基含有単量体、窒素原子含有単量体、オキソ基含有単量体、フッ素原子含有単量体、エポキシ基含有単量体、光安定化単量体、紫外線吸収性単量体等が挙げられる。
前記態様2の架橋重合体中、単量体(A2)に由来する構造単位と単量体(B2)に由来する構造単位との合計含有量は、好ましくは0.01~70質量%、より好ましくは0.01~35質量%、さらに好ましくは5~20質量%である。
前記態様2の架橋重合体中、単量体(A1)に由来する構造単位と、単量体(A2)に由来する構造単位と、単量体(B1)に由来する構造単位と、単量体(B2)に由来する構造単位との合計含有量は、好ましくは20~100質量%、より好ましくは30~100質量%、さらに好ましくは50~100質量%である。
前記態様2の架橋重合体は、さらに単量体(A1)、単量体(A2)、単量体(B1)、及び単量体(B2)以外のその他単量体に由来する構造単位を含んでいてもよい。前記その他単量体としては、単量体(A2)及び単量体(B2)に包含されない単量体(C)や、単量体(AB1)、単量体(AB2)の他、後述のポリオキシアルキレン基含有エチレン性不飽和単量体、スチレン系単量体、ビニルエステル系単量体、シラン基含有単量体、窒素原子含有単量体、オキソ基含有単量体、フッ素原子含有単量体、エポキシ基含有単量体、光安定化単量体、紫外線吸収性単量体等が挙げられる。
単量体(AB2)に由来する構造単位の含有量は、前記態様3の架橋重合体中、好ましくは0.01~100質量%、より好ましくは5~70質量%、さらに好ましくは10~50質量%である。
前記態様3の架橋重合体は、さらに単量体(AB2)以外のその他単量体に由来する構造単位を含んでいてもよい。前記その他単量体としては、単量体(A1)、単量体(A2)、単量体(B1)、単量体(B2)、単量体(C)、及び単量体(AB1)の他、後述のポリオキシアルキレン基含有エチレン性不飽和単量体、スチレン系単量体、ビニルエステル系単量体、シラン基含有単量体、窒素原子含有単量体、オキソ基含有単量体、フッ素原子含有単量体、エポキシ基含有単量体、光安定化単量体、紫外線吸収性単量体等が挙げられる。
特に親水特性をより高める観点、或いは親水性及び滑水性のバランスをより良好なものとする観点からは、上記単量体(AB1)に由来する構造単位(特に、式(1)で表される構造単位)の含有量は、前記態様4の架橋重合体中、45~99.9質量%であることが好ましく、より好ましくは65~99質量%、さらに好ましくは75~95質量%である。
また、単量体(C)(特に、多官能エチレン性不飽和単量体)に由来する構造単位の含有量は、前記態様4の架橋重合体中、0.01~10質量%であってもよく、0.02~8質量%であってもよく、0.04~6質量%であってもよい。
R32で表される炭素数6~20の芳香族炭化水素基としては、1又は2以上の炭素数1~10のアルキル基を有していてもよいフェニル基(ただし、炭素数の合計は20以下)、1又は2以上の炭素数1~10のアルキル基を有していてもよいナフチル基(ただし、炭素数の合計は20以下)等が挙げられる。前記炭素数1~10のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等が挙げられる。中でも、炭素数4~10のアルキル基が好ましく、ノニル基がより好ましい。
R32としては、水素原子、炭素数1~2のアルキル基、炭素数1~10のアルキル基を有していてもよいフェニル基であることが好ましく、水素原子、メチル基、ノニル基を有していてもよいフェニル基であることがより好ましい。
また、単量体(AB1)に由来する構造単位(特に、式(1)で表される構造単位)100質量部に対する、ポリオキシアルキレン基含有エチレン性不飽和単量体に由来する構造単位の含有量は、0.2~30質量部であることが好ましく、より好ましくは2~20質量部、さらに好ましくは5~16質量部である。
また、前記態様4の架橋重合体中、単量体(AB1)に由来する構造単位、単量体(C)に由来する構造単位、及びポリオキシアルキレン基含有エチレン性不飽和単量体に由来する構造単位の合計含有量(特に、式(1)で表される構造単位、多官能エチレン性不飽和単量体に由来する構造単位、及びポリオキシアルキレン基含有エチレン性不飽和単量体に由来する構造単位の合計含有量)は、60~100質量%であることが好ましく、より好ましくは80~100質量%、さらに好ましくは90~100質量%である。また前記合計含有量の上限は、99.9質量%又は99質量%であってもよい。
特に、アクリル酸由来の構造単位、及びアクリル酸の塩由来の構造単位の合計含有量(特に、アクリル酸の塩由来の構造単位の含有量)は、前記態様4の架橋重合体中、0~40質量%であってもよく、5~20質量%であってもよい。
また室外機やカーエアコン等に用いられる熱交換器のフィン材は、都市媒塵、自動車等の排気ガスに含有されるカーボンブラック等の汚染物質にさらされる場合があり、このような汚染物質の付着は塗膜(有形物)の親水性低下に繋がる。前記重合体粒子をコアシェル構造などの多層構造にすると、塗膜(有形物)表面に付着した汚染物質をより簡単に除去できる傾向にある。
また、前記第2重合体において、非水性単量体に由来する構造単位100質量部に対する、多官能エチレン性不飽和単量体に由来する構造単位の含有量は、10~70質量部であることが好ましく、より好ましくは20~60質量部、さらに好ましくは20~50質量部である。
また、前記第2重合体中、非水性単量体に由来する構造単位及び多官能エチレン性不飽和単量体に由来する構造単位の合計含有量は、60~100質量%であることが好ましく、より好ましくは80~100質量%、さらに好ましくは90~100質量%である。また前記合計含有量の上限は、99.9質量%又は99質量%であってもよい。
前記重合体粒子の製造方法は、特に限定されず、従来公知の方法を採用すればよいが、重合体粒子を構成する単量体(以下、これらをまとめて「原料単量体成分」という場合がある)を水系溶媒中で重合し、必要に応じ、部分的に又は完全に加水分解することにより製造することが好ましい。例えば、態様4の架橋重合体を含む重合体粒子を製造する場合、原料単量体成分である、式(2)で表されるヒドロキシメチルアクリル酸系単量体のうちR1が炭素数1~4のアルキル基であるもの(以下、ヒドロキシメチルアクリル酸エステルという)と、多官能エチレン性不飽和単量体と、必要に応じて用いられるポリオキシアルキレン基含有エチレン性不飽和単量体、その他単量体、非水性単量体、及び第2のその他の単量体を水系溶媒中で重合し、必要に応じ、部分的に又は完全に加水分解することにより製造することが好ましい。ヒドロキシメチルアクリル酸エステルを用いることで、有機溶媒を必須としない水系溶媒中で重合しても、生成物を粒子状にできるため、環境負荷低減の観点から好ましい。
本開示の重合体粒子の加水分解率は、親水特性や滑水性をより高める観点から、例えば20~100%、好ましくは40~100%、より好ましくは50~100%である。また、前記加水分解率は、95%以下であってもよく、90%以下であってもよい。なお、加水分解率は、架橋重合体に含まれる加水分解し得る単量体由来の構造単位100モル%に対して添加した塩基性物質の添加量(物質量)により算出することができる。加水分解し得る単量体としては、アクリル酸アルキルエステル等のアクリル系単量体、一般式(2)で表される単量体等が挙げられる。なお重合体から加水分解率を逆算する場合は、アクリル系単量体及び式(2)で表される単量体等の加水分解し得る単量体においてカルボン酸基の全てがエステルとして存在していたと仮定して、加水分解率を計算することができる。
前記有形物は、前述の重合体粒子を含有する組成物(すなわち、親水性持続効果及び/又は滑水性付与剤を含有する組成物)から製造することが好ましい。以下、前記組成物及び有形物について順に説明する。
本発明の組成物は、前述の重合体粒子を含有し、すなわち前述の親水性持続効果及び/又は滑水性付与剤を含有する。組成物における前記親水性持続効果及び/又は滑水性付与剤の固形分(好ましくは前記重合体粒子)の含有量は特に限定されないが、組成物の固形分100質量%中、例えば1~80質量%であり、好ましくは5~50質量%、より好ましくは8~30質量%である。
前記極性官能基としては、カルボキシ基、カルボキシ基の塩が好ましく、カルボキシ基、カルボキシ基のアルカリ金属塩がより好ましく、カルボキシ基、カルボキシ基のナトリウム塩がさらに好ましい。
前記含有量の上限としては、特に制限はないが、親水性樹脂100質量部に対して、200質量部以下であることが好ましく、150質量部以下であることがより好ましい。
すなわち、前記含有量は、親水性樹脂100質量部に対して、0.1~200質量部であることが好ましく、より好ましくは5~200質量部、さらに好ましくは15~200質量部、よりさらに好ましくは40~200質量部、特に好ましくは60~200質量部、最も好ましくは80~150質量部である。
付加重合性オキサゾリンと共重合可能な単量体としては、オキサゾリン基と反応する官能基をもたず、付加重合性オキサゾリンと共重合可能な単量体が好ましい。例えば、アルキル(メタ)アクリレート等の(メタ)アクリル系モノマー;スチレン、α-メチルスチレン、クロロメチルスチレン等のスチレン系モノマー;酢酸ビニル、塩化ビニル、安息香酸ビニル等のビニル系モノマー;アクリロニトリル;アクリルアミド等の(メタ)アクリルアミド系モノマー;エチレン、プロピレン等のオレフィン系モノマー;等が挙げられる。
前記水酸基を有する水溶性の低分子化合物の分子量は、特に限定されないが、例えば50~2,000であり、好ましくは100~2,000である。
前記水酸基を有する高分子化合物の重量平均分子量は、特に限定されないが、例えば3,000~100,000である。
要件2:酸解離定数pKaA(温度:室温(25℃)、溶媒:水)が12以下である。
要件3:少なくとも水酸基を1個有し、1分子中に含まれる水酸基およびカルボキシ基の総数が2個以上である。
要件4:酸解離定数pKa(温度:室温(25℃)、溶媒:水)が12以下の水酸基及びカルボキシ基から選択される高酸性度基を少なくとも1個有する。
前記化合物(A)1分子における、水酸基及びカルボキシ基の総数は、例えば2~30個であり、2~6個が好ましく、3~6個がより好ましい。
前記高酸性度基のpKaは、11以下であることが好ましく、より好ましくは10以下、さらに好ましくは5以下である。
前記化合物(A)1分子が有する前記高酸性度基の個数は、1~3個が好ましく、1個がより好ましい。
要件5:酸解離定数pKa(温度:室温(25℃)、溶媒:水)が12超えの水酸基を少なくとも1個有する。
前記水酸基(2)のpKaは、14以上がより好ましく、15以上がさらに好ましい。また前記水酸基(2)のpKaの上限は特に限定されないが、20以下が好ましい
前記化合物(A)1分子が有する前記水酸基(2)の個数は、1~20個が好ましく、3~5個がより好ましい。
また、上記化合物(A)及び化合物(B)の添加量は、特に制限はないが、前記親水性樹脂100質量部に対し、例えば0~100質量部であり、好ましくは0.1~100質量部、より好ましくは1~50質量部、さらに好ましくは5~30質量部である。
前記組成物(好ましくは樹脂組成物)から形成される有形物としての親水性塗膜は、前述の親水性持続効果及び/又は滑水性付与剤(特に、前述の重合体粒子)を含んでいるため、良好な親水性だけでなく、親水持続効果及び/又は良好な滑水性を有する。また好ましくは、油汚れ付着後の塗膜(有形物)の親水性も向上する。従って、本発明の親水性持続効果及び/又は滑水性付与剤は、親水性と共に親水持続性及び/又は滑水性が求められる有形物に好適に用いられ、特に熱交換器のフィン材に適用される親水性塗膜に好適に用いられる。
(a)後述の実施例における<初期親水性の評価>に記載した方法で測定された初期接触角(θ0)が40°未満
(b)後述の実施例における<ウェット/ドライサイクル後の親水性持続効果の評価2>に記載した方法で測定されたウェット/ドライサイクル後の接触角(θ2)が40°未満
(c)接触角(θ2)≦初期接触角(θ0)
(d)接触角(θ2)>初期接触角(θ0)であって、接触角(θ2)と初期接触角(θ0)との差の絶対値が20°以下
前記有形物における初期接触角(θ0)と接触角(θ2)との関係が、前記(c)を満たす場合、前記接触角(θ2)と初期接触角(θ0)との差の絶対値はいずれであっても好ましいが、1°以上がより好ましく、3°以上がさらに好ましい。また前記差の絶対値の上限は特に限定されないが、例えば15°以下である。
前記有形物における初期接触角(θ0)と接触角(θ2)との関係が、前記(d)を満たす場合、前記接触角(θ2)と初期接触角(θ0)との差の絶対値は小さいほど好ましく、具体的には20°以下、好ましくは15°以下、より好ましくは10°以下である。
(e)接触角(θ1)≦初期接触角(θ0)
(f)接触角(θ1)>初期接触角(θ0)であって、接触角(θ1)と初期接触角(θ0)との差の絶対値が20°以下
前記有形物における初期接触角(θ0)と接触角(θ1)との関係が、前記(e)を満たす場合、前記接触角(θ1)と初期接触角(θ0)との差の絶対値はいずれであっても好ましいが、1°以上がより好ましく、3°以上がさらに好ましい。また前記差の絶対値の上限は特に限定されないが、例えば15°以下である。
前記有形物における初期接触角(θ0)と接触角(θ1)との関係が、前記(f)を満たす場合、前記接触角(θ1)と初期接触角(θ0)との差の絶対値は小さいほど好ましく、具体的には20°以下、好ましくは15°以下、より好ましくは10°以下である。
(g)接触角(θ3)≦初期接触角(θ0)
(h)接触角(θ3)>初期接触角(θ0)であって、接触角(θ3)と初期接触角(θ0)との差の絶対値が20°以下
前記有形物における初期接触角(θ0)と接触角(θ3)との関係が、前記(g)を満たす場合、前記接触角(θ3)と初期接触角(θ0)との差の絶対値はいずれであっても好ましいが、0.1°以上がより好ましい。また前記差の絶対値の上限は特に限定されないが、例えば15°以下である。
前記有形物における初期接触角(θ0)と接触角(θ3)との関係が、前記(h)を満たす場合、前記有形物の接触角(θ3)と初期接触角(θ0)との差の絶対値は小さいほど好ましく、具体的には20°以下、好ましくは15°以下、より好ましくは10°以下である。
(i)後述の実施例における<滑水性の評価>に記載した方法で測定された滑落角(θs)が30°未満
なお、従来の滑落角の測定は、測定基材表面が親水性であることによる液滴の濡れ広がりの影響が考慮されていないものであった。従って、親水性の有形物においては、従来の測定方法で測定された滑落角が良好であるからといって必ずしも滑水性が良好であるとは限らなかった。すなわち、従来の方法では、水滴を置いた有形物を傾けて当該水滴が滑落方向に一定距離動いた際の有形物の傾斜角度を滑落角としていたが、親水化された有形物上に水滴を置いた際には、水滴が濡れ広がる運動が観察される。この状態で滑落角の測定を行うと、滑落と濡れの両方の運動が同時に観測されることになり、正確に滑水性を評価できない場合があった。また濡れ広がる運動が平衡点に達してから滑落角を測定することも考えられるが、平衡点に達するまでに液滴の水分が蒸発することもあり、好ましくない。従って、親水性の特性を有する有形物が良好な滑水性有するというためには、水滴の濡れ広がりの影響が考慮された測定系において、滑落角が小さいことが求められる。
一方で、本発明の滑水性の評価では、後述の通り、滑落方向の水滴の端点移動から、濡れ広がりによる端点移動の影響を排除して、滑落による端点移動を抽出することを意図した評価方法を採用している。この評価方法において、滑落角を小さくすることができる本発明の有形物は、親水性でありながらも滑水性が良好であるといえる。
<体積平均粒子径の測定>
重合体粒子水分散体をイオン交換水で重合体粒子の濃度が0.01~0.05質量%となるように希釈したものを光散乱粒度分布測定機(スペクトリス社製「Zetasizer Ultra」)を用いて測定して、動的光散乱法により、重合体粒子の体積平均粒子径(nm)を求めた。
自動接触角計(協和界面科学社製、「CA-X」)を用いて、25℃の条件下、純水2μLの液滴を作製し、実施例、比較例又は参考例で作製した有形物の表面(成膜試料の塗膜表面)に着液させ、接触角をθ/2法により算出した。なお、着液後30秒後の接触角値を測定値とし、5回測定を行い、最大値と最小値の2点を除く3点の平均値を、有形物(塗膜)の初期接触角とした。なお、以下の基準により有形物(塗膜)の初期親水性を定量的に評価した。
◎:初期接触角が15°未満
○:初期接触角が15°以上40°未満
×:初期接触角が40°以上
実施例1-1~1-5、実施例1-8、比較例1-1~1-2、参考例1-1で作製した有形物(具体的には成膜試料)を純水に6時間浸漬させた後、25℃50%湿度の環境下で、取り出した有形物(成膜試料)を接触角測定面(成膜試料であれば、試料の塗工面)が上面になるようにキムワイプ上に置き、上から別のキムワイプを覆い、5秒間その状態を維持した。その後有形物を取出し、接触角測定面に対し、目視で確認できる水滴がなくなるまでエアブローを行うことで、余分な水分を除去し、送風定温恒温器(ヤマト科学社製「DNF400」)を用いて空気雰囲気下80℃で12時間乾燥させた。これらの操作を5回繰り返し行い、ウェット/ドライサイクル後の有形物(成膜試料)を得た。
自動接触角計(協和界面科学社製、「CA-X」)を用いて、25℃の条件下、純水2μLの液滴を作製し、ウェット/ドライサイクル後の有形物の表面(成膜試料の塗膜表面)に着液させ、接触角をθ/2法により算出した。なお、着液後30秒後の接触角値を測定値とし、5回測定を行い、最大値と最小値の2点を除く3点の平均値を、ウェット/ドライサイクル後の接触角とした。なお、以下の基準により有形物(塗膜)のウェット/ドライサイクル後の親水性持続効果を定量的に評価した。
◎:ウェット/ドライサイクル後の接触角が15°未満
○:ウェット/ドライサイクル後の接触角が15°以上40°未満
×:ウェット/ドライサイクル後の接触角が40°以上
実施例1-6~1-7及び参考例1-2で作製した有形物(成膜試料)を純水に12時間浸漬させた後、取り出した有形物(成膜試料)の余分な水分を拭き取り、風乾させた。これらの操作を5回繰り返し行い、ウェット/ドライサイクル後の有形物(成膜試料)を得た。なお、ウェット/ドライサイクル後の有形物の作製において、余分な水分を拭き取るにあたっては、25℃50%湿度の環境下で、含浸後の有形物を、接触角測定面(成膜試料であれば、試料の塗工面)が上面になるようにキムワイプ上に置き、上から別のキムワイプを覆い、5秒間その状態を維持して余分な水分を拭き取ることが推奨される。また、風乾にあたっては、接触角測定面(成膜試料であれば、試料の塗工面)に対し、目視で確認できる水滴がなくなるまでエアブローを行い、その後25℃50%湿度環境下で、12時間風乾(静置)することが推奨される。
自動接触角計(協和界面科学社製、「CA-X」)を用いて、25℃の条件下、純水2μLの液滴を作製し、ウェット/ドライサイクル後の有形物の表面(成膜試料の塗膜表面)に着液させ、接触角をθ/2法により算出した。なお、着液後30秒後の接触角値を測定値とし、5回測定を行い、最大値と最小値の2点を除く3点の平均値を、水没処理後の接触角とした。なお、以下の基準により有形物(塗膜)のウェット/ドライサイクル後の親水性持続効果を定量的に評価した。
◎:ウェット/ドライサイクル後の接触角が15°未満
○:ウェット/ドライサイクル後の接触角が15°以上40°未満
×:ウェット/ドライサイクル後の接触角が40°以上
実施例1-1~1-5、1-8又は参考例1-1で作製した有形物(具体的には成膜試料)を純水に6時間浸漬させた後、25℃50%湿度の環境下で、取り出した有形物(成膜試料)を接触角測定面(成膜試料であれば、試料の塗工面)が上面になるようにキムワイプ上に置き、上から別のキムワイプを覆い、5秒間その状態を維持した。その後有形物を取出し、接触角測定面に対し、目視で確認できる水滴がなくなるまでエアブローを行うことで、余分な水分を除去し、送風定温恒温器(ヤマト科学社製「DNF400」)を用いて空気雰囲気下80℃で12時間乾燥させて、水没処理後の有形物(成膜試料)を得た。水没処理後の有形物(成膜試料)と模擬汚染物質(油汚れ)であるステアリン酸10gとを、ステンレス角型容器(ロックタイプ、3400mL、アズワン製)内で互いが直接触れないように設置して容器を密閉し、送風定温恒温器(ヤマト科学社製「DNF400」)を用いて100℃で24時間加熱することで、油汚れ付着後の有形物(成膜試料)を得た。自動接触角計(協和界面科学社製、「CA-X」)を用いて、25℃の条件下、純水2μLの液滴を作製し、油汚れ付着後の有形物の表面(成膜試料の塗膜表面)に着液させ、接触角をθ/2法により算出した。なお、着液後30秒後の接触角値を測定値とし、5回測定を行い、最大値と最小値の2点を除く3点の平均値を、油汚れ付着後の接触角とした。なお、以下の基準により有形物(塗膜)の油汚れ付着後の親水性を定量的に評価した。
◎:油汚れ付着後後の接触角が15°未満
○:油汚れ付着後後の接触角が15°以上35°未満
×:油汚れ付着後後の接触角が35°以上
<製造例1-1>
攪拌機、温度計および冷却機を備えたステンレス製の反応釜に、脱イオン水1101質量部およびエーテルサルフェート型アンモニウム塩を主成分とするアニオン性反応性乳化剤アデカリアソープSR-20(有効成分100質量%、ADEKA社製)をイオン交換水で有効成分25質量%に希釈したもの(以下「SR-20(有効成分25質量%)」という)1.92質量部を加え、内温を75℃まで昇温し、同温度に保った。他方、上記反応釜とは異なる容器で、2-ヒドロキシメチルメタクリル酸メチル(以下「RHMA」と称する)180.0質量部とジビニルベンゼン(新日鉄住金化学社製 以下「DVB810」と称する)20.0質量部を混合して、単量体組成物200.0質量部を調製した。上記反応釜内を窒素ガスで置換した後、上記単量体組成物40.0質量部、過酸化水素水(過酸化水素濃度1.28質量%)21.0質量部、およびL-アスコルビン酸水溶液(L-アスコルビン酸濃度1.90質量%)21.0質量部を上記反応釜内に添加して、内温を75℃に保持し、2時間かけて初期重合反応を行った。次いで、上記単量体組成物の残部160.0質量部、過酸化水素水(過酸化水素濃度0.22質量%)479.0質量部、およびL-アスコルビン酸水溶液(L-アスコルビン酸濃度0.33質量%)479.0質量部とSR-20(有効成分25質量%)7.04質量部の混合組成物486.04質量部を、各々異なる投入口より反応釜へ4時間かけて均一に滴下した。滴下終了後、内温を85℃まで昇温し、同温度で2時間保持して熟成した後、反応溶液を冷却して、重合体粒子が分散した重合体水分散体1-1を得た。
前記で得られた重合体水分散体1-1 10質量部、及び塩基性水溶液としてアンモニア水溶液(濃度25.0質量%)1.1質量部を反応釜に加え、25℃で終夜撹拌することにより、部分的に加水分解された重合体粒子(1-1)が分散した重合体粒子水分散体(a1-1)を得た。得られた重合体粒子(1-1)の体積平均粒子径は393nmであった。
塩基性水溶液を水酸化ナトリウム水溶液(濃度20.0%)1.4質量部に変更した以外は製造例1-1と同様にして、加水分解された重合体粒子(1-2)が分散した重合体粒子水分散体(a1-2)を得た。得られた重合体粒子(1-2)の体積平均粒子径は399nmであった。
攪拌機、温度計及び冷却機を備えたステンレス製の第1の反応釜に、脱イオン水1128質量部、及びエーテルサルフェート型アンモニウム塩を主成分とするアニオン性反応性乳化剤アデカリアソープSR-20(有効成分100質量%、ADEKA社製)をイオン交換水で有効成分10質量%に希釈したもの(以下「SR-20(有効成分10質量%)」という)1.05質量部を加え、内温を75℃まで昇温し、同温度に保った。他方、第1の反応釜とは異なる第2の反応釜で、メタクリル酸メチル(以下「MMA」と称する)70質量部とDVB810 30質量部とを混合して、単量体組成物A100質量部を調製した。さらに、第1の反応釜、第2の反応釜とは異なる第3の反応釜で、RHMA90質量部と、DVB810 10質量部とを混合して、単量体組成物B100質量部を調製した。次に、第1の反応釜内を窒素ガスで置換した後、前記単量体組成物A100質量部、過酸化水素水(濃度3.35質量%)20質量部、及びL-アスコルビン酸水溶液(濃度5.0質量%)20質量部を第1の反応釜内に添加して、内温を75℃に保持し、2時間かけて初期重合反応を行った。続いて、前記単量体組成物B100質量部、過酸化水素水(濃度0.83質量%)100質量部、L-アスコルビン酸水溶液(濃度1.25質量%)100質量部、及びSR-20(有効成分10質量%)7.04質量部とアンモニア水溶液(濃度28質量%)0.36質量部とイオン交換水92.6質量%との混合組成物100質量部を、各々異なる投入口より、第1の反応釜へ3時間かけて均一に滴下した。滴下終了後、第1の反応釜の内温を75℃に保持し、同温度で2時間保持して熟成した後、反応溶液を冷却して、重合体粒子が分散した重合体水分散体1-3を得た。
前記で得られた重合体水分散体1-3 10質量部、及び塩基性水溶液としてアンモニア水溶液(濃度25.0質量%)1.1質量部を第1の反応釜に加え、25℃で終夜撹拌することにより、部分的に加水分解された重合体粒子(1-3)が分散した重合体粒子水分散体(a1-3)を得た。得られた重合体粒子(1-3)の体積平均粒子径は331nmであった。
塩基性水溶液を水酸化ナトリウム水溶液(濃度20%)1.4質量部に変更し、反応性乳化剤の量を目的の粒子径になるように適宜調整した以外は製造例1-3と同様にして、加水分解された重合体粒子(1-4)が分散した重合体粒子水分散体(a1-4)を得た。得られた重合体粒子(1-4)の体積平均粒子径は58.4nmであった。
単量体組成物BをRHMA80質量部とDVB810 10質量部と日油社製のブレンマーPME400(以下、PME400)10部に、塩基性水溶液を水酸化ナトリウム水溶液(濃度20%)1.2質量部に変更し、反応性乳化剤の量を目的の粒子径になるように適宜調整した以外は製造例1-3と同様にして、加水分解された重合体粒子(1-5)が分散した重合体粒子水分散体(a1-5)を得た。得られた重合体粒子(1-5)の体積平均粒子径は64.6nmであった。
攪拌機、温度計および冷却機を備えたステンレス製の反応釜に、脱イオン水832.0質量部およびSR-20(有効成分25.0質量%)0.96質量部加え、内温を75℃まで昇温し、同温度に保った。他方、上記反応釜とは異なる容器で、RHMA180.0質量部とDVB810 20.0質量部を混合して、単量体組成物200.0質量部を調製した。
上記反応釜内を窒素ガスで置換した後、上記単量体組成物40.0質量部、過酸化水素水(過酸化水素濃度1.28質量%)21.0質量部、およびL-アスコルビン酸水溶液(L-アスコルビン酸濃度1.90質量%)21.0質量部を上記反応釜内に添加して、初期重合反応を行った。次いで、上記単量体組成物の残部160.0質量部、過酸化水素水(過酸化水素濃度0.22質量%)479.0質量部、およびL-アスコルビン酸水溶液(L-アスコルビン酸濃度0.33質量%)479.0質量部とSR-20(有効成分25.0質量%)7.04質量部との混合組成物486.04質量部を、各々異なる投入口より反応釜へ4時間かけて均一に滴下した。滴下終了後、内温を75℃に保持し、同温度で2時間保持して熟成した後、反応溶液を冷却して、重合体粒子が分散した重合体水分散体1-6を得た。前記重合体粒子の体積平均粒子径は221nmであった。
前記重合体粒子水分散体1-6 100質量部、及び塩基性水溶液として水酸化ナトリウム水溶液(濃度20.0質量%)15質量部を混合し、25℃で終夜撹拌することにより、部分的に加水分解された重合体粒子(1-6)が分散した重合体粒子水分散体(a1-6)を得た。この際、得られた重合体粒子(1-6)の体積平均粒子径は389nmであった。
製造例1-6において水酸化ナトリウム水溶液を、アンモニア水溶液(濃度25.0%)5質量部に変更する以外は、同様にして部分的に加水分解された重合体粒子(1-7)が分散した重合体粒子水分散体(a1-7)を得た。この際、得られた重合体粒子(1-7)の体積平均粒子径は379nmであった。
<成膜試料A1-1の調製>
水系樹脂としてのエポクロスK-2035E((株)日本触媒製;固形分40質量%)と成膜助剤としてのCS-12(JNC社製;有効成分100質量%)とを、有効成分比(質量基準)で100:25の比率になるように配合し、最終固形分が10質量%となるように純水で希釈して、下地塗膜用組成物を得た。
次にアルミ板(縦:150mm、横:60mm、厚さ:0.100mm)に、下地塗膜用組成物を塗工後の膜厚が1.1μmとなるようにバーコーターで塗布し、自動排出型乾燥器(東上熱学社製「AT-101(標準型)」)にて160℃で11秒間乾燥して、下地層塗工済みアルミ板を得た。
親水性樹脂である水系ポリアクリル酸樹脂(重量平均分子量約5000)と重合体粒子水分散体(a1-1)と水系架橋剤((株)日本触媒製「エポクロスWS-700」;固形分25質量%)とを、固形分で100:25:18の比率(質量基準)になるように配合し、最終固形分が5質量%となるように純水で希釈して、塗膜用組成物A1-1を得た。
次に上記で作製した下地層塗工済みアルミ板の下地層塗工面に、塗膜用組成物A1-1を塗工後の膜厚が0.70μmとなるようにバーコーターで塗布し、自動排出型乾燥器(東上熱学社製「AT-101(標準型)」)にて200℃で11秒間乾燥して、塗膜が積層された成膜試料A1-1を得た。得られた成膜試料の評価結果を表2に示す。
<成膜試料A1-2~A1-5の調製>
配合する重合体粒子水分散体を以下に記載のものに変更し、水系ポリアクリル酸樹脂の固形分100部に対する各重合体粒子の添加量が表2に記載のものとなるように変更した以外は、実施例1-1と同様にして成膜試料A1-2~A1-5を調製した。得られた成膜試料の評価結果を表2に示す。
実施例1-2…重合体粒子水分散体(a1-2)
実施例1-3…重合体粒子水分散体(a1-3)
実施例1-4…重合体粒子水分散体(a1-4)
実施例1-5…重合体粒子水分散体(a1-5)
配合する重合体粒子水分散体を以下のものに変更した以外は、実施例1-1と同様にして成膜試料B1-1およびB1-2を調製した。得られた成膜試料の評価結果を表2に示す。
比較例1-1…シリカ粒子(日産化学社製「スノーテックスN」、平均粒子径12nm)
比較例1-2…アクリル粒子((株)日本触媒製「エポスターMX100W」、平均粒子径150nm)
重合体粒子水分散体を配合しなかった以外は、実施例1-1と同様にして成膜試料C1-1を調製した。得られた成膜試料の評価結果を表2に示す。
(1)親水性樹脂の作製
重量平均分子量4000のポリアクリル酸水溶液にモノエタノールアミンを投入し、pHを7.0に調整後、純水で調整することによりポリカルボン酸系樹脂(Z-1)を固形分濃度54%で含むポリカルボン酸系樹脂水溶液(Z-1a)を得た。
(2)塗工用組成物の調製
ポリカルボン酸系樹脂水溶液(Z-1a)と重合体粒子水分散体(a1-6)とを、樹脂(Z-1)と重合体粒子(1-6)が固形分で100:10の比率になるように配合し、最終固形分が5質量%となるように純粋で希釈した後、スターラーチップで十分に攪拌し、塗工用組成物を得た。
(3)成膜試料A1-6の調製
アルミテストパネル(日本テストパネル社製、A1050P、縦:150mm、横:70mm、厚さ:0.800mm)の塗工面をアセトンを含ませたキムワイプで、キムワイプに黒い汚れがつかなくなるまで拭いた。次に、ウルトラシーラーIII(日本ペイント社製)をアセトン洗浄したアルミテストパネルに、塗工後の膜厚が11.5μmとなるようにバーコーターで塗布し、送風定温恒温器(ヤマト科学社製「DNF400」)にて100℃で10分間乾燥して、表面が改質されたアルミテストパネルを準備した。
塗工用組成物を上記で作製したアルミテストパネルの改質面に塗工後の膜厚が45.8μmとなるようにバーコーターで塗布し、送風定温恒温器(ヤマト科学社製「DNF400」)にて200℃1分間乾燥して、塗膜が積層された成膜試料A1-6を得た。得られた成膜試料の評価結果を表2に示す。
配合する重合体粒子水分散体を重合体粒子水分散体(a1-7)に変更し、ポリカルボン酸系樹脂水溶液(Z-1a)と重合体粒子水分散体(a1-7)とを樹脂(Z-1)と重合体粒子(1-7)が固形分で100:20の比率になるように配合した以外は、実施例1-6と同様にして成膜試料A1-7を得た。得られた成膜試料の評価結果を表2に示す。
塗膜用組成物A1-1に代えて、親水性樹脂である水系ポリアクリル酸樹脂(重量平均分子量約5000)と重合体粒子水分散体(a1-5)と水系架橋剤((株)日本触媒製「エポクロスWS-700」;固形分25質量%)とL-アスコルビン酸とを、固形分で100:100:18:20の比率(質量基準)になるように配合し、最終固形分が5質量%となるように純水で希釈して得られた塗膜用組成物A1-8を用いたこと以外は、実施例1-1と同様にして成膜試料A1-8を得た。得られた成膜試料の評価結果を表2に示す。
重合体粒子水分散体を配合しなかった以外は、実施例1-6と同様にして成膜試料C-2を調製した。得られた成膜試料の評価結果を表2に示す。
<体積平均粒子径の測定>
実験例1における<体積平均粒子径の測定>と同様の手法にて、重合体粒子の体積平均粒子径(nm)を求めた。
実験例1における<初期親水性の評価>と同様の手法にて、有形物(塗膜)の初期接触角を求め、以下の基準により有形物(塗膜)の親水性を定量的に評価した。
◎:初期接触角が15°未満
○:初期接触角が15°以上40°未満
×:初期接触角が40°以上
滑落性評価として、有形物の表面(成膜試料の塗膜表面)に対する水滴の滑落角を測定した。
具体的には、有形物(成膜試料)を25℃の条件下、純水流水中に1時間浸漬させた後、25℃50%湿度の環境下で、取り出した有形物(成膜試料)を滑落角測定面(成膜試料であれば、試料の塗工面)が上面になるようにキムワイプ上に置き、上から別のキムワイプを覆い、5秒間その状態を維持した。その後有形物を取出し、滑落角測定面に対し、目視で確認できる水滴がなくなるまでエアブローを行うことで、余分な水分を除去し、送風定温恒温器(ヤマト科学社製「DNF400」)を用いて80℃で2時間乾燥させて、熱交換器使用時のフィン材(凝結水の付着及び加熱乾燥後のフィン材)を再現した有形物(成膜試料)を得た。以下、上記処理が施された有形物を「ヒートサイクル後の有形物」(具体的には、ヒートサイクル後の成膜試料)という。
自動接触角計(協和界面科学社製、「CA-X」)を用いて、25℃の条件下、純水10μLの水滴を作製し、水平に配置したヒートサイクル後の有形物の表面(ヒートサイクル後の成膜試料の塗膜表面)に着液させ、着滴後0.1秒後から0.5°ずつ2°/秒の速度で徐々に傾け、水滴が移動し始める角度を測定値とし、5回測定を行い、最大値と最小値の2点を除く3点の平均値を、滑落角θsとした。そして、以下の基準により有形物(塗膜)の滑水性を定量的に評価した。
◎:滑落角θsが15°未満
○:滑落角θsが15°以上30°未満
×:滑落角θsが30°以上
なお、水滴の移動判定は、図1に示すように、有形物1の表面に着滴してから0.1秒後の水滴(2a)における滑落方向と反対側の端点をR0、滑落方向側の端点をL0とし、傾斜角θの時の水滴(2b)の滑落方向と反対側の端点をRθ、滑落方向側の端点をLθとし、水滴の滑落方向と反対側の端点移動距離dR=-|Rθ-R0|、水滴の滑落方向側の端点移動距離dL=|Lθ-L0|とした時、dR+dL>1.00mmを初めて満たした時に水滴が移動したと判定し、その時の傾斜角θを滑落角θsと定義した。この定義は、滑落方向の水滴の端点移動から、濡れ広がりによる端点移動の影響を排除して、滑落による端点移動を抽出することを意図した評価方法である。
<製造例2-1>
攪拌機、温度計及び冷却機を備えたステンレス製の第1の反応釜に、脱イオン水1128質量部、SR-20(有効成分10質量%)1.05質量部を加え、内温を75℃まで昇温し、同温度に保った。他方、第1の反応釜とは異なる第2の反応釜で、MMA70質量部とDVB810 30質量部とを混合して、単量体組成物A100質量部を調製した。さらに、第1の反応釜、第2の反応釜とは異なる第3の反応釜で、RHMA90質量部と、DVB810 10質量部とを混合して、単量体組成物B100質量部を調製した。次に、第1の反応釜内を窒素ガスで置換した後、前記単量体組成物A100質量部、過酸化水素水(濃度3.35質量%)20質量部、及びL-アスコルビン酸水溶液(濃度5.0質量%)20質量部を第1の反応釜内に添加して、内温を75℃に保持し、2時間かけて初期重合反応を行った。続いて、前記単量体組成物B100質量部、過酸化水素水(濃度0.83質量%)100質量部、L-アスコルビン酸水溶液(濃度1.25質量%)100質量部、及びSR-20(有効成分10質量%)7.04質量部とアンモニア水溶液(濃度28質量%)0.36質量部とイオン交換水92.6質量部との混合組成物100質量部を、各々異なる投入口より、第1の反応釜へ3時間かけて均一に滴下した。滴下終了後、第1の反応釜の内温を75℃に保持し、同温度で2時間保持して熟成した後、反応溶液を冷却して、重合体粒子が分散した重合体水分散体2-1を得た。
前記で得られた重合体水分散体2-1 10質量部、及び塩基性水溶液として水酸化ナトリウム水溶液(濃度20%)1.4質量部を第1の反応釜に加え、25℃で終夜撹拌することにより、加水分解された重合体粒子(2-1)が分散した重合体粒子水分散体(a2-1)を得た。得られた重合体粒子(2-1)の体積平均粒子径は330nmであった。
単量体組成物BをRHMA80質量部とDVB810 10質量部とPME400 10部に変更し、塩基性水溶液を水酸化ナトリウム水溶液(濃度20%)1.2質量部に変更した以外は製造例2-1と同様にして、加水分解された重合体粒子(2-2)が分散した重合体粒子水分散体(a2-2)を得た。得られた重合体粒子(2-2)の体積平均粒子径は302nmであった。
<成膜試料A2-1の調製>
親水性樹脂である水系ポリアクリル酸樹脂(重量平均分子量約5000)と重合体粒子水分散体(a2-1)と水系架橋剤((株)日本触媒製「エポクロスWS-700」;固形分25質量%)とを、固形分で100:100:18の比率(質量基準)になるように配合し、最終固形分が5.45質量%となるように純水で希釈して、塗膜用組成物A2-1を得た。
次にアルミ板(縦:150mm、横:60mm、厚さ:0.100mm)の表面に、塗膜用組成物A2-1を塗工後の膜厚が1.00μmとなるようにバーコーターで塗布し、自動排出型乾燥器(東上熱学社製「AT-101(標準型)」)にて200℃で1分間乾燥して、塗膜が積層された成膜試料A2-1を得た。得られた成膜試料の評価結果を表4に示す。
<成膜試料A2-2>
配合する重合体粒子水分散体を重合体粒子水分散体(a2-2)に変更した以外は、実施例2-1と同様にして成膜試料A2-2を調製した。得られた成膜試料の評価結果を表4に示す。
重合体粒子水分散体を配合しなかった以外は、実施例2-1と同様にして成膜試料C2-1を調製した。得られた成膜試料の評価結果を表4に示す。
2a 着滴してから0.1秒後の水滴
2b 傾斜角θ時の水滴
R0 着滴してから0.1秒後の水滴における滑落方向と反対側の端点
L0 着滴してから0.1秒後の水滴における滑落方向側の端点
Rθ 傾斜角θ時の水滴の滑落方向と反対側の端点
Lθ 傾斜角θ時の水滴の滑落方向側の端点
Claims (17)
- -COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子を構成成分とする親水性持続効果及び/又は滑水性付与剤。
- 前記架橋重合体が、1分子中に1つ以上の-COOR基と1つ以上の水酸基と1つの重合性基とを有する単量体(AB1)に由来する構造単位と、1分子中に2つ以上の重合性基を有する単量体(C)に由来する構造単位とを含む、請求項1に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記架橋重合体が、前記式(1)で表される構造単位であって、R1がアルカリ金属原子又はアンモニウムであるものを含有する、請求項3に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記単量体(AB1)に由来する構造単位の含有量が、前記架橋重合体中、5質量%以上である、請求項2に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記単量体(C)に由来する構造単位の含有量が、前記架橋重合体中、0.01~70質量%である、請求項2に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記架橋重合体が、さらにポリオキシアルキレン基含有エチレン性不飽和単量体に由来する構造単位を含む、請求項2に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記粒子の体積平均粒子径が、10nm~10μmである、請求項1に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記粒子が前記架橋重合体を含む単層粒子であるか、前記架橋重合体をシェル層に含むコアシェル構造の粒子である、請求項1に記載の親水性持続効果及び/又は滑水性付与剤。
- 熱交換器のフィン材用である、請求項1に記載の親水性持続効果及び/又は滑水性付与剤。
- 前記フィン材がアルミニウム製のフィン材用である、請求項10に記載の親水性持続効果及び/又は滑水性付与剤。
- 請求項1~11のいずれかに記載の親水性持続効果及び/又は滑水性付与剤と、親水性樹脂とを有する樹脂組成物。
- 前記親水性樹脂が、カルボキシ基及びカルボキシ基の塩よりなる群から選択される少なくとも1種の極性官能基を側鎖に有する樹脂である、請求項12に記載の樹脂組成物。
- さらに架橋剤を含有する、請求項12に記載の樹脂組成物。
- -COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子を有形物に含有させる、有形物に、持続的親水化及び/又は滑水化を施す方法。
- -COOR基(Rは炭化水素基、水素原子、アルカリ金属原子、又はアンモニウムを表す)および水酸基を有する架橋重合体を含む粒子を含有する組成物を、基材に塗工することにより、前記粒子を含む塗膜を基材表面に形成させる、基材表面に持続的親水化及び/又は滑水化を施す方法。
- 前記基材が、熱交換器のフィン材である、請求項16に記載の方法。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23940796.8A EP4726008A1 (en) | 2023-06-08 | 2023-12-28 | Agent for imparting hydrophilicity-sustaining effect and/or water sliding properties |
| KR1020257040333A KR20260004509A (ko) | 2023-06-08 | 2023-12-28 | 친수성 지속 효과 및/또는 활수성 부여제 |
| JP2025525937A JPWO2024252703A1 (ja) | 2023-06-08 | 2023-12-28 | |
| CN202380099026.3A CN121241114A (zh) | 2023-06-08 | 2023-12-28 | 亲水性持续效果和/或滑水性赋予剂 |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023094540 | 2023-06-08 | ||
| JP2023-094540 | 2023-06-08 | ||
| JP2023162888 | 2023-09-26 | ||
| JP2023-162888 | 2023-09-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024252703A1 true WO2024252703A1 (ja) | 2024-12-12 |
Family
ID=93795794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/047171 Ceased WO2024252703A1 (ja) | 2023-06-08 | 2023-12-28 | 親水性持続効果及び/又は滑水性付与剤 |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP4726008A1 (ja) |
| JP (1) | JPWO2024252703A1 (ja) |
| KR (1) | KR20260004509A (ja) |
| CN (1) | CN121241114A (ja) |
| WO (1) | WO2024252703A1 (ja) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0987576A (ja) | 1995-09-22 | 1997-03-31 | Kansai Paint Co Ltd | 親水化処理用組成物及び親水化処理方法 |
| JP2000328038A (ja) | 1999-05-18 | 2000-11-28 | Kansai Paint Co Ltd | 親水化処理用組成物及び親水化処理方法 |
| JP2013092289A (ja) | 2011-10-25 | 2013-05-16 | Kagawa Univ | 超撥水撥油性熱交換部材とその製造方法並びにそれらを用いた熱交換器 |
| WO2014147782A1 (ja) | 2013-03-21 | 2014-09-25 | 日本パーカライジング株式会社 | 排水性に優れたアルミニウム含有金属製熱交換器の親水性表面処理剤 |
| CN104262552A (zh) * | 2014-09-22 | 2015-01-07 | 玉林师范学院 | 硅溶胶/硅丙纳米核壳复合乳液及其制备方法 |
| CN105199049A (zh) * | 2015-08-28 | 2015-12-30 | 中国海洋石油总公司 | 一种具有核壳结构的羟基丙烯酸乳液及其制备方法 |
| WO2020213485A1 (ja) | 2019-04-18 | 2020-10-22 | Dic株式会社 | 構造体、構造体の製造方法、熱交換機用部材及び熱交換器 |
| JP7162125B2 (ja) * | 2019-03-29 | 2022-10-27 | 株式会社日本触媒 | 樹脂粒子及びその製造方法、並びに該樹脂粒子を含む親水性付与剤 |
| JP2023058950A (ja) * | 2021-10-14 | 2023-04-26 | 株式会社日本触媒 | アンチブロッキング剤 |
| JP2023094540A (ja) | 2021-12-23 | 2023-07-05 | エルジー ディスプレイ カンパニー リミテッド | 表示装置 |
| JP2023162888A (ja) | 2022-04-27 | 2023-11-09 | セイコーエプソン株式会社 | 反射型光学装置、光源装置およびプロジェクター |
| JP2024009825A (ja) * | 2022-07-11 | 2024-01-23 | 株式会社日本触媒 | 親水性持続効果付与剤 |
-
2023
- 2023-12-28 JP JP2025525937A patent/JPWO2024252703A1/ja active Pending
- 2023-12-28 KR KR1020257040333A patent/KR20260004509A/ko active Pending
- 2023-12-28 EP EP23940796.8A patent/EP4726008A1/en active Pending
- 2023-12-28 WO PCT/JP2023/047171 patent/WO2024252703A1/ja not_active Ceased
- 2023-12-28 CN CN202380099026.3A patent/CN121241114A/zh active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0987576A (ja) | 1995-09-22 | 1997-03-31 | Kansai Paint Co Ltd | 親水化処理用組成物及び親水化処理方法 |
| JP2000328038A (ja) | 1999-05-18 | 2000-11-28 | Kansai Paint Co Ltd | 親水化処理用組成物及び親水化処理方法 |
| JP2013092289A (ja) | 2011-10-25 | 2013-05-16 | Kagawa Univ | 超撥水撥油性熱交換部材とその製造方法並びにそれらを用いた熱交換器 |
| WO2014147782A1 (ja) | 2013-03-21 | 2014-09-25 | 日本パーカライジング株式会社 | 排水性に優れたアルミニウム含有金属製熱交換器の親水性表面処理剤 |
| CN104262552A (zh) * | 2014-09-22 | 2015-01-07 | 玉林师范学院 | 硅溶胶/硅丙纳米核壳复合乳液及其制备方法 |
| CN105199049A (zh) * | 2015-08-28 | 2015-12-30 | 中国海洋石油总公司 | 一种具有核壳结构的羟基丙烯酸乳液及其制备方法 |
| JP7162125B2 (ja) * | 2019-03-29 | 2022-10-27 | 株式会社日本触媒 | 樹脂粒子及びその製造方法、並びに該樹脂粒子を含む親水性付与剤 |
| WO2020213485A1 (ja) | 2019-04-18 | 2020-10-22 | Dic株式会社 | 構造体、構造体の製造方法、熱交換機用部材及び熱交換器 |
| JP2023058950A (ja) * | 2021-10-14 | 2023-04-26 | 株式会社日本触媒 | アンチブロッキング剤 |
| JP2023094540A (ja) | 2021-12-23 | 2023-07-05 | エルジー ディスプレイ カンパニー リミテッド | 表示装置 |
| JP2023162888A (ja) | 2022-04-27 | 2023-11-09 | セイコーエプソン株式会社 | 反射型光学装置、光源装置およびプロジェクター |
| JP2024009825A (ja) * | 2022-07-11 | 2024-01-23 | 株式会社日本触媒 | 親水性持続効果付与剤 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN121241114A (zh) | 2025-12-30 |
| EP4726008A1 (en) | 2026-04-15 |
| JPWO2024252703A1 (ja) | 2024-12-12 |
| KR20260004509A (ko) | 2026-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2024009825A (ja) | 親水性持続効果付与剤 | |
| JP5600081B2 (ja) | 熱交換器用プレコートフィン材及び熱交換器 | |
| JP6618903B2 (ja) | アルミニウム製フィン材の親水皮膜被覆方法、アルミニウム製フィン材及びアルミニウム製熱交換器 | |
| JP2009126948A (ja) | 親水化処理剤 | |
| CN112262041B (zh) | 预涂覆铝材 | |
| JP2011148889A (ja) | 親水化処理剤 | |
| JP2016222879A (ja) | 親水化処理剤、親水皮膜形成方法及び親水皮膜 | |
| JP6110777B2 (ja) | 水性塗料組成物及び塗装物品 | |
| WO2024252703A1 (ja) | 親水性持続効果及び/又は滑水性付与剤 | |
| JP4999137B2 (ja) | 親水性ハードコート用組成物、ハードコート用材料及びハードコート膜の形成方法 | |
| KR102636889B1 (ko) | N-비닐카르복실산아미드의 중합체를 포함하는 수성 도공액용 조성물 | |
| WO2017123881A1 (en) | Permanently grafted glaciophobic nanomaterials and methods of making | |
| WO2025225528A1 (ja) | 親水化処理組成物 | |
| JP5881496B2 (ja) | 剥離基材用下塗り剤 | |
| JP7455320B2 (ja) | 制振性塗膜 | |
| CN100572470C (zh) | 涂膜、水性涂覆材料和使用其的涂膜制造方法及形成涂膜的涂装物 | |
| WO2018132069A1 (en) | A polymer dispersion | |
| WO2025225527A1 (ja) | 親水化処理組成物 | |
| TWI822211B (zh) | 防霧層及其利用 | |
| CN107969132A (zh) | 水系表面处理剂、覆膜的制造方法和经表面处理的材料 | |
| TWI822201B (zh) | 防霧層及其利用 | |
| TWI822212B (zh) | 防霧層及其利用 | |
| JP5545860B2 (ja) | 水性樹脂組成物 | |
| JP7825670B2 (ja) | アクリル樹脂及びその製造方法並びにアクリル樹脂組成物 | |
| JP2019112515A (ja) | 塗料組成物及び親水性部材 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23940796 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2025525937 Country of ref document: JP Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2025525937 Country of ref document: JP |
|
| ENP | Entry into the national phase |
Ref document number: 1020257040333 Country of ref document: KR Free format text: ST27 STATUS EVENT CODE: A-0-1-A10-A15-NAP-PA0105 (AS PROVIDED BY THE NATIONAL OFFICE) |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2501008244 Country of ref document: TH Ref document number: 1020257040333 Country of ref document: KR |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2023940796 Country of ref document: EP |
|
| WWP | Wipo information: published in national office |
Ref document number: 1020257040333 Country of ref document: KR |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2023940796 Country of ref document: EP Effective date: 20260108 |
|
| ENP | Entry into the national phase |
Ref document number: 2023940796 Country of ref document: EP Effective date: 20260108 |
|
| ENP | Entry into the national phase |
Ref document number: 2023940796 Country of ref document: EP Effective date: 20260108 |
|
| ENP | Entry into the national phase |
Ref document number: 2023940796 Country of ref document: EP Effective date: 20260108 |
|
| WWP | Wipo information: published in national office |
Ref document number: 2023940796 Country of ref document: EP |










